JPH10182760A - Charge transfer copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject copolymer excellent in a charge transfer property, mechanical characteristics, etc., excellent in a new function-imparting property, and capable of being applied to organic electronic devices by block or graft-copolymerizing plural blocks having specific functions, respectively. SOLUTION: This copolymer is produced by block or graft-copolymerizing a charge-transferring block having at least one kind of structure selected from a structure of formula I [Ar<1> , Ar<2> are each independently an aryl; X<1> is a divalent hydrocarbon having an aromatic ring structure, etc.; X<2> , X<3> are each independently an arylene; L<1> is a divalent hydrocarbon which may contain a branched or ring structure, etc.; (m) is 0.1; (n) is 0, 1] and a structure of formula II (Ar<3> , Ar<4> are each independently an aryl; L<2> is a trivalent hydrocarbon having an aromatic ring structure, etc.) as a repeating unit to an insulating block having at least one kind of structure selected from the structure of formula III (R<1> -R<3> are each independently H, a halogen, an alkyl, etc.; R<4> is a halogen, hydroxyl, carboxyl, etc.) as a repeating unit.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel charge transporting device which utilizes a charge transporting function and which can be applied to electronic devices such as electrophotographic photoreceptors, electroluminescent devices, photorefractive devices, optical sensors, and photovoltaic cells. The present invention relates to a water-soluble copolymer and a method for producing the same.

[0002]

2. Description of the Related Art Organic charge transporting materials have been reported in practical use in electrophotographic photoreceptors, and have been reported, for example, in the 36th Annual Meeting of the Japan Society of Applied Physics, 31-pK-12 (1990). As a key material in organic electronic devices such as electroluminescent devices, photorefractive devices, optical sensors, and photovoltaic cells, their applicability has been attracting attention.
The charge transporting material in these devices is generally
Since it is used as a thin film, mechanical properties such as film-forming properties, flexibility, and strength are required in addition to charge transporting ability.

[0003] In the electrophotographic photoreceptor, a charge transporting polymer typified by polyvinyl carbazole (PVK) having both a charge transporting ability and a film forming property was used at first, but PVK has a mechanical strength. But there are practically essential problems such as low charge mobility and low charge mobility. As a means to solve this problem, it is necessary to separate the charge transporting ability, which is a function required for the charge transporting material, from the mechanical properties such as film-forming properties, flexibility, and strength, and to assign each to a different material. The development of materials based on the concept of function separation has been carried out, and at present, a composite material in which a low-molecular compound having a charge-transporting property, which has charge-transporting ability, is dispersed in an insulating resin, which has mechanical properties, has been developed. It is the mainstream of transport materials.

However, such a low-molecular resin dispersed composite material has a problem in that the dispersed charge-transporting low-molecular compound crystallizes with the passage of time and / or heating, resulting in deterioration of characteristics, and particularly at high temperatures. However, there is a limit to the use of such a device in an electronic device or to a device that generates heat (Joule heat) such as an electroluminescent element. In addition, when used for an electrophotographic photoreceptor for a liquid developing type electrophotographic apparatus capable of obtaining high image quality, contact with the developing solution causes dissolution or crystallization of the charge transporting low-molecular compound, which is required. There are problems such as a change in the characteristics and cracks.
Furthermore, in order to secure a sufficient charge transporting ability in such a composite material, it is necessary to disperse the low-molecular compound having a charge transporting property in a resin at a high concentration of 35 to 60% by weight. Even if a resin having excellent mechanical properties such as flexibility and strength is used, there is a limit in maintaining the mechanical properties of the composite film.

[0005] Further higher performance, longer life, higher durability,
In order to utilize organic charge transport materials widely in the field of organic electronic devices, including electrophotographic photoreceptors that require high speed and low cost, it is essential to overcome the above problems. As a means of this, research and development of high-performance charge transporting polymers replacing polyvinyl carbazole have recently been activated again. To date, many charge-transporting polymers containing a triarylamine skeleton in the main chain or side chain have been developed based on the knowledge that triarylamine-based charge-transporting low-molecular compounds have high charge-transport properties. ing.

For example, US Pat. No. 4,806,443 discloses a charge-transporting polycarbonate obtained by polymerization of a specific dihydroxytriarylamine and bischloroformate, and is disclosed in US Pat. No. 4,806. ,
No. 444 discloses a charge transporting polycarbonate obtained by polymerization of a specific dihydroxytriarylamine and phosgene. Also, U.S. Pat.
No. 517 discloses a charge-transporting polycarbonate obtained by polymerizing bis (hydroxyalkyl) triarylamine with bischloroformate or phosgene, and is disclosed in U.S. Pat. No. 5,959,288 discloses a charge transporting polycarbonate by polymerization of a specific dihydroxytriarylamine or bis (hydroxyalkyl) triarylamine and bischloroformate, or a charge by polymerization of bisacyl halide. Transportable polyesters are disclosed. No. 5,034,296.
In the specification, a charge-transporting polycarbonate or a charge-transporting polyester containing a triarylamine structure having a specific fluorene skeleton is disclosed in US Pat.
No. 83,482 discloses a charge transporting polyurethane. Furthermore, Japanese Patent Application Laid-Open No. 61-20953
JP, JP-A-1-134456, JP-A-1-134
457, 1-134462, 4-13
JP-A Nos. 3065 and 4-133066 propose a charge transporting polymer having a charge transporting skeleton such as hydrazone or triarylamine in a side chain, and an electrophotographic photosensitive member using the same. Have been.

However, it is still difficult to realize all the required characteristics with a homopolymer composed of only a single component, and at present it has been said that a satisfactory product has not yet been obtained.

To solve this problem, see, for example,
No. 1627, No. 7-72640, No. 6-25
No. 6428, No. 5-295096, No. 5-3
Nos. 10904, 5-331238, 5-
No. 202135 proposes a strategy of copolymerizing several kinds of monomers. However, since these copolymers are manufactured by mixing the raw material monomers and performing polymerization in one step, each monomer becomes a random copolymer in which the monomers are randomly bonded, and the properties exhibited when each monomer is polymerized alone are exhibited. I can not pull out enough,
The fundamental problem has not been solved. That is, for example, when the homopolymer composed of only the charge transporting monomer is inferior in flexibility, the flexibility can be improved by adding a flexible monomer to form a random copolymer. In addition, a dilution effect occurs in which the concentration of the transport active component is reduced by the amount of the added monomer, and the charge transport ability is reduced. Further, when the copolymerization component forms a charge trap, a new problem such as a reduction in the charge transport ability beyond the above-described dilution effect occurs.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances in the prior art, and has a novel charge-transporting copolymer which can overcome the above-mentioned problems. It is an object of the present invention to provide a method of manufacturing the same.

