JP2007204721A - Method of processing organic polymer electronic material, method of producing organic polymer electronic material, organic electroluminescence element, electrophotografic organic photoreceptor, image forming apparatus, organic semiconductor transistor device and method of manufacturing the same, and semiconductor apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of processing an organic polymer electronic material which can be suitably used for easily producing a highly pure organic electronic material, an electroluminescence element using a polymer organic electronic material processed by the method, an organic photoreceptor having a long working life and an excellent optical responsivity and an organic semiconductor transistor device having a high working speed and being easily manufactured. <P>SOLUTION: The method of processing an organic polymer electronic material includes the step of dissolving an organic polymer electronic polymer such as a charge transport material in a solvent, and a step of fractionating the organic polymer electronic material by bringing the organic polymer electronic material into contact with porous particles (for example, making the polymer organic electronic material pass through a column with the porous particles filled therein). The electroluminescence element, the organic photoreceptor, and the organic semiconductor transistor device using the organic polymer electronic material processed by the method are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a treatment method for purifying a polymer organic electronic material, a method for producing a polymer organic electronic material using the treatment method, an organic electroluminescent device containing the polymer organic electronic material treated by the treatment method, The present invention relates to an organic photoconductor for electrophotography and an organic semiconductor transistor element, and also relates to an image forming apparatus using the organic photoconductor for electrophotography, a method for producing the organic semiconductor transistor element, and a semiconductor device using the organic semiconductor transistor element. .

  An organic electroluminescent element (hereinafter sometimes referred to as an “EL element”) is a self-luminous all-solid-state element, and is highly visible and resistant to impacts. At present, the one using an inorganic phosphor is the mainstream, but since an AC voltage of 200 V or more is required for driving, there are problems such as high manufacturing cost and insufficient brightness.

  On the other hand, research on EL devices using organic compounds started with a single crystal such as anthracene, but in the case of a single crystal, a film thickness of about 1 mm and a driving voltage of 100 V or more were necessary. For this reason, attempts have been made to reduce the thickness by vapor deposition (see, for example, Non-Patent Document 1). However, the thin film obtained by this method still has a high driving voltage of 30 V, a low density of electron / hole carriers in the film, and a low probability of photon generation due to carrier recombination. It was not obtained.

However, in recent years, in a function-separated EL device in which a thin film of a hole-transporting organic low-molecular compound and a fluorescent organic low-molecular compound having an electron-transporting capability are sequentially stacked by a vacuum deposition method, 1000 cd / s at a low voltage of about 10V. A device capable of obtaining high luminance of m ² or more has been reported (for example, see Non-Patent Document 2), and since then, research and development of stacked EL devices have been actively conducted.

However, in this type of EL element, a thin film of 0.1 μm or less is formed in a plurality of vapor deposition processes, so that pinholes are likely to occur, and in order to obtain sufficient performance, the film thickness is under strictly controlled conditions. It is necessary to control. Therefore, there are problems that productivity is low and it is difficult to increase the area. Further, since this EL element is driven at a high current density of several mA / cm ² , a large amount of Joule heat is generated. For this reason, the phenomenon that hole transporting low molecular weight compounds and fluorescent organic low molecular weight compounds deposited in an amorphous glass state by vapor deposition gradually crystallize and eventually melt, resulting in a decrease in luminance and dielectric breakdown. There is also a problem that the lifetime of the device is reduced as a result. For example, in the case of an electron transport material, oxadiazole derivatives such as 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (PBO) are converted into electrons. Although it has been proposed to be used as a transport material (see, for example, Patent Document 1), the obtained thin film is easily crystallized and is not sufficient from the viewpoint of charge transport / injection characteristics. In addition, there are few types of electron transport materials other than oxadiazole compounds, and there is a demand for the development of further materials excellent in charge transport and injection characteristics from the viewpoint of low voltage driving and high efficiency. .

  On the other hand, with the aim of solving problems related to productivity and large area in stacked organic EL devices, research and development of EL devices with a single-layer structure has been promoted, and conductive polymers such as poly (p-phenylene vinylene) have been developed. Or a device in which an electron transport material and a fluorescent dye are mixed in a hole-transporting polyvinyl carbazole (for example, see Non-Patent Document 4) has been proposed. Luminous efficiency and the like are not as good as those of a stacked organic EL device using an organic low molecular weight compound.

  A material used for an EL element is required to be a high-purity material in order to ensure long-term stability of electrical characteristics and element lifetime. Therefore, the material used for the EL element needs to be highly purified by a purification process after synthesis. In particular, in the case of a polymer material, the polymer obtained after polymerization is subjected to various washing treatments such as solvent washing, acid washing, alkali washing, etc., or by reprecipitation treatment in which the polymer is dissolved in a good solvent and dropped into a poor solvent. We are trying to achieve this requirement. However, in general, purification of a polymer material is difficult as compared with a low molecular compound, and the effect of improving the electrical characteristics of an EL element by these treatments is insufficient. Further, in the polymer charge transporting material used for the EL element, even if a very small amount of impurities is present, the influence on the element is large, and the electrical characteristics and life of the element are reduced.

  In the process of repeating dissolution in a good solvent and reprecipitation in a poor solvent (for example, see Patent Document 2), unreacted monomers and decomposition impurities generated during polymerization could not be completely removed even after repeated times. .

  In addition, a purification method that performs Soxhlet extraction with methanol is disclosed (see, for example, Patent Document 3), but extraction using a poor solvent such as methanol has low solubility, so that unreacted monomers and decomposition impurities are completely removed. It could not be removed.

A purification method for removing low molecular weight components by dialysis (see, for example, Patent Document 4) can be applied only to a water-soluble polymer, and a purification effect was not seen with a hydrophobic polymer.
JP 7-109454 A Japanese Translation of National Publication No. 08-510285 JP 2002-216965 A JP 2002-138133 A Thin Solid Films, Vol. 94, 171 (1982) Appl. Phys. Lett. , Vol. 51,913 (1987) Nature, Vol. 357, 477 (1992) Proceedings of the 38th Joint Conference on Applied Physics 31p-G-12 (1991)

As described above, a high-purity organic electronic material is required to produce an organic EL element having sufficient luminance, stable electrical characteristics, and excellent durability.
In recent years, there has been a strong demand for on-demand document production from the market, and there is a need for technology that can increase output speed and increase the number of printed sheets. There is a strong demand to reduce costs. For this reason, the organic photoreceptor is required to have a longer lifetime and a higher photoresponsiveness.
Further, there is a strong demand for organic semiconductor transistor elements that have a high operating speed and are easy to manufacture.

The present invention has been made in view of the above problems of the prior art, and a method for treating a polymer organic electronic material and a method for producing a polymer organic electronic material that can easily obtain a high-purity organic electronic material. An object of the present invention is to provide an organic electroluminescence device using a polymer organic electronic material treated by the treatment method.
It is another object of the present invention to provide an organic photoreceptor having a long lifetime and excellent photoresponsiveness, and an image forming apparatus using the organic photoreceptor using the polymer organic electronic material treated by the treatment method.
Furthermore, the present invention provides an organic semiconductor transistor element that uses the polymer organic electronic material processed by the above-described processing method, has a high operation speed and is easy to manufacture, a manufacturing method thereof, and a semiconductor device using the organic semiconductor transistor element. With the goal.

  As a result of intensive studies on organic electronic materials to achieve the above object, it was found that the electrical characteristics are improved by bringing the organic electronic material into contact with the porous particles and then fractionating, thereby completing the present invention. It was. It was also found that the polymer charge transport material further improves the charge transport ability and printing durability.

The above conventional problems are solved by the present invention described below. That is, the present invention
<1> A method for treating a polymer organic electronic material, wherein the polymer organic electronic material is dissolved in a solvent and then fractionated by contacting with porous particles.
<2> The method for treating a polymer organic electronic material according to <1>, wherein the polymer organic electronic material is a charge transport material.
<3> The method for treating a polymer organic electronic material according to <1>, wherein the polymer organic electronic material is a light-emitting material.
<4> The method for treating a polymer organic electronic material according to <1>, wherein the polymer organic electronic material is an electron transporting material.

  <5> A step of synthesizing a polymer organic electronic material by dehydrating and condensing a raw material monomer for the polymer organic electronic material in the presence of a metal catalyst, and after dissolving the polymer organic electronic material in a solvent, ion exchange properties A step of fractionating the polymer organic electronic material while removing metal ions resulting from the metal catalyst by contacting with the porous particles. Method.

  <6> At least one is transparent or translucent, and has one or a plurality of organic compound layers between a pair of electrodes composed of an anode or a cathode, and the organic compound layer includes <1> to <4> It is an organic electroluminescent element characterized by including the polymeric organic electronic material processed by the processing method as described in any one of these.

<7> A photosensitive layer is provided on a support, and the photosensitive layer contains a polymeric organic electronic material processed by the processing method according to any one of <1> to <4>. It is an organic photoconductor for electrophotography.
<8> The above <7>, wherein the photosensitive layer has a charge transport layer, and the charge transport layer contains a charge transport material processed by the processing method according to <2>. >. An organic photoconductor for electrophotography described in the above.
<9> The organic photoconductor for electrophotography according to <8>, wherein the charge transport layer is an outermost layer.
<10> The photosensitive layer has a charge generation layer, and the charge generation layer contains at least one selected from a halogenated gallium phthalocyanine crystal, a halogenated tin phthalocyanine crystal, a hydroxygallium phthalocyanine crystal, and an oxytitanium phthalocyanine crystal. The organic photoconductor for electrophotography according to any one of <7> to <9>, wherein the organic photoconductor is for electrophotography.

  <11> An electrophotographic image forming apparatus using the electrophotographic organic photoreceptor according to any one of <7> to <10>.

  <12> a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, a gate electrode insulated from the organic semiconductor and capable of applying an electric field; And the organic semiconductor contains a polymer organic electronic material processed by the processing method according to the above <1>.

<13> By using at least a coating film forming step for forming a coating film containing the solvent and a drying step for drying the coating film using a solution in which a charge transporting material is dissolved in a solvent A method for producing an organic semiconductor transistor element according to <12>, wherein the polymer organic electronic material is treated by the treatment method according to <1> as the charge transporting material. Is a method for producing an organic semiconductor transistor element.
<14> The organic film according to <13>, wherein the coating film containing the solvent is formed by applying an external stimulus to the solution and ejecting the solution in a droplet form from a nozzle. It is a manufacturing method of a semiconductor transistor element.
<15> The method for producing an organic semiconductor transistor element according to <14>, wherein the external stimulus is pressure.
<16> The organic semiconductor transistor element according to any one of <13> to <15>, wherein the drying step is performed in an environment having an oxygen concentration of 100 ppm or less and a water concentration of 100 ppm or less. It is a manufacturing method.

  <17> a substrate and one or more organic semiconductor transistor elements provided on the substrate, wherein the organic semiconductor transistor element according to <12> is used as the organic semiconductor transistor element. It is a semiconductor device.

According to the present invention, a method for treating a polymer organic electronic material, a method for producing a polymer organic electronic material, and a polymer organic electronic material treated by the treatment method capable of easily obtaining a high-purity organic electronic material. The organic electroluminescent element used can be provided.
Further, an organic photoreceptor having a long lifetime and excellent photoresponsiveness, an image forming apparatus using the organic photoreceptor, an organic semiconductor transistor element having a high operation speed and easy to produce, a method for producing the same, and the organic A semiconductor device using a semiconductor transistor element can be provided.

-Processing method for polymer organic electronic materials-
In the treatment method of the present invention, a polymer organic electronic material that has been roughly purified or purified is dissolved in a solvent, and then contacted with porous particles to separate (fractionate) a desired molecular weight range, and the solvent is removed. It is characterized by processing.
When the polymer organic electronic material contains a large amount of low molecular weight components, the proportion of terminal groups in the molecule increases, which impedes device characteristics. In addition, the larger the molecular weight spread, the more the behavior of each molecule varies, which adversely affects the device characteristics. Therefore, it is preferable to use a component having a desired molecular weight range. According to the treatment method of the present invention, a high-purity organic electronic material can be easily obtained, sufficient luminance can be obtained, and stable electric characteristics can be obtained. In addition, a polymer organic electronic material suitable for producing an organic EL device having excellent durability can be obtained.

