JPH09278723A - Amine compound containing hydroxyl group and its production intermediate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as an organic photoconductive material for electrophotography, etc. SOLUTION: This compound is expressed by formula I (R1 is H, an alkyl, etc.; Ar1 is an aryl having at least one amino group, etc.; Ar2 and Ar3 are each independently an arylene), e.g. 4,4'-dimethyl-4''-[2,2-bis(4-methoxyphenyl) vinyl]triphenylamine. The compound can be produced by the cleavage reaction of an ether of a compound of formula II (R6 and R7 are each an alkyl, etc.), etc. A charge generation layer can be produced by coating an aluminized polyester film with a liquid dispersion of the compound.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a hydroxyl group-containing amine compound which is useful as an organic photoconductive material for electrophotography and also as an intermediate for producing various materials derived from a hydroxyl group, and an intermediate for producing the same. And a useful amine compound.

[0002]

2. Description of the Related Art Conventionally, as an organic photoconductive material of a photoreceptor used in an electrophotographic system, for example, poly-N
-Vinyl carbazole, triphenylamine compounds (U.S. Pat. No. 3,180,730), benzidine compounds (U.S. Pat. No. 3,265,496, JP-B-39-11)
Many proposals have been made, such as Japanese Patent Application Laid-Open No. 546 and Japanese Patent Application Laid-Open No. 53-27033. The term "electrophotographic method" as used herein generally means that a photoconductive photoreceptor is first charged in a dark place by, for example, corona discharge, and then imagewise exposure is performed to selectively discharge the charge in the exposed portion. This is one of the image forming methods in which an electrostatic latent image is obtained, and the latent image portion is visualized by developing means using toner or the like to form an image. The basic characteristics required of the photoreceptor in such an electrophotographic system include: 1) being charged to an appropriate potential in a dark place, 2) being less discharged in a dark place, and 3) being irradiated with light. Discharging the charge more quickly.

In recent years, polymer photoconductive materials (US Pat. No. 4,801,517 and US Pat. No. 4,806,4) have been used for the purpose of further improving the mechanical strength of the photoconductor.
No. 43, U.S. Pat. No. 4,806,444,
No. 221522, JP-A-4-11627) have been proposed. However, conventional low-molecular or high-molecular photoconductive materials do not always satisfy the above requirements.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photoconductive material which satisfies all basic electrophotographic properties, and also as an intermediate for producing various materials derived from hydroxyl groups. Another object of the present invention is to provide a novel hydroxyl-containing amine compound which is useful as well as a novel amine compound which is useful as an intermediate for producing the same.

[0005]

According to the present invention, the following general formulas (1), (2), (3), (4), (5),
There is provided a hydroxyl group-containing amine compound (including an ether group- or ester group-containing amine compound) represented by (6), (7) and (8).

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[Chemical 6]

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Embedded image [Formulas (1), (2), (3), (4), (5),
In (6), (7) and (8), R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ₂ and R ₃ represent a hydrogen atom, an acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₄ ,
R ₅ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a halogen atom. R ₆ and R ₇ represent a substituted or unsubstituted alkyl group or acyl group. Ar ₁ represents an aryl group having at least one amino group, a heterocyclic group having at least one amino group, or a substituted or unsubstituted heterocyclic group having an amino moiety. Ar ₂ , Ar ₃ and Ar ₄ represent an arylene group. However, R ₂ and R ₃ , R ₄ and R ₅ , R ₆ and R ₇ , Ar ₂ and A
r ₃ and Ar ₄ may be the same or different from each other. ]

Hereinafter, the hydroxyl group-containing amine compound of the present invention and the ether group- or ester group-containing amine compound of the production intermediate thereof will be described in more detail. The general formulas (1), (2), (3), (4), (5),
In the amine compounds represented by (6), (7) and (8), alkoxy groups in which R _{1 to} R ₇ are substituted or unsubstituted alkyl groups, and when R ₄ and R ₅ are alkoxy groups The following can be mentioned as specific examples of the alkyl group portion constituting It is a C1 to C5 linear or branched alkyl group, and these alkyl groups further contain a phenyl group substituted with a fluorine atom, a cyano group, a phenyl group or a halogen atom or a C1 to C5 alkyl group. Good. Specifically, a methyl group, an ethyl group, n-
Propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-cyanoethyl group, benzyl group, 4-chlorobenzyl group, 4-methyl Examples thereof include a benzyl group.

