JPS6270408A - Stereoregular polymer and its production - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having a high degree of charge transfer and an isotactic structure, by polymerizing a carbazoyl(9)alkyl (meth)acrylate in the presence of a specified catalyst. CONSTITUTION:At least one monomer selected from carbazoyl(9)alkyl (meth) acrylates (A) of formula I [wherein R is H or a lower alkyl and Z is an (alkyleneoxy)alkylene] is dissolved in a solvent (e.g., toluene) to form a solution of a concentration of 1X10<-2>-10<-1>mol/l and reacted at -78-50 deg.C for 1-120hr in the presence of 1-100mol%, based on component A, catalyst (B) selected from an organometallic compound catalyst (a) and a mixed catalyst (b) comprising an alpha,beta-unsaturated ketone or an alpha,beta-unsaturated ester and an organomagnesium halide to obtain the titled polymer having repeating units of at lest one kind, of formula II and an isotactic structure.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a carbazolyl (9) alkyl acrylate (methacrylate) polymer having a tactical structure and a method for producing the same. The present invention also relates to polymeric charge transporters having increased charge mobility compared to conventional polymeric charge transporters.

(Prior Art) Conventionally, poly-N-
Organic polymeric photoconductors such as vinyl carbazole are widely used. Poly-N-vinylcarbazole itself is a substance that has film-forming properties and hole-transporting properties. For example, it can be applied as a charge-transfer complex with an electron-accepting substance (Lewis acid) on a conductive substrate. coating to form a photoconductive layer;
It can be used as an electrophotographic photosensitive material, or a charge generation layer is provided on a conductive substrate, and a poIJ is formed on this charge generation layer.
-N-vinylcarbazole provided with a charge (hole) transport layer is used as an electrophotographic light-sensitive material.

(Problems to be Solved by the Invention) However, the charge mobility of polymeric charge transporters such as poly-N-vinylcarbazole is not yet sufficiently large; , it is desired to develop a polymeric charge transporter with high charge mobility.

Therefore, it is an object of the present invention to provide new polymers with high charge mobility.

Another object of the present invention is to provide a novel polymer having a carbazolyl group in its side chain and a tactical structure, and a method for producing the same.

(Another Means to Solve the Problem) The present inventors have proposed that carbazolyl (9) alkyl acrylate or methacrylate be used as an organometallic compound catalyst or α, β
- When polymerized in the presence of a combination catalyst of an unsaturated ketone or an α,β-unsaturated ester and an organomagnesium no-ride, a new polymer with a nine-tuft structure can be obtained, and this stereoregular polymer has an attack resistance. It has been found that this polymer exhibits significantly superior charge mobility compared to polymers with a tick structure.

That is, according to the present invention, a repeating unit represented by the general formula % (1), where R is a hydrogen atom or a lower alkyl group, and 2 is an alkylene group or alkyleneoxyalkylene, and A stereoregular polymer characterized by having a tactical structure is provided.

According to the present invention, it is also represented by the general formula 1 (2), in which R is a hydrogen atom or a lower alkyl group, and 2 is an alkylene group or an alkyleneoxyalkylene group. (1) organometallic compound, or (11) α,β-unsaturated ketone or α,
A method for producing a stereoregular polymer is provided which comprises stereoregular polymerization in the presence of a catalyst comprising a combination of a β-unsaturated ester and an organomagnesium halide.

The present invention further provides a charge transporter comprising the stereoregular polymer.

(Function) A novel feature of the carbazolyl (9) alkyl acrylate or methacrylate polymer according to the present invention is that it has a tactical structure.

The tactical structure refers to two types of substituents (in this case, a hydrogen atom or a lower alkyl group and a carbazolyl(9)alkyl is defined as having the same configuration along the main chain.

All conventionally known polymers of this type had an atactic structure (i.e., a structure in which the steric configuration of the two substituents around the stereoisomer described above is disordered along the main chain), but the present invention The inventors have discovered that a polymer having a tactical structure can be obtained by anionically polymerizing the above-mentioned monomers in the presence of a specific catalyst.

