JP4546904B2 - Novel arylamine polymer - Google Patents

Description

  The present invention relates to a novel arylamine polymer, and more particularly to a novel arylamine polymer useful as a material for organic electronics such as an organic EL device material, an organic transistor material, and an electrophotographic photosensitive material.

  Organic electroluminescence elements and organic transistor elements have been proposed by utilizing the light emission characteristics and charge transport characteristics of organic materials. By using an organic material for these elements, advantages such as light weight, low cost, low manufacturing cost, and flexibility are expected.

  Various materials of low molecular weight and high molecular weight have been reported as materials for organic thin film EL elements. In low molecular weight systems, it has been reported that high efficiency is achieved by employing various laminated structures, and that durability is improved by well controlling the doping method. However, in the case of low molecular aggregates, it has been reported that the film state changes over time for a long time, and has an essential problem regarding the stability of the film. On the other hand, in the case of polymer materials, energetically studied mainly on π-conjugated polymers such as PPV (poly-p-phenylene vinylene) series and poly-thiophene. However, it is difficult to increase the purity of these material systems and the intrinsically low fluorescence quantum yield is cited as a problem, and at present, high-performance EL devices have not been obtained. . In addition, polymer materials containing an arylamine moiety in the π-conjugated polymer main chain have been studied (Japanese Patent Laid-Open No. 10-310635, Japanese Patent Laid-Open No. 8-157575, Japanese Patent Laid-Open No. 2002-515078, ... Patent Documents 1 to 3, and WO 97/09394, Synth. Met., 84, 269, 1997). In view of the fact that polymer materials are inherently stable in the glass state, if high fluorescence quantum efficiency can be imparted, an excellent EL device can be constructed, and further improvements are being made in this field. .

  On the other hand, various materials of low molecular weight and high molecular weight have been reported for organic thin film transistor elements. For example, among low molecular weight materials, pentacene (Synth. Met., 51, 419, 1992), phthalocyanine (Appl. Phys. Lett., 69, 3066, 1996.), fullerene (JP-A-8-228034, Appl. Phys). Lett., 67, 121, 1995.), anthradithiophene (JP-A-11-195790), thiophene oligomer (Japanese Patent No. 3145294, Chem. Mater., 4,457, 1998.), bisdithieno. Thiophene (Appl. Phys. Lett., 71, 3871, 1997) and the like, and polymer materials such as polythiophene (Appl. Phys. Lett., 69, 4108, 1996.), polythienylene vinylene (Appl. Phys. Lett., 63 1372,1993.), And some of the material, such as is. Furthermore, the present applicant has previously proposed a polyarylamine (Japanese Patent Application No. 2004-174088).

  Low-molecular film formation requires a vacuum process such as vapor deposition, which increases manufacturing costs. However, high-molecular film formation can be performed by a wet process, which can reduce costs. is there. However, in order to enable film formation by a wet process, it is necessary to design a molecule that is soluble in an organic solvent, but polyarylamine (Proc. SPIE. Vol. 3148. P139-150, 1997.・ Non-patent document 1) is poor in solubility and further improvement is desired.

Japanese Patent Laid-Open No. 10-310635 JP-A-8-157575 Special Table 2002-515078 Proc. SPIE. Vol. 3148. P139-150, 1997

  The present invention has been made in view of the above state of the art, and as a polymer material for an organic thin film EL element having excellent light emission characteristics and excellent durability, as a polymer material for an active layer of an organic transistor. Another object of the present invention is to provide a novel arylamine polymer useful as a material for organic electronics such as a material for an electrophotographic photoreceptor.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a novel arylamine polymer containing a specific structural unit, and have completed the present invention.
That is, the said subject is solved by (1)-(6) of this invention.
(1) "Arylamine polymer having a repeating unit represented by the following general formula (I).

（式中、Ｘは置換もしくは無置換の芳香族炭化水素基、または、置換もしくは無置換のアルキル基を表わす。Ａｒ_１、Ａｒ_２は置換もしくは無置換の芳香族炭化水素基の２価基、Ａｒ_３は置換もしくは無置換の芳香族炭化水素基の１価基であり、窒素原子と結合する芳香族炭化水素基であるＡｒ_１、Ａｒ_２、Ａｒ_３を構成する水素原子のうち少なくとも１つがアルキル基またはアルコキシ基もしくはアルキルチオ基により置換されており、複数存在する場合は同一でも別異でもよい。）」；
（２）「前記一般式（Ｉ）で表わされる繰返し単位を有するアリールアミン重合体が、下記一般式（II）で表わされる繰り返し単位を有することを特徴とする前記（１）に記載のアリールアミン重合体。

(In the formula, X represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted alkyl group. Ar ₁ and Ar ₂ are divalent groups of a substituted or unsubstituted aromatic hydrocarbon group; Ar ₃ is a monovalent group of a substituted or unsubstituted aromatic hydrocarbon group, and at least one of hydrogen atoms constituting Ar ₁ , Ar ₂ , and Ar ₃ which are aromatic hydrocarbon groups bonded to a nitrogen atom is Substituted with an alkyl group, an alkoxy group or an alkylthio group, and when there are a plurality thereof, they may be the same or different.) ";
(2) The arylamine according to (1) above, wherein the arylamine polymer having a repeating unit represented by the general formula (I) has a repeating unit represented by the following general formula (II): Polymer.