Further, the above general formulas (1), (2),
Specific examples of amine compounds represented by (3), (4), (5), (6), (7) and (8), wherein R _{1 to} R ₃ are substituted or unsubstituted aryl groups The following can be cited as examples. Phenyl group, naphthyl group, biphenylyl group, terphenylyl group, pyrenyl group,
Examples thereof include fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group and chrysenyl group, which have a lower alkyl group, a lower alkoxy group and a halogen atom as a substituent. Good. Moreover, the group represented by the following general formula (9) can be mentioned.

Embedded image Wherein, X is -O -, - S -, - SO -, - SO 2 -,
-CO- and the following divalent groups are represented.

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Embedded image (Here, R ₈ and R ₉ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, a halogen atom, a substituted or unsubstituted aryl group, an amino group, a nitro group or a cyano group, and n is 1 to 1 12 is an integer, and 1 is an integer of 1 to 3.)]

In the specific examples of the divalent group X in the general formula (9), specific examples of the substituted or unsubstituted alkyl group, alkoxy group and substituted or unsubstituted aryl group for R ₈ and R ₉ are as described above. It is the same as the definition of R _{1 to} R ₇ . Further, specific examples of the amino group include groups represented by the following general formula.

Embedded image (R_Ten, R₁₁Is a hydrogen atom, a substituted or unsubstituted alkyl
And a substituted or unsubstituted aryl group. ) Where R_Ten, R₁₁In the
Specific examples of the alkyl group and the substituted or unsubstituted aryl group
Is R₁~ R₇Is the same as the definition of. Also, R_Ten, R₁₁
May jointly form a ring. Also, charcoal on aryl group
You may form a ring in cooperation with an elementary atom. Specific examples like this
As a piperidino group, a morpholino group, a julolidyl group, etc.
Is mentioned.

Further, when R ₄ , R ₅ , R ₈ and R ₉ are halogen atoms and when R _{1 to} R ₁₁ are groups having a halogen atom, the halogen atom is fluorine, chlorine, bromine and iodine. Is mentioned. Furthermore, in the amine compounds represented by the general formulas (2), (4), (5), (7) and (8), specific examples of the acyl group of R ₂ , R ₃ , R ₆ and R ₇ Examples thereof include an acetyl group, a propionyl group and a benzoyl group.

Further, the above general formulas (2), (4) and (5)
And in the amine compound represented by (8), R ₂ , R ₃
Specific examples of the substituted or unsubstituted heterocyclic group include a monovalent group derived from furan, thiophene, oxazole, pyridine, benzofuran, benzothiophene, etc., and these include a lower alkyl group, a lower alkoxy group and a halogen. It may have an atom as a substituent.

In the amine compounds represented by the above general formulas (1), (3) and (7), the aryl group in which Ar ₁ has at least one amino group is represented by the following general formula (10). Is a group that is

Embedded image (Wherein, R _2, R ₃ is .m representing the same .Ar ₄ is an arylene group and the definition is an integer of 1-3.) Specific examples of where Ar ₄ is derived from the aryl group And a divalent group.

Further, the heterocyclic group in which Ar ₁ has at least one amino group is a group represented by the following general formula (11).

Embedded image (Wherein, R _2, R ₃ is .m representing the same .Ar ₅ divalent heterocyclic group and the definition is an integer of 1-3.) Specific examples of where Ar _5, the 1 A divalent group derived from a valent heterocyclic group can be mentioned.

Furthermore, when Ar ₁ is a substituted or unsubstituted heterocyclic group having an amino moiety, specific examples of the heterocyclic group include pyrrole, pyrazole, imidazole,
Examples thereof include triazole, dioxazole, indole, isoindole, benzimidazole, benzotriazole, benzisoxazine, carbazole and phenoxazine, and these heterocycles are substituted or unsubstituted as defined in the above R _{1 to} R _3. May have an alkyl group, a lower alkoxy group, a halogen atom, or a substituted or unsubstituted aryl group as a substituent.

Further, the above general formulas (1), (2) and (7)
And in the amine compound represented by (8), Ar ₂ ,
Specific examples of the arylene group of Ar ₃ and Ar ₄ include a divalent group derived from the aryl group.