Therefore, the stereoregular polymer according to the present invention exhibits a charge mobility that is approximately one order of magnitude higher than that of the same type of polymer (having an atactic structure) obtained by radical polymerization, and also exhibits electric field dependence of charge mobility. It also has the characteristic that it is smaller than that of the above-mentioned atactic structure.

(Description of preferred embodiments of the invention) The invention will be explained in detail below.

Monomer The monomer used in the present invention is represented by the above general formula (2). In the general formula (2), examples of the lower alkyl group of the group R include alkyl groups having 4 or less carbon atoms such as a methyl group and an ethyl group. The group R is preferably a hydrogen atom or a methyl group. As the divalent group Z, the number of carbon atoms is 1
to 6 linear or branched alkylene groups or alkyleneoxyalkylene groups, suitable examples thereof include ethylene group, 1,3-zolopyrene group, tetramethylene group, ethyleneoxyethylene group and the like. Ethylene groups are generally preferred.

Suitable examples of monomers include, but are not limited to:

(21 flupasolyl (9)) ethyl acrylate, (
2-carbazolyl (9) ) ethyl methacrylate, (
3-carbazolyl (9) ) propyl acrylate, (
4-carbazolyl (9) ) butyl acrylate, (4
-carbazolyl (9)) ethyloxyethyl acrylate.

The above-mentioned monomer is a carbazolyl (9) alcohol represented by the following formula, in which 2 has the above-mentioned meaning, and an acrylic halide or methacrylic halide, represented by the following formula, in which X is a halodane atom. It can be obtained by reaction. The reaction can be carried out in a polar solvent such as tetrahydrofuran in the presence of a dehydrochlorinating agent such as tertiary amines such as triethylamine, pyridine, diethylaniline and the like.

The carbazolyl (9) alcohol of formula (3) is obtained by reacting carbazole with an alkali metal hydride such as sodium hydride in the presence of an aprotic polar solvent such as dimethylformamide F. is an alkali metal and a compound of the formula (6), in which X is a halodane atom, is reacted with a compound of the formula (6), where X is a halodane atom, or by reacting with a carbonate such as ethylene carbonate represented by the formula. It can be obtained by

In the present invention, in addition to using the monomer of the formula (2) alone or in combination of two or more, other acrylates or methacrylates may be used under the condition that the monomer of the formula (2) is the main component. It can be used as a comonomer. Such comonomers include monomers of the general formula %, where R has the above-mentioned meaning and R1 represents an alkyl group, such as methyl methacrylate, ethyl acrylate, inbutyl methacrylate, amyl Examples include acrylate.

Polymerization method According to the present invention, the monomers described above are combined with (1) an organometallic compound catalyst or (It) an α,β-,β-ketone or an α,β-
, stereoregular polymerization in the presence of a catalyst consisting of a combination of β-esters and organomagnesium halides. The latter catalyst is preferable in terms of stereoregularity, ie, isotufficity.

As the α,β-unsaturated ketone or α,β-unsaturated ester, in the following formula, each of R2 and Rρ is a monovalent hydrocarbon group, such as an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, p is a number of zero or 1, especially benzalacetophenone (chalcone), benzalacetone, methyl vinyl ketone, phenyl vinyl ketone, ethyl cinnamate, ethyl crotonate, phenyl cinnamate, Examples include styl oxide. In addition, as the organomagnesium halide, what is generally called a Grignard reagent is generally used with the formula % formula % where R4 is a monovalent hydrocarbon group such as an alkyl group or an aryl group, and Compounds represented by are used, especially ethylmagnesium chloride, ethylmagnesium bromide, phenylmagnesium chloride and the like.

In this catalyst system, the α,β-unsaturated carbide compound of general formula (9) and the Grignard compound of formula 01 are:
It is desirable to use substantially equimolar ratios.

In the present invention, the reason why stereospecific polymerization proceeds by using the above catalyst system has not yet been fully confirmed, but the inventors presume that it is due to the polymerization mechanism shown by the following formula as an example. are doing.