Specific means for contacting with the porous particles includes preparative gel permeation chromatography.
When the polymer organic electronic material dissolved in the solvent is brought into contact with the porous particles and the desired molecular weight range is separated, the treatment is performed by gel permeation chromatography (GPC) if the treatment amount is small. When passing through the column in GPC, the polymeric organic electronic material is eluted according to the size of the molecule. As a column used for separation, a commercially available preparative GPC column can be used. From the viewpoint of increasing the throughput in one treatment, a column having an inner diameter of 20 mm or more is preferable. The eluate separated by the column can be fractionated by a fraction collector, and the target component can be separated from other components.
Further, when the amount of treatment is large, the treatment can be performed by preparing a column in which porous particles are packed in a column tube having a larger inner diameter than the above, and allowing the treatment liquid to pass through the column.
The treatment temperature is not particularly limited as long as it is in the range from room temperature or higher to the boiling point of the solvent used, and it is particularly preferably carried out at 40 ° C.

According to the preparative gel permeation chromatography treatment method, it is possible to separate and recover any component, and a high-molecular organic electronic material having a desired molecular weight range can be obtained with high purity.
In the present invention, impurities (for example, broken molecules) can be removed at the same time when the fraction is brought into contact with the porous particles. From this viewpoint, a high-purity polymer organic electronic material can be obtained. Obtainable. In addition, since the molecular weight range can be selected and impurities can be removed in the treatment method of the present invention as described above, the synthesis of the polymer organic electronic material before performing the treatment method of the present invention is a synthesis method having a wide molecular weight distribution. Alternatively, a synthesis method containing a large amount of impurities may be used, that is, a synthesis method giving priority to a simple point, a point capable of mass production, and the like can be used.

In addition, the molecular weight (weight average molecular weight) of the polymer organic electronic material after performing the above treatment can be measured by the following method.
Using a GPC measuring apparatus “HLC-8120A” (manufactured by Tosoh Corporation), the column is a guard column: TSK guard column Super HL (Φ4.6 × 35 mm, manufactured by Tosoh Corporation), GPC column: TSKgel Super H2000 + 2500 + 3500 ( Tosoh Corporation Φ6.0 × 150 mm) was used. The column oven temperature was set to 40 ° C., THF was used as the mobile phase, the flow rate was 0.6 ml / min, the sample concentration was 0.1%, the injection volume was 10 μl, and the detection was performed by a differential refractometer (manufactured by Tosoh Corporation). )It was used. A standard polystyrene sample manufactured by Tosoh Corp. was used to create a calibration curve, and dedicated software “GPC-8020” was used for analysis.

(Porous particles)
The porous particles (packed particles in the column in the preparative gel permeation chromatography) used in the present invention are not particularly limited as long as they are porous. For example, poly (styrene-divinylbenzene) , Poly (methacrylate), silica gel and the like, among which poly (styrene-divinylbenzene) is particularly preferable.

In addition, as an average pore diameter of the said porous particle, it is preferable that it is 0.001-1 micrometer, and it is more preferable that it is 0.01-0.1 micrometer. When it is 0.001 μm or more, only small molecules such as monomers and oligomers enter the pores, so that improvement in separation efficiency can be expected. Since the depth of penetration into the hole is limited, rapid processing is possible.
Here, the average pore diameter can be measured by a mercury intrusion method.

(solvent)
The solvent used for dissolving the organic electronic material is not particularly limited as long as it dissolves the EL device material. Specific examples include hexane, cyclohexane, methylcyclohexane, methylcyclopentane, toluene, o-xylene, m- Xylene, p-xylene, cumene, mesitylene, terpinolene, o-cymene, p-cymene, anisole, ethyltoluene, ethylxylene, dioxane, tetrahydrofuran (THF), diethyl ether, methanol, ethanol, 1-propanol, Examples include 2-propanol, chloroform, monochlorobenzene, dichlorobenzene, and water, and more preferable examples include THF, chloroform, and water. These can be used alone or in combination.
In addition, as a dissolution rate of the polymeric organic electronic material in the said solvent, 0.01-20 mass% is preferable, and also 0.1-10 mass% is more preferable.

(Polymer organic electronic materials)
The kind of polymer to be treated can be arbitrarily selected as long as it is a polymer organic electronic material that can be used in an organic EL element and can be dissolved in the above solvent. For example, a polyester derivative, a polyether derivative, a polyurethane derivative, a polystyrene derivative , Polymethacrylic acid (ester) derivatives, polyacrylic acid (ester) resin derivatives, polyvinylcarbazole derivatives, polycarbonate derivatives, polyarylene derivatives, polyethylene derivatives, polyfluorene derivatives, polyarylene vinylene derivatives, polythiophene derivatives, and the like.

  Moreover, as a preferable example of the polymer organic electronic material, for example, a polymer having a repeating unit containing at least one selected from the structures represented by the following general formulas (A-1) and (A-2) as a partial structure Is mentioned.

[In the general formulas (A-1) and (A-2), Ar represents a substituted or unsubstituted monovalent phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 3 to 10 aromatic rings. Represents a group, a substituted or unsubstituted monovalent condensed aromatic hydrocarbon group having 2 to 10 aromatic rings, or a substituted or unsubstituted monovalent heterocyclic ring, and X represents a substituted or unsubstituted divalent aromatic group. T represents a divalent linear hydrocarbon group having 1 to 6 carbon atoms or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and k represents 0 or 1 And m represents an integer of 0 to 3. ]

Here, in the general formulas (A-1) and (A-2), the number of aromatic rings constituting the polynuclear aromatic hydrocarbon and the condensed aromatic hydrocarbon selected as the structure representing Ar is 2-10. Are preferable, and those of 2 to 5 are preferable. In the condensed aromatic hydrocarbon, an aromatic hydrocarbon in which all aromatic rings are condensed is preferable. In the present invention, the polynuclear aromatic hydrocarbon and the condensed aromatic hydrocarbon specifically mean a polycyclic aromatic as defined below.
That is, the “polynuclear aromatic hydrocarbon” represents a hydrocarbon compound in which two or more aromatic rings composed of carbon and hydrogen are present and these aromatic rings are bonded to each other through a carbon-carbon bond. Specific examples include biphenyl, terphenyl, stilbene and the like. In addition, “condensed aromatic hydrocarbon” refers to a carbon atom in which two or more aromatic rings composed of carbon and hydrogen exist, and these aromatic rings share a pair of adjacent bonded carbon atoms. Represents a hydrogen compound. Specific examples include naphthalene, anthracene, phenanthrene, pyrene, perylene, and fluorene.

Further, in the general formulas (A-1) and (A-2), the heterocyclic ring selected as the structure representing Ar represents an aromatic ring including elements other than carbon and hydrogen. Nr = 5 and / or 6 is preferably used as the number of atoms (Nr) constituting the ring skeleton. Further, the type and number of atoms (heterogeneous atoms) other than carbon atoms constituting the ring skeleton are not limited. For example, a sulfur atom, a nitrogen atom, an oxygen atom and the like are preferably used. / Or two or more hetero atoms may be contained. In particular, as the heterocyclic ring having a 5-membered ring structure, thiophene, thiophine, pyrrole, furan, or a heterocyclic ring in which the 3- and 4-position carbons thereof are further substituted with nitrogen is preferably used. A pyridine ring is preferably used as the ring.
These may be either all composed of a conjugated system or partly composed of a conjugated system, but those composed entirely of a conjugated system are preferred in terms of charge transportability and light emission efficiency.

  In the general formulas (A-1) and (A-2), examples of the substituent substituted for each group represented by Ar include a hydrogen atom, an alkyl group, an alkoxy group, a phenoxy group, an aryl group, an aralkyl group, and a substituent. An amino group, a halogen atom, etc. are mentioned. As said alkyl group, a C1-C10 thing is preferable, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group etc. are mentioned. As said alkoxy group, a C1-C10 thing is preferable, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group etc. are mentioned. As said aryl group, a C6-C20 thing is preferable, for example, a phenyl group, a toluyl group, etc. are mentioned. As said aralkyl group, a C7-C20 thing is preferable, for example, a benzyl group, a phenethyl group, etc. are mentioned. Examples of the substituent in the substituted amino group include an alkyl group, an aryl group, and an aralkyl group, and specific examples are the same as described above.

  In the general formulas (A-1) and (A-2), the divalent aromatic group represented by X includes a divalent benzene ring, a divalent polynuclear aromatic hydrocarbon, and a divalent condensation. Examples thereof include polycyclic aromatic hydrocarbons and divalent heterocyclic rings. Among them, the structures exemplified below are useful in terms of solubility in a solvent and shortening of the light absorption wavelength. Moreover, as a substituent substituted by the said bivalent aromatic group, the same thing as the substituent substituted by each group represented by said Ar is mentioned.

(R ³ and R ⁴ represent a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 2-ethyl-hexyl group, an n-octyl group, a phenyl group, or a tolyl group.)

  In the general formulas (A-1) and (A-2), the divalent linear hydrocarbon group represented by T preferably has 1 to 6 carbon atoms, and more preferably 2 to 6 carbon atoms. The divalent branched hydrocarbon group preferably has 2 to 10 carbon atoms, and more preferably 3 to 7 carbon atoms. Among these, more specifically, the divalent hydrocarbon groups shown below are particularly preferable.

  Moreover, as a polymeric organic electronic material used for this invention, the polymer shown by the following general formula (B-1)-(B-9) is mentioned.

[In General Formulas (B-1) and (B-2), A represents at least one selected from the structures represented by General Formulas (A-1) and (A-2), and R represents Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, Y represents a dihydric alcohol residue, and Z represents a divalent carboxylic acid residue. B and B ′ each independently represent a group —O— (Y—O) _m —R or a group —O— (Y—O) _m —CO—Z—CO—O—R ′ (wherein , R, Y and Z are the same as above, R ′ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and m is an integer of 1 to 5 M represents an integer of 1 to 5, and p represents an integer of 5 to 5,000. Represent. ]

In general formulas (B-1) and (B-2), the alkyl group represented by R or R ′ is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or an isopropyl group. Is mentioned. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a toluyl group. As the aralkyl group, those having 7 to 20 carbon atoms are preferable, and examples thereof include a benzyl group and a phenethyl group.
Moreover, as a substituent substituted by each group represented by R, a hydrogen atom, an alkyl group, an alkoxy group, a substituted amino group, a halogen atom, etc. are mentioned.

  In the general formulas (B-1) and (B-2), the divalent alcohol residue represented by Y and the divalent carboxylic acid residue represented by Z are more preferably the following formula (b-1): A group selected from-(b-7) is preferred.

[In the above formulas (b-1) to (b-7), R ¹ and R ² are each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted carbon number 1 to 4 represents an alkoxy group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted aralkyl group, a and b each independently represent an integer of 1 to 5, and d and f each independently represents 0 or 1 , C and e each independently represent an integer of 0 to 2, and V represents a group represented by the following (c-1) to (c-11). ]

[In the above formulas (c-1), (c-10) and (c-11), g represents an integer of 1 to 5, and h and i each independently represents an integer of 0 to 5. ]

  In general formulas (B-1) and (B-2), p represents an integer of 5 to 5,000, more preferably in the range of 10 to 1,000.

[In General Formula (B-3), A represents at least one selected from the structures represented by General Formulas (A-1) and (A-2), and R represents a hydrogen atom, A substituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group is represented, and p represents an integer of 5 to 5,000. )

  Examples of R in the general formula (B-3) include the same as R in the general formulas (B-1) and (B-2).

[In General Formulas (B-4) and (B-5), A represents at least one selected from the structures represented by General Formulas (A-1) and (A-2), and R represents Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, T is a divalent linear hydrocarbon group having 1 to 6 carbon atoms or carbon number Represents a divalent branched hydrocarbon group of 2 to 10, Y represents a diisocyanate residue, Z represents a dihydric alcohol residue, m represents 0 or 1, and p represents 5 to 5 Represents an integer of 5,000. ]

  In the general formulas (B-4) and (B-5), the alkyl group, aryl group, and aralkyl group represented by R are the same as R in the general formulas (B-1) and (B-2). Can be mentioned. Preferred examples of the diisocyanate residue represented by Y and the alcohol residue represented by Z include the formulas (b-1) to (b-7).