The hydroxyl group-containing amine compound according to the present invention is a novel substance, and its production method will be described below.
That is, the compounds represented by the general formulas (1) to (6) are
It is synthesized by the ether cleavage reaction or ester cleavage reaction of the compounds represented by the following general formulas (7) and (8).

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Embedded image (In the formula, R ₁ , R ₂ , R ₃ , R ₆ , R ₇ , Ar ₁ , Ar ₂ , and A
r ₃ and Ar ₄ represent the same as defined above. )

Specific examples of the cleavage reaction of the ether include a method using an acidic reagent and a method using a basic reagent.
Examples of the acidic reagent include hydrogen bromide, hydrogen iodide, trifluoroacetic acid, hydrochloride of pyridine, concentrated hydrochloric acid, magnesium iodide ethylate, aluminum chloride, aluminum bromide,
Boron tribromide, boron trichloride, boron triiodide and the like are used as basic reagents such as potassium hydroxide, sodium hydroxide, sodium, lithium, sodium iodide, lithium iodide, lithium diphenylphosphide and sodium thioethiene. A rat etc. can be mentioned. Acetic anhydride, dichloromethane, tetrahydrofuran (TH
F), N, N-dimethylformamide (DMF), pyridine, butanol, and the like. The reaction temperature depends on the reactivity of the reagent to be used.
Performed between 0 ° C.

The compound represented by the general formula (7) is the synthetic scheme shown in Table 1 below, that is, W of the compound represented by the general formula (12) and the compound represented by the general formula (13).
It is synthesized by an ittig reaction or a modified Wittig reaction.

[Table 1] Here, specific examples of R ₁₂ is a straight-chain or branched-chain alkyl group of C ₁ ~ _5, for example, a methyl group, an ethyl group,
n-propyl group, i-propyl group, t-butyl group, s-
Examples thereof include a butyl group, an n-butyl group, an i-butyl group and an n-pentyl group.

In the above reaction, the compound represented by the general formula (14) and the general formula (1) are preferably obtained by a modified Wittig reaction shown in the synthetic scheme shown in Table 2 below.
From the compound represented by 5), the compound represented by the general formula (8) can be synthesized in high yield.

[Table 2] The reaction at this time may be a conventionally known method, for example, DM
It can be easily synthesized by dissolving a phosphonate compound and a formyl compound in a polar solvent such as F and gradually adding a strong base compound such as potassium t-butyrate or sodium methylate under water cooling. Also,
The compounds represented by the general formula (14) and the general formula (15) are each synthesized by a conventionally known method. For example, in the synthesis of phosphonate compounds, Eur. J. Med. Ch
em. It is also synthesized by the method described in (1993) 28, 943-948.

Further, in the hydroxyl group-containing amine compound represented by the general formula (8), when R ₂ and R ₃ are alkyl groups, a primary amine compound represented by the following general formula (16) is used. It can also be produced by reacting an alkyl halide, a dialkyl sulfuric acid, a sulfonic acid ester or the like in the presence of an acid scavenger.

Embedded image (In the formula, R ₆ , R ₇ , Ar ₂ , Ar ₃ and Ar ₄ are the same as those defined above.)

In the hydroxyl group-containing amine compound represented by the general formula (8), when R ₂ and R ₃ are a substituted or unsubstituted aryl group, the above-mentioned general formula (1)
The primary amine compound represented by 6) and an aryl halide are coexistent with copper powder, copper oxide or copper halide, and an alkaline substance in the absence of a solvent or in a solvent under a nitrogen stream of 150 to 250. It can also be produced by reacting at a temperature of ° C. In this case, examples of the alkaline substance include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. Further, as the reaction solvent, nitrobenzene, dichlorobenzene, quinoline, DMF, dimethyl sulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-
And imidazolidinone.

Further, the compound in which R ₂ and R ₃ are different substituted or unsubstituted aryl groups, the hydrogen atom of one of the amino groups of the primary amine compound represented by the general formula (16) is an acyl group or the like. Can be prepared by reacting with an aryl halide, followed by hydrolysis, and then reacting with an aryl halide again. The reaction conditions with the aryl halide are the same as above.

Further, a compound in which R ₂ is a substituted or unsubstituted alkyl group and R ₃ is a substituted or unsubstituted aryl group is reacted with an aryl halide by using, for example, the above-mentioned N-acyl compound as a starting material. After hydrolysis, it is obtained by reacting with a nitrogen alkylating agent.