That is, an object of the present invention is to provide a charge transporting property,
Provided is a novel charge-transporting copolymer which is excellent in mechanical properties, lamination film-forming properties, etc., excellent in imparting new functions, and highly applicable to organic electronic devices such as electrophotographic photoreceptors. It is in. Another object of the present invention is to provide a production method capable of easily producing a novel charge transporting copolymer.

[0011]

Means for Solving the Problems The present inventors have made intensive studies on charge transporting materials and polymer materials, and as a result,
It has been found that multiple functions can be imparted without impairing each function by a method of block copolymerization or graft copolymerization in which a plurality of blocks having desired functions are connected by a covalent bond.

In particular, a charge transporting block containing at least one kind of structure represented by the following general formula (1) or (2) and an insulating block containing at least one kind of structure represented by the following general formula (3) It has been found that a block or graft copolymer composed of has both high charge transportability and excellent mechanical properties.

That is, the charge transporting copolymer of the present invention comprises a charge transporting block containing at least one of the structures represented by the following general formulas (1) and (2), An insulating block including at least one of the structures represented as structural units, each block comprising:
It is characterized by being bonded in a block shape or a graft shape. General formula (1)

[0014]

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(In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group, and X ¹ represents a divalent hydrocarbon group having an aromatic ring structure or a heteroatom-containing hydrocarbon group. , X ² and X ³ each independently represent a substituted or unsubstituted arylene group; L ¹ represents a divalent hydrocarbon group or a heteroatom-containing hydrocarbon group which may have a branched or cyclic structure; Represents an integer selected from 0 or 1, and n represents an integer selected from 0 or 1.) General formula (2)

[0016]

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(Wherein, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, and L ² represents a trivalent hydrocarbon group having an aromatic ring structure or a heteroatom-containing hydrocarbon group. .) General formula (3)

[0018]

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(Wherein, R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group;
⁴ is a halogen atom, a hydroxyl group, a carboxyl group,
A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxyl group,
It represents a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted alkoxycarbonyl group. )

The charge transporting copolymer of the present invention is represented by the general formula (3) and a charge transporting block containing at least one of the structures represented by the general formula (1) or (2). Since the block or the graft copolymer includes, as a constitutional unit, an insulating block containing at least one kind of structure, it has both high charge transportability and excellent mechanical properties and compatibility with multilayering. Further, in the charge transporting copolymer of the present invention, by changing the components of the insulating block, without impairing the charge transporting performance, glass transition temperature, crystallinity, refractive index, adhesion, It is possible to control the adsorptivity, flexibility, solubility, melting property, phase separation property, etc., and it has the potential to be developed into further advanced materials.

Further, the present inventors have found that the charge transporting copolymer has a terminal or a side chain of the charge transporting block,
The present inventors have found that a polymerization initiator can be easily produced by introducing a polymerization initiator and polymerizing the insulating block to a terminal or a side chain of the charge transporting block with the polymerization initiator, thereby completing the present invention.

According to this production method, a block having a desired charge transporting ability is prepared in advance, a suitable polymerization initiator is selected, and a monomer which gives a desired insulating block is polymerized to obtain various properties. A high-performance charge-transporting block copolymer or graft copolymer having the formula (1) can be easily produced.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to embodiments.

As the charge transporting block forming the copolymer of the present invention, at least one of the structures represented by the general formula (1) or (2), which contains a triarylamine structure in its repeating unit, and Any block may be used as long as the block is contained as a repeating unit. However, in terms of film formability, mechanical strength, flexibility, suitability for wet coating, etc., the weight average molecular weight of the block is preferably 2,000 or more and 50 or more.
It is preferably not more than 00000. It is more preferably from 10,000 to 2,000,000, and still more preferably from 20,000 to 1,000,000. Here, the weight average molecular weight of the charge transporting block refers to the weight average value of the molecular weights of all the charge transporting blocks contained in the copolymer of the present invention.

In the above general formula (1), Ar ¹ and Ar ² are each independently selected from a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted aryl group having 6 to 16 carbon atoms. Specific examples include a phenyl group, a biphenyl group, a naphthyl group, a pyrenyl group and the like. Further, as the substituent, a methyl group, an ethyl group,
Examples include a methoxy group and a halogen atom.

X ¹ is selected from a divalent hydrocarbon group having an aromatic ring structure or a heteroatom-containing hydrocarbon group. Among them, a hydrocarbon group having 6 to 20 carbon atoms or a heteroatom-containing hydrocarbon group is preferable. Specific examples thereof include phenylene, biphenylene, terphenylene, naphthylene, methylenediphenyl, cyclohexylidenediphenyl, and oxydiphenyl. Group, thiodiphenyl group and the like, and methyl-substituted, ethyl-substituted, methoxy-substituted, and halogen-substituted thereof, among which a substituted or unsubstituted biphenylene group is preferred from the viewpoint of charge mobility and the like. Are particularly preferred.

X ² and X ³ are each independently selected from a substituted or unsubstituted arylene group, and are preferably a substituted or unsubstituted arylene group having 6 to 18 carbon atoms. Specifically, phenylene group, biphenylene group, Examples include a terphenylene group, a naphthylene group and the like, and a methyl-substituted, ethyl-substituted, methoxy-substituted, and halogen-substituted product thereof.

L ¹ is arbitrarily selected from a divalent hydrocarbon group or a heteroatom-containing hydrocarbon group which may have a branched or cyclic structure, and is selected from the viewpoints of film formability, mechanical strength, flexibility and the like. , Ether bond, ester bond, carbonate bond,
Those containing a bonding group selected from siloxane bonds and the like and having 20 or less carbon atoms are preferable. Specific examples of L ¹ include the following.

[0029]

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M represents an integer selected from 0 or 1, and n represents an integer selected from 0 or 1.

In the above general formula (2), Ar ³ and Ar ⁴ are each independently selected from a substituted or unsubstituted aryl group, and a substituted or unsubstituted aryl group having 6 to 24 carbon atoms is preferable. Specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a pyrenyl group and the like. Further, as the substituent, an alkyl group or alkoxyl group having 1 to 12 carbon atoms, a diarylamino group, a diarylaminoaryl group, a halogen atom and the like are preferable.

L ² is arbitrarily selected from a trivalent hydrocarbon group having an aromatic ring structure or a hetero atom-containing hydrocarbon group, and preferably has 20 or less carbon atoms from the viewpoint of mechanical strength and the like. Specific examples of L ^2, include those shown below.