（式中、Ｘは置換もしくは無置換の芳香族炭化水素基、または、置換もしくは無置換のアルキル基を表わす。Ａｒ_１、Ａｒ_２は置換もしくは無置換の芳香族炭化水素基の２価基を表わす。Ｒ^１はハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基を表わし、ｘは０から５の整数を表わす。そして窒素原子と結合する３個の芳香族炭化水素基を構成する水素原子のうち少なくとも１つがアルキル基またはアルコキシ基もしくはアルキルチオ基により置換されており、複数存在する場合は同一でも別異でもよい。）」；
（３）「前記一般式（II）で表わされる繰返し単位を有するアリールアミン重合体において、該一般式（II）中のＲ^１が長鎖アルキル基であり、ｘは１から５の整数であり、ｘが２から５の整数の場合、Ｒ^１は同一でも別異でもよいことを特徴とする前記（２）に記載のアリールアミン重合体」；
（４）「前記一般式（II）で表わされる繰返し単位を有するアリールアミン重合体が、下記一般式（III）で表わされる繰り返し単位を有することを特徴とする前記（２）または（３）に記載のアリールアミン重合体。

(In the formula, X represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted alkyl group. Ar ₁ and Ar ₂ represent a divalent group of a substituted or unsubstituted aromatic hydrocarbon group. R ¹ represents a halogen atom, a substituted or unsubstituted alkyl group or an alkoxy group or an alkylthio group, x represents an integer of 0 to 5, and three aromatic hydrocarbon groups bonded to the nitrogen atom At least one of the constituent hydrogen atoms is substituted with an alkyl group, an alkoxy group or an alkylthio group, and when there are a plurality of hydrogen atoms, they may be the same or different.
(3) In the arylamine polymer having a repeating unit represented by the general formula (II), R ¹ in the general formula (II) is a long-chain alkyl group, and x is an integer of 1 to 5. , When x is an integer of 2 to 5, R ¹ may be the same or different, and the arylamine polymer as described in (2) above;
(4) In the above (2) or (3), the arylamine polymer having a repeating unit represented by the general formula (II) has a repeating unit represented by the following general formula (III): The arylamine polymer as described.

（式中、Ａｒ_１、Ａｒ_２は置換もしくは無置換の芳香族炭化水素基の２価基を表わす。Ｒ^１は長鎖アルキル基を表わし、ｘは０から５の整数を表わす。Ｒ^２、Ｒ^３はそれぞれ、ハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基を表わし、ｙおよびｚはそれぞれ０から５の整数を表わし、ｙとｚの合計が２以上の場合、Ｒ^２および／またはＲ^３は同一でも別異でもよい。そして窒素原子と結合する３個の芳香族炭化水素基を構成する水素原子のうち少なくとも１つがアルキル基またはアルコキシ基もしくはアルキルチオ基により置換されており、複数存在する場合は同一でも別異でもよい。）」；
（５）「前記一般式（Ｉ）で表わされる繰り返し単位を有するアリールアミン重合体が、下記一般式（IV）で表わされることを特徴とする前記（１）に記載のアリールアミン重合体。

(In the formula, Ar ₁ and Ar ₂ represent a divalent group of a substituted or unsubstituted aromatic hydrocarbon group. R ¹ represents a long-chain alkyl group, and x represents an integer of 0 to 5. R ² , R ³ represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group, y and z each represents an integer of 0 to 5, and when the sum of y and z is 2 or more, R 3 ² and / or R ³ may be the same or different, and at least one of the hydrogen atoms constituting the three aromatic hydrocarbon groups bonded to the nitrogen atom is substituted with an alkyl group, an alkoxy group or an alkylthio group. And if there are multiple, they may be the same or different.) ";
(5) The arylamine polymer as described in (1) above, wherein the arylamine polymer having a repeating unit represented by the general formula (I) is represented by the following general formula (IV).

