JP4199079B2 - Allylene vinylene polymer materials - Google Patents

Description

  The present invention relates to a functional organic compound for an electronic material, and more particularly to an arylene vinylene polymer material which is expected to be used in a wide range of fields as an electroluminescence light-emitting material, a conductive material, or a semiconductor material.

  In recent years, as described above, allylene vinylene-based polymer materials are expected to be used in a wide variety of industries as electroluminescent light-emitting materials, conductive materials, semiconductor materials, and the like.

  Conventionally, various methods for producing these arylene vinylene polymer materials have been proposed. As such an example, an aromatic bishalomethyl compound (monomer: monomer) as shown in the following formula (III) is started. As a substance, a method of polymerizing this in the presence of a base is known.

  (In the formula, for example, X represents a halogen atom such as fluorine, chlorine, bromine or iodine, and Ar represents an arylene derivative such as a phenylene group).

  As another example of the production method, a method of producing an aromatic bishalomethyl compound as a sulfonium salt and then producing it via a precursor polymer as shown in the following formula (IV) is also known.

  (In the formula, for example, X represents a halogen atom such as fluorine, chlorine, bromine or iodine, Ar represents an arylene derivative such as a phenylene group, etc., and R represents a straight chain, branched chain, or bonded to each other to form a ring. Represents an alkyl group or the like.)

A high-molecular-weight body having a high-quality film forming ability can be obtained by the production method.
For example, a bischloromethyl compound is used as a starting material, polymerized with an alkali (t-BuOK), and then heated to obtain a conjugated polymer. Use as an active layer has been proposed (see, for example, Patent Document 1). Alternatively, the bissulfonium salt intermediate is first polymerized in the presence of a base, and the resulting polymer precursor is heat-treated in a reducing atmosphere (containing 15% hydrogen in nitrogen), resulting in conventional high-temperature treatment. It has been proposed to obtain poly (p-phenylene vinylene) that suppresses the formation of the carbonyl group, and apply this to a light emitting diode (see, for example, Patent Document 2).

  However, when an organic compound is applied and developed as an electronic material, it has been pointed out that the incorporation of a trace amount of impurities has a great adverse effect on the material properties, and the importance of increasing the purity of the material has been gradually recognized.

  That is, when a polymer material is applied as a functional material, for example, an electronic material, it is necessary to consider the reduction of structural defects present in the polymer chain in addition to the removal of impurities. Unlike the impurities, the structural defects once formed in the polymer chain during the polymerization reaction cannot be physically removed. Such a structural defect in the polymer chain is usually not expressed in a general formula indicating the chemical structure of the polymer compound, so care must be taken.

  It has been pointed out that the arylene vinylene polymers produced by the methods represented by the above formulas (III) and (IV) also have structural defects characteristic to the polymerization method. For example, according to (Becker) Becker et al. (“New Insights into the Microstructure of GILCH-Polymerized PPVs”), (Germany), Macromolecules, 1999, 32, 4925-4932).

  This structural defect is called a trambisbenzyl defect, and as shown in the following formula (V), the two bonds that should exist as double bonds with an aromatic group in between are a single bond and a triple bond. It is a structural defect that becomes a bond and exists adjacent to each other across an aromatic group. That is, since a single bond exists in this structural defect, the π-conjugated system of the molecule is broken.

  (In the formula, Ar represents an aromatic group, and x and y represent the number of repeating units (natural number).)

  The reason for the generation of the structural defect is considered to be that the regioselectivity of the reaction is incomplete when the quinoid structure formed by the reaction of the monomer with 1 mole of base is polymerized. Since this defect is present in the repeating unit in the polymer in the order of several percent, the π-conjugated system that was expected to be developed throughout the entire polymer main chain is interrupted in the middle, and actually has only a conjugate length at the oligomer level. .

