CN102875395A

CN102875395A - Triphenylamine derivative, a method for manufacturing triphenylamine derivates and electronic photographic photoreceptor

Info

Publication number: CN102875395A
Application number: CN 201210247398
Authority: CN
Inventors: 冈田英树; 菅井章雄; 洼嶋大辅
Original assignee: Kyocera Document Solutions Inc
Current assignee: Kyocera Document Solutions Inc
Priority date: 2008-09-16
Filing date: 2009-08-11
Publication date: 2013-01-16
Anticipated expiration: 2029-08-11
Also published as: CN102875395B; CN101676260B; CN101676260A

Abstract

The present invention provides a triphenylamine derivative having excellent solubilization of a solvent and capable of dissolving with binding resin and improving effectively light sensitivity when the triphenylamine derivative is used as a hole transport agent of electronic photographic photoreceptor, a method for manufacturing the triphenylamine derivative and an electronic photographic photoreceptor. The invention employs triphenylamine derivative represented by formula (1) and (6).

Description

Triphenylamine derivative, its manufacture method and Electrophtography photosensor

The application be for the applying date be that August 11, application number in 2009 are 200910164841.5, denomination of invention divides an application for the application for a patent for invention of " triphenylamine derivative, its manufacture method and Electrophtography photosensor ".

Technical field

The present invention relates to a kind of triphenylamine derivative, its manufacture method and Electrophtography photosensor.Particularly, relate to a kind of solvability to solvent and excellent with the intermiscibility of binding resin, by the cavity conveying agent as Electrophtography photosensor, help effectively to improve triphenylamine derivative, its manufacture method and the Electrophtography photosensor of light sensitivity characteristic.

Background technology

At present, use the Organophotoreceptor (OPC) that consisted of by binding resin (resin glue), charge generating and charge transport agent (cavity conveying agent, electron transporting agent) etc. as the Electrophtography photosensor that carries at image processing system etc.This Organophotoreceptor is compared with inorganic photoreceptor in the past, and when making easily, the options of photoreceptor material is varied, so have the large advantage of the degree of freedom of structure design.

Can enumerate various compounds as the cavity conveying agent of in this Organophotoreceptor, using, but wherein, particularly the charge delivery capability of triphenylamine derivative is excellent, is suitable as the cavity conveying agent.

As this type of triphenylamine derivative, for example compound (HTM-A～B) (for example patent documentation 1) of following formula (a)～(b) expression is disclosed.And, below only use the line segment outstanding from hexagonal summit of representing phenyl ring to represent the methyl that the carbon on phenyl ring is combined.

Patent documentation 1: JP 2005-289877 number

But (so HTM-A～B) because the substituting group in the contraposition of aryl amine is methyl or methoxy is to the solvability of solvent and insufficient with the intermiscibility of binding resin for the triphenylamine derivative of formula (a)～(b) expression.

Find thus, with this type of triphenylamine derivative during as the cavity conveying agent of Electrophtography photosensor because produce easily crystallization in the sensitive layer, disperse bad, so be difficult to the light sensitivity characteristic that obtains expecting.

Summary of the invention

Namely, the object of the invention is to, a kind of solvability to solvent and excellent with the intermiscibility of binding resin is provided, by the cavity conveying agent as Electrophtography photosensor, helps effectively to improve triphenylamine derivative, its manufacture method and the Electrophtography photosensor of light sensitivity characteristic.

According to the present invention, the triphenylamine derivative of following general formula (1) expression is provided, can address the above problem.

In the general formula (1), R ¹～R ¹³Be the respectively independently alkyl of hydrogen atom, carbonatoms 1～8, alkoxyl group, phenoxy group, the aryl of carbonatoms 6～20 or the aralkyl of carbonatoms 7～20 of carbonatoms 1～8, Ar is that the heterocycle of the hydrocarbon ring of alkoxyl group, carbonatoms 3～14 of the alkyl that has or do not have carbonatoms 1～8, carbonatoms 1～8 or 3～10 yuan of rings is as the aryl of substituent carbonatoms 6～20, replacement radix n is 0～4 integer, and repeat number o and p are independently 0～1 integer of difference.

Namely, the triphenylamine derivative of general formula (1) expression is because have the aryloxy of regulation carbonatoms in the contraposition of aryl amine, can improve thus to the solvability of solvent and with the intermiscibility of binding resin, so can effectively be suppressed at the crystallization in the sensitive layer and disperse bad.

Therefore, by with the cavity conveying agent as Electrophtography photosensor of the triphenylamine derivative of general formula (1) expression, can help effectively to improve its light sensitivity characteristic.

In addition, the further alternate manner of the present invention is a kind of manufacture method of triphenylamine derivative, it is characterized in that, it is the manufacture method of the triphenylamine derivative of general formula (1) expression, comprises the operation of the reaction of carrying out following reaction formula (1) expression.

In general formula (2) and (5), X ¹And X ²For distinguishing independently halogen atom, other substituting group in general formula (1)～(5) is identical with the content of explanation in the general formula (1).

That is, by implementing to comprise the manufacture method of this operation, can effectively make the triphenylamine derivative of general formula (1) expression.

In addition, the further alternate manner of the present invention is a kind of Electrophtography photosensor, and it is characterized in that for have the Electrophtography photosensor of sensitive layer at matrix sensitive layer contains the triphenylamine derivative of general formula (1) expression.

That is, Electrophtography photosensor of the present invention can access excellent light sensitivity characteristic.

The further alternate manner according to the present invention, the triphenylamine derivative that provides a kind of following general formula (6) to represent can address the above problem.

In general formula (6), R ¹Be the alkyl of carbonatoms 1～8, R ²～R ⁵Be the alkyl of hydrogen atom, carbonatoms 1～8 or alkoxyl group and the R of carbonatoms 1～8 ²And R ³In at least one be the alkyl of carbonatoms 1～8 or the alkoxyl group of carbonatoms 1～8, R ⁶Be the alkyl of hydrogen atom or carbonatoms 1～6, Ar ¹And Ar ²Independent separately, for the alkoxyl group of hydrogen atom, the alkyl that has or do not have carbonatoms 1～6 or carbonatoms 1～6 as the aryl of substituent carbonatoms 6～20, the cycloalkyl of carbonatoms 3～10 or the heterocycle of 3～10 yuan of rings, and get rid of Ar ¹And Ar ²It all is the situation of hydrogen atom.

That is, the triphenylamine derivative of general formula (6) expression can improve the solvability to solvent owing to have alkyl or the alkoxyl group of regulation carbonatoms at the ortho position of aryl amine, so can effectively be suppressed at the crystallization in the sensitive layer and disperse bad.

In addition, owing to have the alkoxyl group of regulation carbonatoms in the contraposition of aryl amine, so can reduce ionizing potential.

Therefore, the energy gap that the electric charge between the charge generating etc. is given and accepted diminishes, so can effectively improve charge transport efficient.Particularly, when being applicable to laminated electrophotographic photoreceptor that charge generating layer and charge transport layer separate, the electric charge that also can effectively improve in these bed interfaces moves.

And then, when above-mentioned ortho position and contraposition are all introduced respectively the substituting group of regulation, compare when being introduced separately into any one party substituting group, can further effectively improve the deliquescent raising effect of solvent and the reduction effect of ionizing potential.

That is, can obtain the substituting group synergistic effect each other of these regulations.

Thus, by with the cavity conveying agent as Electrophtography photosensor of the triphenylamine derivative of general formula (6) expression, can help effectively to improve its light sensitivity characteristic.

In addition, the further alternate manner of the present invention is a kind of manufacture method of triphenylamine derivative, it is characterized in that, it is the manufacture method of the triphenylamine derivative of general formula (6) expression, comprises the operation of the reaction of carrying out following reaction formula (2) expression.

In the general formula (7), X is halogen atom, and other substituting group in general formula (6)～(8) is identical with the content of explanation in the general formula (6).

That is, by implementing to comprise the manufacture method of this operation, can effectively make the triphenylamine derivative of general formula (6) expression.

In addition, the further alternate manner of the present invention is a kind of Electrophtography photosensor, and it is characterized in that for have the Electrophtography photosensor of sensitive layer at matrix sensitive layer contains the triphenylamine derivative of general formula (6) expression.

Description of drawings

Fig. 1 is the aryloxy of the regulation that is used for the explanation triphenylamine derivative and figure to the relation of the dispersiveness of the solvability of solvent and sensitive layer;

The figure of the relation of the light sensitivity characteristic of the Electrophtography photosensor when Fig. 2 is used as the cavity conveying agent for being used for the explanation triphenylamine derivative to the solvability of solvent and with triphenylamine derivative;

Fig. 3 (a)～(b) is for being used for illustrating the figure of mono-layer electronic photographic photoreceptor of the present invention;

Fig. 4 (a)～(c) is for being used for illustrating the figure of laminated electrophotographic photoreceptor of the present invention;

Fig. 5 is the substituting group of the regulation that is used for the explanation triphenylamine derivative and figure to the relation of the solvability of solvent and ionizing potential;

Fig. 6 is the triphenylamine derivative (HTM-1) of embodiment 1 ¹H-NMR figure;

Fig. 7 is the triphenylamine derivative (HTM-5) of embodiment 13 ¹H-NMR figure;

Fig. 8 is the triphenylamine derivative made among the embodiment 36 ¹H-NMR figure;

Fig. 9 is the triphenylamine derivative made among the embodiment 37 ¹H-NMR figure.

Nomenclature

10: mono-layer electronic photographic photoreceptor

12: matrix

14: sensitive layer

16: the middle layer

20: laminated electrophotographic photoreceptor

20 ': laminated electrophotographic photoreceptor

20 ": laminated electrophotographic photoreceptor

22: charge transport layer

24: charge generating layer

25: the middle layer

Embodiment

[the first embodiment]

The first embodiment is the triphenylamine derivative of a kind of following general formula (1) expression.

(in the general formula (1), R ¹～R ¹³Be the respectively independently alkyl of hydrogen atom, carbonatoms 1～8, alkoxyl group, phenoxy group, the aryl of carbonatoms 6～20 or the aralkyl of carbonatoms 7～20 of carbonatoms 1～8, Ar is the heterocycle of the hydrocarbon ring of the alkoxyl group of alkyl, the carbonatoms 1～8 that can have carbonatoms 1～8, carbonatoms 3～14 or 3～10 yuan of rings aryl as substituent carbonatoms 6～20, replacement radix n is 0～4 integer, and repeat number o and p are independently 0～1 integer of difference.）

Below, the triphenylamine derivative of ad hoc structure with first embodiment is specifically described.

The triphenylamine derivative of the first embodiment is characterised in that it is the compound of above-mentioned general formula (1) expression.

Its result is used as the cavity conveying agent of Electrophtography photosensor by the triphenylamine derivative that will have ad hoc structure of the present invention, thereby can helps effectively to improve its light sensitivity characteristic.

Below, to can be as the substituent R in the triphenylamine derivative of the first embodiment ¹～R ¹³The substituting group that uses carries out example.

At first, can enumerate methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, hexyl, heptyl, n-octyl and iso-octyl etc. as alkyl.

In addition, can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert.-butoxy, pentyloxy, isopentyloxy, neopentyl oxygen, hexyloxy, heptan oxygen base, n-octyloxy and different octyloxy etc. as alkoxyl group.

And then, can enumerate phenmethyl, Alpha-Methyl phenmethyl, styroyl, styryl, cinnamyl, 3-hydrocinnamyl, 4-benzene butyl, 5-benzene amyl group, 6-benzene hexyl etc. as aralkyl.

In addition, can enumerate phenyl, 4-p-methoxy-phenyl, tolyl, xylyl, mesityl, naphthyl, anthryl, phenanthryl etc. as the substituting group that the substituent A r in the triphenylamine derivative of the first embodiment uses.

In addition, substituent A r can have the alkyl of carbonatoms 1～8, the alkoxyl group of carbonatoms 1～8, the hydrocarbon ring of carbonatoms 3～14 or the heterocycle of 3～10 yuan of rings as substituting group.