（式中、Ｘは置換もしくは無置換の芳香族炭化水素基、または、置換もしくは無置換のアルキル基を表わし、Ａｒ_１、Ａｒ_２は置換もしくは無置換の芳香族炭化水素基の２価基を表わす。Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基を表わし、ｔは１から３の整数を表し、ｕは１から４の整数を表わし、ｔまたはｕが２以上の整数の場合、ｔ個のＲ^４はそれぞれ異なっていてもよく、ｕ個のＲ^５もそれぞれ異なっていてもよい。そして窒素原子と結合する３個の芳香族炭化水素基を構成する水素原子のうち少なくとも１つがアルキル基またはアルコキシ基もしくはアルキルチオ基により置換されており、複数存在する場合は同一でも別異でもよい。）」；
（６）「前記一般式（IV）で表わされる繰り返し単位を有するアリールアミン重合体が、下記一般式（Ｖ）で表わされることを特徴とする前記（５）に記載のアリールアミン重合体。

(In the formula, X represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted alkyl group, and Ar ₁ and Ar ₂ represent a divalent group of a substituted or unsubstituted aromatic hydrocarbon group. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group, and t represents an integer of 1 to 3. U represents an integer of 1 to 4, and when t or u is an integer of 2 or more, t R ^{4 s} may be different from each other, and u R ⁵ may be different from each other. When at least one hydrogen atom constituting three aromatic hydrocarbon groups bonded to a nitrogen atom is substituted with an alkyl group, an alkoxy group or an alkylthio group, It may be different, even in the same). ";
(6) The arylamine polymer as described in (5) above, wherein the arylamine polymer having a repeating unit represented by the general formula (IV) is represented by the following general formula (V).

（式中、Ａｒ_１、Ａｒ_２は置換もしくは無置換の芳香族炭化水素基の２価基を表わす。
Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは無置換の、アルキル基またはアルコキシ基もしくはアルキルチオ基を表わし、ｔは１から３の整数を表わし、ｕは１から４の整数を表わし、ｔまたはｕが２以上の整数の場合、ｔ個のＲ^４はそれぞれ異なっていてもよく、ｕ個のＲ^５もそれぞれ異なっていてもよく、ｙおよびｚはそれぞれ０から５の整数を表し、ｙとｚの合計が２以上の場合、Ｒ^２および／またはＲ^３は同一でも別異でもよい。そして窒素原子と結合する３個の芳香族炭化水素基を構成する水素原子のうち少なくとも１つがアルキル基またはアルコキシ基もしくはアルキルチオ基により置換されており、複数存在する場合は同一でも別異でもよい。）」。

(In the formula, Ar ₁ and Ar ₂ represent a divalent group of a substituted or unsubstituted aromatic hydrocarbon group.
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group, and t is 1 to 3 represents an integer of 3, u represents an integer of 1 to 4, and when t or u is an integer of 2 or more, t R ^{4 s} may be different from each other, and u R ⁵ may be different from each other. Y and z each represents an integer of 0 to 5, and when the sum of y and z is 2 or more, R ² and / or R ³ may be the same or different. And at least 1 is replaced by the alkyl group, the alkoxy group, or the alkylthio group among the hydrogen atoms which comprise the three aromatic hydrocarbon groups couple | bonded with a nitrogen atom, and when two or more exist, they may be the same or different. ) "

  The novel arylamine polymer of the present invention has excellent light emission characteristics and excellent durability as a polymer material for an organic thin film EL device, a charge transporting polymer material for an organic transistor, and an electrophotographic photosensitive material. It is useful as a material for organic electronics such as body materials.

  The arylamine polymer of the present invention is useful as a charge transporting polymer material for organic transistors, and as a polymer material for organic thin film EL devices having excellent light emission characteristics and excellent durability.

The method for producing the arylamine polymer of the present invention will be described below.
The production method of the arylamine polymer of the present invention includes, for example, Wittig-Horner reaction using aldehyde and phosphonate, Wittig reaction using aldehyde and phosphonium salt, Heck reaction using vinyl substituent and halide, amine and halide Ullmann reaction using can be used, and can be produced by a known method. In particular, the Wittig-Horner reaction and the Wittig reaction are effective because of the simplicity of the reaction operation.

As an example, a method for producing a polymer in the present invention using a Wittig-Horner reaction will be described.
As shown in the following reaction formula, the polymer in the present invention is polymerized by mixing a solution in which the phosphonate ester compound and the aldehyde compound are present stoichiometrically and a base more than twice the molar amount thereof. The reaction proceeds and can be obtained.

The dialdehyde compound can be synthesized by various known reactions.
For example, the following Vilsmeier reaction,

  Alternatively, a reaction of an aryllithium compound with a formylating agent such as DMF, N-formylmorpholine, N-formylpiperidine,

  Alternatively, the following Gatterman reaction,

  Alternatively, various oxidation reactions of hydroxymethyl compounds,

等を一例として挙げることができる。
本発明においては、これら反応を用いて、目的とする重合体に対応する原料ジアルデヒド化合物を合成することができる。

Etc. can be mentioned as an example.
In the present invention, using these reactions, a raw material dialdehyde compound corresponding to the target polymer can be synthesized.