The hydroxyl group-containing amine compound of the present invention is extremely useful as a photoconductive material in an electrophotographic photoreceptor, and is optically or chemically sensitized by a sensitizer such as a dye or a Lewis acid. . Further, this is particularly useful as a charge-transporting substance in a so-called function separation type, which uses an organic pigment or an inorganic material as a charge-generating substance.

Examples of the sensitizer include triarylmethane dyes such as methyl violet and crystal violet, xanthene dyes such as rose bengal, erythrosine and rhodamine, thiazine dyes such as methylene blue and 2,4,7-trinitro-9. -Fluorenone, 2,
4-dinitro-9-fluorenone and the like.

As the organic pigments, azo pigments such as CI Pigment Blue 25 (CI No. 21180), CI Pigment Red 41 (CI No. 21200) and CI Pigment Red 3 (CI No. 45210), CI Pigment Blue 16 (CIN
o. 74100) and the like, phthalocyanine-based pigments such as CI Eye Bat Brown 5 (CI No. 73410), CI Eye Bat Die (CI No. 73030) and the like, and perylene pigments such as Argo Scarlet B and Indanthren Scarred R. To be Further, inorganic materials such as selenium, selenium-tellurium, cadmium sulfide and α-silicon can also be used.

It is also useful as an intermediate for the production of various materials derived from a hydroxyl group, for example, a polycarbonate resin, polyester resin, polyurethane resin, epoxy resin or the like.

[0027]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

Example 1 40.95 g (0.11 mol) of diethyl [bis (4-methoxyphenyl) methyl] phosphonate and 4,4'-
Dimethyl-4 "-formyltriphenylamine 33.8
DMF 500 m obtained by dehydrating 7 g (0.11 mol)
It was dissolved in 1 liter and heated to 22-25 ° C in a water bath, and then potassium-
With stirring, 19 g (0.16 mol) of t-butyrate was added little by little and reacted. 7 more at room temperature after the addition is complete
After stirring for an hour, it was diluted with 400 ml of water and the product was obtained by filtration. Then, column chromatography with silica gel was performed using a toluene solvent, and recrystallization purification was performed using a mixed solvent of ethanol and toluene.
4,4'-dimethyl-4 "-[2,2-represented by 7)
Bis (4-methoxyphenyl) vinyl] triphenylamine (Compound No. 1) (50.59 g, yield 88%) was obtained. This product is a pale yellow needle crystal with a melting point of 170.8.
It was ~ 171.4 ° C. The results of infrared absorption spectrum, nuclear magnetic resonance spectrum and elemental analysis are shown below.

Embedded image The infrared absorption spectrum (KBr tablet method) is shown in FIG.
The proton nuclear magnetic resonance spectrum (CDCl ₃ solution) is shown in FIG. Elemental analysis value (%) C H N measured value 84.52 6.54 2.52 Calculated value as C ₃₆ H ₃₃ NO ₂ 84.51 6.50 2.74

Examples 2 to 12 Using the phosphonate compound having the structure shown below and the formyl compound shown in Table 1 below as starting materials, the amine compound of the present invention was obtained in the same manner as in Example 1. The physical properties thereof were measured, and the results are shown in Table 2 below.

Phosphonate Compound P-1 Diethyl [bis (4-methoxyphenyl) methyl] phosphonate P-2 Diethyl [bis (3-methoxyphenyl) methyl] phosphonate

[0031]

[Table 1- (1)]

[0032]

[Table 1- (2)]

[0033]

[Table 1- (3)]

[0034]

[Table 2- (1)]

[0035]

[Table 2- (2)]

[0036]

[Table 2- (3)]

[0037]

[Table 2- (4)]

Example 13 45.5 g (8) of the dimethoxy compound obtained in Example 11
1 mmol) and sodium thioethylate 40.0 g
(452 mmol) was added to 300 ml of dried DMF, and the mixture was heated under reflux for 8 hours under a nitrogen stream. After allowing to cool to room temperature, the contents were poured into 600 ml of ice water and acidified with concentrated hydrochloric acid. After extraction with ethyl acetate, the organic layer was washed with water, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure.
A light brown oil was obtained. 100 ml of this oil was added to acetic anhydride.
10 ml of pyridine was added. After 10 minutes, the content was poured into water, and the precipitate was washed with water and dried to obtain 49.0 g (yield 97.8%) of pale yellow powder. This was subjected to column chromatography with silica gel [eluent: toluene] and then recrystallized from a mixed solvent of ethyl acetate and toluene to obtain 45.0 g of a pale yellow needle-like crystal diacetoxy compound (yield 89.8).
%) Was obtained. The melting point, infrared absorption spectrum, and elemental analysis results of the obtained compound are also shown in Table 3.