Therefore, when the above polymer material system is used as an electronic material, there is a problem that this structural defect has a tremendous adverse effect on the charge transport characteristics, and when this material system is used as an electroluminescent material. However, it has been pointed out that this structural defect significantly reduces the lifetime of the electroluminescence element.
Japanese National Patent Publication No. 9-501022 JP-A-7-188331

  The present invention has been made in view of the current state of the prior art, and improves the charge transport characteristics and electroluminescence device characteristics by modifying the structural defects and suppressing the division of the π-conjugated system in the polymer. It is an object of the present invention to provide an allylene vinylene polymer material and a method for modifying such a material.

  As a result of intensive studies, the present inventors have obtained a polymer obtained by polymerizing a monomer as a starting material in the presence of a base when obtaining an arylene vinylene polymer material, and further dehydrating with an oxidizing agent. The present inventors have found that the above-mentioned problems can be solved by introducing an elementary reaction step and modifying it, and have reached the present invention. Hereinafter, the present invention will be specifically described.

  The invention of claim 1 provides the following general formula (I):

  (In the formula, Ar represents a substituted or unsubstituted aromatic group, and L represents a leaving group.)

A compound represented by the following general formula (II) obtained by polymerizing the starting material in the presence of a base:

  (In the formula, Ar represents a substituted or unsubstituted aromatic group, and when a plurality of Ar are present, they may be the same or different. N represents a natural number.)

An arylene vinylene-based polymer material obtained by modifying a polymer having a structure represented by the above formula and a tranbisbenzyl defect structure by dehydrogenation treatment with an oxidizing agent It is.

  The invention according to claim 2 is the arylene vinylene polymer material according to claim 1, which is obtained by further removing the oxidizing agent after the treatment with the oxidizing agent.

  The invention according to claim 3 is the arylene vinylene polymer material according to claim 1 or 2, wherein the oxidizing agent is selected from at least one of DDQ, o-chloranil, and chloranil.

  In the invention of claim 4, the aromatic group (Ar) in the general formula (I) has at least one substituted or unsubstituted alkyl group, alkoxy group, or thioalkoxy group having 1 to 25 carbon atoms. The arylene vinylene polymer material according to any one of claims 1 to 3.

  In the invention of claim 5, the aromatic group (Ar) in the general formula (II) has at least one substituted or unsubstituted alkyl group, alkoxy group, or thioalkoxy group having 1 to 25 carbon atoms. The arylene vinylene polymer material according to any one of claims 1 to 3.

  The invention of claim 6 provides the following general formula (I):

  (In the formula, Ar represents a substituted or unsubstituted aromatic group, and L represents a leaving group.)

A step of polymerizing the compound represented by formula (II) in the presence of a base, and the following general formula (II) obtained by the polymerization step:

(In the formula, Ar represents a substituted or unsubstituted aromatic group, and when a plurality of Ar are present, they may be the same or different. N represents a natural number.)
In the structure shown, seen including a trunk bis benzyl defect structure, a step of dehydrogenation treatment with an oxidizing agent a polymer having, treating dehydrogenation reaction, to modify the trunk bis benzyl defect structure This is a method for modifying an arylene vinylene polymer material.

  The invention of claim 7 further comprises a step of removing the oxidant after the step of dehydrogenating the polymer with an oxidant, and the step of removing the oxidant. This is a method for modifying a material.

  The invention according to claim 8 is characterized in that the oxidizing agent is selected from at least one of DDQ, o-chloranil and chloranil, and the method for modifying an arylene vinylene polymer material according to claim 6 or 7 It is.

  The invention of claim 9 is an organic electroluminescent device comprising a light emitting layer or a plurality of thin layers including a light emitting layer between a pair of electrodes, wherein the light emitting layer or a plurality of thin layers including the light emitting layer is a claim 1. It is an organic electroluminescent element characterized by including the layer which consists of arylene vinylene type polymer materials in any one of -5.

  The invention according to claim 10 is a charge transport material having a charge transport function, which is used as a functional organic compound, and the material comprises the arylene vinylene polymer material according to any one of claims 1 to 5. Charge transport material characterized by the above.