  The phosphonic acid diester compound can also be synthesized by various known reactions, but the following Michaelis-Arbuzov reaction is particularly easy.

A base is used for the polymerization reaction, and the base is not particularly limited as long as a phosphonate carbanion is formed, and examples thereof include metal alkoxides, metal hydrides, organolithium compounds, and the like, such as potassium t-butoxide, Sodium t-butoxide, lithium t-butoxide, potassium 2-methyl-2-butoxide, sodium 2-methyl-2-butoxide, sodium methoxide, sodium ethoxide, potassium ethoxide, potassium methoxide, sodium hydride, hydrogenation Examples include potassium, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, phenyl lithium, lithium naphthylide, lithium amide, lithium diisopropylamide and the like.
The amount of the base used in the reaction is usually only the same amount as the polymerization active point of the phosphonate ester compound, but an excessive amount can be used.

  The above-mentioned base may be added to the reaction system in a solid state or a suspended solution state, but it is particularly preferable to add it as a homogeneous solution in order to improve the homogeneity of the resulting polymer. As the solvent for dissolving the base, a solvent that forms a stable solution with the base to be used must be selected, but as other factors, those having a high solubility of the base are preferable, and the high molecular weight product produced in the reaction system is also preferred. Those that do not impair the solubility in the reaction solvent are good. Further, the solvent in which the high molecular weight product to be formed dissolves well is good. Depending on the characteristics of the base used and the high molecular weight to be produced, generally known alcohols and ethers are used. It can be arbitrarily selected from a system, an amine system, a hydrocarbon solvent and the like.

  Examples of a combination of a base and a solvent for uniformly dissolving the base include, for example, a methanol solution of sodium methoxide, an ethanol solution of sodium ethoxide, a 2-propanol solution of potassium t-butoxide, and 2-methyl-2-methyl ester of potassium t-butoxide. Propanol solution, potassium t-butoxide in tetrahydrofuran, potassium t-butoxide in dioxane, n-butyllithium in hexane, methyllithium in ether, lithium t-butoxide in tetrahydrofuran, lithium diisopropylamide in cyclohexane, potassium bis There are various combinations of solutions including a toluene solution of trimethylsilylamide and the like, and some solutions are easily available as commercial products. From the viewpoint of mild reaction conditions and ease of handling, a metal alkoxide-based solution is preferably used, such as solubility of the polymer to be produced, ease of handling, efficiency of the reaction, solubility of the polymer to be produced, etc. From the viewpoint, an ether system of metal t-butoxide is preferably used, and a tetrahydrofuran solution of potassium t-butoxide is more preferably used.

In the above polymerization reaction, a base solution may be added to the solution of the phosphonate ester compound and the aldehyde compound, a solution of the phosphonate ester compound and the aldehyde compound may be added to the base solution, and may be added to the reaction system at the same time. There is no restriction on the order of addition.
The polymerization time in the above polymerization reaction may be appropriately set according to the reactivity of the monomers used or the molecular weight of the desired polymer, but is preferably 0.2 hours to 30 hours.
The reaction temperature in the above polymerization reaction does not need to be controlled and the polymerization reaction proceeds favorably at room temperature. However, it is possible to heat or cool to raise the reaction efficiency to a milder condition.

It is also possible to add a molecular weight modifier in the above polymerization operation, or a sealing agent for sealing the end of the polymer as a terminal modifying group during the reaction, at the start of the reaction. It is also possible to add it. Therefore, a substituent based on a terminator may be bonded to the terminal of the arylamine polymer in the present invention.
Examples of the molecular weight regulator and terminal blocking agent include compounds having one reactive group such as diethyl benzylphosphonate and benzaldehyde.

The preferred molecular weight of the polymer of the present invention is 1,000 to 1,000,000, more preferably 2000 to 500,000 in terms of polystyrene-reduced number average molecular weight. When the molecular weight is too small, the film forming property such as the generation of cracks is deteriorated and the practicality becomes poor. On the other hand, when the molecular weight is too large, the solubility in a general organic solvent is deteriorated, the viscosity of the solution becomes high and the coating becomes difficult, which also causes a problem in practical use.
Also, a small amount of a branching agent can be added during the polymerization in order to improve the mechanical properties. The branching agent used is a compound having three or more polymerization reaction active groups (which may be the same or different). These branching agents may be used alone or in combination.

  The arylamine polymer obtained as described above is preferably used after removing impurities such as the base, unreacted monomer, terminal stopper, and inorganic salt generated during the polymerization. For these purification operations, conventionally known methods such as reprecipitation, extraction, Soxhlet extraction, ultrafiltration, dialysis and the like can be used.