In the formula, Et represents an ethyl group, CEA represents (2-carbazolyl (9)) ethyl acrylate, R represents a 2-carbazolyl (9) ethyl group, and P represents a benzalacetophenone residue.

Although the isotuffity of the produced polymer is slightly inferior to that of the catalyst system described above, it is possible to use organometallic compounds such as propyllithium, dithyllithium, pentyl sodium, phenyl sodium, triphenylmethyl sodium, and p/tyl potassium. can.

Polymerization can be carried out in a solvent in the presence of the above catalyst.

As the solvent, aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane and isoparaffinic solvents; ethers such as ethyl ether, tetrahydrofuran and dioxane; or a combination of two or more can be used.

The catalyst is preferably added to the polymerization system in an amount of 1 to 100 mole, especially 10 to 20 mole per monomer, and the monomer concentration in the polymerization system is generally from lXl0-2 to Ix
10-' moL/l, especially 2 x 10-2 to 5
It is preferable to set it in the range of X10 movl. The temperature of the polymerization system is anionic polymerization, so it proceeds satisfactorily even at low temperatures, generally -78 to 50°C, especially -10 to 40°C.
The polymerization is preferably carried out at a temperature of 1 to 120 hours, especially 5 to 48 hours.

(Structure and Physical Properties of Polymer) The polymer according to the present invention is characterized in that it mainly consists of repeating units represented by the general formula (1) and has a tactical structure.

This polymer has R and/or among the repeating units of general formula (1).
or each of 2 may be the same or different in each repeating unit. Suitable examples of homopolymers include, but are not limited to, poly(2-carbazolyl(9))ethyl acrylate, poly(2-carbazolyl(9))ethyl methacrylate, etc.
On the other hand, an example of the copolymer is a (2-carbazolyl (9)) ethyl acrylate/(2-carbazolyl (9)) ethyl methacrylate copolymer. In addition, 10 molti or more, especially 50 molti or more of all repeating units have the general formula (1)
Repeating units consisting of conventional acrylates or methacrylates may also be incorporated, provided that the repeating units consist of repeating units of acrylate or methacrylate. In the present invention, in terms of charge mobility, at least 50 moles of repeating units are (2-carbazolyl(
9)) It is preferable to consist of ethyl acrylate units, but from the viewpoint of solubility in organic solvents, film processability, flexibility, and coating film adhesion, among the repeating units represented by general formula (1), (2-Cal-Zogryl (9)) It may be preferable to incorporate units other than ethyl acrylate units or other acrylate or methacrylate units in amounts of 10 to 80 mol.

Figure 1 shows the H1 nuclear magnetic resonance (H' NMR) spectrum of poly(2-carbazolyl(9))-ethyl acrylate, where curve A is the spectrum of an atactic polymer obtained by radical polymerization, and curve B is the spectrum of an atactic polymer obtained by radical polymerization. 1 shows a spectrum of a tactical polymer produced by the method of the present invention. From the results shown in Figure 1, in the atactic polymer A produced by radical polymerization, the area of the beak S due to the syndiotactic structure and the area of the beak 1 due to the atactic structure. While the area of I is almost the same, in the polymer with a tactical structure according to the present invention, almost no beak S due to a syndiotactic structure is observed, and the beak I of a tactical structure is overwhelmingly observed. , I.

The degree of isotactic structure in the polymer structure, that is, isotacticity (I), is expressed by the following formula, where Pl is the area of the characteristic peak due to the tactical structure of the % group in the H'NMR spectrum, and Ps is H
'Representing the area of a characteristic peak due to the syndiotactic structure of cH2 groups in an NMR spectrum.
Isotuffity of 0% or more, especially 90 or more
)t- It is desirable to have.

Polymers according to the invention should generally have a molecular weight sufficient to form a film and are generally GPC (flt9
- a number average molecular weight (Mn) of 5000 to 100000, especially 8.
It is desirable that the number be in the range of 000 to 50,000. In a polymerization system in which the produced polymer is insoluble in the polymerization solvent, the molecular weight of the produced polymer tends to be small.