[In the general formulas (B-6) to (B-8), Z represents at least one selected from the structures represented by the following general formulas (A-3) and (A-4), or a charge transporting ability or R ¹ , R ² and R ³ are each independently a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted Or an unsubstituted monovalent polynuclear aromatic hydrocarbon group, or a substituted or unsubstituted monovalent condensed aromatic hydrocarbon group, X represents a substituted or unsubstituted divalent aromatic group, and T Represents a divalent straight-chain hydrocarbon group having 1 to 6 carbon atoms or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, k represents 0 or 1, l, m and n represents an integer greater than or equal to 1 each independently. ]

[In the general formulas (A-3) and (A-4), Ar represents a substituted or unsubstituted monovalent phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon group, a substituted or unsubstituted group. A monovalent condensed aromatic hydrocarbon group or a substituted or unsubstituted monovalent heterocyclic ring is represented, X represents a substituted or unsubstituted divalent aromatic group, and k represents 0 or 1. ]

  In the general formulas (A-3) and (A-4), examples of Ar and X include those similar to Ar and X in the general formulas (A-1) and (A-2).

In the general formulas (B-6) to (B-8), examples of the alkyl group, aryl group, and aralkyl group represented by R ¹ , R ^2, and R ³ include the general formulas (B-1) and (B -2) are the same as those represented by R ¹ , R ² and R ³ , and examples of the monovalent polynuclear aromatic hydrocarbon group and condensed aromatic hydrocarbon group include those represented by the general formula (A-1). And the same monovalent polynuclear aromatic hydrocarbon group and condensed aromatic hydrocarbon group represented by Ar in (A-2). Further, in the general formulas (B-6) to (B-8), a divalent aromatic group represented by X, a divalent linear hydrocarbon group represented by T, and a branched chain Examples of the hydrocarbon group include those similar to X and T in the general formulas (A-1) and (A-2), respectively.

  In the general formulas (B-6) to (B-8), examples of the molecular structure having charge transporting ability or light emitting ability represented by Z include monovalent condensed aromatic hydrocarbons or heterocyclic rings. And compounds and their derivatives. Specific examples include phenyl, naphthalene, anthracene, phenanthrene, pyrene, perylene, rubrene, fluorene, thiophene, and carbazole.

[In General Formula (B-9), X represents a structure containing at least one selected from the structures represented by General Formulas (A-1) and (A-2), or a charge transporting ability or a light emitting ability. The molecular structure is represented, and p represents an integer of 5 to 5,000. ]

  In the general formula (B-9), the molecular structure having the charge transport ability or light emission ability represented by X is the charge transport represented by Z in the general formulas (B-6) to (B-8). And a divalent compound having a molecular structure having a light-emitting ability or a light-emitting ability.

  Furthermore, among the polymers having a repeating structure represented by the above general formula, more preferred examples include the following compounds (I-1) to (I-5), and particularly preferred are compounds (I-1) to (I-5). -3).

In the compounds (I-1) to (I-3), n is preferably 10 to 1000, and more preferably 10 to 500.
In the above compounds (I-4) to (I-5), x is preferably 10 to 1000, and more preferably 10 to 500. Further, m is preferably 1 to 20, and more preferably 1 to 10.

(Synthesis of polymer organic electronic materials)
The method for synthesizing the polymer organic electronic material is not particularly limited, and any known method may be used.

(1) Synthesis Method Using Metal Catalyst A preferred synthesis method is a method of synthesizing a polymer organic electronic material by dehydrating and condensing a raw material monomer for a polymer organic electronic material in the presence of a metal catalyst. The raw material monomer for the polymer organic electronic material is appropriately selected according to the polymer organic electronic material to be produced.

The metal catalyst for dehydrating and condensing the raw material monomer for the polymer organic electronic material is appropriately selected depending on the type of monomer used. For example, Na, Mg methylate; zinc borate, zinc typified by zinc acetate, Examples thereof include fatty acid salts and carbonates such as Cd, Mn, Co, Ca and Ba; metal Mg; oxides such as Pb, Zn, Sb and Ge; alkoxides of Ti and Sn.
A polymer organic electronic material is synthesized using a raw material monomer for a polymer organic electronic material in an appropriate solvent or in the absence of a solvent (no solvent).

  In the case of a polymer synthesized in the presence of a metal catalyst as described above, an ion-exchangeable filler (porous particles) is used in the treatment method of the present invention. It is preferable to remove the metal ions resulting from the metal catalyst at the same time that the molecular organic electronic material is fractionated. By removing metal ions using an ion-exchangeable filler, electrical characteristics can be improved when a polymer is used in an organic EL element.

Examples of the ion-exchangeable porous particles include Diaion RCP series, Diaion PK200 series, and Amberlist. Among these, Amberlist is particularly preferable.
There are two types of ion-exchangeable porous particles, cation exchange and anion exchange, and cation exchange is effective for removing metal ions. However, a mixture of a cation exchange property and an anion exchange property can be used as the ion exchange resin when the cation exchange acidity is high and the polymer organic electronic material may be hydrolyzed. Thereby, hydrolysis of the polymer organic electronic material (decrease in molecular weight of the polymer organic electronic material) can be suppressed. As a result, it is possible to suppress degradation of dissolution characteristics, film formation characteristics, and device characteristics.

  If there is a possibility that impurities such as uncrosslinked resin in the ion-exchangeable porous particles are eluted by the organic solvent contained in the polymer organic electronic material solution, the ion-exchangeability is previously determined by the organic solvent used. Improvement in removal efficiency can be expected by washing the porous particles.

(2) Other Synthetic Methods In addition, as described above, the polymer organic electronic material in the present invention contains impurities (for example, unreacted substances, oligomers, decomposed substances, etc.) during fractionation by contact with porous particles. Since removal can be performed at the same time, priority is given to the point of simplicity, mass production, etc. without considering the wide molecular weight distribution and the point that many impurities are included. You can also choose.

Synthetic methods giving priority to the above-mentioned simple points and mass production are radical polymerization, living radical polymerization, anionic polymerization, living anion polymerization, cationic polymerization, living cationic polymerization, coordination polymerization, group transfer polymerization. , Photopolymerization, radiation polymerization, ring-opening polymerization, polycondensation, cyclization polycondensation, plasma polymerization, electrolytic polymerization, oxidation polymerization, Heck reaction, Scholl reaction, Suzuki reaction, Yamamoto reaction, cross-coupling reaction and the like.
By employing these synthesis methods, the manufacturing process can be simplified and the cost can be reduced.

-Organic electroluminescence device-
The layer structure of the organic electroluminescent element (organic EL element) using the polymer organic electronic material processed by the processing method of the present invention is not particularly limited. An organic EL device using an organic electronic material purified by the treatment method of the present invention includes a pair of electrodes, at least one of which is transparent or translucent, and one or a plurality of light emitting layers sandwiched between the electrodes. It consists of an organic compound layer. In the present invention, when there is one organic compound layer, the organic compound layer means a light emitting layer having a charge transporting ability. When there are a plurality of organic compound layers, one of them is a light emitting layer, and the other organic compound layer is a charge transport layer, that is, a hole transport layer, an electron transport layer, or a hole transport layer and an electron transport layer. And at least one of these contains the material purified according to the present invention. Specifically, for example, it is composed of a light emitting layer and an electron transport layer, is composed of a hole transport layer, a light emitting layer and an electron transport layer, or is composed of a hole transport layer and a light emitting layer. And those containing at least one layer of the material purified by the present invention. Furthermore, for example, the organic compound layer is composed only of the light emitting layer, and the light emitting layer contains a material purified by the present invention.

  In the case of a single organic compound layer, the light emitting layer having a charge transporting ability has a light emitting material dispersed in an amount of 50% by mass or less based on the charge transporting material provided with a function (hole transporting ability or electron transporting ability) according to the purpose. The organic compound layer is formed by mixing and dispersing an electron transporting compound in the range of 1% by mass to 30% by mass in order to adjust the balance between holes and electrons injected into the organic EL element. Also good.

  In the light emitting layer, a compound showing a high fluorescence quantum yield in the solid state is used as the light emitting material. When the light emitting material is an organic low molecule, it is preferable that a good thin film can be formed by applying and drying a solution or dispersion containing a low molecular weight and a binder resin. In the case of a polymer, it is preferable that a good thin film can be formed by applying and drying a solution or dispersion containing itself. Preferably, in the case of small organic molecules, chelate-type organometallic complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives, coumarin derivatives, styryl arylene derivatives, silole derivatives, oxazole derivatives, oxathiazole derivatives, oxadiazole derivatives, etc. In the case of a polymer, examples include polyparaphenylene derivatives, polyparaphenylene vinylene derivatives, polythiophene derivatives, polyacetylene derivatives, and the like. As preferred specific examples, the following compounds (II-1) to (II-17) are used, but are not limited thereto.

  In addition, for the purpose of improving the durability of the organic EL element or improving the light emission efficiency, the light emitting material may be doped with a dye compound different from the light emitting material as a guest material. When the light emitting layer is formed by vacuum deposition, doping is performed by co-evaporation, and when the light emitting layer is formed by applying and drying a solution or dispersion, doping is performed by mixing in the solution or dispersion. The doping ratio of the dye compound in the light emitting layer is 0.001% by mass to 40% by mass, preferably 0.01% by mass to 10% by mass. As the coloring compound used for such doping, an organic compound that has good compatibility with the light emitting material and does not prevent the formation of a good thin film of the light emitting layer is used, preferably a DCM derivative, a quinacridone derivative, a rubrene derivative. Porphyrin compounds, metal complex compounds such as Ir, Eu, and Pt are used. Preferable specific examples include, but are not limited to, the following dye compounds (III-1) to (III-6).

The hole transport material may be formed of a single charge transport compound having a function (hole transport ability) according to the purpose, but for the purpose of further improving the electrical characteristics, the hole mobility is increased. In order to adjust, a specific organic low molecular weight compound may be mixed and dispersed in the range of 0.1% by mass to 50% by mass. Preferred examples of the organic low molecular weight compound in this case include a tetraphenylenediamine derivative, a triphenylamine derivative, a carbazole derivative, a stilbene derivative, an aryl hydrazone derivative, and a porphyrin compound.
As the electron transport material, an organic compound that does not exhibit a strong electron interaction with the charge transport material is used. Moreover, you may dope the pigment | dye compound different from a luminescent material.

  Furthermore, in order to improve the film formability, it may be mixed with other general-purpose resins. Specific resins include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, polystyrene resin, polyvinyl acetate resin, styrene butadiene copolymer, vinylidene chloride-acrylonitrile. Copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, silicone resins, poly-N-vinyl carbazole resins, polysilane resins, polythiophenes, polypyrrole, and other conductive resins can be used. Moreover, as an additive, a well-known antioxidant, a ultraviolet absorber, a plasticizer, etc. can be used.

  When there are a plurality of organic compound layers, the hole transport layer may be formed of a charge transport compound having a function (hole transport ability) according to the purpose, but the electrical characteristics are further improved. For the purpose, in order to adjust the hole mobility, the organic low molecular weight compound other than the polymer charge transporting material may be mixed and dispersed in the range of 0.1% by mass to 50% by mass. Furthermore, in order to improve the film formability, it may be mixed with other general-purpose resins. Specific examples are as described above.

  In these organic EL devices of the present invention, a hole transport layer or a light emitting layer is first formed on a transparent electrode according to the layer structure of each organic EL device. The hole transport layer and the light-emitting layer are respectively a hole transport material, a light-emitting material, or a vacuum deposition method, or dissolved or dispersed in an organic solvent, and a spin coating method on the transparent electrode using the obtained coating solution, It can be formed by forming a film using a dip method or the like.

  The film thicknesses of the hole transport layer, the light emitting layer and the electron transport layer to be formed are each preferably 0.1 μm or less, particularly preferably in the range of 0.03 to 0.08 μm. Further, the thickness of the light emitting layer having carrier transporting ability is preferably 0.03 to 0.2 μm.