  The polymer of the present invention obtained by the production method by the polymerization reaction is a known film formation method such as spin coating method, casting method, dipping method, ink jet method, doctor blade method, screen printing method, spray coating, etc. A good thin film excellent in strength, toughness, durability and the like without cracks can be produced, and can be suitably used as a material for organic EL elements, organic transistor elements, and the like.

Next, the repeating units (I), (II), (III), (IV) and (V) of the polymer of the present invention will be described in more detail.
The substituted or unsubstituted aromatic hydrocarbon group Ar ₃ in the general formula (I) may be a monocyclic group or a polycyclic group (a condensed polycyclic group or a non-condensed polycyclic group). Can be mentioned.

Examples include phenyl group, naphthyl group, pyrenyl group, fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrycenyl group, biphenyl group, terphenyl group, etc., and the general formulas (I), (II), (III) In (IV) and (V), the substituted or unsubstituted aromatic hydrocarbon groups Ar ₁ and Ar ₂ are monocyclic, non-condensed polycyclic or condensed polycyclic aromatic hydrocarbon groups, etc. As an example, the divalent group of the aromatic group mentioned as an example of Ar ₃ can be mentioned.

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

  The arylamine polymer having a repeating unit represented by the general formulas (I), (II), (III), (IV) and (V) of the present invention is substituted or substituted on an aromatic ring bonded to a nitrogen atom. It has an unsubstituted alkyl group, alkoxy group, or alkylthio group as a substituent. From the viewpoint of improving solubility in a solvent, it has a substituted or unsubstituted alkyl group, alkoxy group, or alkylthio group. Is preferred. If the number of carbons of these substituents increases, the solubility will be improved, but on the other hand, the properties such as charge transportability will decrease, so that the desired properties can be obtained within the range where the solubility is not impaired. It is preferred to select a substituent. Examples of suitable substituents in that case include alkyl groups, alkoxy groups and alkylthio groups having 1 to 25 carbon atoms. In the case of having a plurality of these substituents, a plurality of the same ones may be introduced, or a plurality of different ones may be introduced. These alkyl groups, alkoxy groups and alkylthio groups are further halogen atoms, cyano groups, aryl groups, hydroxyl groups, carboxyl groups, linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms, alkoxy groups or An aryl group substituted with an alkylthio group may be contained.

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

  In X in the general formulas (I), (II) and (IV), preferred examples of the substituted or unsubstituted aromatic hydrocarbon group include a monocyclic group, a polycyclic group (a condensed polycyclic group, a non-condensed polycyclic group). Any of (cyclic group) may be used, and examples thereof include the following.

  Examples thereof include a phenyl group, a naphthyl group, a pyrenyl group, a fluorenyl group, an azulenyl group, an anthryl group, a triphenylenyl group, a chrycenyl group, a biphenyl group, and a terphenyl group.

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

  Specific examples of the substituted or unsubstituted alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, and pentyl. Group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, 2-ethylhexyl group, trifluoromethyl group, 2-cyanoethyl group, benzyl group, 4-chlorobenzyl group, 4 -A methylbenzyl group, a cyclopentyl group, a cyclohexyl group, etc. can be mentioned as an example.

  The polymer of the present invention has improved solubility in a solvent due to the presence of an alkyl group, an alkoxy group, or an alkylthio group. It is important to improve the solubility of these materials because the manufacturing tolerance of the wet film-forming process is increased when manufacturing organic EL elements and organic transistor elements. For example, the choice of coating solvent is expanded, the temperature range during solution preparation is expanded, the temperature and pressure range during solvent drying is expanded, and the high processability results in high purity and high uniformity. The possibility of obtaining a high-quality thin film increases.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by these examples unless it exceeds the gist.

Example 1
Synthesis of polymer 1

２００ｍｌ四つ口フラスコに、上記のジアルデヒド１．４６５ｇ（３．８ｍｍｏｌ）及びジホスホネート２．０１６ｇ（３．８ｍｍｏｌ）を入れ、窒素置換してテトラヒドロフラン６０ｍｌ、およびベンズアルデヒド１０ｍｇ（０．０９５ｍｍｏｌ）を加えた。この溶液にカリウムｔ−ブトキシドの１．０ｍｏｌ ｄｍ^−３テトラヒドロフラン溶液１１．４ｍｌ（１１．４ｍｍｏｌ）を滴下し室温で２時間撹拌した後、ベンジルホスホン酸ジエチル８９．３ｍｇ（０．３９１ｍｍｏｌ）を加え、さらに１時間撹拌した。酢酸およそ０．４ｍｌを加えて反応を終了し、反応溶液を水洗した。溶媒を減圧留去した後テトラヒドロフラン及びメタノールを用いて再沈澱による精製を行ない、重合体１を２．２０ｇ得た。収率９４％。
元素分析値（計算値）；Ｃ：９０．８３％（９１．０７％）、Ｈ：６．７６％（６．６７％）、Ｎ：２．０２％（２．２６％）。
示差走査熱量測定から求めたガラス転移温度は１０３．５℃であった。
ＧＰＣにより測定したポリスチレン換算の数平均分子量は３８００、重量平均分子量は１８００であった。
赤外吸収スペクトル（ＮａＣｌキャスト膜）を図１に示した。