And, can enumerate above-mentioned substituting group as the alkyl of carbonatoms 1～8, the alkoxyl group of carbonatoms 1～8.In addition, can enumerate tetramethylene, suberane, hexanaphthene, naphthalene nucleus, phenyl ring etc. as the hydrocarbon ring of carbonatoms 3～14.And then, can enumerate furan nucleus, thiphene ring, pyridine ring etc. as the heterocycle of 3～10 yuan of rings.

Then, use Fig. 1 illustrate triphenylamine derivative regulation aryloxy with to the solvability of solvent and the relation of the dispersiveness in the sensitive layer.

Namely, Fig. 1 represents that transverse axis adopts triphenylamine derivative to the solubleness (%) as the tetrahydrofuran (THF) (THF) of solvent, and the longitudinal axis adopts the stain that uses when this triphenylamine derivative formed image as the Electrophtography photosensor of cavity conveying agent to produce the rational curve of number (individual/A4 paper).

Here, produce number as the index of the dispersiveness of estimating the triphenylamine derivative in the sensitive layer and determined at the stain that the longitudinal axis adopts.

If this is because the dispersiveness of the triphenylamine derivative in the sensitive layer reduces, perhaps crystallization, thus this compound exists with the state of excessive gathering, then when implementing charged operation, produce leakage current by this habitat easily, thereby on the formation portrait, produce easily stain.

In addition, as two kinds of marks describing characteristic basis corresponding triphenylamine derivative with constructional feature shown below respectively.

◇: the aryloxy that has regulation in the contraposition of aryl amine

●: the aryloxy that does not have regulation in the contraposition of aryl amine

In addition, Electrophtography photosensor constitutes mono-layer electronic photographic photoreceptor.In addition, solubleness and the stain measuring method etc. that produces number is recorded among the embodiment.

By the rational curve of Fig. 1 as can be known, solubility values is larger, and it is fewer that stain produces number.

Be appreciated that thus by the solubility values that makes triphenylamine derivative to become large that the dispersiveness that contains in the sensitive layer of this triphenylamine derivative is improved.

In addition, if pay close attention to the mark as characteristic basis, then as can be known solubility values be value more than 15% and stain produce number be the triphenylamine derivative of the following value of 50/A4 paper for have the triphenylamine derivative (◇) of the aryloxy of regulation in the contraposition of aryl amine, be the triphenylamine derivative of general formula (1) expression.

On the other hand, solubility values produces the aryloxy of triphenylamine derivative for not having regulation in the contraposition of aryl amine that number exceeds the value of 70/A4 paper less than 15% value and stain, is the triphenylamine derivative (●) beyond the scope of general formula (1).

Hence one can see that, and the triphenylamine derivative of general formula (1) expression is owing to the solvability to solvent is excellent, so can help to improve the dispersiveness in the sensitive layer.

In addition, solvent has the characteristic of the binding resin that dissolves sensitive layer as its necessary characteristic.

Therefore, when triphenylamine derivative is excellent to the solvability of solvent, also excellent with the intermiscibility of binding resin.

Then, use Fig. 2 illustrate triphenylamine derivative to the solvability of solvent with the relation of this triphenylamine derivative as the light sensitivity characteristic of the Electrophtography photosensor of cavity conveying agent.

That is, Fig. 2 represents that transverse axis adopts triphenylamine derivative to the solubleness (%) of tetrahydrofuran (THF) (THF), and the longitudinal axis adopts the rational curve as the rest potential (V) of the index of light sensitivity characteristic.

In addition, Electrophtography photosensor constitutes mono-layer electronic photographic photoreceptor.In addition, the detailed content of measuring method of rest potential etc. is recorded among the embodiment.

By the rational curve of Fig. 2 as can be known, larger to the solubility values of THF, can make the rest potential value less, thereby the light sensitivity characteristic of Electrophtography photosensor is improved.

More specifically, be value more than 15% by making solubility values to THF as can be known, can with the rest potential value stabilization be controlled in the scope below the 130V.

Therefore, be appreciated that by triphenylamine derivative of the present invention is used as the cavity conveying agent by above-mentioned Fig. 1 and Fig. 2, can effectively improve the light sensitivity characteristic of Electrophtography photosensor.

In addition, when consisting of triphenylamine derivative of the present invention, the substituent A r in the general formula (1) is preferably can have methyl or methoxy as substituent phenyl.

Its reason is, by electing such substituting group as, polarity and the planarity of the triphenylamine derivative molecule of ad hoc structure can be adjusted to more suitably state, thus can further improve to the solvability of solvent and with the intermiscibility of binding resin.

In addition, two phenyl vinyl structures in the preferred formula (1) or phenyl butenyl structure are arranged in the contraposition of the phenyl of fluorine-triphenylamine structure simultaneously.

Its reason is because the distribution situation of π-electron is adjusted to more suitably state, can improve further charge transport efficient.

In addition, the repeat number o in the preferred formula (1) and p are 1.

Its reason is because the distribution situation of π-electron is adjusted to more suitably state, can further improve charge transport efficient.

In addition, the substituent R in the preferred formula (1) ¹～R ¹³It all is hydrogen atom.

Below, as the concrete example example of triphenylamine derivative of the present invention compound (HTM-1 ~ 7) with formula (9)～(15) expression.

[the second embodiment]

The second embodiment is the manufacture method of triphenylamine derivative, it is characterized in that, it is the manufacture method of triphenylamine derivative of general formula (1) expression of the first embodiment, comprises the operation of the reaction of carrying out following reaction formula (1) expression.

(in general formula (2) and (5), X ¹And X ²For distinguishing independently halogen atom, other substituting group in general formula (2)～(5) is identical with the content of explanation in the general formula (1).）

Below, by with the first embodiment in the record content difference centered by, the second embodiment is carried out

Specify.

1, preparatory process

This preparatory process is for being used for obtaining as the following general formula of usefulness (2) of the material substance of reaction formula (1) and the operation of the compound that (5) represent.

In addition, because the compound of general formula (2) and (5) expression can obtain by same processes, so the preparatory process of the compound of general formula (2) expression only is described, omit the preparatory process of the compound of mutual-through type (5) expression.

(substituting group in the general formula (2) is identical with content in the reaction formula (1).）

(substituting group in the general formula (5) is identical with content in the reaction formula (1).）

At first, shown in following reaction formula (3), preferably make the compound of general formula (16) expression obtain the compound that general formula (17) represents with the triethyl-phosphite reaction.

In addition, the X in the general formula (16) ¹' expression halogen atom.

At this moment, the reaction ratio (mol ratio) of the compound of general formula (16) expression and triethyl-phosphite is preferably the interior ratio of scope of 1:1～1:2.5.

Its reason is, if the adding proportion of triethyl-phosphite less than lower value (1:1), then the productive rate of the compound of general formula (17) expression might be excessively low.On the other hand, if the adding proportion of triethyl-phosphite greater than higher limit (1:2.5), then unreacted triethyl-phosphite excessively increases, thus the refining too difficulty that might become of the compound of general formula (17) expression.

In addition, temperature of reaction is preferably the value in 160～200 ℃ of scopes, and the reaction times is preferably 2～10 hours values in the scope.

Then, in the presence of catalyzer, shown in following reaction (4), preferably make the compound of general formula (17) expression obtain the compound (Wittig reaction) that general formula (2) represents with the compound reaction of general formula (18) expression.

At this moment, the reaction ratio (mol ratio) of the compound of the compound of general formula (17) expression and general formula (18) expression is preferably the interior ratio of scope of 1:1～1:2.5.

Its reason is, if the adding proportion of the compound of general formula (17) expression less than lower value (1:2.5), then the productive rate of the compound of general formula (2) expression might be excessively low.On the other hand, if the adding proportion of the compound of general formula (17) expression greater than higher limit (1:1), then the compound of unreacted general formula (17) expression excessively increases, thus the refining too difficulty that might become of the compound of general formula (2) expression.

In addition, temperature of reaction is preferably the value in-20～30 ℃ of scopes, and the reaction times is preferably 5～30 hours values in the scope.

In addition, used catalyzer can be enumerated sodium alkoxide such as sodium methylate, sodium ethylate in the reaction of reaction formula (4) expression; The metal hydride such as sodium hydride, potassium hydride KH; The metal-salts such as n-Butyl Lithium etc.Catalyzer can be used alone, and also can make up two or more uses.

In addition, with respect to 1 mole of the compound of general formula (18) expression, the addition of catalyzer is preferably the value in 1～2 molar range.

Its reason is, if the addition of catalyzer is the value less than 1 mole, then the reactivity of the compound of the compound of general formula (17) expression and general formula (18) expression might significantly reduce.On the other hand, if the reaction of the compound that the compound that the addition of catalyzer for surpassing 2 moles value, then might be difficult to control general formula (17) expression and general formula (18) represent.

In addition, as carry out reaction formula (3) and (4) expression reaction the time solvent, can enumerate ethers such as diethyl ether, tetrahydrofuran (THF), diox; The halohydrocarbon such as methylene dichloride, trichloromethane, ethylene dichloride; The aromatic hydrocarbons such as benzene, toluene.

2, reaction formula (1)

Then, the second embodiment is characterised in that, shown in following reaction formula (1), by compound reaction of the compound that makes the general formula (2) that obtains in the preparatory process and (5) expression and general formula (3) expression of preparing in addition, make the triphenylamine derivative (linked reaction) as general formula (1) expression of ultimate aim thing.

(in general formula (2) and (5), X ¹And X ²For distinguishing independently halogen atom, other substituting group in general formula (1)～(5) is identical with the content of explanation in the general formula (1).）

That is, at first, will carry out the reaction of following reaction formula (1-1) expression as feature.

(in the general formula (2), X ¹Be halogen atom, other substituting group in general formula (2)～(4) is identical with the content of explanation in the general formula (1).）

At this moment, the reaction ratio (mol ratio) of the compound of the compound of general formula (2) expression and general formula (3) expression is preferably the interior ratio of scope of 5:1～1:2.

Its reason is, if the adding proportion of the compound of general formula (2) expression less than lower value (1:2), then the productive rate of the triphenylamine derivative of general formula (4) expression might be excessively low.On the other hand, if the adding proportion of the compound of general formula (2) expression greater than higher limit (5:1), then the compound of unreacted general formula (2) expression excessively increases, thus the refining too difficulty that might become of the compound of general formula (4) expression.

Therefore, the reaction ratio (mol ratio) of the compound of the compound of general formula (2) expression and general formula (3) expression is the interior ratio of scope of 3:1～1:1 more preferably, more preferably the ratio in the scope of 2:1～1:1.

In addition, temperature of reaction is preferably the value in 80～140 ℃ of scopes, and the reaction times is preferably 2～10 hours values in the scope.

In addition, in the reaction of reaction formula (1-1) expression, preferably use palladium compound as catalyzer.

Its reason is by palladium compound is used as catalyzer, can further improve the productive rate of the compound of general formula (4) expression, so can further improve the productive rate of the triphenylamine derivative of general formula (1) expression.

That is, palladium compound can reduce the activation energy in the reaction of reaction formula (1-1) expression effectively.

Such palladium compound can be enumerated such as chlordene and close the sour sodium tetrahydrate of palladium (IV) and chlordene closes the tetravalence palladium compound classes such as the sour potassium tetrahydrate of palladium (IV), Palladous chloride (II), palladium bromide (II), acid chloride (II), palladium acetylacetonate (II), dichloro two (benzonitrile) closes palladium (II), dichloro-two (triphenyl phosphine) closes palladium (II), the dichloro tetramine closes palladium (II) and dichloro (ring suffering-1,5-diene) closes the divalence palladium compound classes such as palladium (II), three (dibenzalacetones) close two palladiums (O), three (dibenzalacetones) close two palladium trichloromethane complex compounds (O) and four (triphenyl phosphines) close the palladium compound classes such as palladium (O).