[0033]

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The charge transporting block only needs to have at least one of the structures represented by the general formulas (1) and / or (2) in the repeating unit, and includes several types of structures. In that case, the concatenation form is random,
Arbitrary ones such as block and alternate may be used. Further, the charge transporting block may include a structure other than the structure represented by the general formula (1) and / or the general formula (2) in its repeating unit. In that case, in the charge transporting block, The proportion of the structure represented by the general formula (1) or (2) occupying is preferably 25% by weight or more. It is more preferably at least 40% by weight, and even more preferably at least 60% by weight. If the proportion of the repeating unit in the charge transporting block is less than 25% by weight, sufficient charge transporting properties will not be exhibited. The glass transition temperature of the charge transporting block is durability, mechanical strength, flexibility,
From the viewpoints of chemical stability, low adhesion and contamination, etc., the temperature is preferably 20 ° C. or higher, more preferably 60 ° C. or higher, and further preferably 90 ° C. or higher.

As the insulating block forming the copolymer of the present invention, any insulating block containing at least one of the structures represented by the general formula (3) as a repeating unit and exhibiting insulating properties can be used. However, the block may have a weight average molecular weight of 2,000 to 500,000 in terms of film formability, mechanical strength, flexibility, suitability for wet coating, and the like.
It is preferably 0 or less. More preferably 1000
0 or more and 2,000,000 or less, more preferably 2
It is 0000 or more and 1,000,000 or less. Here, the weight average molecular weight of the insulating block refers to the weight average value of the molecular weights of all the insulating blocks contained in the copolymer of the present invention.

In the general formula (3), R ^{1 to} R ³ are each independently selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. The substituted or unsubstituted alkyl group preferably has 1 to 8 carbon atoms, and the substituted or unsubstituted aryl group preferably has 6 to 8 carbon atoms. Specific examples include a methyl group, an ethyl group, a chloromethyl group, a phenyl group, and a tolyl group.

R ⁴ represents a halogen atom, a hydroxyl group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyl group. It is arbitrarily selected from a substituted acyloxy group or a substituted or unsubstituted alkoxycarbonyl group and may have a branched or cyclic structure, but has 1 to 2 carbon atoms.
0 is preferred.

Electrophotographic exposure requiring high-speed response
Applications such as body, light sensor, photorefractive element, etc.
In such a case, among the compounds represented by the general formula (3), R
¹ ~ R ^Three Are each independently a hydrogen atom, branched or
A monovalent hydrocarbon group which may contain a ring structure, and
^Four May have a branched or cyclic structure.
Those which are hydrogen groups are particularly preferred. These compounds
Has no polar group in its structure, so its polarity is low,
Charge transfer due to small charge trapping effect due to dielectric polarization
This is particularly preferable in that the degree of charge, charge life, and the like are increased. Ma
In addition, the hygroscopicity is reduced and the humidity dependency is reduced.
Good effect is also exhibited. Demonstrate such favorable effects
To determine the ratio of the repeating unit in the insulating block,
Preferably, the total content is 50% by weight or more. More preferred
Or more than 70% by weight.

For applications such as electrophotographic photoreceptors and electroluminescent devices which require high mechanical strength and solvent resistance, among the compounds represented by the general formula (3), R ⁴ is a halogen atom, A hydroxyl group, a mercapto group, a nitrile group, a carboxyl group, a carbonyl halide group, a halogenated sulfonyl group, an isocyanate group, an amino group, and a substituted alkyl group having at least one reactive group selected from alkoxysilyl groups as a substituent, A substituted aryl group,
Those which are a substituted alkoxyl group, a substituted acyl group, a substituted acyloxy group, or a substituted alkoxycarbonyl group are preferred. Depending on the presence of the reactive substituent, these compounds may be used alone or in combination with a curing aid to form a charge-transporting copolymer in which the charge-transporting copolymer is three-dimensionally crosslinked. Can give coalescence. The three-dimensionally crosslinked charge-transporting copolymer exhibits favorable effects such as high mechanical strength and solvent resistance due to the three-dimensionally crosslinked structure. In order to exhibit such a favorable effect, the proportion of the repeating unit in the insulating block is preferably 5% by weight or more. It is more preferably at least 10% by weight. However, if the proportion of the repeating unit in the insulating block is too large, the reaction in the coating solution cannot be ignored, and the pot life tends to decrease. Needs special attention.

It is sufficient that the insulating block has at least one of the structures represented by the general formula (3) in the repeating unit. When the insulating block includes several types of structures, the connection form is Arbitrary ones such as random, block, and alternate may be used. Further, the insulating block has a general formula (3)
May be included in the repeating unit, and in that case, the proportion of the structure represented by the general formula (3) in the insulating block is preferably 30% by weight or more. It is more preferably at least 50% by weight, and even more preferably at least 70% by weight.

The glass transition temperature of the insulating block is:
From the viewpoints of durability, mechanical strength, flexibility, chemical stability, low adhesion contamination and the like, the temperature is preferably 20 ° C. or more, more preferably 60 ° C. or more, and further preferably 90 ° C. or more.
° C or higher. Tables 1 to 7 show specific structural examples of the repeating unit represented by the general formula (3) that gives such a preferable glass transition temperature.

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

[Table 6]

[0048]

[Table 7]

In the charge transporting copolymer of the present invention, specific examples of the structural formula represented by the above general formula (1), which is contained as a repeating unit in the charge transporting block, are shown in Tables 8 and 9. Table 10 shows specific examples of the structural formula represented by the general formula (2).

[0050]

[Table 8]

[0051]

[Table 9]

[0052]

[Table 10]

Tables 11 to 17 show specific examples of the structural formula represented by the above general formula (3) which is contained as a repeating unit in the insulating block, but the present invention is not limited to these. .

[0054]

[Table 11]

[0055]

[Table 12]

[0056]

[Table 13]

[0057]

[Table 14]

[0058]

[Table 15]

[0059]

[Table 16]

[0060]

[Table 17]

The copolymer of the present invention, even if it is a block copolymer in which the above-mentioned blocks are connected to each other in a block shape, is obtained by connecting one block as a main chain and the other block as a side chain. It may be a graft copolymer made of any of the above, and its constituent blocks may be connected in any manner. That is, if the charge transporting block is represented by A and the insulating block is represented by B, AB type, ABA type, BAB type,
(AB) n-type, (AB) nA-type, and B (AB) n-type block copolymers, a graft copolymer having a charge transporting block as a main chain and an insulating block as a side chain, and an insulating block. Examples include a graft copolymer having a main chain and a charge transporting block as a side chain, and a block-graft copolymer obtained by grafting A and / or B to a side chain of an AB-type block copolymer or the like.