Into a 200 ml four-necked flask, put 1.465 g (3.8 mmol) of the above dialdehyde and 2.016 g (3.8 mmol) of diphosphonate, purge with nitrogen and add 60 ml of tetrahydrofuran and 10 mg (0.095 mmol) of benzaldehyde. It was. To this solution, 11.4 ml (11.4 mmol) of 1.0 mol dm ^-3 tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred at room temperature for 2 hours, and then 89.3 mg (0.391 mmol) of diethyl benzylphosphonate was added, The mixture was further stirred for 1 hour. About 0.4 ml of acetic acid was added to complete the reaction, and the reaction solution was washed with water. After the solvent was distilled off under reduced pressure, purification by reprecipitation was performed using tetrahydrofuran and methanol to obtain 2.20 g of Polymer 1. Yield 94%.
Elemental analysis value (calculated value); C: 90.83% (91.07%), H: 6.76% (6.67%), N: 2.02% (2.26%).
The glass transition temperature determined from differential scanning calorimetry was 103.5 ° C.
The number average molecular weight in terms of polystyrene measured by GPC was 3,800, and the weight average molecular weight was 1,800.
The infrared absorption spectrum (NaCl cast film) is shown in FIG.

Example 2
Synthesis of polymer 2

２００ｍｌ四つ口フラスコに、上記のジアルデヒド１．０００ｇ（３．１７ｍｍｏｌ）及びジホスホネート１．６８２ｇ（３．１７ｍｍｏｌ）を入れ、窒素置換してジメチルホルムアミド９０ｍｌ、およびベンズアルデヒド１０ｍｇ（０．０９５ｍｍｏｌ）を加えた。この溶液にカリウムｔ−ブトキシドの１．０ｍｏｌ ｄｍ^−３テトラヒドロフラン溶液７．９３ｍｌ（７．９３ｍｍｏｌ）を滴下し室温で２時間撹拌した後、ベンジルホスホン酸ジエチル１４４．７ｍｇ（０．６３４ｍｍｏｌ）を加え、さらに１時間撹拌した。酢酸およそ０．３ｍｌを加えて反応を終了し、反応溶液を水洗した。溶媒を減圧留去した後テトラヒドロフラン及びメタノールを用いて再沈澱による精製を行ない、重合体２を１．２０ｇ得た。収率７２％。
元素分析値（計算値）；Ｃ：９１．８２％（９１．５８％）、Ｈ：５．８５％（５．８１％）、Ｎ：２．５５％（２．６０％）。
ＧＰＣにより測定したポリスチレン換算の数平均分子量は１８００、重量平均分子量は１２００であった。
赤外吸収スペクトル（ＮａＣｌキャスト膜）を図２に示した。

In a 200 ml four-necked flask, put 1.000 g (3.17 mmol) of the above dialdehyde and 1.682 g (3.17 mmol) of diphosphonate, and purge with nitrogen to give 90 ml of dimethylformamide and 10 mg (0.095 mmol) of benzaldehyde. added. To this solution, 7.93 ml (7.93 mmol) of 1.0 mol dm ^-3 tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred at room temperature for 2 hours, and then 144.7 mg (0.634 mmol) of diethyl benzylphosphonate was added, The mixture was further stirred for 1 hour. About 0.3 ml of acetic acid was added to complete the reaction, and the reaction solution was washed with water. After the solvent was distilled off under reduced pressure, purification by reprecipitation was performed using tetrahydrofuran and methanol to obtain 1.20 g of polymer 2. Yield 72%.
Elemental analysis value (calculated value); C: 91.82% (91.58%), H: 5.85% (5.81%), N: 2.55% (2.60%).
The number average molecular weight in terms of polystyrene measured by GPC was 1800, and the weight average molecular weight was 1200.
The infrared absorption spectrum (NaCl cast film) is shown in FIG.