FIG. 2 shows the tactical streamer (2) according to the present invention.
-Carbazolyl (9)) This is an infrared absorption spectrum of ethyl acrylate, with a wave number of 172, which is unique to acrylate.
A characteristic absorption peak at 0 m-' and a characteristic absorption peak at a wave number of 755.725 m-', which is unique to the carbazolyl group, are observed.

The glass transition point (Tg) of the polymer of the present invention varies depending on the type of repeating unit and molecular weight, but is generally in the range of 90 to 920°C, particularly 95 to 110°C.

Figure 3 shows the X-ray diffraction image of poly(2-carbazolyl (9)) ethyl acrylate using α-rays for Cu-, where curve A is the diffraction image of an atactic polymer obtained by radical polymerization, and curve B is the diffraction image of the atactic polymer produced by the radical polymerization method. 1 shows a diffraction image of a tactical polymer according to the invention. From FIG. 3, it is understood that the polymer according to the present invention has a diffraction peak at 2θ=4.2 degrees and is crystalline. Generally, poly(2-carbazolyl(9)
) Methacrylate polymers such as ethyl methacrylate have a higher degree of crystallinity than corresponding acrylate polymers because they have a methyl group in the α-position. Of course, the crystallinity of the polymer of the present invention can be increased by heat treatment, or can be reduced by supercooling from a molten or softened state.

Since the polymer according to the present invention is soluble in an organic solvent, it can be used in the form of a solution in an organic solvent for film formation or coating film formation. Examples of such organic solvents include halodated aromatic hydrocarbon solvents such as chlorobenzene and 0-diclobenzene; 710rn aliphatic hydrocarbons such as chloroethane and chloroform; and nitrated aromatic hydrocarbon baths such as nitrobenzene. Examples include dimethyl sulfoxide.

The carbazolyl group-containing acrylate or methacrylate polymer having a tactical structure according to the present invention exhibits a charge mobility that is about one order of magnitude higher than that of the same type of polymer having an etantic structure.

Table 1 below shows that a layer of a carbazolyl group-containing polymer is provided on a conductive substrate, and a charge generation layer of selenium is provided on the conductive substrate. The results of measuring the charge (hole) mobility of the coalescence are shown.

Table 1 1.0X1051.0X10-5 4.0X1054.9X10-5 poly-CIEA 5 (a t a) *32-0 ×10 3.0 ×10
-'PVK" 2.0X105 4.0X10-
'NIPC/PC*52.0X1054.0X10-7
*1) Poly(2-carbazolyl (9)) ethyl acrylate, *2) Tactical structure, *3) Etantic structure, *4) Poly-N-vinylcarbazole, *5) N-1 Soprovir Carpa Sol, polycarbonate dispersion system.

The results in Table 1 show the surprising fact that the atactic ink structure exhibits a charge mobility that is completely one order of magnitude higher than that of the atactic structure. Furthermore, it becomes clear that the stereoregular polymer according to the present invention exhibits a charge mobility that is two orders of magnitude higher than that of polyvinylcarbazole (PVK). The carbazolyl group density of PVK is 5.2 m-mo&♂, whereas the i of the present invention
Since the carbazolyl group density of go-Po 1y (CFJA) is rather low at 3.8 m-mo[7-, it is clear that the above improvement in charge mobility is unexpected.

FIG. 4 is a diagram showing the dependence of charge mobility (μ) on electric field (E), where curve A is for ata-PCEA and curve B is for iao-PCgA. This result reveals the fact that the polymer according to the present invention has less electric field dependence of charge mobility (μ) than that of the polymer having an atactic structure.

Next, FIG. 5 shows the fluorescence spectrum of PCEA in a film state, where curve A is for ata-PCF, A, and curve B is for 1so-PCEA. In these spectra, excimer emission, which is considered to be a deep trap, is not seen in the range of 380 to 450 nm. In particular, 1so-PCEA has luminescence around 500 nm that is not observed in ata-PCgA, but this is due to the -0-! This is probably because the carbazole group, which is a chromophore, is spaced regularly and sufficiently far from the main chain.