Specific examples of the structure of the charge transporting copolymer of the present invention are shown in Tables 18 and 19 below, but the present invention is not limited thereto.

[0063]

[Table 18]

[0064]

[Table 19]

The method for synthesizing the copolymer of the present invention is described in “Experimental Chemistry Lecture, 28th edition, Polymer Synthesis” (Maruzen, 199).
2), Macromonomer chemistry and industry (IPC, 1
990), polymer compatibilization and evaluation technology (Technical Information Association,
1992) and any suitable method capable of providing a block copolymer or a graft copolymer described in New Polymer OnePoint 12 Polymer Alloy (Kyoritsu, 1988) can be used.

The method for producing the copolymer of the present invention includes, for example, (1) a method in which a charge transporting polymer and an insulating polymer are separately synthesized in advance, and the polymers are reacted and bonded to each other. A method for obtaining a block copolymer,
(2) When the polymerization form of the monomer forming the charge transporting block and the monomer forming the insulating block are the same and the reactivities of the two are greatly different, simply polymerizing a mixture of these monomers first After the higher reactive monomer is polymerized and the monomer is consumed,
A method in which the lower reactivity monomer is polymerized to obtain a desired block copolymer; (3) a polymer of one of the monomers is synthesized in advance, and azo or peroxy is added to the terminal and / or side chain of the polymer. Acid esters, peroxy, dithiocarbamates,
By introducing a polymerization initiator containing a group having a polymerization initiation ability such as an alkali metal alcoholate or an alkali metal alkyl, and polymerizing the other monomer with the polymerization initiator, a desired block copolymer or graft copolymer is obtained. Examples of the method include a method of obtaining a united state. According to the method (3), a di- or tri-block copolymer composed of a polycondensation or polyaddition polymer and an addition polymerization or ring-opening polymerization polymer,
And a graft copolymer can be easily provided,
preferable. Among the polymerization initiators used herein, azo-type polymerization initiators are particularly preferable because they are relatively stable and easy to handle, and have radical polymerization initiation ability for a wide range of vinyl monomers.

In addition, (4) a compound having a plurality of groups having a polymerization initiating ability such as azo, peroxyester, peroxy, etc. in a molecule is used. A method of obtaining a desired block copolymer also by polymerizing and then polymerizing the other monomer from the remaining polymerization initiating group, (5) a cationic living polymerization method, an anion living polymerization method, a radical living polymerization method, etc. And a method of obtaining a desired block copolymer by sequentially polymerizing each monomer by the living polymerization method. The living polymerization method can easily control the molecular weight of each block and can provide a polymer having a narrow molecular weight distribution.

Further, (6) Immortal polymerization method, Inif
The desired block copolymer can also be obtained by sequentially polymerizing each monomer by an erter method or the like. Furthermore, a desired graft copolymer can be obtained by synthesizing a macromonomer in which the other monomer has been introduced into the terminal of the polymer of one monomer in advance, and polymerizing the macromonomer.

As a method for producing the three-dimensionally crosslinked charge-transporting copolymer, the charge-transporting copolymer having a reactive substituent may be used, if necessary, together with a curing aid and / or a curing catalyst. A method of dissolving or suspending in a solvent, applying the liquid, forming a film, and then performing a heat treatment and / or a water treatment, or the like. Known curing aids can be used, for example, water, polyhydric alcohols, polyhydric amines,
Examples include polyvalent isocyanates and polyacid anhydrides. Known curing catalysts can be used, for example, acids,
Bases, tin compounds, titanium compounds and the like can be mentioned.

The molecular weight of the copolymer of the present invention may be any value, but is desirably 2000 or more in order to exhibit high polymer properties such as film formability and flexibility. There is no particular limitation on the upper limit of the molecular weight in terms of electrical characteristics, but when forming a film by a wet coating method, it is necessary that the molecular weight be within a range that gives an appropriate solution viscosity.
It is preferably 0000 or less.

As is well known in the field of polymer blends and polymer alloys, different polymers are generally incompatible with each other, and their mixtures and block or graft copolymers have a phase-separated state. take. In general, a simple mixture, that is, a polymer blend, has a macroscopic phase separation scale of several μm or more (macrophase separation), and the phase separation scale greatly changes depending on film formation conditions and the like. Is difficult to obtain with good reproducibility. On the other hand, in block copolymers and graft copolymers in which each component is connected by a covalent bond, the scale of phase separation is regulated by the length of the block, so that a fine and uniform submicron or less Gives a phase separation state (micro phase separation). It is known that the scale of phase separation in block copolymers and graft copolymers is generally about the same as the average length of each block, and approximately proportional to the 2/3 root of the molecular weight.

The block copolymer or graft copolymer of the present invention also generally assumes a microphase-separated state.

In general, the state of phase separation in a phase-separable block copolymer or graft copolymer depends on the type and molecular weight of the constituent blocks, the composition ratio of both blocks, and the like.
The thermodynamically most stable structure exists, and in the copolymer consisting of A block and B block, A
/ B dependent only on the composition ratio, and as the A / B ratio increased, A was a spherical domain and B was a matrix, A was a rod-shaped domain and B was a matrix, A / B alternating layers, B was a rod-shaped domain and A was a matrix , B is a globular domain and A is systematically transformed into a matrix.

However, when a film is formed by a wet coating method, the phase separation state can be arbitrarily controlled depending on the solvent used, the drying speed, and the like. For example, even when the A / B ratio is large and a B-sphere A matrix is used thermodynamically, if a solvent that is a good solvent for B and a poor solvent for A is selected as a coating solvent, the A-sphere B matrix structure can be obtained. Can be obtained. When a good solvent for both A and B is used and the solvent is rapidly removed, a phase separation structure (modulation structure) frozen in a spinodal decomposition state may be obtained. Also, A / B
When a polymer having only B and being compatible with B is added to a copolymer having a large ratio and thermodynamically taking a matrix of B spheres A, the B spheres are enlarged with an increase in the amount of addition, and the final amount is increased. Gives a phase-separated structure in which A is a sphere, and a polymer compatible only with B and B is a matrix. In the charge transporting copolymer of the present invention, the higher the molecular weight of the structural blocks and the farther the solubility parameters of both blocks are, the higher the phase separation property. Those having a high phase separation property and forming a phase separation structure in which the charge transporting phase is a domain and the insulating phase is a matrix function effectively as a non-uniform charge transporting layer for an S-shaped photoreceptor. .