  2. The arylene vinylene polymer material according to claim 1, wherein the polymer obtained by polymerization in the presence of a base is further improved in structural defects by a dehydrogenation reaction step using an oxidizing agent, and the molecular π-conjugated system is fragmented. Can be suppressed. As a result, it is possible to provide an arylene vinylene polymer material with improved charge transport characteristics and electroluminescent element characteristics.

  In the arylene vinylene polymer material according to the second aspect, since the oxidizing agent is removed, the conductivity can be reduced without inducing the doping of the oxidizing agent into the conjugated polymer. For this reason, it is possible to apply also to the use (for example, use as a luminescent material or an optical material) which does not require electroconductivity.

  In the arylene vinylene polymer material according to claim 3, in order to promote the dehydrogenation reaction without adversely affecting the polymer skeleton of the polymer material to be modified, the π-conjugated system of the molecule is improved. It can be done well. As a result, it is possible to provide an arylene vinylene polymer material with further improved charge transport characteristics and electroluminescent element characteristics.

  According to claim 4 or 5, the aromatic group of the general formula (I) or the general formula (II) is at least a substituted or unsubstituted alkyl group having 1 to 25 carbon atoms, an alkoxy group, or a thioalkoxy group, respectively. By having one, in addition to the above-mentioned effects, good solubility in a solvent is imparted. In addition, desired charge transport characteristics can be exhibited while maintaining the solubility of the polymer material. As a result, it is possible to provide an arylene vinylene polymer material in which workability and charge transport properties are balanced.

  According to the modification method of claim 6, it is possible to provide a modification method for obtaining an arylene vinylene polymer material having improved charge transport characteristics and electroluminescent element characteristics.

  According to the modification method of claim 7, since the conductivity can be reduced, it is possible to provide a modification method for obtaining an arylene vinylene-based polymer material that is applied to applications that do not require conductivity. It is.

  According to the eighth aspect, the arylene vinylene system which can satisfactorily suppress fragmentation of the π-conjugated system of molecules without adversely affecting the polymer skeleton of the polymer material, and has excellent charge transport characteristics and electroluminescent element characteristics. It is possible to provide a modification method for obtaining a polymeric material.

  According to claim 9, by using the modified arylene vinylene polymer material of the present invention as a light-emitting layer or a material for a plurality of thin layers including a light-emitting layer, an electroluminescent device having improved device lifetime. A sense element can be provided.

  According to the tenth aspect, it is possible to provide a functional polymer material excellent in charge transporting ability that can be applied to electronic materials and the like.

  As described above, the present invention is obtained by polymerizing a compound represented by the general formula (I) as a starting material (monomer) in the presence of a base (using a basic compound). The arylene vinylene-based polymer material obtained by further modifying the polymer represented by the general formula (II) by treatment with an oxidizing agent.

  Examples of basic compounds used in the polymerization reaction include alkali metal and alkaline earth metal hydroxides, carbonates, acetates, alkoxides, and various amines (primary, secondary, tertiary). Etc.).

  In the polymer represented by the general formula (II) obtained in the presence of the above base, there is a tranbisbenzyl defect as shown in (a) of the following formula (VI) before treatment with an oxidizing agent. This defect has a structure in which a dehydrogenation reaction occurs as shown in the following formula (VI) (b) by introducing the treatment step using an oxidizing agent in the present invention, and a π-conjugated system that has been cut by the defect is continuous. And the effective conjugate length increases.

  (In the formula, Ar represents a substituted or unsubstituted aromatic group, and each Ar may be the same or different. X and y represent natural numbers.)

The disappearance of the structural defect as shown in (b) of the above formula (VI) has the same meaning as the increase in the degree of purification of the polymer material.
Therefore, the polymer (arylene vinylene-based polymer material) that has undergone the treatment step with the oxidizing agent in the present invention has dramatically improved charge transport characteristics, such as a semiconductor layer of an organic thin film transistor, an organic electroluminescence element (organic EL element), and the like. It can be suitably used as a light emitting layer or a charge transport layer.