  The layer structure of the organic EL device of the present invention having a layer containing a charge transporting polymer treated by the treatment method of the present invention will be described in detail. The organic EL device of the present invention is composed of a pair of electrodes, at least one of which is transparent or translucent, and one or a plurality of organic compound layers including a light emitting layer sandwiched between the electrodes. In the present invention, when there is one organic compound layer, the organic compound layer means a light emitting layer having a carrier transport ability. When there are a plurality of organic compound layers, one of them is a light emitting layer, and the other organic compound layer is a carrier transport layer, that is, a hole transport layer, an electron transport layer, or a hole transport layer and an electron transport layer. Means something.

  1, 2, 3 and 4 are schematic cross-sectional views for explaining the layer structure of the organic EL device of the present invention. In the case of FIG. 1, FIG. 2, and FIG. FIG. 3 shows an example in which there is a single organic compound layer. In the figure, 1 is a transparent insulator substrate, 2 is a transparent electrode, 3 is a hole transport layer, 4 is a light-emitting layer, 5 is an electron transport layer, 6 is a light-emitting layer having carrier transport ability, and 7 is a back electrode.

  The transparent insulator substrate 1 is preferably transparent in order to extract emitted light, and glass, plastic film or the like is used. The transparent electrode 2 is transparent in order to extract emitted light in the same manner as the transparent insulator substrate, and preferably has a high work function for injecting charges. Indium tin oxide (ITO), tin oxide (NESA), oxidation An oxide film such as indium and zinc oxide, and semi-transparent deposited or sputtered gold, platinum, palladium, or the like is used.

  In the case of the layer structure of the organic EL device shown in FIGS. 1 and 3, the organic compound layer composed of the charge transporting polymer acts as the light emitting layer 6 mixed with the π-conjugated polymer and having a carrier transporting ability. In the case of the layer structure of the organic EL element shown in FIGS. 2 and 4, it acts as the hole transport layer 3.

  In the case of the layer structure of the organic EL device shown in FIGS. 2 and 4, the hole transport layer 3 may be formed of a charge transporting polymer alone, but in order to adjust the charge mobility, a tetraphenylenediamine derivative is used. Etc. may be dispersed in the range of 1% by mass to 50% by mass.

  1, 3, and 4, the above light emitting material is used for the light emitting layer 6 having a carrier transport ability.

  In the case of the layer structure of the organic EL device of FIG. 3, the light emitting layer 6 having a carrier transporting ability is an organic compound layer in which the above light emitting material is dispersed in at least 50% by mass in a charge transporting polymer and injected into the organic EL device. The electron transport material may be dispersed in an amount of 10% by mass to 50% by mass in order to adjust the balance between the generated charge and the electrons, or between the light emitting layer 6 having the carrier transport ability and the back electrode 7 by the electron transport material. An electron transport layer may be inserted. As such an electron transport material, an organic compound that does not exhibit a strong electron interaction with the charge transport polymer is used, and the following compound (IV) is preferably used, but is not limited thereto.

  Similarly, an appropriate amount of tetraphenylenediamine derivative may be dispersed and used in order to adjust the charge mobility.

  For the back electrode 7, a metal that can be vacuum-deposited and has a small work function for electron injection is used. Magnesium, aluminum, calcium, silver, indium, and alloys thereof are particularly preferable.

  In these organic EL devices of the present invention, the charge transport layer 3 or the light emitting layer 6 is composed of the charge transport polymer alone, or the charge transport polymer and the light emitting material, and if necessary, the electron transport material and the charge transport material in an organic solvent. It is formed by forming a film using the spin coating method, the dip method or the like on the transparent electrode using the obtained coating solution. The thickness of the charge transport layer or the light emitting layer is preferably about 0.03 to 0.2 μm. The dispersion state of the light emitting material may be a molecular dispersion state or a fine particle dispersion state. In order to achieve a molecular dispersion state, it is necessary to use a common solvent for the charge transporting polymer, light emitting material, electron transporting material, and charge transporting material as the dispersion solvent. It is necessary to select in consideration of dispersibility and solubility of the electron transport material, the charge transport material, and the charge transport polymer. In order to disperse into fine particles, a ball mill, a sand mill, a paint shaker, an attritor ball mill, a homogenizer, an ultrasonic method, or the like can be used.

Next, on the layer containing the charge transporting polymer formed as described above, a light emitting material, an electron transporting material, and a back electrode are respectively formed by vacuum deposition according to the layer configuration of each organic EL element. Form. Thereby, an organic EL element can be easily produced. The thicknesses of the light emitting layer and the electron transport layer having the electron transport ability to be stacked are each preferably 0.1 μm or less, particularly preferably in the range of 0.03 to 0.08 μm. The organic EL device of the present invention can emit light by applying a direct current voltage of 1 to 200 mA / cm ² at a current density of, for example, 4 to 20 V between a pair of electrodes.

-Organic photoconductor for electrophotography-
Next, the organic photoreceptor of the present invention will be described.
The electrophotographic organic photoreceptor of the present invention has a photosensitive layer on a support, and the photosensitive layer contains a polymer charge transport material obtained by the processing method of the present invention. The polymer compound is not limited to a homopolymer, and can be used after being copolymerized for the purpose of adjusting various physical properties as a functional layer, such as adjustment of ionization potential.

  The polymer charge transport materials described so far preferably use phthalocyanines as charge generation materials. Specifically, the halogenated gallium phthalocyanine crystal disclosed in JP-A-5-98181, the tin halide phthalocyanine crystal disclosed in JP-A-5-140472 and JP-A-5-140473, Hydroxygallium phthalocyanine crystal disclosed in Kaihei 5-263007 and JP-A-5-279591, oxytitanium phthalocyanine hydrate disclosed in JP-A-4-189873 and JP-A-5-43813 By using them, an electrophotographic photosensitive member having particularly high sensitivity and excellent repeat stability can be obtained.

  The chlorogallium phthalocyanine crystal used in the present invention is an mortar, planetary mill, vibration mill, CF, chlorogallium phthalocyanine crystal produced by a known method, as disclosed in JP-A-5-98181. It can be produced by mechanically dry pulverizing with a mill, roller mill, sand mill, kneader or the like, or by dry pulverization and then performing wet pulverization with a solvent using a ball mill, mortar, sand mill, kneader or the like. Solvents used in the above treatment are aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), aliphatic polyvalents. Alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetic ester, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, ether (Diethyl ether, tetrahydrofuran, etc.), several mixed systems, and mixed systems of water and these organic solvents. The solvent used is 1 to 200% by mass, preferably 10 to 100% by mass, based on chlorogallium phthalocyanine. The treatment temperature is 0 ° C. to the boiling point of the solvent, preferably 10 to 60 ° C. In addition, grinding aids such as sodium chloride and sodium nitrate can be used during grinding. The grinding aid may be used in a mass ratio of 0.5 to 20 times, preferably 1 to 10 times that of the pigment.

  As disclosed in JP-A-5-140472 and JP-A-5-140473, the dichlorotin phthalocyanine crystal is obtained by converting dichlorotin phthalocyanine crystal produced by a known method in the same manner as the chlorogallium phthalocyanine. It can be obtained by pulverization and solvent treatment.

  As disclosed in JP-A-5-263007 and JP-A-5-279591, a hydroxygallium phthalocyanine crystal is obtained by hydrolyzing a chlorogallium phthalocyanine crystal produced by a known method in an acid or alkaline solution. Decomposition or acid pasting to synthesize hydroxygallium phthalocyanine crystals and directly solvent treatment, or wet hydroxygallium phthalocyanine crystals obtained by synthesis using a ball mill, mortar, sand mill, kneader, etc. together with solvent It can be manufactured by performing a pulverization process or performing a dry pulverization process without using a solvent and then performing a solvent process. Solvents used in the above treatment include aromatics (toluene, chlorobenzene, etc.), amides (dimethylformamide, N-methylpyrrolidone, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), aliphatic poly Monohydric alcohols (ethylene glycol, glycerin, polyethylene glycol, etc.), aromatic alcohols (benzyl alcohol, phenethyl alcohol, etc.), esters (acetic ester, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, etc.), dimethyl sulfoxide, Examples thereof include ethers (diethyl ether, tetrahydrofuran, etc.), several mixed systems, mixed systems of water and these organic solvents, and the like. The solvent used is 1 to 200% by mass, preferably 10 to 100% by mass, based on hydroxygallium phthalocyanine. The treatment temperature is 0 to 150 ° C, preferably room temperature to 100 ° C. In addition, grinding aids such as sodium chloride and sodium nitrate can be used during grinding. The grinding aid is used in a mass ratio of 0.5 to 20 times, preferably 1 to 10 times that of the pigment.

  As disclosed in JP-A-4-189873 and JP-A-5-43813, the oxytitanium phthalocyanine hydrate crystal is obtained by converting acid-pace oxytitanium phthalocyanine hydrate crystal produced by a known method. Or by performing milling with an inorganic salt using a ball mill, mortar, sand mill, kneader, etc., and having a relatively low crystallinity oxytitanium phthalocyanine crystal having a peak at 27.2 in the X-ray diffraction spectrum Then, it can be produced by directly solvent treatment or by wet pulverization with a solvent using a ball mill, mortar, sand mill, kneader or the like. As an acid used for acid pasting, sulfuric acid is preferable, and a concentration of 70 to 100% by mass, preferably 95 to 100% by mass is used, and a dissolution temperature is in a range of −20 to 100 ° C., preferably 0 to 60 ° C. Set to The amount of concentrated sulfuric acid is set in the range of 1 to 100 times, preferably 3 to 50 times the mass of the oxytitanium phthalocyanine crystal. As a solvent to be precipitated, water or a mixed solvent of water and an organic solvent is used in an arbitrary amount, and water and an alcohol solvent such as methanol or ethanol, or a mixture of water and an aromatic solvent such as benzene or toluene. A solvent is particularly preferred. The temperature for precipitation is not particularly limited, but it is preferably cooled with ice or the like in order to prevent heat generation. The ratio of the oxytitanium phthalocyanine crystal and the inorganic salt is 1 / 0.1 to 1/20 in mass ratio, and preferably in the range of 1 / 0.5 to 1/5. Solvents used in the above solvent treatment include aromatics (toluene, chlorobenzene, etc.), aliphatic alcohols (methanol, ethanol, butanol, etc.), halogenated hydrocarbons (dichloromethane, chloroform, trichloroethane, etc.), and There are several types of mixed systems, mixed systems of water and these organic solvents, and the like. The solvent used is used in a mass ratio of 1 to 100 times, preferably 5 to 50 times that of oxytitanium phthalocyanine. The treatment temperature is set in the range of room temperature to 100 ° C, preferably 50 to 100 ° C. The grinding aid may be used 0.5 to 20 times, preferably 1 to 10 times the pigment.

  Next, the layer structure of the photoreceptor of the present invention will be described. Here, a preferred embodiment of the photoconductor of the present invention will be described in detail mainly using a function-separated type photoconductor (laminated photoconductor) as an example.

  FIG. 5 is a cross-sectional view schematically showing a preferred embodiment of a function-separated type photoconductor (laminated photoconductor) according to the present invention. In FIG. 5, a photosensitive layer 15 is formed by laminating an undercoat layer 12, a charge generation layer 13, and a charge transport layer 14 in this order on a conductive support 11.

  Plastics provided with thin films such as metals such as aluminum, nickel, chromium, and stainless steel, and aluminum, titanium, nickel, chromium, stainless steel, gold, vanadium, tin oxide, indium oxide, ITO, etc. Examples thereof include a film, a paper coated with or impregnated with a conductivity imparting agent, and a plastic film. These conductive supports are used in an appropriate shape such as a drum shape, a sheet shape, and a plate shape, but are not limited thereto. Furthermore, if necessary, the surface of the conductive support can be subjected to various treatments within a range that does not affect the image quality. For example, surface oxidation treatment, chemical treatment, coloring treatment, or irregular reflection treatment such as graining can be performed. Further, an undercoat layer may be further provided between the conductive support and the charge generation layer. This undercoat layer prevents the injection of charges from the conductive support to the photosensitive layer and charges the photosensitive layer integrally with the conductive support when the photosensitive layer having a laminated structure is charged. It exhibits an action as a layer, or an antireflection effect of light of the conductive support depending on the case.