However, the block copolymer or graft copolymer of the present invention is not necessarily limited to those having a microphase separation state. Some do not cause The molecular weight of each block is low, and / or
Alternatively, when the solubility parameter difference between them is small, they show compatibility and are suitably used as a material for a uniform charge transport layer for a J-shaped photoreceptor. The S-shaped photoconductor is a photoconductor whose light-induced potential decay curve shows an inverted S-shape.
A photoreceptor is a photoreceptor whose light-induced potential decay curve shows an inverted J-shape.

The composition ratio of the charge transporting block and the insulating block in the copolymer may be any.
The range is preferably from 0: 1 to 1:10, and more preferably from 4: 1 to 1: 4. When the composition ratio of the charge transport block exceeds the upper limit, mechanical properties tend to deteriorate, and when the composition ratio of the charge transport block falls below the lower limit, sufficient charge transport ability may not be exhibited. is there.

The weight average molecular weight of each block constituting the copolymer of the present invention and the composition ratio of the two are determined by the G value of the copolymer.
It can be calculated from PC and NMR measurement data.

Since the novel copolymer of the present invention has both high charge transporting ability and excellent mechanical properties, it is suitably used for various organic electronic devices. For example, those having high charge transporting ability, film forming property, adsorbing property to pigment and adhesiveness are excellent in function-separated laminated electrophotographic photoreceptor by dispersing pigment having charge generating ability in it. Charge generating layer and a single-layer type electrophotographic photoreceptor. Further, a material having both high charge transporting ability, mechanical strength and chemical stability is effective as a material for a uniform charge transporting layer or a surface protective layer for a function-separated laminated electrophotographic photosensitive member. Those having both high charge transport ability and phase separation ability are S
It is effective as a material for a non-uniform charge transport layer for a letter-shaped photoreceptor.

[0079]

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples, and those skilled in the art can modify the following examples based on known knowledge of synthetic polymer chemistry and organic synthetic chemistry.

(Synthesis Example 1) Reactive polymerization initiator 4, 4 '
Synthesis of -Azobis (4-cyanovaleric chloride) Thionyl chloride (220 ml) was ice-cooled, and 4,4'-azobis (4-cyanovaleric acid) (100 g) was gradually added. 30 ° C
For 6 hours, and excess thionyl chloride was distilled off under reduced pressure. The residue was recrystallized from chloroform to give 42 g of 4,
4′-Azobis (4-cyanovaleric chloride) crystals were obtained.

(Synthesis Example 2) Synthesis of charge transporting polymer having hydroxy groups at both terminals 3,3'-dimethyl-N, N'-bis (p, m-dimethylphenyl) -N, N'-bis 100 g of [4- (2-methoxycarbonylethyl) phenyl]-[1,1′-biphenyl] -4,4′-diamine, 200 g of ethylene glycol and 5 g of tetrabutoxytitanium were heated to reflux for 3 hours under a nitrogen stream. 3,3′-dimethyl-N,
N'-bis (p, m-dimethylphenyl) -N, N'-
After confirming that bis [4- (2-methoxycarbonylethyl) phenyl]-[1,1'-biphenyl] -4,4'-diamine was consumed, the pressure was reduced to 0.5 mmHg and ethylene glycol was distilled off. While heating to 230 ° C., the reaction was further continued for 3 hours. Thereafter, the mixture was cooled to room temperature, methylene chloride was added to dissolve the insoluble matter, and the precipitate was reprecipitated from acetone to obtain 90 g of a charge transporting polymer having hydroxyl groups at both ends represented by the following structural formula. The weight average molecular weight of the obtained polymer measured by GPC and NMR was 2.4 × 10 ⁴ .

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Example 1 (Synthesis of block copolymer represented by the following structural formula (1)) 72 g of the charge transporting polymer having hydroxyl groups at both ends obtained in Synthesis Example 2 above and triethylamine 1.
8 g was dissolved in 140 ml of toluene and cooled to 0 ° C.
Here, 9.5 g of 4,4′-azobis (4-cyanovaleric acid chloride) obtained in Synthesis Example 1 above was added to toluene 25
The liquid suspended in ml was dropped. After reacting at room temperature for 1 hour, the mixture was heated to 30 ° C. and further reacted for 6 hours. The reaction solution was added dropwise to methanol, stirred for 1 hour, and filtered. This reprecipitation operation was repeated twice more. The residue was dried to obtain 68 g of a charge transporting polymer having an azo type polymerization initiator at a terminal.

1.0 g of a charge-transporting polymer having an azo-type polymerization initiator at its end and 2.0 g of a styrene monomer were dissolved in 3 ml of toluene.
Heat for 5 hours. This solution was added dropwise to methanol, stirred for 1 hour, and filtered off. The obtained solid is a mixture of the target block copolymer and a styrene monomer homopolymer (polystyrene), and the styrene monomer homopolymer is removed by the following purification method utilizing the difference in solubility. Was obtained. That is, the reaction mixture was dissolved in toluene, a solvent in which both the charge transporting polymer of Synthesis Example 2 and polystyrene were easily soluble, and the solution was synthesized in Synthesis Example 2.
The charge transporting polymer was insoluble and was added dropwise to cyclohexane, a solvent in which polystyrene was soluble, and reprecipitated to obtain 1.5 g of the desired block copolymer.

¹ H-NMR of the obtained block copolymer
The spectrum is shown in FIG. From the integral ratio of the peaks corresponding to the protons specific to both blocks, the weight composition ratio of the charge transporting block and the insulating block, which is a styrene polymer, is calculated to be approximately 55:45. The weight average molecular weight of the charge transporting block of Synthesis Example 2 used here was 2.4 × 1.
Since it is 0 ⁴ , the weight average molecular weight of the insulating block is calculated to be 1.0 × 10 ⁴ . The glass transition temperature of polystyrene forming the insulating block of the present block copolymer is 100 ° C., and the glass transition temperature of the charge transporting polymer of Synthesis Example 2 forming the charge transporting block of the present block copolymer. The temperature is 110 ° C. Further, as a result of TEM observation, it was found that the block copolymer of this example had microphase separation properties.