  The schematic diagram of FIG. 1 shows a simple schematic configuration example of an organic EL element provided with a light emitting layer or a plurality of thin layers including a light emitting layer (using the allylene vinylene polymer material of the present invention in a required portion). . A dielectric layer may be provided between each electrode and the light emitting layer as necessary. Such a dielectric layer may be provided for charge transport, for example.

  As the oxidant used for the dehydrogenation reaction in the present invention, a known general one may be used. However, in the case of an oxidant that proceeds the dehydrogenation reaction at the dibenzyl site but does not adversely affect other polymer skeletons. It may be arbitrarily selected depending on the situation. As such an oxidizing agent, for example, DDQ (2,3-dichloro-5,6-dicyanobenzoquinone), o-chloranil, or chloranil is preferably used.

The oxidizing agent treatment step is usually performed in the presence of a solvent. Any solvent can be used as long as the dehydrogenation reaction activity is maintained. Examples include benzene, chloroform, toluene, tetrahydrofuran, dioxane, dichloroethane and the like. The amount of the solvent used is usually 10 to 2000 times the weight ratio of the polymer material to be treated.
In addition, there is no special restriction | limiting in the temperature conditions in the case of an oxidizing agent process, Usually, it processes in the boiling point temperature of a solvent from 0 degreeC.

  The oxidant treatment step induces doping of the conjugated polymer with the oxidant, and changes in absorption spectrum, metallic luster, and fluorescence quenching based on this doping are observed. Therefore, when the arylene vinylene-based material after treatment with an oxidizing agent is used as a conductive medium, it can be used as it is without removing the oxidizing agent. When used in applications such as optical materials and optical materials, an oxidizing agent removal process may be performed.

  A known technique can be applied as a method for removing the oxidizing agent. Examples of such techniques include various methods including dialysis, Soxhlet extraction, solution washing, reprecipitation, electrochemical techniques, and the like.

  By removing the oxidizing agent, the absorption wavelength of the arylene vinylene-based material after the treatment is almost equal to or slightly red-shifted before the oxidation treatment, and also exhibits the light emission characteristics. Therefore, if the allylene vinylene polymer material of the present invention is used as a charge transport layer or a light emitting layer as in the conventional case, an electroluminescent device with improved characteristics can be produced.

  The aromatic group (Ar) in the general formula (I) of the monomer (monomer) that is the starting material used in the present invention and the general formula (II) of the polymer is a substituted or unsubstituted aromatic. And when there are a plurality of groups, they may be the same or different.

  Specific examples of such an aromatic group (Ar) include monocyclic and polycyclic aromatic hydrocarbon groups (condensed polycyclic groups and non-condensed polycyclic groups). Can be mentioned. Examples include a phenyl group, a naphthyl group, a pyrenyl group, a fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrycenyl group, a biphenyl group, and a terphenyl group. Heteroaromatic groups are also exemplified, and examples include five-membered ring heterocyclic groups including thiophene, pyrrole, furan, and oxazole, or condensed polycyclic groups and non-condensed polycyclic groups in which they are further substituted. Can be mentioned.

Moreover, these aromatic groups may have the substituent shown below.
(1) Halogen atom, trifluoromethyl group, cyano group, nitro group.
(2) An unsubstituted or substituted alkyl group or alkoxy group having 1 to 25 carbon atoms.
(3) Aryloxy group. (Examples of the aryl group include an aryloxy group having a phenyl group or a naphthyl group. These include an unsubstituted or substituted alkyl group having 1 to 25 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 25 carbon atoms, Alternatively, a halogen atom may be contained as a substituent (specifically, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 4-chlorophenoxy group). Group, 6-methyl-2-naphthyloxy group and the like.)
(4) An alkylthio group or an arylthio group. (Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group.)
(5) An alkyl-substituted amino group. (Specifically, diethylamino group, N-methyl-N-phenylamino group, N 2, N-diphenylamino group, N 2, N-di (p-tolyl) amino group, dibenzylamino group, piperidino group, morpholino group And a urolidyl group.)
(6) Acyl group. (Specific examples include an acetyl group, a propionyl group, a butyryl group, a malonyl group, and a benzoyl group.)