  The binder used for the undercoat layer is polyethylene resin, polypropylene resin, acrylic resin, methacrylic resin, polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polycarbonate resin, polyurethane resin, polyimide resin, vinylidene chloride resin , Polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose, casein, gelatin, polyglutamic acid, starch, starch acetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate Known materials such as compounds, titanium chelate compounds, titanium alkoxide compounds, organic titanium compounds, and silane coupling agents can be used. The thickness of the undercoat layer is 0.01 to 10 μm, preferably 0.05 to 2 μm. Furthermore, as an application method used when providing this undercoat layer, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used. Can be used.

  The charge generation layer preferably uses the phthalocyanine crystal described above as a charge generation material, but any known charge generation material such as a bisazo pigment, a phthalocyanine pigment, a squarylium pigment, a perylene pigment, or dibromoanthanthrone may be used. Can do. The binder resin used for the charge generation layer can be selected from a wide range of insulating resins. It can also be selected from organic photoconductive polyesters such as poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene and polysilane. Preferred binder resins include polyvinyl butyral resin, polyarylate resin (polycondensate of bisphenol A and phthalic acid, etc.), polycarbonate resin, polyester resin, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, acrylic resin. Insulating resin such as polyacrylamide resin, polyvinyl pyridine resin, cellulose resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin can be used, but is not limited thereto. These binder resins can be used alone or in admixture of two or more.

  Further, the blending ratio (mass ratio) of the charge generation material and the binder resin is preferably in the range of 10: 1 to 1:10. In addition, as a method for dispersing these, usual methods such as a ball mill dispersion method, an attritor dispersion method, and a sand mill dispersion method can be used. Further, at the time of this dispersion, it is effective to make the particles have a particle size of 0.5 μm or less, preferably 0.3 μm or less, more preferably 0.15 μm or less. Moreover, as a solvent used for these dispersions, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, n-butyl acetate, dioxane, Ordinary organic solvents such as tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, and toluene can be used alone or in admixture of two or more. The thickness of the charge generation layer is 0.01 to 10 μm, preferably 0.05 to 5 μm. Furthermore, as a coating method used when providing this charge generation layer, a normal method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used. Can be used.

  For the charge transport layer, the polymer charge transport material of the present invention may be used alone, or a known binder resin, other hydrazone charge transport material, triarylamine charge transport material, stilbene charge transport material, etc. You may use together. When the binder resin is used, specifically, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer, vinylidene chloride. -Acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N- Known resins such as vinyl carbazole and polysilane can be used, but are not limited thereto. The thickness of the charge transport layer is 5 to 100 μm, preferably 10 to 70 μm. Furthermore, as a coating method used when providing this charge transport layer, a usual method such as a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, or a curtain coating method is used. Can be used.

(Image forming device)
Next, the image forming apparatus of the present invention using the electrophotographic organic photoreceptor is described with reference to the drawings.
FIG. 6 shows an example of a schematic configuration diagram of an electrophotographic image forming apparatus using the electrophotographic photosensitive member of the present invention.
In the image forming apparatus 20 shown in FIG. 6, the organic photoreceptor 21 is rotatable at a predetermined rotation speed in the direction of the arrow. In the image forming apparatus 20, a charging device 22, an exposure device 23, a developing device 24, a transfer device 25, and a cleaning device 27 are arranged in this order along the photosensitive member 21 and its rotation direction. An image fixing device 26 is provided to which the transferred transfer medium 28 is conveyed.

  The charging device 22 used in the image forming apparatus will be described. The conductive member in the charging device may have any shape such as a brush shape, a blade shape, a pin electrode shape, or a roller shape, but it is preferable to use a roller-shaped member. Usually, the roller-shaped member is preferably composed of a resistance layer, an elastic layer that supports them, and a core material from the outside. Furthermore, a protective layer can be provided outside the resistance layer as necessary.

The core material is electrically conductive, and generally iron, copper, brass, stainless steel, aluminum, nickel, etc. are used. In addition, a resin molded product in which conductive particles or the like are dispersed can be used. The elastic layer is made of a material having conductivity or semiconductivity, and generally a material obtained by dispersing conductive particles or semiconducting particles in a rubber material is used. As the rubber material, EPDM, polybutadiene, natural rubber, polyisobutylene, SBR, CR, NBR, silicone rubber, urethane rubber, epichlorohydrin rubber, SBS, thermoplastic elastomer, norbone rubber, fluorosilicone rubber, ethylene oxide rubber and the like are used. Examples of the conductive particles or semiconductive particles include carbon black, zinc, aluminum, copper, iron, nickel, chromium, titanium, and other metals, ZnO—Al ₂ O ₃ , SnO ₂ —Sb ₂ O ₃ , In ₂ O ₃ — Metal oxides such as SnO ₂ , ZnO—TiO ₂ , MgO—Al ₂ O ₃ , FeO—TiO ₂ , TiO ₂ , SnO ₂ , Sb ₂ O ₃ , In ₂ O ₃ , ZnO, MgO can be used, These materials may be used alone or in admixture of two or more, and fine particles of fluororesin can be used as the fine particles.

As the material of the resistance layer and the protective layer, conductive particles or semiconductive particles are dispersed in a binder resin and the resistance is controlled. The resistivity is 10 ³ to 10 ¹⁴ Ωcm, preferably 10 ⁵ to 10 ¹² [Omega] cm, more preferably be set to 10 ⁷ ~10 ¹² Ωcm. The film thickness may be set to 0.01 to 1000 μm, preferably 0.1 to 500 μm, more preferably 0.5 to 100 μm. Binder resins include acrylic resin, cellulose resin, polyamide resin, methoxymethylene nylon, ethoxymethylated nylon, polyurethane resin, polycarbonate resin, polyester resin, polyethylene resin, polyvinyl resin, polyarylate resin, polythiophene resin, polyethylene terephthalate (PET ), Polyolefin resin, styrene butadiene resin or the like is used. As the conductive particles or semiconductive particles, the same carbon black, metal, and metal oxide as those used for the elastic layer are used.

  Moreover, antioxidants, such as hindered phenol and hindered amine, fillers, such as clay and carion, and lubricants, such as silicone oil, can be added as needed. As a means for forming these layers, a blade coating method, a wire bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, a vacuum deposition method, a plasma coating method, or the like is used. be able to.

  In an image forming apparatus provided with a charging device using these conductive members, when charging the electrophotographic organic photoreceptor of the present invention, a voltage is applied to the conductive member, but the applied voltage is a DC voltage. In this case, it is difficult to obtain uniform charging with only the DC voltage. The voltage range is preferably a positive or negative range of 50 to 2000 V, particularly preferably 100 to 1500 V, with respect to the DC voltage. As the alternating voltage to be superimposed, the peak-to-peak voltage is in the range of 400 to 1800V, preferably 800 to 1800V, and more preferably 1200 to 1800V. When the peak-to-peak voltage exceeds 1800 V, uniform charging cannot be obtained as compared with the case where no AC voltage is superimposed. The frequency of the AC voltage is preferably 100 to 2000 Hz.

  Further, as the exposure device 23 in the image forming apparatus shown in FIG. 6, an optical system device capable of exposing a light source such as a semiconductor laser, an LED (light emitting diode), and a liquid crystal shutter on the surface of the photosensitive member 21 in a desired image-like manner. Can be used. Among them, it is preferable to use an exposure apparatus capable of exposing non-interference light in that interference fringes between the conductive support (substrate) of the photoreceptor 21 and the photosensitive layer can be prevented.

  The developing device 24 may use either a one-component developer or a two-component developer, and the developer may be either magnetic or non-magnetic. Further, the developing device 24 may be for a monochrome image or a color image.

  Examples of the transfer device 25 include a contact transfer charger using a belt, a roller, a film, a rubber blade, etc., a scorotron transfer charger using a corona discharge, a corotron transfer charger, and the like. Can be used.

  Examples of the fixing device 26 include a heating roller, an IH heater belt, and a xenon flashlight, and can be appropriately selected and used.

  The cleaning device 27 is for removing residual toner adhering to the surface of the photosensitive member 21 after the transfer process. The cleaned photosensitive member 21 is charged, exposed, developed, transferred, and cleaned. The image forming process is repeatedly used. As the cleaning device 27, for example, blade cleaning, brush cleaning, roll cleaning, and the like can be used, but it is preferable to use blade cleaning.

  In addition, the material of the cleaning blade in blade cleaning has elasticity, and includes an elastic body such as rubber, elastomer, resin, etc. in terms of durability and easy compatibility with the surface of the electrophotographic photosensitive member, among which rubber is preferable, For example, urethane rubber, neoprene rubber, silicone rubber and the like.

  In addition, this embodiment is an example of embodiment in this invention, Naturally, it is not limited to this. For example, the image forming apparatus 20 shown in FIG. 6 may be applicable to a process cartridge including the photosensitive member 21, the developing device 24 and / or the cleaning device 27. By using such a process cartridge, maintenance can be performed more easily.

  The apparatus shown in FIG. 6 directly transfers the toner image formed on the surface of the photosensitive member 21 to the transfer medium 28, but the image forming apparatus 20 of the present invention further includes an intermediate transfer member. There may be. As a result, the toner image on the surface of the photosensitive member 21 can be transferred to the intermediate transfer member and then transferred from the intermediate transfer member to the transfer medium 28. As such an intermediate transfer member, one having a structure in which an elastic layer containing rubber, elastomer, resin, etc. and at least one coating layer are laminated on a conductive support can be suitably used.

  Furthermore, the photoreceptor according to the present invention can be suitably applied not only to a monochrome electrophotographic apparatus but also to a color electrophotographic apparatus. As a color image output method, a method in which a toner image of a plurality of colors is formed on a photoconductor and each color toner image is transferred onto a transfer paper, or a toner image formed on the photoconductor is transferred to an intermediate transfer material, A method of further transferring the toner image on the transfer member to the transfer medium, a method of superimposing a plurality of toner images on the photosensitive member to form a color toner image corresponding to the image, and transferring the color toner images collectively, etc. Can be mentioned.

-Organic semiconductor transistor element-
Next, the configuration of the organic semiconductor transistor element of the present invention will be described in detail with specific examples.

  The organic semiconductor transistor element of the present invention includes a source electrode, a drain electrode, an organic semiconductor provided to be conductive with the source electrode and the drain electrode, and an electric field insulated from the organic semiconductor and applying an electric field. A possible gate electrode.

  Here, the organic semiconductor includes a polymer organic electronic material processed by the processing method of the present invention described above. In addition, although the shape of the organic semiconductor transistor element of this invention can be made into a desired shape as needed, it is preferable that it is a thin film form.

  Hereinafter, the configuration of the organic semiconductor transistor element of the present invention will be described in more detail with reference to the drawings, but is not limited thereto.

  7 to 9 are schematic cross-sectional views showing an example of the configuration of the organic semiconductor transistor element of the present invention. 7 and 8 show a case where the organic semiconductor transistor element of the present invention has a field effect transistor (Field Effect Transistor) structure. FIG. 9 shows a case where the organic semiconductor transistor element of the present invention has a static induction transistor (StatIc InductIon TransItor) structure.

  7 to 9, members having common functions are denoted by the same reference numerals, 31 is a substrate, 32 is a source electrode, 33 is a drain electrode, 34 is an organic semiconductor layer, 35 is a gate electrode, and 36 is insulated. Represents a layer. Hereinafter, the structure of the organic semiconductor transistor element of the present invention shown in FIGS.

  In the organic semiconductor transistor element of the present invention shown in FIG. 7, a gate electrode 35 and an insulating layer 36 are provided in this order on a substrate 31, and the source electrode 32 and the drain electrode 33 are separated from each other on the insulating layer 36. An organic semiconductor layer 34 is provided so as to cover the source electrode 32 and the drain electrode 33.

  Further, in the organic semiconductor transistor element of the present invention shown in FIG. 8, a gate electrode 35 and an insulating layer 36 are provided in this order on a substrate 31, and a source electrode 32 and an insulation of the source electrode 32 are provided on the insulating layer 36. An organic semiconductor layer 34 is provided so as to cover the surface opposite to the side in contact with the layer 36. Further, the drain electrode 33 is provided on the surface of the organic semiconductor layer 34 opposite to the side on which the insulating layer 36 is provided, at a position separated from the source electrode 32 in the planar direction of the substrate 31.