Example 14 A diacetoxy compound shown in Table 3 was obtained in the same manner as in Example 13 except that the dimethoxy compound obtained in Example 12 was used. The results are shown in Table 3.

Example 15 A diacetoxy compound shown in Table 3 was obtained in the same manner as in Example 13 except that the dimethoxy compound obtained in Example 7 was used. The results are shown in Table 3.

[0041]

[Table 3]

Example 16 4,4'-Dimethyl-4 "-[2 obtained in Example 1
2-bis (4-methoxyphenyl) vinyl] triphenylamine (Compound No. 1) 11.0 g (21.5 mm
ol) and sodium thioethylate 10.0 g (107
(mmol) was taken in 110 ml of dried DMF and heated under reflux for 3 hours under a nitrogen stream. After cooling to room temperature,
The contents were poured into ice water and neutralized with concentrated hydrochloric acid. This was extracted with ethyl acetate, the organic layer was washed with water, dried and the solvent was distilled off, followed by column chromatography with silica gel [eluent: toluene / ethyl acetate (7/1 vol.)] To give a yellow powder 1.
0.87 g was obtained. This is recrystallized from a mixed solvent of cyclohexane and toluene, dried under reduced pressure and dried in a yellow powder form, 4- [2,2-bis (4-hydroxyphenyl) vinyl] phenyl- represented by the following structural formula (18). Bis (4-methylphenyl) amine (Compound No. 16)
9.59 g (yield 92.3%) was obtained. Most of this substance was amorphous and did not show a clear melting point, but the melting point of the partially crystallized part was 172.5 ° C.

Embedded image The results of infrared absorption spectrum, nuclear magnetic resonance spectrum and elemental analysis of the obtained compound are shown below. The infrared absorption spectrum (KBr tablet method) is shown in FIG. Proton nuclear magnetic resonance spectra (d _6-DMSO solution) shown in FIG. 21. Elemental analysis value (%) C H N measured value 84.58 6.21 2.92 calculated value as C ₃₄ H ₂₉ NO ₂ 84.44 6.04 2.90

Examples 17 to 27 Hydroxyl group-containing amine compounds of the present invention were obtained in the same manner as in Example 16 using the precursor amine compounds obtained in Examples 2 to 12 as raw materials. The physical properties and the like were measured, and the results are shown in Table 4 below.

[0044]

[Table 4- (1)]

[0045]

[Table 4- (2)]

[0046]

[Table 4- (3)]

[0047]

[Table 4- (4)]

Application Example 1 7.5 parts of a trisazo compound represented by the following structural formula (19) as a charge generating substance

Embedded image And polyester resin [Byron 20 manufactured by Toyobo Co., Ltd.
0] of 0.5% tetrahydrofuran solution was pulverized and mixed in a ball mill, and the obtained dispersion liquid was applied onto an aluminum vapor-deposited polyester film with a doctor blade and naturally dried to form a charge generation layer having a thickness of about 1 μm. did.
Next, 1 part of the amine compound (Compound No. 1) obtained in Example 1 as a charge transport substance was added to a resin solution of 1 part of a polycarbonate resin [Panlite K-1300 manufactured by Teijin Limited] and 8 parts of tetrahydrofuran. Dissolve and apply this solution on the charge generation layer with a doctor blade,
For about 20 μm after drying for 5 minutes at 120 ° C
A charge transporting layer was formed to prepare a photoconductor. Next, in order to enhance the sensitivity in the visible range of the laminated electrophotographic photoconductor thus obtained, an electrostatic copying paper test apparatus [K.
[Kawaguchi Denki Seisakusho's SP428 type]
After corona discharge of V was performed for 20 seconds for charging, the surface potential Vm (V) of the photoconductor was measured, and the surface potential Vo (V) was measured after standing for 20 seconds in a dark place. Then, the illuminance of the tungsten lamp light on the surface of the photoconductor is 4.5 lu.
The exposure amount E _1/2 (lux · sec) until Vo was reduced to _1/2 was measured by irradiating so as to obtain x. Vm = -1310V Vo = -740V E1 _{/ 2} = 0.51 lux.sec