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Example 2 (Synthesis of Block Copolymer Represented by Structural Formula (2)) 43 g of the charge-transporting polymer having hydroxyl groups at both ends obtained in Synthesis Example 2 and 0.1 g of triethylamine.
5 g was dissolved in 120 ml of dichloromethane and cooled to 0 ° C. A solution of 5.6 g of 4,4′-azobis (4-cyanovaleric acid chloride) obtained in Synthesis Example 1 above in 20 ml of dichloromethane was added dropwise. After reacting at room temperature for 1 hour, the mixture was heated to 30 ° C. and further reacted for 4 hours. The solvent was distilled off from this, and it was dissolved by adding tetrahydrofuran, added dropwise to methanol, stirred for 1 hour, and filtered. This reprecipitation operation was repeated twice more.
The residue was dried to obtain 41 g of a charge transporting polymer having an azo type polymerization initiator at a terminal.

5.5 g of a charge-transporting polymer having an azo-type polymerization initiator at its terminal and 5.5 g of n-dodecyl methacrylate were dissolved in 120 ml of toluene, followed by purging with nitrogen and heating at 60 ° C. for 65 hours. The solvent was removed therefrom, tetrahydrofuran was added, the solution was added dropwise to methanol, and the mixture was stirred for 1 hour and filtered. The obtained solid was sufficiently washed with n-hexane, which is a good solvent for poly (n-dodecyl methacrylate), to obtain 6.3 g of a desired block copolymer.

¹ H-NMR of the obtained block copolymer
The spectrum is shown in FIG. From the integral ratio of the peaks corresponding to the protons specific to both blocks, the charge transporting block and n
The weight composition ratio of the insulating block, which is a polymer of dodecyl methacrylate, is calculated to be approximately 70:30. In the same manner as in Example 1, the molecular weights of the charge transporting block and the insulating block of the block copolymer of this example are calculated to be 2.4 × 10 ⁴ and 5.1 × 10 ³ , respectively.
The glass transition temperature of poly (n-dodecyl methacrylate) forming the insulating block of the block copolymer is-
65 ° C., and the glass transition temperature of the charge transporting copolymer of Synthesis Example 2 which forms the charge transporting block of the block copolymer is 110 ° C. Further, as a result of TEM observation, it was found that the block copolymer of this example had microphase separation properties.

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Example 3 (Synthesis of block copolymer represented by the following structural formula (3)) 10 g of the charge transporting polymer having an azo type polymerization initiator at the terminal obtained in Example 2 and n-butyl 20 g of methacrylate was dissolved in 100 ml of tetrahydrofuran, and after purging with nitrogen, heated at 60 ° C. for 65 hours. This solution was added dropwise to methanol, stirred for 1 hour, and filtered off. The obtained solid was sufficiently washed with n-hexane, which is a good solvent for poly (n-butyl methacrylate), to obtain 6 g of a desired block copolymer. ¹ of the resulting block copolymer
The H-NMR spectrum is shown in FIG. From the integral ratio of the peaks corresponding to the protons specific to both blocks, the weight composition ratio of the charge transporting block and the insulating block which is a polymer of n-butyl methacrylate is calculated to be about 80:20. In the same manner as in Example 1, the molecular weights of the charge transporting block and the insulating block of the block copolymer of this example are calculated to be 2.4 × 10 ⁴ and 3.0 × 10 ³ , respectively. The glass transition temperature of poly (n-butyl methacrylate) forming the insulating block of the block copolymer is 20 ° C., and the charge transport of Synthesis Example 2 forming the charge transport block of the block copolymer is performed. The glass transition temperature of the hydrophilic copolymer is 110 ° C. Further, as a result of TEM observation, it was found that the block copolymer of this example had microphase separation properties.

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Example 4 (Synthesis of a block copolymer represented by the following structural formula (4)) 16.5 g of the charge transporting polymer having an azo type polymerization initiator at the terminal obtained in Example 1 and tert 24.3 g of -butyl methacrylate and 2.7 g of 2-hydroxyethyl methacrylate were dissolved in 390 ml of toluene, and the mixture was purged with nitrogen and heated at 60 ° C for 95 hours. This solution was added dropwise to methanol, stirred for 1 hour, and filtered off. The obtained solid was sufficiently washed with n-butanol to obtain 25 g of the desired block copolymer. FIG. 4 shows the ¹ H-NMR spectrum of the obtained block copolymer. The charge transporting block, tert-butyl methacrylate, and 2-
The weight composition ratio of the insulating block, which is a random copolymer of hydroxyethyl methacrylate, is calculated to be approximately 60:40. Similarly, from the ¹ H-NMR spectrum, the ratio of the repeating unit derived from 2-hydroxyethyl methacrylate in the insulating block is calculated to be 10% by weight. In the same manner as in Example 1, the molecular weights of the charge transporting block and the insulating block of the block copolymer of this example are calculated to be 2.4 × 10 ⁴ and 8.0 × 10 ³ , respectively. The glass transition temperature of poly (tert-butyl methacrylate) forming the insulating block of the present block copolymer is 107 ° C., and the charge transport of Synthesis Example 2 forming the charge transporting block of the present block copolymer. The glass transition temperature of the hydrophilic copolymer is 110 ° C. Further, as a result of TEM observation, it was found that the block copolymer of this example had microphase separation properties.

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Example 5 (Synthesis of a block copolymer represented by the following structural formula (5)) 16.5 g of the charge transporting polymer having an azo type polymerization initiator at the terminal obtained in Example 1 and tert -Butyl methacrylate (24.3 g) and 3-trimethoxysilylpropyl methacrylate (2.7 g) were added to tetrahydrofuran (390).
After dissolving in nitrogen and purging with nitrogen, the mixture was heated at 60 ° C. for 95 hours. This solution was added dropwise to acetone, stirred for 1 hour, and filtered off. The obtained solid was sufficiently washed with cyclohexane to obtain 23 g of a desired block copolymer. FIG. 5 shows the ¹ H-NMR spectrum of the obtained block copolymer.
Shown in From the integral ratio of the peaks corresponding to the protons specific to both blocks, the weight composition ratio of the charge transporting block and the insulating block, which is a random copolymer of tert-butyl methacrylate and 3-trimethoxysilylpropyl methacrylate, is approximately 60:40. Is calculated. Similarly, from the ¹ H-NMR spectrum, the proportion of the repeating unit derived from 3-trimethoxysilylpropyl methacrylate in the insulating block is calculated to be 10% by weight. In the same manner as in Example 1, the molecular weights of the charge transporting block and the insulating block of the block copolymer of this example are calculated to be 2.4 × 10 ⁴ and 8.0 × 10 ³ , respectively.
The glass transition temperature of poly (tert-butyl methacrylate), which constitutes the majority of the insulating block of the present block copolymer, is 107 ° C., and Synthesis Example 2, which forms the charge transporting block of the present block copolymer. The glass transition temperature of the charge transporting polymer is 110 ° C. Further, as a result of TEM observation, it was found that the block copolymer of this example had microphase separation properties.