  Further, in the organic semiconductor transistor element of the present invention shown in FIG. 9, a source electrode 32, an organic semiconductor layer 34, and a drain electrode 33 are laminated on a substrate 31 in this order, and a plurality of gate electrodes 35 are formed in the organic semiconductor layer 34. (In the example shown in FIG. 9, the four gate electrodes 35 are arranged in parallel with the planar direction of the substrate 31 and at equal intervals).

  The gate electrode 35 is arranged in a direction perpendicular to the paper surface so as to be parallel to both the source electrode 32 and the drain electrode 33, and the gate electrodes 35 are also provided so as to be parallel to each other. Yes. In FIG. 9, the gate electrode 35 and the organic semiconductor layer 34 are insulated by an insulating layer (not shown) provided at the interface between them.

  In the organic semiconductor transistor element as shown in FIGS. 7 to 9, the current flowing between the source electrode 32 and the drain electrode 33 can be controlled by the voltage applied to the gate electrode 35.

  In addition, when producing any electronic device using the organic semiconductor transistor element of the present invention, it is used as a configuration (semiconductor device) in which one or more organic semiconductor transistor elements of the present invention are mounted on a substrate. A desired electronic device can be manufactured by combining this semiconductor device with another element or circuit.

  Next, each member which comprises the organic-semiconductor element and semiconductor device of this invention except an organic-semiconductor part is demonstrated in detail.

  As an electrode material used for the source electrode, the drain electrode, and the gate electrode, a material capable of efficiently injecting charges is used. Specifically, a metal, a metal oxide, a conductive polymer, or the like is used.

  Examples of the metal include magnesium, aluminum, gold, silver, copper, chromium, tantalum, indium, palladium, lithium, calcium, and alloys thereof. Examples of the metal oxide include metal oxide films such as lithium oxide, magnesium oxide, aluminum oxide, indium tin oxide (ITO), tin oxide (NESA), indium oxide, zinc oxide, and indium zinc oxide.

  Examples of the conductive polymer include polyaniline, polythiophene, polythiophene derivatives, polypyrrole, polypyridine, and a complex of polyethylenedioxythiophene and polystyrene sulfonic acid. In addition, if the difference in ionization potential between the material used for the electrode and the above-described polymer compound used for the organic semiconductor (layer) is large, the charge injection characteristics are deteriorated. Therefore, the material used for the drain electrode and / or the source electrode The difference in ionization potential between the ionization potential and the polymer compound used for the organic semiconductor (layer) is preferably within 1.0 eV, more preferably within 0.5 eV. In view of the difference in ionization potential between the electrode and the polymer compound, it is particularly preferable to use Au as the electrode material.

  As a method for forming an electrode, a thin film produced by using a known thin film forming method such as a vapor deposition method or sputtering as the electrode material described above is formed using a known photolithography method or a lift-off method, or an inkjet or the like. Thus, a method of etching into a desired pattern (electrode shape) using a resist or a method of directly transferring an electrode material such as aluminum can be used. When a conductive polymer is used as the electrode material, it may be dissolved in a solvent and patterned by ink jet or the like.

  Insulating members that insulate between each electrode or between the gate electrode and the organic semiconductor (layer) include inorganic substances such as silicon dioxide, silicon nitride, tantalum oxide, aluminum oxide, titanium oxide, polycarbonate resin, polyester resin, methacrylic resin, acrylic Resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, polystyrene styrene resin, polyvinyl acetate resin, styrene butadiene copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer Examples thereof include, but are not limited to, organic insulating polymers such as silicon resin. As the substrate, silicon single crystal or glass doped with phosphorus or the like in high concentration, glass resin, polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, police styrene resin, polyvinyl acetate Examples thereof include, but are not limited to, resins, styrene butadiene copolymers, vinyl chloride-acrylonitrile copolymers, vinyl chloride-vinyl acetate-maleic anhydride copolymers, plastic substrates such as silicone resins, and the like.

  In particular, when the organic semiconductor transistor element of the present invention is used in an electronic circuit used in an electronic device (hereinafter referred to as “flexible electronic device”) that is required to be flexible, such as electronic paper, digital paper, or portable electronic equipment. It is desirable to use a flexible substrate as the substrate. In particular, by using a substrate having a flexural modulus of 1000 MPa or more, more preferably 5000 MPa or more as the substrate, the substrate can be applied to a flexible display element drive circuit or electronic circuit.

  This is because the organic semiconductor transistor element of the present invention has sufficient elasticity that the organic semiconductor portion contains the above-described polymer compound as a main component, and the element is placed on a flexible substrate. This is because even if formed, it can withstand large deformations and repeated deformations and can maintain stable performance. On the other hand, in an inorganic semiconductor transistor element, since the semiconductor portion is made of an inorganic material and lacks elasticity, it is extremely difficult to use it based on such deformation. Further, the process for manufacturing the inorganic semiconductor transistor element has a disadvantage that plastic cannot be used for the substrate because it requires a high temperature. In addition, even in an organic semiconductor transistor element in which the organic semiconductor portion is mainly composed of a low molecular material, since it lacks elasticity like a polymer material, it is difficult to use it assuming such deformation. Or it is inferior in reliability.

  In the present invention, the term “flexible electronic device” refers to [1] a usage state from a flat state, regardless of whether the power is on or off, such as the electronic paper and digital paper described above. It can be bent, bent, bent, or vice versa. [2] The substrate is provided with one or more components on the substrate. [3] means an electronic device that is required to be flexible at least in the substrate portion provided with the organic semiconductor transistor element.

  As a method of forming the organic semiconductor portion in a layered manner, it is particularly preferable to use a liquid phase film forming method, for example, spin coating method, casting method, dipping method, die coating method, roll coating method, bar coating method, ink jet method, Each printing method is used, but is not limited thereto.

  However, since it is not necessary to form a pattern by etching after coating, the manufacturing process can be simplified, and high productivity can be obtained even when a large number of organic semiconductor transistor elements are formed on a large-area substrate. Is preferably used.

  That is, an image forming technique based on ink jet recording used in an ink jet printer can be used for forming an organic semiconductor portion of an organic semiconductor transistor element.

  In this case, instead of ink, a solution containing at least one charge transporting material dissolved in a solvent (hereinafter referred to as “inkjet organic semiconductor solution” is used only for inkjet printing, and is limited to inkjet printing) Otherwise, it may be referred to simply as “organic semiconductor solution”), and the droplet-shaped organic semiconductor solution is ejected from the nozzle of the droplet ejection head to obtain a desired film thickness at a desired position on the substrate. -A shaped organic semiconductor can be formed.

  In addition, as a droplet discharge head, the same basic configuration and principle as those of a recording head used in an ink jet printer can be used. That is, by applying an external stimulus such as pressure or heat to the organic semiconductor solution, a method of ejecting the organic semiconductor solution for inkjet from the nozzle into droplets (a so-called piezoelectric inkjet method using a piezoelectric element, utilizing a thermal boiling phenomenon) Can be used.

  However, in the production of the organic semiconductor transistor element of the present invention, the external stimulus is more preferably pressure than heat. When the external stimulus is heat, in the inkjet printing process of forming (solidifying) a coating film by volatilization of the solvent of the organic semiconductor solution that has landed on the substrate from ejection of the inkjet organic semiconductor solution from the nozzle, Since the viscosity of the organic semiconductor solution is greatly changed by heat, it may be difficult to control leveling properties and patterning accuracy. In addition to this, charge transporting polyesters that are inferior in heat resistance cannot be used, and material options may be narrowed.

  Moreover, as an apparatus used for manufacturing the organic semiconductor transistor element of the present invention using the inkjet method, in addition to the above-described droplet discharge head, for example, an organic semiconductor transistor element is formed as necessary. A fixing or conveying means for the substrate or the like, or a droplet discharge head scanning means for scanning the droplet discharge head with respect to the substrate plane direction may be provided.

  The composition and physical properties of the organic semiconductor solution for inkjet are not particularly limited as long as the organic semiconductor solution for inkjet includes at least the charge transporting material and the solvent as described above. Although it varies depending on the film thickness to be formed, it is preferably within a range of 0.01 to 1000 cps at approximately 25 ° C., and preferably within a range of 1 to 100 cps.

  When the viscosity is less than 0.01 cps, the organic semiconductor solution that has landed on the substrate tends to spread in the plane direction of the substrate, making it difficult to control the film thickness, and patterning accuracy may be degraded. Moreover, when the viscosity exceeds 1000 cps, the viscosity of the organic semiconductor solution for inkjet may be too high, which may cause ejection failure.

  In addition, the viscosity of the organic semiconductor solution for inkjet is set to a desired value by controlling the charge transporting material, the content of other additive components added as necessary, the molecular weight of the charge transporting material, and the like. Can be adjusted.

  The solvent used in the organic semiconductor solution for inkjet is not particularly limited as long as it can dissolve the charge transporting material. For example, organic solvents such as hydrocarbon solvents, ester solvents, ether solvents, halogen solvents Examples thereof include a solvent, an alcohol solvent, water, a mixed solvent thereof, and the like.

  Here, examples of the hydrocarbon solvent include toluene, benzene, xylene, hexane, octane, hexadecane, cyclohexane, cyclohexanone, lactone, tetralin, cumene and the like, and examples of the ester solvent include methyl acetate. , Ethyl acetate, isopropyl acetate, amyl acetate, and the like. Examples of the ether solvent include dibutyl ether and dibenzyl ether. Examples of the halogen solvent include 1,1-dichloroethane, 1 -Fluoroethane, 2,2,2-trifluoroethane, 2,2,3,3,3-pentafluoropropane, chloroform, carbon tetrachloride, monochlorobenzene, o-dichlorobenzene and the like, and the alcohol solvent As methanol, ethanol , I- and propyl alcohol.

  In addition, when manufacturing an organic semiconductor transistor element using the inkjet method as described above or other liquid phase film forming methods, the organic semiconductor portion uses an organic semiconductor solution and forms a coating film containing a solvent. The coating film is formed by at least a coating film forming process and a drying process of drying the coating film to form a film made of an organic semiconductor.

Here, the drying step is preferably performed in an environment where the oxygen concentration is 100 ppm or less and the water concentration is 100 ppm or less. If the oxygen concentration or water concentration exceeds 100 ppm, oxygen atoms present as oxygen molecules or water molecules in the atmosphere may deteriorate the charge transporting polyether. If the heat treatment temperature during drying is high, this is the case. This is because excessive deterioration is more likely to occur.
The oxygen concentration is more preferably 50 ppm or less, and further preferably 10 ppm or less. The water concentration is more preferably 50 ppm or less, and further preferably 10 ppm or less.

Further, a protective layer may be provided in order to prevent deterioration of the organic semiconductor transistor element due to moisture or oxygen. Specific materials for the protective layer include metals such as In, Sn, Pb, Au, Cu, Ag, and Al, metal oxides such as MgO, SIO ₂ , and TIO ₂ , polyethylene resins, polyurea resins, polyimide resins, and the like. Resin. For forming the protective layer, a vacuum deposition method, a sputtering method, a plasma polymerization method, a CVD method, or a coating method can be applied.

As described above, the organic semiconductor transistor element of the present invention has an on / off ratio of about 10 ² to 10 ⁵ by appropriately selecting the type of polymer compound used in the organic semiconductor portion, the structure of the element, and the like. Within the range, it can be adjusted according to the use of the organic semiconductor transistor element.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, each of these Examples does not restrict | limit this invention. In the examples, “parts” and “%” are based on mass.