Application Example 2 7.5 parts of a bisazo compound represented by the following structural formula (20) as a charge generating substance

Embedded image And polyester resin [Byron 20 manufactured by Toyobo Co., Ltd.]
0.5] of a 0.5% tetrahydrofuran solution in a ball mill, and the resulting dispersion is applied on an aluminum-evaporated polyester film with a doctor blade and air-dried to form a charge generating layer having a thickness of about 1 μm. did.
Next, a hydroxyl group-containing amine compound (compound No. 16) obtained in Example 10 as a charge transport substance was added to a resin solution of 1 part of a polycarbonate resin [Panlite K-1300 manufactured by Teijin Limited] and 8 parts of tetrahydrofuran. 1 part is dissolved, and this solution is applied onto the charge generation layer with a doctor blade, and dried at 80 ° C. for 2 minutes and then at 120 ° C. for 5 minutes to form a charge transport layer having a thickness of about 20 μm. Was produced. Next, in order to examine the sensitivity of the laminated electrophotographic photosensitive member thus obtained in the visible region, an electrostatic copying paper test apparatus [SP428 manufactured by Kawaguchi Electric Co., Ltd.
Mold] to perform corona discharge of −6 KV in a dark place for 20 seconds to charge the surface, measure the surface potential Vm (V) of the photoconductor, and leave it in the dark for 20 seconds.
(V) was measured. Next, a tungsten lamp light is irradiated so that the illuminance on the surface of the photoconductor becomes 4.5 lux, and the exposure amount E _1/2 (lux.
sec) was measured. Vm = -1014V Vo = -323V E1 _{/ 2} = 0.80 lux.sec

Application Examples 3 to 8 Photosensitive members were prepared and evaluated in the same manner as in Application Example 2 except that the following structural formulas obtained in Examples were used as the charge transport material. The results are shown in Table 5 below. .

[0051]

[Table 5]

Application Example 9 <Application Example as Polymer Raw Material> Hydroxyl group-containing amine compound obtained in Example 16 (Compound No. 16)
Tetrahydrofuran (TH
F) Dissolved in 40 parts and added with 3.06 parts of triethylamine with stirring under a nitrogen gas stream, and then dissolved in bischloroformate of diethylene glycol 2.32 parts in THF 8 parts was cooled to 20 ° C. in a water bath. While dropping, the solution was added dropwise over 30 minutes. Then, the mixture was stirred and reacted at room temperature for another hour, and 1 part of a 4 wt% phenol solution in THF was added to terminate the reaction. Then, the precipitated salt was removed by filtration, and the obtained reaction solution was dropped into 1500 parts of methanol to obtain a polycarbonate resin. This product was filtered and dried, taken out again, dissolved again in 70 parts of THF, and dropped again into 1500 parts of methanol, and the reprecipitation operation was repeated twice to obtain a polycarbonate resin represented by the following structural formula (21).

Embedded image When the molecular weight of the obtained polycarbonate resin was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows. Number average molecular weight 17,000 Weight average molecular weight 32300

[0053]

The hydroxyl group-containing amine compound according to the present invention effectively functions as a photoconductive material as described above, and is optically or chemically sensitized by a sensitizer such as a dye or a Lewis acid. Therefore, it is preferably used as a charge-transporting substance or the like in the photosensitive layer of an electrophotographic photoreceptor, and particularly useful as a charge-transporting substance in a so-called function-separated type photosensitive layer in which a charge-generating layer and a charge-transporting layer are divided into two layers. It is a thing. It is also useful as an intermediate for the production of various materials derived from hydroxyl groups, for example, polycarbonate resins, polyester resins, polyurethane resins, epoxy resins and the like.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram (KBr tablet method) of an amine compound (Compound No. 1) of the present invention.

FIG. 2 is a nuclear magnetic resonance spectrum diagram (CDCl ₃ solution) of the amine compound (Compound No. 1) of the present invention.

FIG. 3 is an infrared absorption spectrum diagram (KBr tablet method) of the amine compound of the present invention (Compound No. 2).