Catalyzer can be used alone, and also can make up two or more uses.

In addition, with respect to 1 mole of the compound of general formula (3) expression, the addition of palladium compound is preferably the value in 0.00025～20 molar range, more preferably the value in 0.0005～10 molar range.

In addition, preferably in the presence of alkali, carry out the reaction of reaction formula (1-1) expression.

Its reason is, by in the presence of alkali, implementing the reaction of reaction formula (1-1) expression, and the hydrogen halide that produces in the neutralized system rapidly, catalyst activity is improved thus, so can further improve the productive rate of the triphenylamine derivative that general formula (1) represents.

In addition, this type of alkali can be selected from mineral alkali, organic bases, without particular limitation of, but the alkali metal alcoholates such as particular methanol sodium, sodium ethylate, potassium methylate, potassium ethylate, trimethyl carbinol lithium, sodium tert-butoxide and potassium tert.-butoxide, particularly preferably sodium tert-butoxide.In addition, the mineral alkali such as Tripotassium phosphate and cesium fluoride also is effective.

In addition, although the addition of this type of alkali also depends on the amount of palladium compound, for example with respect to 1 mole of the compound of general formula (3) expression, when adding 0.005 mole of palladium compound, the addition of this type of alkali is preferably the value in 0.995～5 molar range, more preferably the value in 1～5 molar range.

In addition, solvent can be enumerated such as dimethylbenzene etc.

Then, will carry out the reaction of following reaction formula (1-2) expression as feature.

In addition, when the compound of the compound of general formula (2) expression and general formula (5) expression is identical compound, when carrying out the reaction of above-mentioned reaction formula (1-1) expression, also can carry out the reaction of following reaction formula (1-2) expression, so need not to carry out in addition the reaction of following reaction formula (1-2) expression.

But this moment, preferably making the addition of compound, catalyzer and the alkali etc. of formula (2) expression when carrying out the reaction of reaction formula (1-1) expression is common 2 times.

(in the general formula (5), X ²Be halogen atom, other substituting group in general formula (1) and (4)～(5) is identical with the content of explanation in the general formula (1).）

At this moment, the reaction ratio (mol ratio) of the compound of the compound of general formula (5) expression and general formula (4) expression is preferably the interior ratio of scope of 5:1～1:2.

Its reason is, if the adding proportion of the compound of general formula (5) expression less than lower value (1:2), then the productive rate of the triphenylamine derivative of general formula (1) expression might be excessively low.On the other hand, if the adding proportion of the compound of general formula (5) expression greater than higher limit (5:1), then the compound of unreacted general formula (5) expression excessively increases, thus the refining too difficulty that might become of the triphenylamine derivative of general formula (1) expression.

Therefore, the reaction ratio (mol ratio) of the compound of the compound of general formula (5) expression and general formula (4) expression is the interior ratio of scope of 3:1～1:1 more preferably, more preferably the ratio in the scope of 2:1～1:1.

And then, for catalyzer, alkali, solvent etc., can use the catalyzer same with the reacting phase of reaction formula (1-1) expression, alkali, solvent etc.

[the 3rd embodiment]

The 3rd embodiment is a kind of Electrophtography photosensor, and it is characterized in that for have the Electrophtography photosensor of sensitive layer at matrix sensitive layer contains the triphenylamine derivative of general formula (1) expression.

Below, by with the first embodiment and the second embodiment in centered by the difference of record content, the 3rd embodiment is divided into mono-layer electronic photographic photoreceptor and laminated electrophotographic photoreceptor is specifically described.

1, mono-layer electronic photographic photoreceptor

The Electrophtography photosensor that preferably will contain the triphenylamine derivative of the first～the second embodiment constitutes mono-layer electronic photographic photoreceptor.

Its reason is, the Electrophtography photosensor of the triphenylamine derivative by will containing the first～the second embodiment constitutes mono-layer electronic photographic photoreceptor, can especially effectively bring into play the effect that has as the triphenylamine derivative of the ad hoc structure of cavity conveying agent.

Namely, if Electrophtography photosensor constitutes mono-layer electronic photographic photoreceptor, then be necessary in same layer, to concentrate and contain cavity conveying agent, electron transporting agent and charge generating, therefore with Electrophtography photosensor constituted laminated electrophotographic photoreceptor compare, the dispersiveness of the cavity conveying agent in the sensitive layer reduces, thereby the light sensitivity characteristic reduces easily.On the other hand, that uses in the first～the second embodiment has triphenylamine derivative as the ad hoc structure of cavity conveying agent because the excellent dispersion in sensitive layer, even so when Electrophtography photosensor constituted mono-layer electronic photographic photoreceptor, also can access excellent light sensitivity characteristic.

(1) basic comprising

Shown in Fig. 3 (a), mono-layer electronic photographic photoreceptor 10 can consist of by at matrix 12 single sensitive layer 14 being set.

And, shown in Fig. 3 (b), mono-layer electronic photographic photoreceptor of the present invention also can for, in the scope of not damaging the photoreceptor characteristic, between matrix 12 and sensitive layer 14, be formed with the mono-layer electronic photographic photoreceptor 10 in middle layer 16 '.

(2) matrix

As the matrix of Fig. 3 example, can use the various materials with electroconductibility.Can enumerate the matrix that metals such as iron, aluminium, copper, tin, platinum, silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless steel and brass forms, evaporation or lamination the matrix that forms of the plastic material of above-mentioned metal, the matrix of the glass system that perhaps covers with aluminum iodide, alumite, stannic oxide, Indium sesquioxide etc. etc.

That is can be that matrix itself has electroconductibility, or matrix surface have electroconductibility.In addition, matrix is preferably the matrix that has in use sufficient mechanicalness intensity.

And the shape of matrix can be any one shapes such as sheet, drum type according to the structure of the image processing system that uses.

(3) middle layer

Shown in Fig. 3 (b), also can contain matrix 12 setting the middle layer 16 of the fine powder of the binding resin of regulation and regulation.

Its reason is, by contain the binding resin of regulation in this middle layer, when improving the adaptation of matrix and sensitive layer, by contain the fine powder of regulation in this middle layer, make the incident light scattering, suppress the generation of interference fringe, and the charge injection from matrix to sensitive layer can suppress to cause the non-exposure of photographic fog or stain the time.As this fine powder, if having scattering of light, dispersed fine powder then without particular limitation of, such as using the white pigments such as titanium oxide, zinc oxide, zinc white, zinc sulphide, white lead, lithopone; Aluminum oxide, calcium carbonate, barium sulfate etc. are as the mineral dye of pigment extender; Perhaps fluoro-resin particle, benzo guanamine resin particle, styrene resin particle etc.

In addition, the thickness in middle layer is preferably the value in 0.1～50 mu m range.

(4) sensitive layer

In addition, more than one that contained charge generating is preferably selected from the group that metal-free phthalocyanine (τ type or X-type), titanyl phthalocyanine (α type or Y type), hydroxy gallium phthalocyanine (V-type) and gallium chlorine phthalocyaninate (II type) consist of in the sensitive layer.

In addition, with respect to binding resin 100 weight parts of charge generating layer, the content of this charge generating is preferably the value in 0.2～40 weight part scope.

In addition, cavity conveying agent contained in the sensitive layer is elected as the triphenylamine derivative of general formula (1) expression as feature.

Its reason is as describing in detail in the first embodiment, to have the triphenylamine derivative of this ad hoc structure as cavity conveying agent use, thereby can access excellent light sensitivity characteristic.

In addition, with respect to binding resin 100 weight parts in the sensitive layer, the content of the triphenylamine derivative of general formula (1) expression is preferably the value in 20～150 weight part scopes.

Its reason is, is located in this scope by the content with the triphenylamine derivative of ad hoc structure, more can improve the dispersiveness of triphenylamine derivative in sensitive layer with ad hoc structure, can obtain further excellent light sensitivity characteristic.

That is, be the value that is lower than 20 weight parts if having the content of the triphenylamine derivative of ad hoc structure, then its absolute magnitude is excessively not enough, is difficult to obtain sufficient light sensitivity characteristic.On the other hand, be the value that exceeds 150 weight parts if having the content of the triphenylamine derivative of ad hoc structure, then the dispersiveness in sensitive layer is excessively low, therefore possible easily crystallization, or charge transport decrease in efficiency.

Therefore, with respect to binding resin 100 weight parts of sensitive layer, have the content more preferably value in 25～125 weight part scopes, the more preferably value in 30～100 weight part scopes of the triphenylamine derivative of ad hoc structure.

In addition, sensitive layer also can contain other cavity conveying agent.

Can enumerate for example triphenylamine compound except the triphenylamine derivative of general formula (1) expression, 2,5-two (4-methylamino phenyl)-1, the oxadiazole based compounds such as 3,4-oxadiazole, 9-(4-diethylin styryl) the styryl based compound such as anthracene, the carbazole based compounds such as polyvinyl carbazole, the organopolysilane compound, 1-phenyl-3-(is to dimethylaminophenyl) the pyrazoline based compound such as pyrazoline, the hydrazone based compound, indoles based compound oxazole based compound isoxazole based compound, thiazole compound, the thiadiazoles based compound, imidazole compound, the pyrazoles based compound, the nitrogenous ring compounds such as three azole compounds, fused-polycyclic compounds etc.In addition, the cavity conveying agent can be used alone, and also can make up two or more uses.

In addition, when containing this other cavity conveying agent, with respect to triphenylamine derivative 100 weight parts of general formula (1) expression, preferably the value in 20～150 weight part scopes contains.

In addition, contained electron transporting agent can be enumerated quinone derivative, anthraquinone derivative, propane dinitrile derivative, thiapyran derivative, trinitro-thioxanthone derivates, 3 in the sensitive layer, 4,5,7-tetranitro-9-Fluorenone derivative, dinitrobenzene anthracene derivant, dinitrobenzene acridine derivatives, nitroanthraquinone derivative, dinitroanthraquinone derivative, tetracyanoethylene, 2,4,8-trinitro-thioxanthone derivates, dinitrobenzene, dinitrobenzene anthracene, dinitrobenzene acridine, nitroanthraquinone, dinitroanthraquinone, succinyl oxide, maleic anhydride, two bromo maleic anhydrides etc.In addition, electron transporting agent can be used alone, and also can make up two or more uses.

In addition, with respect to binding resin 100 weight parts of sensitive layer, the content of this electron transporting agent is preferably the value in 10～70 weight part scopes.

As binding resin used in the sensitive layer, first-selection is used for example polycarbonate resin, vibrin, polyarylate resin, and can use styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-maleic acid copolymer, acrylate copolymer, the styrene-propene acid copolymer, polyethylene, vinyl-vinyl acetate copolymer, chlorinatedpolyethylene, polyvinyl chloride, polypropylene, ionomer, vinyl chloride vinyl acetate copolymer, Synolac, polymeric amide, urethane, polysulfones, diallyl phthalate ester resin, ketone resin, polyvinyl butyral resin, the thermoplastic resins such as polyether resin; Silicone resin, Resins, epoxy, resol, urea resin, melamine resin and other bridging property thermosetting resin; The light-cured resin such as epoxy acrylate, polyurethane-acrylate etc.

These binding resins can use separately, perhaps mix or the two or more uses of copolymerization.

In addition, the thickness of sensitive layer is preferably the value in 5～100 mu m ranges.

In addition, mono-layer electronic photographic photoreceptor for example can be by making such as following step.

At first, by making charge generating, having triphenylamine derivative, electron transporting agent, binding resin and additive etc. as the ad hoc structure of cavity conveying agent and contain and in solvent, prepare the sensitive layer coating fluid.Use coating methods such as dip coating, spraying method, drop coating method (bead coating), spread coating, rolling method to be applied on the conductive substrate (aluminum pipe base) coating fluid that obtains like this.

Afterwards, under for example 100 ℃, 40 minutes condition, carry out warm air drying, thereby can form the sensitive layer of regulation thickness.