Example 3
Synthesis of polymer 3

５０ｍｌ三つ口フラスコに、上記のジアルデヒド０．４１７ｇ（１．０ｍｍｏｌ）及びジホスホネート０．５９０ｇ（１．０ｍｍｏｌ）を入れ、窒素置換してテトラヒドロフラン１７ｍｌ、およびベンズアルデヒド２ｍｇ（０．０１８ｍｍｏｌ）を加えた。この溶液にカリウムｔ−ブトキシドの１．０ｍｏｌ ｄｍ^−３テトラヒドロフラン溶液３．０ｍｌ（３．０ｍｍｏｌ）を滴下し室温で２時間撹拌した後、４０℃にて１時間攪拌した。その後、ベンジルホスホン酸ジエチル３２．０ｍｇ（０．１４０ｍｍｏｌ）を加え、さらに１時間撹拌した。酢酸およそ０．２ｍｌを加えて反応を終了し、反応溶液を水洗した。溶媒を減圧留去した後テトラヒドロフラン及びメタノールを用いて再沈澱による精製を行ない、重合体３を０．３６４ｇ得た。収率５２％。
元素分析値（計算値）；Ｃ：８７．２１％（８７．５２％）、Ｈ：６．１８％（５．９０％）、Ｎ：１．９４％（２．００％）。
ＧＰＣにより測定したポリスチレン換算の数平均分子量は２８００、重量平均分子量は５８００であった。
赤外吸収スペクトル（ＮａＣｌキャスト膜）を図３に示した。

In a 50 ml three-necked flask, add 0.417 g (1.0 mmol) of the above dialdehyde and 0.590 g (1.0 mmol) of diphosphonate, purge with nitrogen and add 17 ml of tetrahydrofuran and 2 mg (0.018 mmol) of benzaldehyde. It was. To this solution, 3.0 ml (3.0 mmol) of a 1.0 mol dm ^-3 tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred at room temperature for 2 hours, and then stirred at 40 ° C for 1 hour. Thereafter, 32.0 mg (0.140 mmol) of diethyl benzylphosphonate was added, and the mixture was further stirred for 1 hour. About 0.2 ml of acetic acid was added to terminate the reaction, and the reaction solution was washed with water. After the solvent was distilled off under reduced pressure, purification by reprecipitation was performed using tetrahydrofuran and methanol to obtain 0.364 g of Polymer 3. Yield 52%.
Elemental analysis value (calculated value); C: 87.21% (87.52%), H: 6.18% (5.90%), N: 1.94% (2.00%).
The number average molecular weight in terms of polystyrene measured by GPC was 2,800, and the weight average molecular weight was 5,800.
The infrared absorption spectrum (NaCl cast film) is shown in FIG.

Example 4
Synthesis of polymer 4

５０ｍｌ三つ口フラスコに、上記のジアルデヒド０．４７５ｇ（１．１１ｍｍｏｌ）及びジホスホネート０．５８６ｇ（１．１１ｍｍｏｌ）を入れ、窒素置換してテトラヒドロフラン１５ｍｌを加えた。この溶液にカリウムｔ−ブトキシドの１．０ｍｏｌ ｄｍ^−３テトラヒドロフラン溶液３．３ｍｌ（３．３ｍｍｏｌ）を滴下し室温で１時間撹拌した後、さらに４０℃にて３時間攪拌した。その後、ベンズアルデヒド３１ｍｇ（０．０３０ｍｍｏｌ）を加え、１時間撹拌した後、続けて、ベンジルホスホン酸ジエチル４５．３ｍｇ（０．１９８ｍｍｏｌ）を加え、さらに１時間撹拌した。酢酸およそ０．２ｍｌを加えて反応を終了し、反応溶液を水洗した。溶媒を減圧留去した後テトラヒドロフラン及びメタノールを用いて再沈澱による精製を行ない、重合体４を０．４３２ｇ得た。収率６０％。
元素分析値（計算値）；Ｃ：８８．１５％（８８．４４％）、Ｈ：６．７１％（６．９６％）、Ｎ：２．１８％（２．１５％）。
ＧＰＣにより測定したポリスチレン換算の数平均分子量は１８００、重量平均分子量は３３００であった。
赤外吸収スペクトル（ＮａＣｌキャスト膜）を図４に示した。

In a 50 ml three-necked flask, 0.475 g (1.11 mmol) of the dialdehyde and 0.586 g (1.11 mmol) of diphosphonate were placed, and the atmosphere was replaced with nitrogen, and 15 ml of tetrahydrofuran was added. To this solution, 3.3 ml (3.3 mmol) of a 1.0 mol dm ^-3 tetrahydrofuran solution of potassium t-butoxide was added dropwise and stirred at room temperature for 1 hour, and further stirred at 40 ° C for 3 hours. Thereafter, 31 mg (0.030 mmol) of benzaldehyde was added and stirred for 1 hour, and then 45.3 mg (0.198 mmol) of diethyl benzylphosphonate was added and further stirred for 1 hour. About 0.2 ml of acetic acid was added to terminate the reaction, and the reaction solution was washed with water. After the solvent was distilled off under reduced pressure, purification by reprecipitation was performed using tetrahydrofuran and methanol to obtain 0.432 g of polymer 4. Yield 60%.
Elemental analysis value (calculated value); C: 88.15% (88.44%), H: 6.71% (6.96%), N: 2.18% (2.15%).
The number average molecular weight in terms of polystyrene measured by GPC was 1,800, and the weight average molecular weight was 3,300.
The infrared absorption spectrum (NaCl cast film) is shown in FIG.