[0096]

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Example 6 (Synthesis of Three-Dimensional Cross-Linked Copolymer from Block Copolymer Represented by Structural Formula (4) and Polyvalent Isocyanate) The charge transport property of Synthesis Example 2 obtained in Example 4 10 g of a block copolymer formed from a charge transporting block composed of a copolymer, an insulating block composed of a random copolymer of tert-butyl methacrylate and 2-hydroxyethyl methacrylate, and diphenylmethane-4,4′-diisocyanate (product) A solution prepared by dissolving 0.9 g of the name “Millionate MT” (produced by Nippon Polyurethane Industry Co., Ltd.) in 90 g of cyclohexanenone was applied on a glass plate by a dip coating method, and heated at 150 ° C. for 1 hour to obtain a block copolymer. A divalent isocyanate, diphenylmethacrylate, is formed between the hydroxyl groups derived from 2-hydroxyethyl methacrylate in the coalescence. Ligated with down-4,4'-diisocyanate, to obtain a three-dimensional crosslinked polymer of interest. Note that the film after the heat treatment was swollen by cyclohexanone but was not dissolved, and it was confirmed that crosslinking and curing were achieved.

An application example for confirming the usefulness of the copolymer obtained from the above example will be described below. In addition, the application of the charge transporting copolymer of the present invention is not limited to the following examples, and can be applied to any electronic device that requires a charge transport function.

Application Example 1 A zirconium alkoxide compound (trade name:
23 parts by weight of ORGATICS ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd., 3 parts by weight of a silane compound (trade name: A1100, manufactured by Nippon Unicar), 1 part by weight of polyvinyl butyral resin (trade name: Eslex BM-S, manufactured by Sekisui Chemical) And a solution consisting of 25 parts by weight of isopropanol and 25 parts by weight of butanol by dip coating.
The film was dried by heating at 0 ° C. for 15 minutes to form an undercoat layer having a thickness of 1 μm. Next, in an X-ray diffraction spectrum using CuKα as a radiation source, at least the Bragg angle (2θ ± 0.
2 °) is 7.4 °, 16.6 °, 25.5 °, and 2
4 parts by weight of chlorogallium phthalocyanine microcrystals having a strong diffraction peak at 8.3 ° were mixed with 2 parts by weight of a vinyl chloride-vinyl acetate copolymer (trade name: UCAR Solution Vinyl Resin VMCH, manufactured by Union Carbide) and 67 parts by weight of xylene Parts, and 33 parts by weight of butyl acetate,
After dispersion treatment with glass beads for 2 hours by a paint shake method, the resulting dispersion is applied on the undercoat layer by a dip coating method, and dried by heating at 100 ° C. for 10 minutes to generate a charge having a thickness of 0.3 μm. A layer was formed.

Next, a solution prepared by dissolving 10 parts by weight of the block copolymer obtained in Example 3 in 90 parts by weight of chlorobenzene was applied on the charge generation layer by dip coating. Heat and dry for 60 minutes,
A 0 μm charge transport layer was formed. The laminated electrophotographic photoconductor obtained in this manner is applied to a laser printer (L
printer Press 4105, manufactured by Fuji Xerox Co., Ltd.), and a printing test was performed. At this time, in order to obtain an optimal exposure amount, an ND filter was inserted in the optical path of the laser beam, and the exposure intensity was adjusted. Image quality evaluation is 1st sheet and 5th
A print sample after continuous printing of 000 sheets was visually observed. The obtained print quality was good and 1
No difference was observed between the 5,000th sheet and the 5,000th sheet, and the durability was good.

With respect to the block copolymer obtained in Example 1, preparation and evaluation of an electrophotographic photosensitive member were performed in the same manner, and similar results were obtained. The block copolymer obtained in Example 2 was similarly prepared and evaluated for an electrophotographic photoreceptor. The initial image quality was good, but the image density was improved by continuous printing. Decline,
Background fogging, streak-like image quality defects, etc. occurred. This is presumably because the glass transition temperature of the insulating block of the block copolymer obtained in Example 2 was as low as −65 ° C., and the surface layer composed of the block copolymer was deteriorated by the mechanical stress caused by the cleaning blade. Is done.

Application Example 2 A laminated electrophotography was performed in the same manner as in Application Example 1, except that the resin for the charge generation layer was changed from a vinyl chloride-vinyl acetate copolymer to the block copolymer obtained in Example 2. A photoreceptor was prepared, mounted on a laser printer in the same manner as in Application Example 1, and subjected to a printing test. The obtained print image quality was good, no difference was observed between the first and 5,000th sheets, and the durability was also good. With respect to the block copolymers obtained in Example 3 and Example 4, preparation and evaluation of an electrophotographic photoreceptor were similarly performed, and similar results were obtained.

Application Example 3 An X-ray diffraction spectrum using CuKα as a radiation source has at least a Bragg angle (2θ ± 0.2 °) of 8.3 ° on an anodized aluminum drum of 40 mmφ. 10 parts by weight of dichlorotin phthalocyanine crystals having strong diffraction peaks at 13.7 ° and 28.3 ° were combined with 10 parts by weight of the block copolymer obtained in Example 3,
After mixing with 80 parts by weight of chlorobenzene and dispersing with a stainless steel bead for 48 hours by a ball mill method, the resulting dispersion is applied by a dip coating method, and dried by heating at 135 ° C. for 60 minutes to form a single layer having a thickness of 20 μm. A type electrophotographic photosensitive member was prepared.

The thus-obtained single-layer type electrophotographic photoreceptor was mounted on a laser printer and subjected to a printing test in the same manner as in Application Example 1. The obtained print image quality was good, no difference was observed between the first and 5,000th sheets, and the durability was also good.

With respect to the block copolymers obtained in Examples 4 and 5, an electrophotographic photosensitive member was prepared and evaluated in the same manner, and similar results were obtained.

Application Example 4 On the aluminum drum having the undercoat layer and the charge generation layer obtained in Application Example 1, 10 parts by weight of the block copolymer obtained in Example 4 and the following as a curing aid: A solution prepared by dissolving 1 part by weight of a trivalent isocyanate represented by the structural formula (a) (trade name “Sumidur N3200”, manufactured by Sumitomo Bayer Urethane Co., Ltd.) in 100 parts by weight of cyclohexanone was applied to the above-mentioned charge generating layer by dip coating. Then, the mixture was heated and cured at 150 ° C. for 60 minutes to form a first charge transport layer having a thickness of 3 μm.