In addition, above-mentioned solvent can use various organic solvents, can enumerate alcohols such as methyl alcohol, ethanol, Virahol, butanols; The aliphatic hydrocarbons such as normal hexane, octane, hexanaphthene; The aromatic hydrocarbonss such as benzene,toluene,xylene; The halohydrocarbon such as methylene dichloride, ethylene dichloride, trichloromethane, tetracol phenixin, chlorobenzene; Dme, diethyl ether, tetrahydrofuran (THF), glycol dimethyl ether, diglyme, 1, the ethers such as 3-dioxa penta ring, Isosorbide-5-Nitrae-dioxs; The ketones such as acetone, butanone, pimelinketone; The ester such as ethyl acetate, methyl acetate class; Dimethylformaldehyde, dimethyl formamide, methyl-sulphoxide etc.These solvents use separately or mix two or more uses.

2, laminated electrophotographic photoreceptor

In addition, the Electrophtography photosensor that contains the triphenylamine derivative of general formula (1) expression can be constituted laminated electrophotographic photoreceptor.

Namely, shown in Fig. 4 (a), the Electrophtography photosensor that contains the triphenylamine derivative of general formula (1) expression can be constituted at matrix 12 charge generating layer 24 that contains charge generating etc. is set, the laminated electrophotographic photoreceptor 20 of the charge transport layer 22 that contains charge transport agent etc. is set thereon again.

In addition, shown in Fig. 4 (b), can form charge transport layer 22 at matrix 12 on the contrary with said structure, form charge generating layer 24 thereon.

In addition, shown in Fig. 4 (c), preferably on matrix 12, also form middle layer 25.

In addition, usually preferably only contain the cavity conveying agent in the charge transport layer 22, but also can contain simultaneously cavity conveying agent and electron transporting agent.

In addition, the matrix that uses in the laminated electrophotographic photoreceptor, organic materials can be basically identical with mono-layer electronic photographic photoreceptor.

In addition, with respect to binding resin 100 weight parts of charge transport layer, the content of the triphenylamine derivative of general formula (1) expression is preferably the value in 20～150 weight part scopes.

And then with respect to binding resin 100 weight parts of charge generating layer, the content of charge generating is preferably the value in 5～1000 weight part scopes.

In addition, the thickness of charge transport layer is preferably the value in 5～50 mu m ranges, and the thickness of charge generating layer is preferably the value in 0.1～5 mu m range.

[the 4th embodiment]

The 4th embodiment is the triphenylamine derivative of a kind of following general formula (6) expression.

(in the general formula (6), R ¹Be the alkyl of carbonatoms 1～8, R ²～R ⁵Be the alkyl of hydrogen atom, carbonatoms 1～8 or alkoxyl group and the R of carbonatoms 1～8 ²And R ³In at least one be the alkyl of carbonatoms 1～8 or the alkoxyl group of carbonatoms 1～8, R ⁶Be the alkyl of hydrogen atom or carbonatoms 1～6, Ar ¹And Ar ²Independent separately, for the alkoxyl group of hydrogen atom, the alkyl that can have carbonatoms 1～6 or carbonatoms 1～6 as the aryl of substituent carbonatoms 6～20, the cycloalkyl of carbonatoms 3～10 or the heterocycle of 3～10 yuan of rings, and get rid of Ar ¹And Ar ²It all is the situation of hydrogen atom.）

Below, the triphenylamine derivative of ad hoc structure with the 4th embodiment is specifically described.

The triphenylamine derivative of the 4th embodiment is characterised in that it is the compound of above-mentioned general formula (6) expression.

In addition, this triphenylamine derivative is owing to having the alkoxyl group of regulation carbonatoms in the contraposition of aryl amine, so can reduce ionizing potential.

Therefore, and the energy gap that the electric charge between the charge generating etc. is given and accepted diminishes, so can effectively improve charge transport efficient.Particularly, even when this triphenylamine derivative was applicable to laminated electrophotographic photoreceptor that charge generating layer and charge transport layer separate, the electric charge that also can effectively improve in these bed interfaces moved.

And then, in this triphenylamine derivative, when above-mentioned ortho position and contraposition are all introduced respectively the substituting group of regulation, to compare during with the substituting group that is introduced separately into any one party, deliquescent raising effect and the ionizing potential that can further effectively improve solvent reduce effect.

Thus, the triphenylamine derivative of the ad hoc structure by will having the 4th embodiment can help effectively to improve its light sensitivity characteristic as the cavity conveying agent of Electrophtography photosensor, particularly suppresses rest potential.

In addition, R ¹Alkyl in more preferably 1～7 of carbonatoms, more preferably 1～6.Thus, can give the electron donability that helps to reduce ionizing potential.

In addition, R ²And R ³More preferably 1～6 of carbonatoms during for alkyl and alkoxyl group, more preferably 1～4.Thus, can give the deliquescent fat-soluble and steric effect that helps to improve to solvent.

Below, to as the substituent R in the triphenylamine derivative of the 4th embodiment ¹～R ⁵Operable alkyl and alkoxyl group carry out example.

At first, as alkyl and alkoxyl group, can enumerate the substituent R as the triphenylamine derivative of general formula (1) expression of example in the first embodiment ¹～R ¹³Operable alkyl and alkoxyl group.

In addition, as Ar ¹And Ar ²Operable aryl can be enumerated phenyl, tolyl, xylyl, mesityl, naphthyl, anthryl, phenanthryl etc.

In addition, can enumerate tetramethylene, suberane, hexanaphthene etc. as the cycloalkyl of carbonatoms 3～10.And then, can enumerate furan nucleus, thiphene ring, pyridine ring etc. as the heterocycle of 3～10 yuan of rings.

And then, as R ⁶Operable alkyl can be enumerated methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the tertiary butyl, amyl group, isopentyl, neo-pentyl, hexyl etc.

Then, use Fig. 5 illustrate triphenylamine derivative regulation substituting group with to the solvability of solvent and the relation of ionizing potential.

That is, Fig. 5 represents that transverse axis adopts triphenylamine derivative to the solubleness (%) as the tetrahydrofuran (THF) (THF) of solvent, and the longitudinal axis adopts the distribution plan of the ionizing potential (eV) of triphenylamine derivative.

Here, the corresponding triphenylamine derivative with constructional feature shown below respectively of four kinds of marks in the distribution plan.

Zero: the substituting group that has regulation at the ortho position of aryl amine, the substituting group that also has regulation in contraposition.

: the substituting group that has regulation at the ortho position of aryl amine, and the substituting group that does not have regulation in contraposition.

◇: the substituting group that does not have regulation at the ortho position of aryl amine, and the substituting group that has regulation in contraposition.

●: the substituting group that does not have regulation at the ortho position of aryl amine, the substituting group that does not also have regulation in contraposition.

In addition, solubleness among Fig. 5 is, under 25 ℃ condition, after the 100mg triphenylamine derivative added a small amount of tetrahydrofuran (THF), repeat vibration and place operation, obtain the tetrahydrofuran (THF) addition X(mg of being dissolved as of triphenylamine derivative when saturated), according to this addition X, the value of calculating with following formula.

Solubleness (%)=100/(100+X)

By the distribution plan of Fig. 5 as can be known, the triphenylamine derivative of the 4th embodiment of mark (zero) expression is owing to have simultaneously two substituting groups of regulation, so be value 18% or more to the solubility values of THF, simultaneously, the value of ionizing potential is the value below the 5.41eV.

Hence one can see that, is used as the cavity conveying agent by the triphenylamine derivative with the 4th embodiment, and crystallization and the dispersion that can effectively suppress in the sensitive layer are bad, and can effectively improve charge transport efficient.

On the other hand, the triphenylamine derivative of mark () expression is owing to the substituting group that does not have regulation in the contraposition of aryl amine as can be known, so the value of ionizing potential is too high, on the contrary, the triphenylamine derivative of mark (◇) expression is owing to the substituting group that does not have regulation at the ortho position of aryl amine, so solubility values is excessively low.

In addition, the triphenylamine derivative of mark (●) expression is not owing to all have the substituting group of these regulations as can be known, so the value of ionizing potential is too high, and solubility values is excessively low.

And then, if relatively mark (zero), () and plot point (◇) are as can be known, by introduce respectively the substituting group of regulation in ortho position and contraposition, can play synergistic effect.

That is, (zero) when being introduced separately into the substituting group that helps any one effect (and ◇) compares when introducing simultaneously two substituting groups of regulation, can more effectively improve simultaneously the deliquescent raising effect of solvent and the reduction effect of ionizing potential as can be known.

On the contrary, by the distribution plan of Fig. 5 as can be known, when only introducing a substituting group in two substituting groups of regulation (and ◇), the deliquescent raising effect of solvent and the reduction effect of ionizing potential are not all reached desired standard.

In addition, when having confirmed in an embodiment the triphenylamine derivative of the mark in the distribution plan of Fig. 5 (zero) as the cavity conveying agent of Electrophtography photosensor, can be stably the absolute value of rest potential be controlled at the following value of regulation.

On the other hand, confirmed in an embodiment with mark (, ◇ and ●) triphenylamine derivative during as the cavity conveying agent of Electrophtography photosensor, be difficult to the absolute value of rest potential is controlled at the following value of regulation, perhaps produce crystallization.

In addition, in the triphenylamine derivative of the 4th embodiment, the substituent R in the preferred formula (6) ²And R ³In only have an alkoxyl group for the alkyl of carbonatoms 1～8 or atomicity 1～8.

Its reason is can pass through suitably saboteur's symmetry, the further solvability that improves solvent.

In addition, the substituent A r in the preferred formula (6) ¹And Ar ²In only have one for the alkoxyl group that can have the alkyl of carbonatoms 1～6 or carbonatoms 1～6 as the aryl of substituent carbonatoms 6～20, the cycloalkyl of carbonatoms 3～10 or the heterocycle of 3～10 yuan of rings.

Its reason is, can be adjusted to by the distribution situation with π-electron more suitably state, further improves charge transport efficient.

In addition, the substituent R in the general formula (1) ⁶Be preferably hydrogen atom.

Below, as the concrete example example of triphenylamine derivative of the present invention (HTM-8～14) with formula (19)～(25) expression.

[the 5th embodiment]

The 5th embodiment is the manufacture method of triphenylamine derivative, it is characterized in that, it is the manufacture method of triphenylamine derivative of general formula (6) expression of the 4th embodiment, comprises the operation of the reaction of carrying out following reaction formula (2) expression.

(in the general formula (7), X is halogen atom, and other substituting group in general formula (6)～(8) is identical with the content of explanation in the general formula (6).）

Below, by with the 4th embodiment in the record content difference centered by, the 5th embodiment is specifically described.

1, preparatory process

This preparatory process is for being used for obtaining the operation as the compound of the following general formula of usefulness (7) expression of the material substance of reaction formula (2).

(substituting group in the general formula (7) is identical with content in the reaction formula (2).）

At first, shown in following reaction formula (5), preferably make the compound of general formula (26) expression obtain the compound that general formula (27) represents with the triethyl-phosphite reaction.

In addition, the X ' expression halogen atom in the general formula (26).

At this moment, the reaction ratio (mol ratio) of the compound of general formula (26) expression and triethyl-phosphite is preferably the interior ratio of scope of 1:1～1:2.5.

Its reason is, if the adding proportion of triethyl-phosphite less than lower value (1:1), then the productive rate of the compound of general formula (27) expression might be excessively low.On the other hand, if the adding proportion of triethyl-phosphite greater than higher limit (1:2.5), then unreacted triethyl-phosphite excessively increases, thus the refining too difficulty that might become of the compound of general formula (27) expression.

Then, in the presence of catalyzer, shown in following reaction (6), preferably make the compound of resulting general formula (27) expression obtain the compound (Wittig reaction) that general formula (7) represents with the compound reaction of general formula (28) expression.

At this moment, the reaction ratio (mol ratio) of the compound of the compound of general formula (27) expression and general formula (28) expression is preferably the interior ratio of scope of 1:1～1:2.5.