  From the viewpoint of solubility in an organic solvent that is important in the oxidation process or subsequent processes, it is more preferable to have a substituent on the aromatic ring, and examples thereof include an alkyl group, an alkoxy group, and an alkylthio group. It is done.

  If the number of carbons of these substituents increases, the solubility will be improved, but on the other hand, the properties such as charge transportability will decrease, so that the desired properties can be obtained within the range where the solubility is not impaired. It is preferred to select a substituent. Examples of suitable substituents in that case include an alkyl group having 1 to 25 carbon atoms, an alkoxy group, and an alkylthio group.

  More preferable examples include an alkyl group having 2 to 18 carbon atoms, an alkoxy group, and an alkylthio group. A plurality of the same substituents may be introduced, or a plurality of different substituents may be introduced. These alkyl groups, alkoxy groups and alkylthio groups are further halogen atoms, cyano groups, phenyl groups, hydroxyl groups, carboxyl groups, linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, alkoxy groups, alkylthio groups. A phenyl group substituted with a group may be contained.

  Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, pentyl group, hexyl group, Heptyl, octyl, nonyl, decyl, 3,7-dimethyloctyl, 2-ethylhexyl, trifluoromethyl, 2-cyanoethyl, benzyl, 4-chlorobenzyl, 4-methylbenzyl, A cyclopentyl group, a cyclohexyl group, etc. can be mentioned as an example, As an alkoxy group and an alkylthio group, what made the alkoxy group and the alkylthio group by inserting an oxygen atom or a sulfur atom in the bond position of the said alkyl group is mentioned as an example. .

  Examples of the leaving group (L) in the monomer represented by the general formula (I) include a sulfonium salt derived from a halogen atom or thioether. The halogen atom is preferably chlorine, bromine or iodine, and the sulfonium salt is preferably a sulfonium salt derived from the halomethyl compound, dialkyl sulfide or tetrahydrothiophene.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples unless it exceeds the gist.
First, poly [2- (3,7-dimethyloctyloxy) -5-methoxy-p-phenylene vinylene (abbreviated, polyparaphenylene vinylene (A)) and poly (2-octyloxy-5- 5] used in the examples were used. Synthesis examples of methoxy-p-phenylene vinylene (abbreviated, polyparaphenylene vinylene (B)) are shown below as Reference Example 1 and Reference Example 2.

Reference Example 1: Synthesis of polyparaphenylene vinylene (A) Poly [2- (3,7-dimethyloctyloxy) -5-methoxy-p-phenylene vinylene was synthesized under the following conditions according to the following formula (VII). .

Into a 1 L four-necked flask, 820 ml of 1,4-dioxane was placed, and nitrogen gas was bubbled for 15 minutes. To this was added 5.00 g (13.84 mmol) of 2,5- (bischloromethyl) -1- (3,7-dimethyloctyloxy) -4-methoxybenzene and heated to 100 ° C. To this solution, 36 ml (36 mmol) of 1.0M tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred for 5 minutes, and then 28 ml (28 mmol) of 1.0M tetrahydrofuran solution of potassium t-butoxide was added dropwise. Stir for 4 hours. Thereafter, 5.5 ml of acetic acid was added to stop the reaction, and the reaction solution was added dropwise to 1 L of water. The precipitated polymer was separated by filtration, washed with water and methanol, and dried. Further purification by reprecipitation using tetrahydrofuran and methanol gave 2.15 g of a red polymer. The polymer emitted red to orange fluorescence.
Elemental analysis (calculated); C: 79.15% (79.12%), H: 10.04% (9.79%).
The weight average molecular weight in terms of polystyrene measured by GPC was 988000, and the number average molecular weight was 113,000.

Reference Example 2: Synthesis of polyparaphenylene vinylene (B) Poly (2-octyloxy-5-methoxy-p-phenylene vinylene) was synthesized in the same manner as in Reference Example 1 along the following formula (VIII).