2 is an infrared absorption spectrum diagram of the arylamine polymer obtained in Example 1. FIG. 2 is an infrared absorption spectrum diagram of the arylamine polymer obtained in Example 2. FIG. 2 is an infrared absorption spectrum diagram of the arylamine polymer obtained in Example 3. FIG. 4 is an infrared absorption spectrum diagram of the arylamine polymer obtained in Example 4. FIG.

Claims (6)

An arylamine polymer having a repeating unit represented by the following general formula (I).

(In the formula, X represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted alkyl group. Ar ₁ and Ar ₂ are divalent groups of a substituted or unsubstituted aromatic hydrocarbon group; Ar ₃ is a monovalent group of a substituted or unsubstituted aromatic hydrocarbon group, and at least one of hydrogen atoms constituting Ar ₁ , Ar ₂ , and Ar ₃ which are aromatic hydrocarbon groups bonded to a nitrogen atom is (It is substituted by an alkyl group, an alkoxy group or an alkylthio group, and when there are plural groups, they may be the same or different.) The arylamine polymer according to claim 1, wherein the arylamine polymer having a repeating unit represented by the general formula (I) has a repeating unit represented by the following general formula (II).

(In the formula, X represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted alkyl group. Ar ₁ and Ar ₂ represent a divalent group of a substituted or unsubstituted aromatic hydrocarbon group. R ¹ represents a halogen atom, a substituted or unsubstituted alkyl group or an alkoxy group or an alkylthio group, x represents an integer of 0 to 5, and three aromatic hydrocarbon groups bonded to the nitrogen atom (At least one of the constituent hydrogen atoms is substituted with an alkyl group, an alkoxy group or an alkylthio group, and when there are a plurality of hydrogen atoms, they may be the same or different.) In the arylamine polymer having a repeating unit represented by the general formula (II), R ¹ in the general formula (II) is a long-chain alkyl group, x is an integer of 1 to 5, and x is 2 The arylamine polymer according to claim 2, wherein R ¹ may be the same or different in the case of an integer from ¹ to 5. The arylamine polymer according to claim 2 or 3, wherein the arylamine polymer having a repeating unit represented by the general formula (II) has a repeating unit represented by the following general formula (III).

(In the formula, Ar ₁ and Ar ₂ represent a divalent group of a substituted or unsubstituted aromatic hydrocarbon group. R ¹ represents a long-chain alkyl group, and x represents an integer of 0 to 5. R ² , R ³ represents a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group, y and z each represents an integer of 0 to 5, and when the sum of y and z is 2 or more, R 3 ² and / or R ³ may be the same or different, and at least one of the hydrogen atoms constituting the three aromatic hydrocarbon groups bonded to the nitrogen atom is substituted with an alkyl group, an alkoxy group or an alkylthio group. If there are multiple, they may be the same or different.) The arylamine polymer according to claim 1, wherein the arylamine polymer having a repeating unit represented by the general formula (I) is represented by the following general formula (IV).

(In the formula, X represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted alkyl group, and Ar ₁ and Ar ₂ represent a divalent group of a substituted or unsubstituted aromatic hydrocarbon group. R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group, and t represents an integer of 1 to 3. U represents an integer of 1 to 4, and when t or u is an integer of 2 or more, t R ^{4 s} may be different from each other, and u R ⁵ may be different from each other. When at least one hydrogen atom constituting three aromatic hydrocarbon groups bonded to a nitrogen atom is substituted with an alkyl group, an alkoxy group or an alkylthio group, It may be different, even in the same.) The arylamine polymer according to claim 5, wherein the arylamine polymer having a repeating unit represented by the general formula (IV) is represented by the following general formula (V).

(In the formula, Ar ₁ and Ar ₂ represent a divalent group of a substituted or unsubstituted aromatic hydrocarbon group.
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an alkylthio group, and t is 1 to 3 represents an integer of 3, u represents an integer of 1 to 4, and when t or u is an integer of 2 or more, t R ^{4 s} may be different from each other, and u R ⁵ may be different from each other. Y and z each represents an integer of 0 to 5, and when the sum of y and z is 2 or more, R ² and / or R ³ may be the same or different. And at least 1 is replaced by the alkyl group, the alkoxy group, or the alkylthio group among the hydrogen atoms which comprise the three aromatic hydrocarbon groups couple | bonded with a nitrogen atom, and when two or more exist, they may be the same or different. )

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