[Synthesis Example 1-Preparation of purified polymer (1)]
N, N′-bis (3,4-dimethylphenyl) -N, N′-bis [4- (2-methoxycarbonylethyl) phenyl]-(1,1′-biphenyl) -4,4′-diamine 2 Part, 8 parts of ethylene glycol and 0.1 part of tetrabutoxytitanium were placed in a 50 ml flask and heated and stirred at 200 ° C. for 4 hours under a nitrogen stream. N, N′-bis (3,4-dimethylphenyl) -N, N′-bis [4- (2-methoxycarbonylethyl) phenyl]-(1,1′-biphenyl) -4,4′-diamine After confirming consumption, the pressure was reduced to 0.5 mmHg and the mixture was heated to 210 ° C. while distilling off ethylene glycol, and the reaction was continued for 5 hours. Then, it cooled to room temperature, melt | dissolved in 50 parts of toluene, and filtered the insoluble matter with the 0.5 micrometer polytetrafluoroethylene (PTFE) filter. The obtained filtrate was added dropwise to a large excess of stirred methanol to precipitate a polymer. The obtained polymer dispersion was filtered, sufficiently washed with methanol and dried to obtain 1.8 parts of a hole transporting polyester (Exemplary Compound (1)). The molecular weight was measured by GPC, and was Mw = 9.42 × 10 ⁴ (styrene conversion) and Mw / Mn = 2.96. At this time, the peak end was 9.7 min. Moreover, when the titanium content of the obtained polymer was measured using an ICP emission spectroscopic analyzer (ICP-AES: SPS1200VR manufactured by Seiko Denshi Kogyo), it was 3.6 ppm.

Next, a column (trade name: TS Kgel G2000HHR + 2500HHR + 3000HHR manufactured by Tosoh Corporation) was prepared and attached to a preparative gel permeation chromatography (GPC) apparatus. After 200 mg of the exemplified compound (1) was dissolved in 20 ml of THF, The solution was allowed to flow at a rate of 7.7 ml / min, and a desired molecular weight range was collected, and after the solution was concentrated, the precipitated polymer was dropped by dripping into a large excess of methanol, separated by filtration, dried, and purified polymer. 100 mg of (1) was obtained.
When the molecular weight was measured by GPC, it was Mw = 1.03 × 10 ⁵ and Mw / Mn = 2.17. At this time, the titanium content was below the detection limit.

[Synthesis Example 2-Preparation of purified polymer (2)]
The monomer is N, N′-bis (3,4-dimethylphenyl) -N, N′-bis [4- (2-methoxycarbonylethyl) phenyl]-(1,1′-terphenyl) -4,4 ′. -Except having changed into diamine, operation similar to the synthesis example 1 was performed, and 1.8 parts of exemplary compound (2) was obtained. The molecular weight was Mw = 7.92 × 10 ⁴ (in terms of styrene) and Mw / Mn = 3.04. Moreover, when titanium content was measured by ICP-AES, it was 4.6 ppm.

Subsequently, it processed with the preparative gel permeation chromatography (GPC) apparatus on the same conditions as the synthesis example 1, and fractionated the desired molecular weight range. After concentration of the solution, it was dropped into a large excess of methanol, and the precipitated polymer was separated by filtration. After drying, 100 mg of purified polymer (2) was obtained.
When the molecular weight was measured by GPC, it was Mw = 8.15 × 10 ⁴ and Mw / Mn = 2.87. At this time, the titanium content was below the detection limit.

[Synthesis Example 3-Preparation of purified polymer (3)]
Monomer to N, N′-bis (4-phenoxyphenyl) -N, N′-bis [4- (2-methoxycarbonylethyl) phenyl]-(1,1′-biphenyl) -4,4′-diamine Except having changed, it carried out similarly to the synthesis example 1, and obtained 1.8 parts of exemplary compound (3). The molecular weight was Mw = 1.50 × 10 ⁵ (in terms of styrene) and Mw / Mn = 4.96. Moreover, when titanium content was measured by ICP-AES, it was 3.2 ppm.

Subsequently, it processed with the preparative gel permeation chromatography (GPC) apparatus on the same conditions as the synthesis example 1, and fractionated the desired molecular weight range. After concentration of the solution, it was dropped into a large excess of methanol, and the precipitated polymer was separated by filtration. After drying, 100 mg of purified polymer (3) was obtained.
When the molecular weight was measured by GPC, it was Mw = 1.56 × 10 ⁵ and Mw / Mn = 3.84. At this time, the titanium content was below the detection limit.

[Synthesis Example 4-Preparation of purified polymer (4)]
Other than changing the monomer to N, N′-bis (biphenyl) -N, N′-bis [4- (2-methoxycarbonylethyl) phenyl]-(1,1′-biphenyl) -4,4′-diamine Were the same as in Synthesis Example 1 to obtain 1.8 parts of Exemplified Compound (4). The molecular weight was Mw = 6 × 10 ⁴ (styrene conversion) and Mw / Mn = 2.96. Moreover, when titanium content was measured by ICP-AES, it was 5.2 ppm.

Subsequently, it processed with the preparative gel permeation chromatography (GPC) apparatus on the same conditions as the synthesis example 1, and fractionated the desired molecular weight range. After concentration of the solution, it was dropped into a large excess of methanol, and the precipitated polymer was separated by filtration. After drying, 100 mg of purified polymer (4) was obtained.
When the molecular weight was measured by GPC, it was Mw = 6.59 × 10 ⁴ and Mw / Mn = 1.84. At this time, the titanium content was below the detection limit.

[Synthesis Example 5-Preparation of purified polymer (5)]
3 parts of N-vinylcarbazole was dissolved in 15 parts of methylene chloride, cooled to −60 ° C., and then 0.01 part of boron fluoride diethyl ether was added for polymerization. After 10 minutes, concentrated aqueous ammonia was added to stop, and the resulting solution was dropped into a large excess of methanol to precipitate a polymer. The obtained polymer dispersion was filtered, thoroughly washed with methanol and dried to obtain 2.8 parts of the compound (I-3). The molecular weight was measured by GPC, and was Mw = 9.5 × 10 ⁴ (styrene conversion) and Mw / Mn = 2.30.
Subsequently, it processed with the preparative gel permeation chromatography (GPC) apparatus on the same conditions as the synthesis example 1, and fractionated the desired molecular weight range. After concentration of the solution, it was dropped into a large excess of methanol, and the precipitated polymer was separated by filtration. After drying, 100 mg of purified polymer (5) was obtained. The molecular weight was Mw = 9.7 × 10 ⁴ (in terms of styrene) and Mw / Mn = 2.06.

[Examples of organic EL elements]
Example 1
Using the purified polymer (1), an organic EL device was produced as follows.
The ITO glass substrate etched into a 2 mm wide strip was ultrasonically cleaned with 2-propanol (for electronics industry, manufactured by Kanto Chemical) and then dried. On this substrate, the purified polymer (1) was dissolved in dichloroethane at a ratio of 5%, and a solution obtained by filtering through a 0.1 μm polytetrafluoroethylene (PTFE) filter was applied by the dip method to obtain a film thickness of 0. A hole transport layer having a thickness of 0.050 μm was formed. After sufficiently drying, the compound (II-1) purified by sublimation as a light-emitting material having a carrier transport ability is put in a tungsten boat and deposited by a vacuum deposition method to have a film thickness of 0.05 μm on the hole transport layer. A light emitting layer was formed. The degree of vacuum at this time was 10 ⁻⁵ Torr, and the boat temperature was 300 ° C. Subsequently, a Mg—Ag alloy was deposited by co-evaporation to form a back electrode having a width of 2 mm and a thickness of 0.15 μm so as to cross the ITO electrode. The effective area of the formed organic EL element was 0.04 cm ² .

(Example 2)
The ITO glass substrate etched into a 2 mm wide strip was ultrasonically cleaned with 2-propanol (for electronics industry, manufactured by Kanto Chemical) and then dried. Next, 1 part of the purified polymer (2), 4 parts of poly (N-vinylcarbazole), and 0.1 part of the compound (II-1) were prepared so as to be a 10% dichloroethane solution. Filtered with a PTFE filter. Using this solution, a thin film having a thickness of about 0.15 μm was formed by spin coating on a glass substrate on which a 2 mm wide strip-shaped ITO electrode was formed by etching. After sufficiently drying, LiF was 0.0008 μm and Al was sequentially deposited by 0.15 μm to form a back electrode having a width of 2 mm and a thickness of 0.15 μm so as to cross the ITO electrode. The effective area of the formed organic electroluminescent element was 0.04 cm ² .

(Example 3)
First, a hole transport layer was formed on an ITO glass substrate etched and washed in the same manner as in Example 1 except that the purified polymer (1) used was changed to the purified polymer (3). Subsequently, the same as Example 1 except that the compound (II-1) used was changed to a mixture of the compound (II-1) and the compound (III-1) (mixing mass ratio 99: 1). A light emitting layer having a thickness of 0.065 μm was formed by the method. Further, an electron transport layer having a thickness of 0.030 μm was formed by the same method as the formation of the light emitting layer except that the compound used was changed to the exemplified compound (II-9). Subsequently, LiF was 0.0008 μm and Al was sequentially deposited by 0.15 μm to form a back electrode having a width of 2 mm and a thickness of 0.15 μm so as to intersect the ITO electrode. The effective area of the formed organic electroluminescent element was 0.04 cm ² .

Example 4
The ITO glass substrate etched into a 2 mm wide strip was ultrasonically cleaned with 2-propanol (for electronics industry, manufactured by Kanto Chemical) and then dried. On this substrate, the purified polymer (4) was dissolved in dichloroethane at a ratio of 5%, and a solution obtained by filtering through a 0.1 μm polytetrafluoroethylene (PTFE) filter was applied by an ink jet method to obtain a film thickness of 0. A hole transport layer having a thickness of 0.050 μm was formed. After sufficiently drying, a mixture (mixing mass ratio 99: 1) of the compound (II-17) and the compound (III-5) purified by sublimation as a light-emitting material having a carrier transport ability is applied by a spin coater method. Thus, a light emitting layer having a thickness of 0.065 μm was formed on the hole transport layer. After sufficiently drying, a back electrode having a width of 2 mm and a total thickness of 0.23 μm was formed so as to intersect the ITO electrode by vapor-depositing Ca to a thickness of 0.08 μm and Al to a thickness of 0.15 μm. The effective area of the formed organic electroluminescent element was 0.04 cm ² .

(Example 5)
An organic EL device was produced in the same manner as in Example 1 except that the purified polymer (5) was used instead of the purified polymer (1).

(Comparative Example 1)
An organic EL device was produced in the same manner as in Example 1 except that the exemplified compound (1) that was not treated with GPC was used instead of the purified polymer (1).

(Comparative Example 2)
An organic EL device was produced in the same manner as in Example 2, except that instead of the purified polymer (2), the exemplified compound (2) that was not treated with GPC was used.

(Comparative Example 3)
An organic EL device was produced in the same manner as in Example 3 except that the exemplified compound (3) not treated with GPC was used instead of the purified polymer (3).

(Comparative Example 4)
An organic EL device was produced in the same manner as in Example 4 except that the exemplified compound (4) not treated with GPC was used instead of the purified polymer (4).

(Comparative Example 5)
An organic EL device was produced in the same manner as in Example 5 except that the exemplified compound (I-3) that was not treated with GPC was used instead of the purified polymer (5).

= Evaluation =
The organic EL device manufactured as described above was measured for light emission by applying a direct current voltage in vacuum (10 ⁻³ Torr) with the ITO electrode side positive and the Mg-Ag back electrode negative, and the light emission at this time The luminance of the device at the starting voltage and the driving current = 20 mA / cm ² was evaluated.
Moreover, the light emission lifetime of the organic EL element was evaluated in dry nitrogen. In the measurement of the light emission lifetime, the current value was set so that the initial luminance was 50 cd / cm ^2, and the time until the luminance was reduced by half from the initial value by low current driving was defined as the element lifetime (Hour). The results are shown in Table 1.

[Examples of organic photoreceptor]
(Example 6)
On a roughened 20 mmφ stainless steel cylindrical substrate, 100 parts of a zirconium compound (trade name: Orgatics ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 10 parts of a silane compound (trade name: A1110, manufactured by Nippon Junker Co., Ltd.) and i-propanol A solution composed of 400 parts and 200 parts of butanol was applied by a dip coating method and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer having a thickness of 0.5 μm. 10 parts of dichlorotin phthalocyanine as a charge generating material is mixed with 10 parts of polyvinyl butyral resin (trade name: ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 500 parts of n-butyl acetate and treated with glass beads for 1 hour in a paint shaker. Then, the obtained coating solution was applied onto the undercoat layer by a dip coating method and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer.
Next, 7 parts of the purified polymer (1) was dissolved in 38 parts of monochlorobenzene, and the obtained coating solution was applied on a stainless steel cylindrical substrate on which a charge generation layer was formed by a dip coating method, And dried for 1 hour to form a charge transport layer having a thickness of 55 μm.