Its reason is, if the adding proportion of the compound of general formula (27) expression less than lower value (1:2.5), then the productive rate of the compound of general formula (7) expression might be excessively low.On the other hand, if the adding proportion of the compound of general formula (27) expression greater than higher limit (1:1), then the compound of unreacted general formula (27) expression excessively increases, thus the refining too difficulty that might become of the compound of general formula (7) expression.

In addition, used catalyzer can be enumerated sodium alkoxide such as sodium methylate, sodium ethylate in the reaction of reaction formula (6) expression; The metal hydride such as sodium hydride, potassium hydride KH; The metal-salts such as n-Butyl Lithium etc.Catalyzer can be used alone, and also can make up two or more uses.

In addition, with respect to 1 mole of the compound of general formula (28) expression, the addition of catalyzer is preferably the value in 1～2 molar range.

Its reason is, if the addition of catalyzer is the value less than 1 mole, then the reactivity of the compound of the compound of general formula (27) expression and general formula (28) expression might significantly reduce.On the other hand, if the reaction of the compound that the compound that the addition of catalyzer for surpassing 2 moles value, then might be difficult to control general formula (27) expression and general formula (28) represent.

In addition, as carry out reaction formula (5) and (6) expression reaction the time solvent, can enumerate ethers such as diethyl ether, tetrahydrofuran (THF), diox; The halohydrocarbon such as methylene dichloride, trichloromethane, ethylene dichloride; The aromatic hydrocarbons such as benzene, toluene.

2, reaction formula (2)

Then, the 5th embodiment is characterised in that, shown in following reaction formula (2), by the compound reaction of the compound that makes general formula (7) expression that obtains in the preparatory process and general formula (8) expression of preparing in addition, make the triphenylamine derivative (linked reaction) as general formula (6) expression of ultimate aim thing.

At this moment, the reaction ratio (mol ratio) of the compound of the compound of general formula (7) expression and general formula (8) expression is preferably the interior ratio of scope of 5:1～1:1.

Its reason is, if the adding proportion of the compound of general formula (7) expression less than lower value (1:1), then the productive rate of the triphenylamine derivative of general formula (6) expression might be excessively low.On the other hand, if the adding proportion of the compound of general formula (7) expression greater than higher limit (5:1), then the compound of unreacted general formula (7) expression excessively increases, thus the refining too difficulty that might become of the compound of general formula (6) expression.

Therefore, the reaction ratio (mol ratio) of the compound of the compound of general formula (7) expression and general formula (8) expression is the interior ratio of scope of 3:1～1:1 more preferably, more preferably the ratio in the scope of 2:1～1:1.

In addition, in the reaction of reaction formula (2) expression, preferably use palladium compound as catalyzer.

Its reason is by palladium compound is used as catalyzer, can further improve the productive rate of the triphenylamine derivative of general formula (6) expression.

That is, palladium compound can reduce the activation energy in the reaction of reaction formula (2) expression effectively.

This type of palladium compound can be enumerated the palladium compound of example in the second embodiment.

In addition, catalyzer can be used alone, and also can make up two or more uses.

In addition, with respect to 1 mole of the compound of general formula (8) expression, the addition of palladium compound is preferably the value in 0.0005～20 molar range, more preferably the value in 0.001～10 molar range.

In addition, preferably in the presence of alkali, carry out the reaction of reaction formula (2) expression.

Its reason is, by in the presence of alkali, implementing the reaction of reaction formula (2) expression, and the hydrogen halide that produces in the neutralized system rapidly, catalyst activity is improved thus, so can further improve the productive rate of the triphenylamine derivative that general formula (6) represents.

In addition, this type of alkali can be enumerated the alkali of example in the second embodiment.

In addition, although the addition of this type of alkali also depends on the amount of palladium compound, for example with respect to 1 mole of the compound of general formula (8) expression, when adding 0.005 mole of palladium compound, the addition of this type of alkali is preferably the value in 1～10 molar range, more preferably the value in 1～5 molar range.

In addition, solvent can be enumerated such as dimethylbenzene, toluene, tetrahydrofuran (THF), dimethyl formamide etc.

[the 6th embodiment]

The 6th embodiment is a kind of Electrophtography photosensor, and it is characterized in that for have the Electrophtography photosensor of sensitive layer at matrix sensitive layer contains the triphenylamine derivative of general formula (6) expression.

Below, by with the 3rd～the 5th embodiment in centered by the difference of record content, the 6th embodiment is divided into mono-layer electronic photographic photoreceptor and laminated electrophotographic photoreceptor is specifically described.

1, laminated electrophotographic photoreceptor

The Electrophtography photosensor that preferably will contain the triphenylamine derivative of the 4th～the 5th embodiment constitutes mono-layer electronic photographic photoreceptor.

Its reason is, the Electrophtography photosensor of the triphenylamine derivative by will containing the 4th～the 5th embodiment constitutes laminated electrophotographic photoreceptor, can especially effectively bring into play the effect that has as the triphenylamine derivative of the ad hoc structure of cavity conveying agent.

That is, if Electrophtography photosensor constitutes laminated electrophotographic photoreceptor, then need by the bed interface of charge generating layer and the charge transport layer electric charge of giving and accepting, therefore the potential energy by this bed interface might easily suppress charge transport efficient.On the other hand, has triphenylamine derivative as the ad hoc structure of the cavity conveying agent that is used for the 4th～the 5th embodiment because ionizing potential is low, so in these bed interfaces, also can make the movement of charge stable ground.

(1) basic comprising

Shown in Fig. 4 (a), laminated electrophotographic photoreceptor 20 can wait the charge transport layer 22 that forms successively the charge generating layer 24 that contains charge generating etc. and contain charge transport agent etc. on matrix 12 to make by coating.

In addition, shown in Fig. 4 (b), with said structure on the contrary, also can form charge transport layers 22 at matrix 12, form charge generating layer 24 thereon.

But, when forming like this, because that the thickness of charge generating layer 24 is compared with the thickness of charge transport layer 22 is very thin, so might be damaged easily.Therefore, preferably shown in Fig. 4 (a), form charge transport layer 22 at charge generating layer 24.

In addition, shown in Fig. 4 (c), preferably form middle layer 25 at matrix 12.

In addition, usually preferably only contain the cavity conveying agent in the charge transport layer 22, but also can use simultaneously cavity conveying agent and electron transporting agent.

(2) matrix

The matrix 12 of Fig. 4 example can use the material identical with the 3rd embodiment or the matrix of shape.

(3) middle layer

Shown in Fig. 4 (c), the middle layer 25 of the binding resin that contains regulation can be set at matrix 12 also.The thickness that the reason in middle layer, fine powder material that the middle layer is contained and middle layer are set is identical with the 3rd embodiment.

(4) charge generating layer

In addition, with respect to binding resin 100 weight parts of charge generating layer, the content of this charge generating is preferably the value in 5～1000 weight part scopes.

Used binding resin can be enumerated for example bisphenol A-type in the sensitive layer, the polycarbonate resin of bisphenol Z type or bisphenol-c type etc., vibrin, methacrylic resin, acrylic resin, polyvinyl chloride (PVC) RESINS, polystyrene resin, vinylite, the styrene-butadiene copolymer resin, the vinylidene chloride-acrylonitrile copolymer resin, vinylchlorid-vinyl acetate-maleic anhydride resin, silicone resin, organosilicon-Synolac, resol, vinylbenzene-Synolac, being used alone or two or more combinations of N-vinylcarbazole etc.

In addition, the thickness of charge generating is preferably the value in 0.1～5 mu m range.

(5) charge transport layer

In addition, be that the triphenylamine derivative of general formula (6) expression is as feature with cavity conveying agent contained in the charge transport layer.

Its reason is, as describing in detail in the 4th embodiment, has the triphenylamine derivative of this ad hoc structure by using as cavity conveying agent, can access excellent light sensitivity characteristic.

In addition, with respect to binding resin 100 weight parts in the charge transport layer, the content of the triphenylamine derivative of general formula (6) expression is preferably the value in 30～100 weight part scopes.

Its reason is, the content of the triphenylamine derivative by will having ad hoc structure is located in this scope, more can improve the dispersiveness of triphenylamine derivative in sensitive layer with ad hoc structure, can obtain further excellent light sensitivity characteristic.

That is, be the value that is lower than 30 weight parts if having the content of the triphenylamine derivative of ad hoc structure, then its absolute magnitude is excessively not enough, is difficult to obtain sufficient light sensitivity characteristic.On the other hand, be the value that exceeds 100 weight parts if having the content of the triphenylamine derivative of ad hoc structure, then the dispersiveness in charge transport layer is excessively low, therefore possible easily crystallization, or charge transport decrease in efficiency.

Therefore, with respect to binding resin 100 weight parts of charge transport layer, have the content more preferably value in 35～95 weight part scopes, the more preferably value in 40～90 weight part scopes of the triphenylamine derivative of ad hoc structure.

In addition, charge transport layer also can contain other cavity conveying agent.

Can enumerate for example triphenylamine compound except the triphenylamine derivative of general formula (6) expression, 2,5-two (4-methylamino phenyl)-1, the oxadiazole based compounds such as 3,4-oxadiazole, 9-(4-diethylin styryl) the styryl based compound such as anthracene, the carbazole based compounds such as polyvinyl carbazole, the organopolysilane compound, 1-phenyl-3-(is to dimethylaminophenyl) the pyrazoline based compound such as pyrazoline, the hydrazone based compound, indoles based compound oxazole based compound isoxazole based compound, thiazole compound, the thiadiazoles based compound, imidazole compound, the pyrazoles based compound, the nitrogenous ring compounds such as three azole compounds, fused-polycyclic compounds etc.In addition, the cavity conveying agent can be used alone, and also can make up two or more uses.

In addition, when containing this other cavity conveying agent, with respect to triphenylamine derivative 100 weight parts of general formula (6) expression, preferably the value within containing 1～100 weight part scope contains.

In addition, charge transport layer can contain the electron transporting agent identical with the contained electron transporting agent of sensitive layer in the 3rd embodiment.In addition, the same with the 3rd embodiment, electron transporting agent can be used alone, and also can make up two or more uses.

In addition, with respect to triphenylamine derivative 100 weight parts of general formula (6) expression, the content of this electron transporting agent is preferably the value in 1～50 weight part scope.

In addition, in charge transport layer, can contain the binding resin identical with the contained binding resin of sensitive layer in the 3rd embodiment as binding resin.

These binding resins are the same with the 3rd embodiment, can use separately, perhaps mix or the two or more uses of copolymerization.

In addition, the thickness of charge transport layer is preferably the value in 5～50 mu m ranges.

In addition, laminated electrophotographic photoreceptor for example can be by making such as following step.

At first, by being contained, charge generating, binding resin and additive etc. in solvent, prepare the charge generating layer coating fluid.Use coating methods such as dip coating, spraying method, drop coating method, spread coating, rolling method to be applied on the conductive substrate (aluminum pipe base) coating fluid that obtains like this.

Afterwards, under for example 100 ℃, 40 minutes condition, carry out warm air drying, thereby can form the charge generating layer of regulation thickness.

In addition, above-mentioned solvent can use with the 3rd embodiment in sensitive layer with the used solvent phase of the preparation of coating fluid with solvent.The same with the 3rd embodiment, these solvents use separately or mix two or more uses.

Next, prepare the charge transport layer coating fluid by triphenylamine derivative, binding resin and the additive etc. that in above-mentioned solvent, disperse to have ad hoc structure.Afterwards, be applied to charge generating layer on coating fluid this charge transport layer after, carry out drying and come to form charge transport layer.

In addition, the manufacture method of coating fluid, coating and drying means can be identical when making charge generating layer.

2, mono-layer electronic photographic photoreceptor

In addition, the Electrophtography photosensor that contains the triphenylamine derivative of general formula (6) expression can be constituted mono-layer electronic photographic photoreceptor.