Next, a polycarbonate resin 30 composed of 20 parts by weight of a low-molecular compound having a charge transporting property represented by the following structural formula (b) and a repeating unit represented by the following structural formula (c)
Parts by weight were dissolved in 200 parts by weight of toluene, and the resulting solution was applied on the charge transport layer by dip coating to form a second charge transport layer.

[0108]

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[0109]

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[0110]

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The laminated electrophotographic photosensitive member thus obtained was mounted on a laser printer in the same manner as in Application Example 1, and a printing test was performed. The obtained print image quality was good, no difference was observed between the first and 5,000th sheets, and the durability was also good.

When the first charge transport layer is formed without using the isocyanate, when the second charge transport layer is applied, the first charge transport layer is coated with the second charge transport layer coating solvent. And a coating film defect occurred. With respect to the block copolymer obtained in Example 5, preparation and evaluation of an electrophotographic photosensitive member were performed in the same manner, and similar results were obtained.
However, in forming the first charge transport layer, no curing aid was used, and instead, 1.0 part by weight of acetic acid was used as a curing catalyst.

As is clear from each of the above-mentioned application examples, the novel copolymer of the present invention is applied to an electrophotographic photoreceptor,
It was confirmed that desired characteristics were exhibited.

[0114]

The charge-transporting copolymer of the present invention is a block or graft copolymer having a specific structural unit, and has both excellent charge-transporting properties and excellent mechanical properties. An electrophotographic photoreceptor using the above has an excellent effect of high performance and excellent durability, and easy multilayering.

The charge-transporting copolymer of the present invention is a novel substance having both excellent charge-transporting properties and excellent mechanical properties, and is applicable not only to electrophotographic photosensitive members but also to a wide range of electronic devices. Is applicable.

[Brief description of the drawings]

FIG. 1 ¹ H-NMR of the block copolymer of Example 1
It is a spectrum.

FIG. 2 ¹ H-NMR of the block copolymer of Example 2
It is a spectrum.

FIG. 3 ¹ H-NMR of the block copolymer of Example 3
It is a spectrum.

FIG. 4 ¹ H-NMR of the block copolymer of Example 4
It is a spectrum.

FIG. 5 ¹ H-NMR of the block copolymer of Example 5
It is a spectrum.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G01J 1/02 G01J 1/02 R G03G 5/07 103 G03G 5/07 103 (72) Inventor Ryosaku Igarashi 1600 Takematsu, Minamiashigara-shi, Kanagawa Address Fuji Xerox Co., Ltd. (72) Inventor Taketoshi Hoshizaki 1600 Takematsu, Minami Ashigara City, Kanagawa Prefecture Fuji Xerox Co., Ltd.

Claims (13)

[Claims] 1. A charge-transporting block having at least one kind of a structure represented by the following general formula (1) or (2) as a repeating unit;
A charge transporting copolymer obtained by block copolymerization or graft copolymerization with an insulating block having at least one of the structures represented by the following as a repeating unit. General formula (1) (Wherein, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group, X ¹ is a divalent hydrocarbon group or a hetero atom-containing hydrocarbon group having an aromatic ring structure, X ² And X ³ each independently represent a substituted or unsubstituted arylene group; L ¹ represents a divalent hydrocarbon group or a heteroatom-containing hydrocarbon group which may have a branched or ring structure; Or n represents an integer selected from 1 and n represents an integer selected from 0 or 1.) General formula (2) (In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group, and L ² represents a trivalent hydrocarbon group having an aromatic ring structure or a heteroatom-containing hydrocarbon group.) Formula (3) (Wherein, R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and R ⁴ represents a halogen atom, a hydroxyl group, a carboxyl group, A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
It represents a substituted or unsubstituted alkoxyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted alkoxycarbonyl group. ) 2. In the general formula (3), R ^{1 to} R ³
Is independently a hydrogen atom, a monovalent hydrocarbon group which may have a branched or cyclic structure, and R ⁴
Is a monovalent hydrocarbon group which may have a branched or cyclic structure, The charge transporting copolymer according to claim 1, wherein 3. In the general formula (3), R ⁴ represents a halogen atom, a hydroxy group, a mercapto group, a nitrile group,
At least one selected from the group consisting of a carboxyl group, a carbonyl halide group, a sulfonyl halide group, an isocyanate group, an amino group, and an alkoxysilyl group
The charge-transporting copolymer according to claim 1, which is a substituted alkyl group, a substituted aryl group, a substituted alkoxy group, a substituted acyl group, a substituted acyloxy group, or a substituted alkoxycarbonyl group having a species as a substituent. . 4. The charge transporting copolymer according to claim 1, wherein the glass transition temperature of the insulating block is 20 ° C. or higher. 5. The charge transporting block according to claim 1, wherein the glass transition temperature is 20 ° C. or higher.
The charge transporting copolymer according to any one of the above. 6. The charge transport block and the insulating block each have a weight average molecular weight of 2,000 to 500,000.
The charge transporting copolymer according to any one of claims 1 to 5, which is 0 or less. 7. The charge transport block and the insulating block each have a weight average molecular weight of 20,000 to 10,000.
The charge-transporting copolymer according to any one of claims 1 to 6, wherein the charge-transporting copolymer is at most 00. 8. The charge transporting copolymer according to claim 1, wherein the charge transporting block and the insulating block are incompatible with each other. 9. The charge transporting compound according to claim 1, wherein X ¹ in the general formula (1) is a substituted or unsubstituted biphenylene group. Coalescing. 10. A charge transporting block having at least one of the structures represented by the general formula (1) or the general formula (2) as a repeating unit is prepared, and a terminal or a side chain of the charge transporting block is Introduce a polymerization initiator,
By polymerizing a vinyl monomer corresponding to the general formula (3) with the polymerization initiator, at least one of the structures represented by the general formula (3) is repeated at the terminal or side chain of the charge transporting block. The method for producing a charge transporting copolymer for producing a charge transporting copolymer according to any one of claims 1 to 9, wherein an insulating block having a unit is formed. 11. The method for producing a charge-transporting copolymer according to claim 10, wherein the polymerization initiator is an azo-type polymerization initiator. 12. A three-dimensional crosslinked charge transport, characterized in that at least the charge transportable copolymer according to claim 3 is crosslinked and cured by heat treatment and / or water treatment. Production method of functional copolymer. 13. A three-dimensionally crosslinked charge transporting copolymer produced by the production method according to claim 12.