The electric field/temperature dependence of charge mobility in a photoconductive polymer is shown by the following formula.

μ=μ. expC-(To/'l')2]exp(FA
o) −(13T = σ ・・
・・・・・・・・・(13a)E = (σ/2Beρ)(T
/T ) --... (13b) K = 7400
k/eV ---(13e)B=0.15
・・・・・・・・・ (13d) In the formula, μ
is the charge mobility of a system without disordered states, σ is the width of the Gaussian site energy density distribution of states, 1, B is a constant that averages whittling in all directions, and ρ is the site energy The distance between

FIG. 6 shows the results of determining the temperature dependence of charge mobility for 1so-PCEA and examining the electric field dependence of the apparent T, which is the slope thereof. From the slope of this straight line in Figure 6, KBe
-crnlv is obtained at ρ = 9.8 x 10-5,
Since the distance between sites of this polymer is ρ=7.351, a value of B=0.18 is obtained. It can be seen that this value is very close to B=0.15, which is calculated from the theoretical formula. Also, T from the intercept of the graph in FIG. =538°K
was obtained, and from this a value of σ" 0.073 eV was obtained. This is the value of σ" for an actuic polymer.
``This is a lower value compared to 0.128 eV.

From these facts, the reason why the charge mobility of the tactical polymer at room temperature is higher than that of the active polymer is due to the stereoregularity of the polymer main chain and the high degree of alignment between the polymers. The reason for this is thought to be that the width of the density of state distribution of site energy is small, and therefore the temperature dependence of charge mobility is reduced.

Applications The tactical polymer according to the present invention can be used in applications such as electrophotographic light-sensitive materials or solar cells by utilizing the above-mentioned excellent charge transport properties.

The electrophotographic light-sensitive material of the present invention may have any layer structure and composition as long as it satisfies the condition that it includes a layer containing the above-mentioned tactical polymer.

For example, the polymer is electron donating in nature;
It is used as a photoconductive layer in the form of a charge transfer complex with an electron-donating substance. Appropriate examples of electron-accepting substances)! , 2-nitro-
9-fluorenone, 2,7-sinitro-9-fluorenone, 2,4.7-) dinitro-9-fluorenone, 2
, 4,5.7-tetranitro-9-fluorenone, 2-
Nitrobenzothiophene, 2.4.8-)linitrothioxanthone, dinitroanthracene, dinitroacridine, di-0anthraquinone, and the like. The blending ratio of the isotactic polymer of the present invention and the electron-accepting substance is preferably 1:0.1 to 1:1 by weight. Further, the thickness of the photoconductive layer is preferably 5 to 50 mm.

The conductive substrate on which this photoelectric layer is provided is a sheet or drum-shaped metal foil or plate made of aluminum, copper, tin, tin, etc., and these metals are used to form a film such as biaxially stretched polyester film. Those applied to the substrate, glass, etc. by means such as vacuum evaporation, sulfate ring, electroless plating, etc., NESA glass, etc. are used.

In another aspect of the invention, a charge generating pigment is dispersed in a charge transport medium comprising the polymer described above, and the composition is provided as a photosensitive layer on a conductive substrate.

As the charge-generating pigment, organic or inorganic photoconductive pigments which are known per se can be used. Among the pigments of Cholera, phthalocyanine pigments, perylene pigments, quinacridone pigments, pyranthrone pigments, disazo pigments,
It is desirable to use photoconductive organic pigments such as trisazo pigments alone or in combination of two or more. The charge generating pigment is 1 to 30 parts by weight per 100 parts by weight of the charge transporter;
In particular, it is preferable to use it in an amount of 4 to 20 parts by weight.

The thickness of this coating layer is preferably 5 to 50 microns on a dry basis.