That is, shown in Fig. 3 (a), the Electrophtography photosensor that contains the triphenylamine derivative of general formula (6) expression can be constituted the mono-layer electronic photographic photoreceptor 10 that single sensitive layer 14 is set at matrix 12.

In addition, shown in Fig. 3 (b), mono-layer electronic photographic photoreceptor can for, in the scope of not damaging the photoreceptor characteristic, between matrix 12 and sensitive layer 14, be formed with the mono-layer electronic photographic photoreceptor 10 in middle layer 16 '.

In addition, the matrix that uses in the mono-layer electronic photographic photoreceptor, organic materials can be basically identical with laminated electrophotographic photoreceptor.

In addition, with respect to binding resin 100 weight parts of sensitive layer, the content of the triphenylamine derivative of general formula (6) expression is preferably the value in 20～120 weight part scopes.

In addition, in mono-layer electronic photographic photoreceptor, sensitive layer contains charge generating, electron transporting agent, cavity conveying agent simultaneously, for the content of charge transport agent, with respect to binding resin 100 weight parts of sensitive layer, be preferably the value in 10～70 weight part scopes.

And then, for the content of charge generating, with respect to binding resin 100 weight parts of sensitive layer, be preferably the value in 0.2～40 weight part scope.

[embodiment]

Below, further describe the first～the 3rd embodiment based on embodiment 1～35 and comparative example 1～10.

[embodiment 1]

1, the manufacturing of triphenylamine derivative

At first, by carrying out the reaction of following reaction formula (3 ') expression, obtain the compound of formula (17 ') expression.

That is, the compound 15.2g(0.1mol of loading type in 200 milliliters flask (16 ') expression) and triethyl-phosphite 25g(0.15mol) after, under 180 ℃ temperature condition, stirred this flask 8 hours.

Then, this flask is cooled to room temperature after, superfluous triethyl-phosphite is removed in underpressure distillation, obtains compound (white liquid) the 24.1g(productive rate of formula (17 ') expression: 90%).

Then, by carrying out the reaction of following reaction formula (4 ') expression, obtain the compound of formula (2 ') expression.

That is, the compound 13g(0.05mol of the resulting formula of in 500 milliliters twoport flask, packing into (17 ') expression) after, carry out argon replaces.And then, add the sodium methylate 9.3g(0.05mol of 100 milliliters of dry tetrahydrofuran (THF)s (THF) and 28% in this flask) after, this flask of stirring is 30 minutes under 0 ℃ temperature condition.

Then, the liquid after stir is with the compound 7g(0.05mol of formula (18 ') expression) with after adding under the state that is dissolved in 300 milliliters of THF, at room temperature stirred 12 hours.

Then, be injected into the liquid after stirring in the ion exchanged water after, with the toluene extraction, and then with ion-exchange water washing organic layer 5 times.Afterwards, so with behind the anhydrous sodium sulfate drying organic layer, the distillation desolventizing, thus residue obtained.

Then, to the residue that obtains, make with extra care by the recrystallize with the mixed solvent of toluene and methanol=20 milliliter/100 milliliters, obtain compound (white crystals) the 10.22g(productive rate of formula (2 ') expression: 85%).

Then, by carrying out the reaction of following reaction formula (1 ') expression, obtain the triphenylamine derivative (HTM-1) of formula (9) expression.

That is, the compound 12g(0.05mol of loading type (2 ') expression in 2 liters twoport flask), tricyclohexyl phosphine (Pcy) 0.0662g(0.000189mol), three (benzylidene-acetones) close two palladium (Pd ₂(dba) ₃) 0.0864g(0.0000944mol), sodium tert-butoxide (t-BuONa) 7.68g(0.08mol) and the compound 4.62g(0.025mol of formula (3 ') expression), and then after adding 500 milliliters of the o-Xylols of distillation, carry out argon replaces.Then, under 120 ℃ temperature condition, stirred this flask 5 hours.

Then, the liquid cooling after stirring to room temperature, is used ion-exchange water washing organic layer 3 times.Afterwards, and then after using anhydrous sodium sulphate and atlapulgite that organic layer is carried out drying and adsorption treatment, o-Xylol is removed in underpressure distillation, thereby obtains residue.

Then, with column chromatography (developing solvent: trichloromethane/hexane) refining resulting residue obtains triphenylamine derivative (HTM-1) the 11.8g(productive rate 80% that formula (9) represents).The triphenylamine derivative that obtains ¹H-NMR figure is illustrated among Fig. 6.

In addition, should ¹H-NMR figure is measured by the AC magnetic field of 300MHz.In addition, use CDCl as solvent ₃, use TMS as primary standard.

2, the manufacturing of mono-layer electronic photographic photoreceptor

At first, will be as X-type crystallization 5 weight parts of the metal-free phthalocyanine (CGM-1) of the following formula (29) of charge generating expression, as triphenylamine derivative (HTM-1) 80 weight parts of formula (9) expression of cavity conveying agent, as connection para benzoquinone (ETM-1) 50 weight parts of following formula (30) expression of electron transporting agent, as polycarbonate resin 100 weight parts of following formula (31) expression of binding resin, pack in the container as tetrahydrofuran (THF) 800 weight parts of solvent, obtain their mixture.Afterwards, mix, disperseed 50 hours with the mixture of ball mill with them, obtain the sensitive layer coating fluid.

Then, the speed with 5mm/s under the state that the aluminum substrate (support substrate) of diameter 30mm, long 238.5mm is made progress with the one end is impregnated into sensitive layer with in the coating fluid, thereby to this aluminum substrate photosensitive coated layer coating fluid.Afterwards, this aluminum substrate is carried out warm air drying under 100 ℃, 30 minutes condition, forming thickness is the sensitive layer of 25 μ m.Thus, obtain mono-layer electronic photographic photoreceptor.

3, estimate

(1) the solvability evaluation of triphenylamine derivative

The solvability as the triphenylamine derivative of cavity conveying agent that obtains is estimated.

That is, under 25 ℃ condition, in the 100mg triphenylamine derivative that obtains, add a small amount of tetrahydrofuran (THF) after, repeat vibration and place operation, obtain the dissolving of the triphenylamine derivative tetrahydrofuran (THF) addition X(mg when saturated), according to this addition X, calculate solubleness with following formula.The result who obtains is illustrated in the table 1.

Solubleness (%)=100/(100+X)

(2) evaluation of mono-layer electronic photographic photoreceptor

(the evaluation of 2) –, 1 rest potential

Rest potential to the mono-layer electronic photographic photoreceptor that obtains is estimated.

That is, use surface charging that drum sensitivity test machine (manufacturings of GENTEC company) makes the mono-layer electronic photographic photoreceptor that obtains extremely+700V.

Monochromatic ray (half amplitude: 20nm, the exposure: 1.5 μ J/cm of the 780nm wavelength that then, will from the white light of halide lamp, take out with bandpass filter ²) to mono-layer electronic photographic photoreceptor surface irradiation 1.5 seconds, simultaneously, be determined at irradiation and begin surface potential through moment of 0.5 second.So, with the surface potential measured as rest potential (V).The result who obtains is illustrated in the table 1.

(the evaluation of 2) –, 2 crystallizations

Having or not of crystallization to the sensitive layer of the mono-layer electronic photographic photoreceptor that obtains estimated.

That is, confirm that with opticmicroscope the surface of mono-layer electronic photographic photoreceptor has or not crystallization, estimate based on following standard.The result who obtains is illustrated in the table 1.

Zero: crystallization is not identified out

△: confirm a little crystallization

*: confirm crystallization

[embodiment 2]

In embodiment 2, when carrying out the manufacturing of mono-layer electronic photographic photoreceptor, use the naphthoquinone compound (ETM-2) of following formula (32) expression as electron transporting agent, make similarly to Example 1 in addition triphenylamine derivative and mono-layer electronic photographic photoreceptor and estimate.The result who obtains is illustrated in the table 1.

[embodiment 3]

In embodiment 3, when carrying out the manufacturing of mono-layer electronic photographic photoreceptor, use the Y type crystallization of the titanyl phthalocyanine compound (CGM-2) of following formula (33) expression as charge generating, make similarly to Example 2 in addition triphenylamine derivative and mono-layer electronic photographic photoreceptor and estimate.The result who obtains is illustrated in the table 1.

[embodiment 4～6]

In embodiment 4～6, as the material substance in the manufacturing of triphenylamine derivative, (compound of 2 ") expressions replaces the compound of formula (2 ') expression; obtain the triphenylamine derivative (HTM-2) of formula (10) expression, similarly makes triphenylamine derivative and mono-layer electronic photographic photoreceptor with embodiment 1～3 in addition and estimates with following formula.The result who obtains is illustrated in the table 1.

[embodiment 7～9]

In embodiment 7～9, as the material substance in the manufacturing of triphenylamine derivative, the compound that replaces formula (2 ') expression with the compound of following formula (2 " ') expression; obtain the triphenylamine derivative (HTM-3) of formula (11) expression is similarly made triphenylamine derivative and mono-layer electronic photographic photoreceptor with embodiment 1～3 in addition and is estimated.The result who obtains is illustrated in the table 1.

[embodiment 10～12]

In embodiment 10～12, as the material substance in the manufacturing of triphenylamine derivative, compound except formula (2 ') expression, and then the compound of also using following formula (5 ') expression carries out following formula, and (reaction of 1 ") expression; obtain the triphenylamine derivative (HTM-4) of formula (12) expression is similarly made triphenylamine derivative and mono-layer electronic photographic photoreceptor with embodiment 1～3 in addition and is estimated.The result who obtains is illustrated in the table 1.

[embodiment 13～15]

In embodiment 13～15, as the material substance in the manufacturing of triphenylamine derivative, (compound of 3 ") expressions replaces the compound of formula (3 ') expression; obtain the triphenylamine derivative (HTM-5) of formula (13) expression, similarly makes triphenylamine derivative and mono-layer electronic photographic photoreceptor with embodiment 1～3 in addition and estimates with following formula.The result who obtains is illustrated in the table 1.

In addition, the triphenylamine derivative of the embodiment 13 that obtains ¹H-NMR figure is illustrated among Fig. 7.In addition, should ¹H-NMR figure measures under the condition identical with embodiment 1.

[embodiment 16～18]

In embodiment 16～18, as the material substance in the manufacturing of triphenylamine derivative, the compound that replaces formula (3 ') expression with the compound of following formula (3 " ') expression; obtain the triphenylamine derivative (HTM-6) of formula (14) expression is similarly made triphenylamine derivative and mono-layer electronic photographic photoreceptor with embodiment 1～3 in addition and is estimated.The result who obtains is illustrated in the table 1.

[embodiment 19～21]

In embodiment 19～21, as the material substance in the manufacturing of triphenylamine derivative, with following formula (3 " ") compound of expression replaces the compound of formula (3 ') expression, obtain the triphenylamine derivative (HTM-7) of formula (15) expression, similarly make triphenylamine derivative and mono-layer electronic photographic photoreceptor with embodiment 1～3 in addition and estimate.The result who obtains is illustrated in the table 1.

As shown in table 1, in the photoreceptor of embodiment 1～21 is estimated, shown low rest potential, there is not crystallization in the crystallization evaluation yet, confirmed thus good.

[comparative example 1～3]

In comparative example 1～3, as the material substance in the manufacturing of triphenylamine derivative, the compound that replaces formula (3 ') expression with the compound of following formula (3a) expression, obtain the triphenylamine derivative (HTM-A) of formula (a) expression, similarly make triphenylamine derivative and mono-layer electronic photographic photoreceptor with embodiment 1～3 in addition and estimate.The result who obtains is illustrated in the table 1.

[comparative example 4～6]

In comparative example 4～6, as the material substance in the manufacturing of triphenylamine derivative, the compound that replaces formula (3 ') expression with the compound of following formula (3b) expression, obtain the triphenylamine derivative (HTM-B) of formula (b) expression, similarly make triphenylamine derivative and mono-layer electronic photographic photoreceptor with embodiment 1～3 in addition and estimate.The result who obtains is illustrated in the table 1.