= Evaluation =
The electrophotographic characteristics of the electrophotographic photoreceptor thus obtained were measured in a normal environment (20 ° C.) using a laser beam printer test model-1 (A-4 lateral direction, 36 sheets per minute) manufactured by Fuji Xerox Co., Ltd. , 50% RH), and a print test was performed to evaluate the image quality after the first and 5000 copies. The exposure amount was adjusted using a filter depending on the sensitivity of the charge generation material. The results are shown in Table 2.

(Example 7)
An organic photoreceptor was prepared in the same manner as in Example 6 except that the charge generation material was changed to chlorogallium phthalocyanine, and the image quality was evaluated.

(Example 8)
An organic photoreceptor was prepared in the same manner as in Example 6 except that the charge generation material was changed to hydroxygallium phthalocyanine, and the image quality was evaluated.

Example 9
An organic photoreceptor was prepared in the same manner as in Example 6 except that the charge generation material was changed to oxotitanium phthalocyanine, and the image quality was evaluated.

(Example 10)
An organic photoreceptor was prepared in the same manner as in Example 6 except that the charge transport material was changed to the purified polymer (2), and the image quality was evaluated.

(Example 11)
An organic photoreceptor was prepared in the same manner as in Example 7 except that the charge transport material was changed to the purified polymer (2), and image quality evaluation was performed.

(Example 12)
An organic photoreceptor was prepared in the same manner as in Example 8 except that the charge transporting material was changed to the purified polymer (2), and the image quality was evaluated.

(Example 13)
An organic photoreceptor was prepared in the same manner as in Example 9 except that the charge transport material was changed to the purified polymer (2), and the image quality was evaluated.

(Example 14)
An organic photoreceptor was prepared in the same manner as in Example 6 except that the charge transport material was changed to the purified polymer (3), and the image quality was evaluated.

(Example 15)
An organic photoreceptor was prepared in the same manner as in Example 7 except that the charge transport material was changed to the purified polymer (3), and the image quality was evaluated.

(Example 16)
An organic photoreceptor was prepared in the same manner as in Example 8 except that the charge transport material was changed to the purified polymer (3), and the image quality was evaluated.

(Example 17)
An organic photoreceptor was prepared in the same manner as in Example 9 except that the charge transport material was changed to the purified polymer (3), and image quality evaluation was performed.

(Example 18)
An organic photoreceptor was prepared in the same manner as in Example 6 except that the charge transporting material was changed to the purified polymer (4), and the image quality was evaluated.

Example 19
An organic photoreceptor was prepared in the same manner as in Example 7 except that the charge transport material was changed to the purified polymer (4), and image quality evaluation was performed.

(Example 20)
An organic photoreceptor was prepared in the same manner as in Example 8 except that the charge transport material was changed to the purified polymer (4), and the image quality was evaluated.

(Example 21)
An organic photoreceptor was prepared in the same manner as in Example 9 except that the charge transport material was changed to the purified polymer (4), and the image quality was evaluated.

(Comparative Example 6)
An organic photoreceptor was prepared in the same manner as in Example 6 except that the charge transporting material was changed to the exemplary compound (1) that was not treated with GPC, and the image quality was evaluated.

(Comparative Example 7)
An organic photoreceptor was prepared in the same manner as in Comparative Example 6 except that the charge generation material was changed to chlorogallium phthalocyanine, and the image quality was evaluated.

(Comparative Example 8)
An organic photoreceptor was prepared in the same manner as in Comparative Example 6 except that the charge generation material was changed to hydroxygallium phthalocyanine, and the image quality was evaluated.

(Comparative Example 9)
An organic photoreceptor was prepared in the same manner as in Comparative Example 6 except that the charge generation material was changed to oxotitanium phthalocyanine, and the image quality was evaluated.

(Comparative Example 10)
An organic photoreceptor was prepared in the same manner as in Comparative Example 6 except that the charge transporting material was changed to the exemplified compound (2) that was not treated with GPC, and the image quality was evaluated.

(Comparative Example 11)
An organic photoreceptor was prepared in the same manner as in Comparative Example 10 except that the charge generation material was changed to chlorogallium phthalocyanine, and the image quality was evaluated.

(Comparative Example 12)
An organic photoreceptor was prepared in the same manner as in Comparative Example 10 except that the charge generation material was changed to hydroxygallium phthalocyanine, and the image quality was evaluated.

(Comparative Example 13)
An organic photoreceptor was prepared in the same manner as in Comparative Example 10 except that the charge generation material was changed to oxotitanium phthalocyanine, and the image quality was evaluated.

(Comparative Example 14)
An organic photoreceptor was prepared in the same manner as in Comparative Example 6 except that the charge transporting material was changed to the exemplified compound (3) that was not treated with GPC, and the image quality was evaluated.

(Comparative Example 15)
An organic photoreceptor was prepared in the same manner as in Comparative Example 14 except that the charge generation material was changed to chlorogallium phthalocyanine, and the image quality was evaluated.

(Comparative Example 16)
An organic photoreceptor was prepared in the same manner as in Comparative Example 14 except that the charge generation material was changed to hydroxygallium phthalocyanine, and the image quality was evaluated.

(Comparative Example 17)
An organic photoreceptor was prepared in the same manner as in Comparative Example 14 except that the charge generation material was changed to oxotitanium phthalocyanine, and the image quality was evaluated.

[Examples of organic semiconductor transistor elements]
(Example 22)
A gold film was formed to a thickness of 100 nm on a glass substrate by vacuum vapor deposition to obtain a gate electrode. Then, the SiO ₂ to form an insulating layer with a film thickness of 300nm by sputtering on the gate electrode, further, by forming a gold film thickness of 150nm through a metal mask as a source electrode and a drain electrode. Note that the distance between the source electrode and the drain electrode is 50 μm.
Thereafter, an organic semiconductor solution obtained by filtering a dichloroethane solution containing 5% of the purified polymer (1) through a PTFE filter having an opening of 0.1 μm so as to be conductive with the source electrode and the drain electrode is 0.15 μm thick by a dipping method. The organic semiconductor layer was formed to produce an organic semiconductor transistor element.

  The organic semiconductor thin film is formed by a dip method in a state where the source electrode and the drain electrode face each other in advance and masked with a resist except for a part of the source electrode and the drain electrode in contact with the region. Subsequently, this coating film was formed through a process of drying at 130 ° C. in an inert gas atmosphere having an oxygen concentration of 5 ppm and a water concentration of 5 ppm.

(Example 23)
An organic semiconductor transistor element was produced in the same manner as in Example 22 except that the purified polymer (2) was used instead of the purified polymer (1) used in Example 22.

(Example 24)
An organic semiconductor transistor element was produced in the same manner as in Example 22 except that the purified polymer (3) was used instead of the purified polymer (1) used in Example 22.

(Example 25)
Organic semiconductor as in Example 22 except that the purified polymer (4) was used instead of the purified polymer (1) used in Example 22 and the formation of the organic semiconductor layer was performed by the ink jet method instead of the dipping method. A transistor element was produced.

(Comparative Example 18)
An organic semiconductor transistor element was produced in the same manner as in Example 22 except that instead of the purified polymer (1) used in Example 22, Exemplified Compound (1) that was not treated with GPC was used.

(Comparative Example 19)
An organic semiconductor transistor element was produced in the same manner as in Example 22 except that instead of the purified polymer (1) used in Example 22, the exemplified compound (2) that was not treated with GPC was used.

= Evaluation =
The organic semiconductor transistor elements obtained in Examples and Comparative Examples were measured for current-voltage characteristics when a gate voltage was applied using a semiconductor parameter analyzer (manufactured by Agilent Technologies, 4155C), and carrier mobility (linear region) ) And the on / off ratio were calculated.
Table 3 shows the on / off ratio of the organic semiconductor transistor element manufactured as described above, together with the carrier mobility of the charge transporting material used for forming the organic compound layer.

As can be seen from Table 3, the drain-source current flowing between the source electrode, the organic semiconductor layer, and the drain electrode in accordance with the change in the voltage applied to the gate electrode (gate voltage) in the organic semiconductor transistor element shown in any of the examples. It shows changing switching characteristics and a good on / off ratio.
However, in the comparative example, it can be seen that the on / off ratio is inferior to the element of the example because the carrier mobility of the charge transporting material used for forming the organic semiconductor thin film is low. Further, when forming an organic semiconductor thin film, there is a case where a liquid phase film forming method cannot be used / a vapor phase film forming method must be used.

It is typical sectional drawing which shows an example of the laminated constitution of the organic electroluminescent element of this invention. It is typical sectional drawing which shows an example of the laminated constitution of the organic electroluminescent element of this invention. It is typical sectional drawing which shows an example of the laminated constitution of the organic electroluminescent element of this invention. It is typical sectional drawing which shows an example of the laminated constitution of the organic electroluminescent element of this invention. 1 is a schematic cross-sectional view showing an example of a layer configuration of an electrophotographic organic photoreceptor of the present invention. 1 is a schematic configuration diagram illustrating an example of an electrophotographic image forming apparatus of the present invention. It is a schematic cross section which shows an example of a structure of the organic-semiconductor transistor element of this invention. It is a schematic cross section which shows an example of a structure of the organic-semiconductor transistor element of this invention. It is a schematic cross section which shows an example of a structure of the organic-semiconductor transistor element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent insulator board | substrate 2 Transparent electrode 3 Hole transport layer 4 Light emitting layer 5 Electron transport layer 6 Light emitting layer with carrier transport ability 7 Back electrode 11 Conductive support 12 Subbing layer 13 Charge generation layer 14 Charge transport layer 15 Photosensitive Layer 20 Image forming device 21 Electrophotographic organic photoconductor 22 Charging device 23 Exposure device 24 Developing device 25 Transfer device 26 Image fixing device 27 Cleaning device 28 Transfer medium 31 Substrate 32 Source electrode 33 Drain electrode 34 Organic semiconductor layer 35 Gate electrode 36 Insulating layer

Claims (8)

  A method for treating a polymer organic electronic material, comprising: dissolving a polymer organic electronic material in a solvent; and then bringing the polymer organic electronic material into contact with porous particles for fractionation. A step of synthesizing a polymer organic electronic material by dehydrating and condensing a raw material monomer for the polymer organic electronic material in the presence of a metal catalyst;
After the polymer organic electronic material is dissolved in a solvent, the polymer organic electronic material is fractionated while removing metal ions caused by the metal catalyst by contacting with the ion-exchangeable porous particles. Process,
A method for producing a polymer organic electronic material, comprising: At least one is transparent or translucent and has one or more organic compound layers between a pair of electrodes consisting of an anode or a cathode,
An organic electroluminescent device comprising a polymer organic electronic material treated by the treatment method according to claim 1 in the organic compound layer.   An organic photoconductor for electrophotography comprising a photosensitive layer on a support, and the photosensitive layer containing a polymeric organic electronic material processed by the processing method according to claim 1.   An electrophotographic image forming apparatus comprising the electrophotographic organic photoreceptor according to claim 4. A source electrode; a drain electrode; an organic semiconductor provided so as to be conductive with the source electrode and the drain electrode; and a gate electrode insulated from the organic semiconductor and capable of applying an electric field. ,
An organic semiconductor transistor element, wherein the organic semiconductor contains a polymer organic electronic material processed by the processing method according to claim 1. 7. A coating film forming step for forming a coating film containing the solvent using a solution in which a charge transporting material is dissolved in a solvent, and a drying step for drying the coating film, and at least a drying process. An organic semiconductor transistor device manufacturing method for manufacturing the organic semiconductor transistor device according to claim 1,
A method for producing an organic semiconductor transistor element, wherein a polymer organic electronic material treated by the treatment method according to claim 1 is used as the charge transporting material. A substrate, and one or more organic semiconductor transistor elements provided on the substrate,
A semiconductor device comprising the organic semiconductor transistor element according to claim 6 as the organic semiconductor transistor element.

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