The resulting poly (2-octyloxy-5-methoxy-p-phenylenevinylene) was a red polymer that emitted red to orange fluorescence.
Elemental analysis (calculated); C: 78.09% (78.42%), H: 9.62% (9.29%).
The weight average molecular weight in terms of polystyrene measured by GPC was 310000, and the number average molecular weight was 60000.

(Example 1)
A 500 ml flask was charged with 492.3 mg of polyparaphenylene vinylene (A) obtained in Reference Example 1, 420 ml of 1,4-dioxane, and 100 mg of DDQ, and refluxed for 24 hours. The solvent was distilled off under reduced pressure to obtain a dark green glossy polymer. This polymer had conductivity.

  Further, the polymer obtained above was thoroughly washed with methanol, and then reprecipitation purification was repeated using tetrahydrofuran and methanol. The obtained polymer was further dissolved in chloroform, and this solution was repeatedly washed with ion-exchanged water. After the solvent was distilled off under reduced pressure, the residue was dried under reduced pressure to obtain 460 mg of a red polymer.

  No CN stretching was observed in the infrared absorption spectrum of this polymer. The proton NMR spectrum of the deuterated chloroform solution of the polymer before and after the oxidation treatment is shown in FIG. It was confirmed that the bisbenzyl structure was changed to the vinylene structure by the oxidation treatment. Moreover, the absorption spectrum of the tetrahydrofuran solution of the polymer before an oxidation process and the polymer which removed the oxidizing agent after the oxidation process is shown in FIG. Almost no change in absorption maximum wavelength was observed, but an increase in extinction coefficient was observed. As inferred from the absorption spectrum, the fluorescent color was the same color.

(Example 2)
The polyparaphenylene vinylene (B) obtained in Reference Example 2 was subjected to an oxidation treatment by the same method as in Example 1 to obtain a dark green glossy polymer. This polymer had conductivity.
Further, the oxidizing agent was removed by the same method as in Example 1 to obtain a red polymer. Proton NMR measurement confirmed that the bisbenzyl structure was changed to the vinylene structure.

(Example 3)
A 3 wt% tetrahydrofuran solution of the polymer (oxidized polyparaphenylene vinylene (A)) obtained in Example 1 was prepared. This solution was applied by a doctor blade onto a polyethylene terephthalate substrate (PET substrate) on which aluminum (for electrodes) was deposited, to produce a film of approximately 10 μm. A gold electrode was further deposited on this film to produce a sandwich cell (see FIG. 4). When the carrier mobility was measured by the time-of-flight method using the element configured as described above, high-speed hole transportability of 1.19 × 10 ⁻⁴ cm ² V ⁻¹ s ^{−1 at} an electric field strength of 2000 Vcm ⁻¹ . showed that.

Example 4
Using the polymer obtained in Example 2 above, a device was produced in the same manner as in Example 3, and the carrier mobility was measured by the same method. As a result, the hole transportability was almost as high as that in Example 3. Was observed.

(Comparative Example 1)
A cell was prepared in the same manner as in Example 3 using the polymer obtained in Reference Example 1 as it was without being subjected to oxidation treatment, and the carrier mobility was measured in the same manner as in Example 3. As a result, it showed a hole mobility of 1.76 × 10 ⁻⁶ cm ² V ⁻¹ s ⁻¹ at an electric field strength of 150 kVcm ⁻¹ , which was two orders of magnitude lower than the result of Example 3.

(Comparative Example 2)
A cell was produced in the same manner as in Example 3 using the polymer obtained in Reference Example 2 as it was without subjecting it to an oxidation treatment, and the carrier mobility was measured by the same method as in Example 3. As a result, the hole mobility was 1.57 × 10 ⁻⁷ cm ² V ⁻¹ s ⁻¹ at an electric field strength of 130 kVcm ⁻¹ , which was three orders of magnitude lower than the result of Example 4.