FIG. 4 is a nuclear magnetic resonance spectrum diagram (CDCl ₃ solution) of the amine compound of the present invention (Compound No. 2).

FIG. 5 is an infrared absorption spectrum diagram (KBr tablet method) of the amine compound (Compound No. 3) of the present invention.

FIG. 6 is a nuclear magnetic resonance spectrum diagram (CDCl ₃ solution) of the amine compound of the present invention (Compound No. ₃ ).

FIG. 7 is an infrared absorption spectrum diagram (KBr tablet method) of the amine compound (Compound No. 4) of the present invention.

FIG. 8 is an infrared absorption spectrum diagram (KBr tablet method) of the amine compound of the present invention (Compound No. 5).

FIG. 9 is an infrared absorption spectrum diagram (KBr tablet method) of the amine compound of the present invention (Compound No. 6).

FIG. 10 is an infrared absorption spectrum diagram (KBr tablet method) of the amine compound of the present invention (Compound No. 7).

FIG. 11 is a nuclear magnetic resonance spectrum diagram (CDCl ₃ solution) of the amine compound of the present invention (Compound No. 7).

FIG. 12 is an infrared absorption spectrum diagram (KBr tablet method) of the amine compound of the present invention (Compound No. 8).

FIG. 13 is an infrared absorption spectrum diagram (KBr tablet method) of the amine compound of the present invention (Compound No. 9).

FIG. 14: Amine compound of the present invention (Compound No. 10)
Infrared absorption spectrum (KBr tablet method).

FIG. 15: Amine compound of the present invention (Compound No. 11)
Infrared absorption spectrum (KBr tablet method).

FIG. 16: Amine compound of the present invention (Compound No. 12)
Infrared absorption spectrum (KBr tablet method).

FIG. 17: Amine compound of the present invention (Compound No. 13)
Infrared absorption spectrum (KBr tablet method).

FIG. 18: Amine compound of the present invention (Compound No. 14)
Infrared absorption spectrum (KBr tablet method).

FIG. 19: Amine compound of the present invention (Compound No. 15)
Infrared absorption spectrum (KBr tablet method).

FIG. 20 is an infrared absorption spectrum diagram (KBr) of the hydroxyl group-containing amine compound of the present invention (Compound No. 16).
Tablet method).

FIG. 21 is a nuclear magnetic resonance spectrum diagram (d ₆ ) of the hydroxyl group-containing amine compound of the present invention (Compound No. 16).
-DMSO solution).

FIG. 22 is an infrared absorption spectrum diagram (KBr) of a hydroxyl group-containing amine compound (Compound No. 17) of the present invention.
Tablet method).

FIG. 23 is a nuclear magnetic resonance spectrum diagram (d ₆ ) of the hydroxyl group-containing amine compound of the present invention (Compound No. 17).
-DMSO solution).

FIG. 24 is an infrared absorption spectrum diagram (KBr) of the hydroxyl group-containing amine compound (Compound No. 18) of the present invention.
Tablet method).

FIG. 25 is a nuclear magnetic resonance spectrum (d ₆ ) of the hydroxyl group-containing amine compound of the present invention (Compound No. 18).
-DMSO solution).

FIG. 26 is an infrared absorption spectrum diagram (KBr) of the hydroxyl group-containing amine compound of the present invention (Compound No. 19).
Tablet method).

FIG. 27 is an infrared absorption spectrum diagram (KBr) of the hydroxyl group-containing amine compound of the present invention (Compound No. 20).
Tablet method).

FIG. 28 is an infrared absorption spectrum diagram (KBr) of the hydroxyl group-containing amine compound of the present invention (Compound No. 21).
Tablet method).

FIG. 29 is an infrared absorption spectrum diagram (KBr) of the hydroxyl group-containing amine compound (Compound No. 22) of the present invention.
Tablet method).

FIG. 30 is a nuclear magnetic resonance spectrum diagram (d ₆ ) of the hydroxyl group-containing amine compound of the present invention (Compound No. 22).
-DMSO solution).

FIG. 31 is an infrared absorption spectrum diagram (KBr) of the hydroxyl group-containing amine compound of the present invention (Compound No. 23).
Tablet method).

FIG. 32 is an infrared absorption spectrum diagram (KBr) of the hydroxyl group-containing amine compound of the present invention (Compound No. 24).
Tablet method).