As shown in table 1, during the photoreceptor in the comparative example 1～6 was estimated, rest potential was high, or because crystallization can not be measured, confirmed to have separated out crystallization in the crystallization evaluation, had confirmed thus existing problems.

[table 1]

[embodiment 22]

In embodiment 22, when carrying out the manufacturing of mono-layer electronic photographic photoreceptor, use two naphthoquinone compounds (ETM-3) of following formula (34) expression as electron transporting agent, make similarly to Example 1 in addition triphenylamine derivative and mono-layer electronic photographic photoreceptor, and estimate the stain that produces in the formation image.

Namely, with the mono-layer electronic photographic photoreceptor that obtains be installed on printer (Kyocera Mita company makes, DP-560) after, under the envrionment conditions of 40 ℃ of temperature, humidity 90%, to upper 5000 images of continuous printing of A4 paper (company of Fuji-Xerox makes, high-quality PPC paper using).

Afterwards, above-mentioned printer placed 6 hours after, the blank sheet of paper original copy of A4 paper is printed, statistics is estimated with following benchmark when the stain that this A4 paper produces produces number.The result who obtains is illustrated in the table 2.

Zero: it is to be lower than 50 value that the stain of every A4 paper produces number.

*: the stain generation number of every A4 paper is the value more than 50.

[embodiment 23]

In embodiment 23, when carrying out the manufacturing of mono-layer electronic photographic photoreceptor, use the Y type crystallization of the titanyl phthalocyanine compound (CGM-2) of formula (33) expression as charge generating, make similarly to Example 22 in addition mono-layer electronic photographic photoreceptor and estimate.The result who obtains is illustrated in the table 2.

[embodiment 24～25]

In embodiment 24～25, as the triphenylamine derivative (HTM-2) of cavity conveying agent manufacturing and use formula (10) expression, similarly make mono-layer electronic photographic photoreceptor with embodiment 22～23 in addition and estimate.The result who obtains is illustrated in the table 2.

[embodiment 26～27]

In embodiment 26～27, as the triphenylamine derivative (HTM-3) of cavity conveying agent manufacturing and use formula (11) expression, similarly make mono-layer electronic photographic photoreceptor with embodiment 22～23 in addition and estimate.The result who obtains is illustrated in the table 2.

[embodiment 28～29]

In embodiment 28～29, as the triphenylamine derivative (HTM-4) of cavity conveying agent manufacturing and use formula (12) expression, similarly make mono-layer electronic photographic photoreceptor with embodiment 22～23 in addition and estimate.The result who obtains is illustrated in the table 2.

[embodiment 30～31]

In embodiment 30～31, as the triphenylamine derivative (HTM-5) of cavity conveying agent manufacturing and use formula (13) expression, similarly make mono-layer electronic photographic photoreceptor with embodiment 22～23 in addition and estimate.The result who obtains is illustrated in the table 2.

[embodiment 32～33]

In embodiment 32～33, as the triphenylamine derivative (HTM-6) of cavity conveying agent manufacturing and use formula (14) expression, similarly make mono-layer electronic photographic photoreceptor with embodiment 22～23 in addition and estimate.The result who obtains is illustrated in the table 2.

[embodiment 34～35]

In embodiment 34～35, as the triphenylamine derivative (HTM-7) of cavity conveying agent manufacturing and use formula (15) expression, similarly make mono-layer electronic photographic photoreceptor with embodiment 22～23 in addition and estimate.The result who obtains is illustrated in the table 2.

As shown in table 2, during the photoreceptor of embodiment 22～35 was estimated, rest potential was low, does not have crystallization in the crystallization evaluation, had confirmed thus good.

[comparative example 7～8]

In comparative example 7～8, as the triphenylamine derivative (HTM-A) of cavity conveying agent manufacturing and use formula (a) expression, similarly make mono-layer electronic photographic photoreceptor with embodiment 22～23 in addition and estimate.The result who obtains is illustrated in the table 2.

[comparative example 9～10]

In comparative example 9～10, as the triphenylamine derivative (HTM-B) of cavity conveying agent manufacturing and use formula (b) expression, similarly make mono-layer electronic photographic photoreceptor with embodiment 22～23 in addition and estimate.The result who obtains is illustrated in the table 2.

As shown in table 2, during the photoreceptor of comparative example 7～10 was estimated, rest potential was high, or because crystallization can not be measured, confirmed to have separated out crystallization in the crystallization evaluation, had confirmed thus existing problems.

[table 2]

Below, further describe the 4th～the 6th embodiment based on embodiment 36～57 and comparative example 11～25.

[embodiment 36]

1, the manufacturing of triphenylamine derivative

At first, in the same manner as in Example 1, by carrying out the reaction of reaction formula (3 ') expression, obtain the compound of formula (17 ') expression.

Then, in the same manner as in Example 1, by carrying out the reaction of reaction formula (4 ') expression, obtain the compound of formula (2 ') expression.

Then, by carrying out the reaction of following reaction formula (2 ') expression, obtain the triphenylamine derivative (HTM-8) of formula (19) expression.

That is, the compound 12g(0.05mol of loading type (7 ') expression in 2 liters twoport flask), tricyclohexyl phosphine (Pcy) 0.0662g(0.000189mol), three (benzylidene-acetones) close two palladium (Pd ₂(dba) ₃) 0.0864g(0.0000944mol), sodium tert-butoxide (t-BuONa) 7.68g(0.08mol) and the compound 3.42g(0.025mol of formula (8a) expression), and then after adding 500 milliliters of the o-Xylols of distillation, carry out argon replaces.Then, under 120 ℃ temperature condition, stirred this flask 5 hours.

Then, with column chromatography (developing solvent: trichloromethane/hexane) refining resulting residue obtains triphenylamine derivative (HTM-8) the 11.6g(productive rate 85% that formula (19) represents).The triphenylamine derivative that obtains ¹H-NMR figure is illustrated among Fig. 8.

In addition, should ¹H-NMR figure measures under the condition identical with embodiment 1.

2, the manufacturing of laminated electrophotographic photoreceptor

(1) formation in middle layer

At first, with titanium oxide (SMT-02, after carrying out surface treatment with aluminum oxide and silicon oxide, carrying out surface-treated number average primary particle size with the hydrogenated methyl polysiloxane when wet type is disperseed is the 10nm(TAYCA system)) 280 weight parts, copolyamide resin (DAICEL-DEGUSSA(strain) make, ダイアミ De X4685) 100 weight parts and mix, disperse 5 hours with ball mill as ethanol 1000 weight parts of solvent and propyl carbinol 200 weight parts after, carry out filtration treatment with 5 microns strainers, thereby obtain the middle layer coating fluid.

Then, the speed with 5mm/s under the state that the aluminum substrate (support substrate) of diameter 30mm, long 238.5mm is made progress with the one end is impregnated into the middle layer with in the coating fluid, thereby to this aluminum substrate coating middle layer coating fluid.Afterwards, this aluminum substrate is cured processing under 100 ℃, 30 minutes condition, forming thickness is the middle layer of 1.5 μ m.

(2) formation of charge generating layer

Then, will be as Y type crystallization 100 weight parts of the titanyl phthalocyanine (CGM-2) of the formula (33) of charge generating expression, as polyvinyl butyral resin (electrochemical industry (strain) system of binding resin, デ Application カ Block チラ-Le #6000EP) 100 weight parts and mix, disperse 2 hours with ball mill as propylene glycol monomethyl ether 4000 weight parts of solvent and tetrahydrofuran (THF) 4000 weight parts after, carry out filtration treatment with 3 microns strainers, thereby obtain the charge generating layer coating fluid.After the resulting charge generating layer of above-mentioned middle layer coating is with coating fluid, carrying out drying with dip coating under 50 ℃, 5 minutes condition, is the charge generating layer of 0.3 μ m thereby form thickness.

(3) formation of charge transport layer

Then, will be as triphenylamine derivative (HTM-8) 70 weight parts of the formula (19) of cavity conveying agent expression, as BHT(two-tert-p-cresols of additive) meta-terphenyl 5 weight parts, (Supreme Being people changes into society's system as the Z-type polycarbonate resin of following formula (31) expression of the viscosity-average molecular weight 50000 of binding resin, TS2050) (Resin-1) 100 weight parts and pack in the ultrasonic dispersing machine as tetrahydrofuran (THF) 430 weight parts of solvent and toluene 430 weight parts, dispersion treatment 10 minutes, thus the charge transport layer coating fluid obtained.

With charge generating layer with coating fluid similarly, after the resulting charge transport layer of charge generating layer coating is with coating fluid, under 130 ℃, 30 minutes condition, carry out drying, forming thickness is the charge transport layer of 20 μ m.Thus, obtain laminated electrophotographic photoreceptor.

3, estimate

(1) evaluation of triphenylamine derivative

(1) –, 1 deliquescent evaluation

With the method identical with embodiment 1 solvability as the triphenylamine derivative of cavity conveying agent that obtains is estimated.

(2)-2 the evaluation of ionizing potential

In addition, the ionizing potential of the triphenylamine derivative that obtains is estimated.

That is, (reason is ground gauge (strain) system, AC-1) measures with air atmosphere type ultraviolet electronics analytical equipment.The result who obtains is illustrated in the table 3.

(2) evaluation of laminated electrophotographic photoreceptor

(2)-1 the evaluation of rest potential

Rest potential to the laminated electrophotographic photoreceptor that obtains is estimated.

That is, the surface charging that makes the laminated electrophotographic photoreceptor that obtains is to-700V the time, and making the monochromatic exposure to the photosensitive surface irradiation is 0.4 μ J/cm ², measure similarly to Example 1 in addition rest potential.What obtain the results are shown in the table 3.

(2)-2 the evaluation of crystallization

Whether the surface with the method evaluation resulting laminated electrophotographic photoreceptor identical with embodiment 1 has crystallization.What obtain the results are shown in the table 3.

[embodiment 37]

In embodiment 37, when making the reaction formula (2 ') of triphenylamine derivative, the compound that the compound that represents with following formula (8b) replaces formula (8a) to represent obtains the triphenylamine derivative (HTM-9) that formula (20) represents.The triphenylamine derivative that obtains ¹H-NMR figure is illustrated among Fig. 9.

In addition, when making laminated electrophotographic photoreceptor, the triphenylamine derivative (HTM-9) of this formula (20) expression is used in agent as cavity conveying.

Similarly make triphenylamine derivative and laminated electrophotographic photoreceptor with embodiment 36 in addition and estimate.The result who obtains is illustrated in the table 3.

[embodiment 38]

In embodiment 38, when making the reaction formula (2 ') of triphenylamine derivative, the compound that the compound that represents with following formula (8c) replaces formula (8a) to represent obtains the triphenylamine derivative (HTM-10) that formula (21) represents.

In addition, when making laminated electrophotographic photoreceptor, the triphenylamine derivative (HTM-10) of this formula (21) expression is used in agent as cavity conveying.

[embodiment 39]

In embodiment 39, when making the reaction formula (2 ') of triphenylamine derivative, the compound that the compound that represents with following formula (8d) replaces formula (8a) to represent obtains the triphenylamine derivative (HTM-11) that formula (22) represents.

In addition, when making laminated electrophotographic photoreceptor, the triphenylamine derivative (HTM-11) of this formula (22) expression is used in agent as cavity conveying.

[embodiment 40]

In embodiment 40, when making the reaction formula (2 ') of triphenylamine derivative, the compound that the compound that represents with following formula (8e) replaces formula (8a) to represent obtains the triphenylamine derivative (HTM-12) that formula (23) represents.

In addition, when making laminated electrophotographic photoreceptor, the triphenylamine derivative (HTM-12) of this formula (23) expression is used in agent as cavity conveying.

[embodiment 41]

In embodiment 41, when making the reaction formula (2 ') of triphenylamine derivative, the compound that the compound that represents with following formula (8f) replaces formula (8a) to represent obtains the triphenylamine derivative (HTM-13) that formula (24) represents.