  From the above results, treatment with the oxidant in the present invention improves the defect structure of the molecule, changes the π-conjugated system to a continuous structure, and dramatically improves the charge transfer characteristics. confirmed. Therefore, the material (arylene vinylene-based polymer material) that has undergone the treatment process of the present invention can be suitably used as a semiconductor layer of an organic thin film transistor, a light emitting layer of an organic EL element, or a charge transport layer. Application expansion is expected.

It is a schematic diagram which shows the example of schematic structure of the organic EL element using the arylene vinylene type polymer material of this invention. It is a proton NMR spectrum of a deuterated chloroform solution before and after the oxidation treatment of the arylene vinylene polymer material (polymer) according to the present invention. Example 1 It is an absorption spectrum of the polymer before oxidation processing which concerns on this invention, and the tetrahydrofuran solution of the polymer which removed the oxidizing agent after oxidation processing. Example 1 It is a schematic block diagram of the sandwich cell for measuring a charge transfer characteristic.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Organic EL element 2 Substrate 3 Electrode 4 Light emitting layer or plural thin layers including light emitting layer 5 Electrode 6 Polyethylene terephthalate substrate (PET substrate)
7 Aluminum electrode 8 Polymer (oxidized polyparaphenylene vinylene)
9 Gold electrode

Claims (10)

The following general formula (I):

(In the formula, Ar represents a substituted or unsubstituted aromatic group, and L represents a leaving group.)
A compound represented by the following general formula (II) obtained by polymerizing the starting material in the presence of a base:

(In the formula, Ar represents a substituted or unsubstituted aromatic group, and when a plurality of Ar are present, they may be the same or different. N represents a natural number.)
An arylene vinylene-based polymer material obtained by modifying a polymer having a structure represented by the above formula and a tranbisbenzyl defect structure by dehydrogenation treatment with an oxidizing agent .   2. The allylene vinylene-based polymer material according to claim 1, obtained by further removing the oxidizing agent after the treatment with the oxidizing agent.   The arylene vinylene polymer according to claim 1 or 2, wherein the oxidizing agent is selected from at least one of 2,3-dichloro-5,6-dicyanobenzoquinone, o-chloranil, and chloranil. material.   The aromatic group (Ar) in the general formula (I) has at least one substituted or unsubstituted alkyl group, alkoxy group, or thioalkoxy group having 1 to 25 carbon atoms. The allylene vinylene-based polymer material according to any one of?   The aromatic group (Ar) in the general formula (II) has at least one substituted or unsubstituted alkyl group, alkoxy group, or thioalkoxy group having 1 to 25 carbon atoms. The allylene vinylene-based polymer material according to any one of? The following general formula (I):

(In the formula, Ar represents a substituted or unsubstituted aromatic group, and L represents a leaving group.)
A step of polymerizing the compound represented by formula (II) in the presence of a base, and the following general formula (II) obtained by the polymerization step:

(In the formula, Ar represents a substituted or unsubstituted aromatic group, and when a plurality of Ar are present, they may be the same or different. N represents a natural number.)
Seen containing a structure in shown, and Tran-bis benzyl defect structure, a step of dehydrogenation treatment with an oxidizing agent a polymer having,
The method of modifying an arylene vinylene polymer material , wherein the dehydrogenation treatment process modifies the trambisbenzyl defect structure .   The method for modifying an arylene vinylene polymer material according to claim 6, further comprising a step of removing the oxidant after the step of dehydrogenating the polymer with an oxidant.   The arylene vinylene polymer according to claim 6 or 7, wherein the oxidizing agent is selected from at least one of 2,3-dichloro-5,6-dicyanobenzoquinone, o-chloranil, and chloranil. Material modification method.   In the organic electroluminescent element provided with the light emitting layer or multiple thin layers including the light emitting layer between the pair of electrodes, the light emitting layer or the multiple thin layers including the light emitting layer is any one of claims 1 to 5. An organic electroluminescence device characterized in that it comprises a layer made of an allylene vinylene polymer material.   A charge transport material having a charge transport function used as a functional organic compound, wherein the material is an arylene vinylene polymer material according to any one of claims 1 to 5. material.

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