FIG. 33 is an infrared absorption spectrum diagram (KBr) of the hydroxyl group-containing amine compound of the present invention (Compound No. 25).
Tablet method).

FIG. 34 is an infrared absorption spectrum diagram (KBr) of the hydroxyl group-containing amine compound of the present invention (Compound No. 26).
Tablet method).

FIG. 35 is an infrared absorption spectrum diagram (KBr) of the hydroxyl group-containing amine compound of the present invention (Compound No. 27).
Tablet method).

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Hiroshi Tamura 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh (72) Inventor Tetsuro Suzuki 1-3-6 Nakamagome, Ota-ku, Tokyo Shares Inside Ricoh Company (72) Inventor Tomoyuki Shimada 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh (72) Inventor Chihaya Adachi 1-3-6 Nakamagome, Tokyo Ota-ku Stock Company (72) Inventor Chiaki 1-3-6 Nakamagome Nakatamagome, Ota-ku, Tokyo (72) Inventor Akira Katayama 1-3-3 Nakamagome Nakatagome, Ota-ku, Tokyo (72) Invention Nozomu Tamoto 1-3-6 Nakamagome, Ota-ku, Tokyo Within Ricoh Co., Ltd. (72) Inventor Koji Kishida 1-3-3 Nakamagome, Ota-ku, Tokyo Re Inside the Coe (72) Inventor Mitsutoshi Anzai 66-2 Horikawa-cho, Sachi-ku, Kawasaki-shi, Kanagawa Hodogaya Chemical Industry Co., Ltd. Chemical Industry Co., Ltd.

Claims (8)

[Claims] 1. A hydroxyl group-containing amine compound represented by the following general formula (1). Embedded image (In the formula, R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ₁
Represents an aryl group having at least one amino group, a heterocyclic group having at least one amino group, and a substituted or unsubstituted heterocyclic group having an amino moiety. Ar ₂ ,
Ar ₃ represents an arylene group. However, Ar ₂ and Ar ₃ may be the same or different from each other. ) 2. A hydroxyl group-containing amine compound represented by the following general formula (2). Embedded image (In the formula, R ₂ and R ₃ represent a hydrogen atom, an acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Ar ₂ , A
r ₃ and Ar ₄ represent an arylene group. However, R ₂ and R ₃ , A
r ₂ , Ar ₃ and Ar ₄ may be the same or different from each other. ) 3. A hydroxyl group-containing amine compound represented by the following general formula (3). Embedded image (In the formula, R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Ar ₁
Represents an aryl group having at least one amino group, a heterocyclic group having at least one amino group, and a substituted or unsubstituted heterocyclic group having an amino moiety. ) 4. A hydroxyl group-containing amine compound represented by the following general formula (4). Embedded image (Represented in the formula, R _2, R ₃ is a hydrogen atom, an acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group. However, R ₂
And R ₃ may be the same or different from each other. ) 5. A hydroxyl group-containing amine compound represented by the following general formula (5). Embedded image (Represented in the formula, R _2, R ₃ is a hydrogen atom, an acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group. However, R ₂
And R ₃ may be the same or different from each other. ) 6. A hydroxyl group-containing amine compound represented by the following general formula (6). [Chemical 6] (In the formula, R ₄ and R ₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a halogen atom, provided that R ₄ and R ₅ are the same or different from each other. Good too.) 7. An amine compound represented by the following general formula (7). Embedded image (In the formula, R ₁ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. R ₆ ,
R ₇ represents a substituted or unsubstituted alkyl group or acyl group. Ar ₁ represents an aryl group having at least one amino group, a heterocyclic group having at least one amino group, or a substituted or unsubstituted heterocyclic group having an amino moiety. Ar ₂ and Ar ₃ represent an arylene group. However, R ₆ and R ₇ ,
Ar ₂ and Ar ₃ may be the same or different from each other. ) 8. An amine compound represented by the following general formula (8). Embedded image (In the formula, R ₂ and R ₃ represent a hydrogen atom, an acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₆ and R ₇ are substituted Alternatively, it represents an unsubstituted alkyl group or an acyl group.
r ₂ , Ar ₃ and Ar ₄ represent an arylene group. However, R ₂ and R ₃ , R ₆ and R ₇ , Ar ₂ and Ar ₃ and Ar ₄ may be the same or different from each other. )