In addition, when making laminated electrophotographic photoreceptor, the triphenylamine derivative (HTM-13) of this formula (24) expression is used in agent as cavity conveying.

[embodiment 42]

In embodiment 42, when making the reaction formula (2 ') of triphenylamine derivative, the compound that the compound that represents with following formula (8g) replaces formula (8a) to represent obtains the triphenylamine derivative (HTM-14) that formula (25) represents.

In addition, when making laminated electrophotographic photoreceptor, the triphenylamine derivative (HTM-14) of this formula (25) expression is used in agent as cavity conveying.

As shown in Figure 3, during the photoreceptor of embodiment 36～42 was estimated, rest potential was low, does not have crystallization in the crystallization evaluation, had confirmed good.

[comparative example 11]

In comparative example 11, when making the reaction formula (2 ') of triphenylamine derivative, the compound that the compound that represents with following formula (8h) replaces formula (8a) to represent obtains the triphenylamine derivative (HTM-B) that formula (b) represents.

In addition, when making laminated electrophotographic photoreceptor, the triphenylamine derivative (HTM-B) of this formula (b) expression is used in agent as cavity conveying.

[comparative example 12]

In comparative example 12, when making the reaction formula (2 ') of triphenylamine derivative, the compound that the compound that represents with following formula (8i) replaces formula (8a) to represent obtains the triphenylamine derivative (HTM-C) that following formula (c) represents.

In addition, when making laminated electrophotographic photoreceptor, the triphenylamine derivative (HTM-C) of this formula (c) expression is used in agent as cavity conveying.

[comparative example 13]

In comparative example 13, when making the reaction formula (2 ') of triphenylamine derivative, the compound that the compound that represents with following formula (8j) replaces formula (8a) to represent obtains the triphenylamine derivative (HTM-D) that following formula (d) represents.

In addition, when making laminated electrophotographic photoreceptor, the triphenylamine derivative (HTM-D) of this formula (d) expression is used in agent as cavity conveying.

[comparative example 14]

In comparative example 14, when making the reaction formula (2 ') of triphenylamine derivative, the compound that the compound that represents with following formula (8k) replaces formula (8a) to represent obtains the triphenylamine derivative (HTM-A) that formula (a) represents.

In addition, when making laminated electrophotographic photoreceptor, the triphenylamine derivative (HTM-A) of this formula (a) expression is used in agent as cavity conveying.

[comparative example 15]

In comparative example 15, when making the reaction formula (2 ') of triphenylamine derivative, the compound that the compound that represents with following formula (8l) replaces formula (8a) to represent obtains the triphenylamine derivative (HTM-E) that following formula (e) represents.

In addition, when making laminated electrophotographic photoreceptor, the triphenylamine derivative (HTM-E) of this formula (e) expression is used in agent as cavity conveying.

As shown in Figure 3, during the photoreceptor of comparative example 11～15 was estimated, rest potential was high, perhaps confirmed to have separated out crystallization in the crystallization evaluation, had confirmed existing problems.

[table 3]

[embodiment 43]

In embodiment 43, manufacturing mono-layer electronic photographic photoreceptor as described below is also estimated.

1, the manufacturing of mono-layer electronic photographic photoreceptor

At first, will be as X-type crystallization 5 weight parts of the metal-free phthalocyanine (CGM-1) of the following formula (29) of charge generating expression, as triphenylamine derivative (HTM-8) 80 weight parts of formula (19) expression of cavity conveying agent, as connection para benzoquinone (ETM-1) 50 weight parts of formula (30) expression of electron transporting agent, as polycarbonate resin 100 weight parts of formula (31) expression of binding resin, pack in the container as tetrahydrofuran (THF) 800 weight parts of solvent, obtain their mixture.Afterwards, with ball mill this mixture is mixed, disperseed 50 hours, obtain the sensitive layer coating fluid.

Then, the speed with 5mm/s under the state that the aluminum substrate (carrier matrix) of diameter 30mm, long 238.5mm is made progress with the one end is impregnated into sensitive layer with in the coating fluid, to this aluminum substrate photosensitive coated layer coating fluid.Afterwards, be cured processing under 100 ℃, 30 minutes condition, forming thickness is the sensitive layer of 25 μ m.Thus, obtain mono-layer electronic photographic photoreceptor.

2, the evaluation of mono-layer electronic photographic photoreceptor

(1) evaluation of rest potential

That is, measure in the same manner as in Example 1 rest potential.The result who obtains is illustrated in the table 4.

(2) evaluation of crystallization

Whether the surface with the method evaluation resulting mono-layer electronic photographic photoreceptor identical with embodiment 1 has crystallization.The result who obtains is illustrated in the table 4.

[embodiment 44]

In embodiment 44, use the compound (ETM-2) of formula (32) expression as electron transporting agent, similarly make mono-layer electronic photographic photoreceptor with embodiment 43 in addition and estimate.The result who obtains is illustrated in the table 4.

[embodiment 45]

In embodiment 45, use the Y type crystallization of the titanyl phthalocyanine (CGM-2) of formula (33) expression as charge generating, similarly make mono-layer electronic photographic photoreceptor with embodiment 44 in addition and estimate.The result who obtains is illustrated in the table 4.

[embodiment 46～48]

In embodiment 46～48, use the triphenylamine derivative (HTM-9) of formula (20) expression as the cavity conveying agent, similarly make mono-layer electronic photographic photoreceptor with embodiment 43～45 respectively in addition and estimate.The result who obtains is illustrated in the table 4.

[embodiment 49～51]

In embodiment 49～51, use the triphenylamine derivative (HTM-13) of formula (24) expression as the cavity conveying agent, similarly make mono-layer electronic photographic photoreceptor with embodiment 43～45 respectively in addition and estimate.The result who obtains is illustrated in the table 4.

As shown in table 4, during the photoreceptor of embodiment 43～51 was estimated, rest potential was low, does not have crystallization in the crystallization evaluation, had confirmed good.

[comparative example 16～18]

In comparative example 16～18, use the triphenylamine derivative (HTM-A) of formula (a) expression as the cavity conveying agent, similarly make mono-layer electronic photographic photoreceptor with embodiment 43～45 respectively in addition and estimate.The result who obtains is illustrated in the table 4.

[comparative example 19～21]

In comparative example 19～21, use the triphenylamine derivative (HTM-B) of formula (b) expression as the cavity conveying agent, similarly make mono-layer electronic photographic photoreceptor with embodiment 43～45 respectively in addition and estimate.The result who obtains is illustrated in the table 4.

As shown in table 4, during the photoreceptor of comparative example 16～21 was estimated, rest potential was high, perhaps confirmed to have separated out crystallization in the crystallization evaluation, had confirmed existing problems.

[table 4]

[embodiment 52]

In embodiment 52, manufacturing mono-layer electronic photographic photoreceptor as described below is also estimated.

In embodiment 52, use two naphthoquinone compounds (ETM-3) of formula (34) expression as electron transporting agent, similarly make mono-layer electronic photographic photoreceptor with embodiment 43 in addition, similarly to Example 22 the stain generation that forms in the image is estimated.The result who obtains is illustrated in the table 5.

[embodiment 53]

In embodiment 53, use the Y type crystallization of the titanyl phthalocyanine (CGM-2) of formula (33) expression as charge generating, similarly make mono-layer electronic photographic photoreceptor with embodiment 52 in addition and estimate.The result who obtains is illustrated in the table 5.

[embodiment 54～55]

In embodiment 54～55, use the triphenylamine derivative (HTM-9) of formula (20) expression as the cavity conveying agent, similarly make mono-layer electronic photographic photoreceptor with embodiment 52～53 respectively in addition and estimate.The result who obtains is illustrated in the table 5.

[embodiment 56～57]

In embodiment 56～57, use the triphenylamine derivative (HTM-13) of formula (24) expression as the cavity conveying agent, similarly make mono-layer electronic photographic photoreceptor with embodiment 52 ~ 53 respectively in addition and estimate.The result who obtains is illustrated in the table 5.

As shown in table 5, during the photoreceptor of embodiment 52～57 is estimated, confirmed in the low and crystallization evaluation of rest potential without crystallization to be good.

[comparative example 22～23]

In comparative example 22～23, use the triphenylamine derivative (HTM-A) of formula (a) expression as the cavity conveying agent, similarly make mono-layer electronic photographic photoreceptor with embodiment 52 ~ 53 respectively in addition and estimate.The result who obtains is illustrated in the table 5.

[comparative example 24～25]

In comparative example 24～25, use the triphenylamine derivative (HTM-B) of formula (b) expression as the cavity conveying agent, similarly make mono-layer electronic photographic photoreceptor with embodiment 52 ~ 53 respectively in addition and estimate.The result who obtains is illustrated in the table 5.

As shown in table 5, during the photoreceptor of comparative example 22～25 was estimated, rest potential was high, perhaps confirmed to have separated out crystallization in the crystallization evaluation, had confirmed existing problems.

[table 5]

Utilizability on the industry

As mentioned above, according to the present invention, for triphenylamine derivative, introduce the aryloxy of regulation carbonatoms in the contraposition of aryl amine, thus can effectively improve to the solvability of solvent and with the intermiscibility of binding resin.

Therefore, be used as the cavity conveying agent of Electrophtography photosensor by the triphenylamine derivative that will have this ad hoc structure, crystallization and the dispersion that can effectively be suppressed in the sensitive layer are bad, so can effectively improve the light sensitivity characteristic of Electrophtography photosensor.

Therefore, wait in expectation triphenylamine derivative of the present invention and manufacture method thereof and Electrophtography photosensor helps high speed, the high performance of the various image processing systems such as duplicating machine, printer.

Claims

1. triphenylamine derivative represents with following general formula (1):

In general formula (1), R ¹Be the alkyl of carbonatoms 1～3, R ⁴～R ⁵Be hydrogen atom, R ²And R ³In at least one be methyl, methoxy or ethoxy, R ⁶Be hydrogen atom, Ar ¹And Ar ²Be phenyl.

2. triphenylamine derivative according to claim 1 is characterized in that, the substituent R in described general formula (1) ²And R ³In, only have one to be methyl, methoxy or ethoxy.

3. the manufacture method of a triphenylamine derivative is characterized in that, it is the manufacture method of the triphenylamine derivative of general formula claimed in claim 1 (1) expression, comprises the operation of the reaction of carrying out following reaction formula (1) expression:

In general formula (3), X is halogen atom, and other substituting group in general formula (2)～(4) is identical with the content of explanation in the general formula claimed in claim 1 (1).

4. the manufacture method of triphenylamine derivative according to claim 3 is characterized in that, in the reaction of described reaction formula (1) expression, uses palladium compound as catalyzer.

5. the manufacture method of triphenylamine derivative according to claim 4 is characterized in that, with respect to 1 mole of the compound of general formula (4) expression, the addition of described palladium compound is the value in 0.0005～20 molar range.

6. according to claim 3 or the manufacture method of 4 described triphenylamine derivatives, it is characterized in that, in the presence of alkali, carry out the reaction of described reaction formula (1) expression.

7. the manufacture method of triphenylamine derivative according to claim 6 is characterized in that, with respect to 1 mole of the compound of described general formula (4) expression, when adding 0.005 mole of described palladium compound, the addition of described alkali is the value in 1～10 molar range.

8. Electrophtography photosensor, it is characterized in that for have the Electrophtography photosensor of sensitive layer at matrix described sensitive layer contains the triphenylamine derivative of general formula claimed in claim 1 (1) expression.

9. Electrophtography photosensor according to claim 8 is characterized in that, described sensitive layer is the laminated-type sensitive layer.

10. Electrophtography photosensor according to claim 9, it is characterized in that, with respect to binding resin 100 weight parts of the charge transport layer in the described laminated-type sensitive layer, the content of the triphenylamine derivative of described general formula (1) expression in the described laminated-type sensitive layer is the value in 30～100 weight part scopes.