According to another aspect of the present invention, a charge generation layer containing the charge generation pigment described above is provided on a conductive substrate, and a charge transport layer containing the tactical polymer described above is provided on the charge generation layer. establish. The charge generation layer may be formed by vapor depositing the charge generation pigment described above on a substrate, or may be formed by coating and drying a mixture dispersed in a suitable organic solvent.

Alternatively, the composition may be formed by coating a conductive substrate with a composition in which a charge generating pigment is dispersed in a binder resin.

The thickness of the charge generating layer can vary from O,X microns for vapor deposition to 3 microns for resin-pigment dispersions, while the charge transport layer preferably has a thickness of 5 to 30 microns.

In the electrophotographic photosensitive material of the present invention, in addition to using a tactical polymer alone as a charge transporter, a tactical polymer derived from a polyester resin, especially bisphenols, and terephthalic acid and/or isophthalic acid is used for the purpose of reinforcing the film. A polyester resin can be blended with this and used. That is, the polymer of the present invention has good compatibility with these reinforcing polyesters. Month? The realester may be blended in an amount of 0.1 to 0.3 parts by weight based on the polymer.

The charge transporters of the present invention can also be used as a component of photoconductive toners.

That is, a charge transport complex is produced from the charge transporter of the present invention and an electron-accepting substance in the same manner as described above, and this charge transport complex is granulated into a toner. Alternatively, a composition is prepared in which a charge generating pigment is dispersed in the charge transporter of the present invention, and this composition is granulated.

In the case of solution-based granulation from these complexes or compositions, toner can be formed by methods such as spray granulation,
In the case of a melt-kneaded product, the toner can be manufactured by a pulverization and granulation method. In this case, if necessary, a styrene resin, acrylic resin, etc. may be added as a component to enhance fixing properties. The particle size of the toner is generally in the range of 5 to 35 μm, particularly 10 to 20 μm.

Furthermore, this charge transporter can be used for applications such as solar cells by dispersing charge generating pigments therein.

(Effects of the Invention) According to the present invention, an acrylate or methacrylate polymer having a carbazolyl alkyl group in a side chain and a tactical structure has been provided for the first time. This new polymer exhibited charge mobility that was one order of magnitude higher than that of the atactic structure, and the temperature dependence of charge mobility was also small. Therefore, extremely high sensitivity can be obtained when this charge transporter is used as an electrophotographic photosensitive layer or a photoconductive toner.

Example The invention is illustrated by the following example.

Example I Synthesis of N-(2-hydroxyethyl)carbazole Carbazole (50!L) was dried rw (500Tn
l). Hydrogenate this for 1 hour while cooling with water and stirring. Add IJum (so, p) little by little. After addition, stir further for 3 hours. Ethylene bromohydrin (300 d) was added dropwise to this over 2 hours, and the mixture was stirred for 1 day and night. To this solution, add ethanol (20
0 ml of the solution was added to stop the reaction, and the solvent was distilled off. The residue was purified by silica column chromatography (eluent: benzene, ethyl acetate). Yield 60 cm, p 82°C (literature value 81-82°C) Synthesis of (2-N-carbazolylethyl)acrylate N-(2-hydroxyethyl)carbazole (220,
9), hydroquinone (2,2,9), and triethylamine (200m) are dissolved in tetrahydro7ran (1/). Tetrahydrofuran (50%
Acrylic acid chloride (10
o1 was added dropwise over 3 hours. After stirring for one day after dropping,
The reaction solution was filtered and the solvent was distilled off. The residue is recrystallized from ethanol to obtain the desired product. Yield: 92 cm. It was further purified by silica dal chromatography (eluent: benzene).

m, p, 75°C (Literature value *74-75°C) Synthesis of tactical poly N-(2-carbazolylethyl) acrylate Preparation of zero catalyst Under high vacuum (10”-3 mHg or less) in a vacuum angle ,
EtMgCtl, 4 mol/l, diethyl ether solution (1d) was added dropwise to chalcone (0,31) dissolved in anhydrous diethyl ether (9III).

0 polymerization under high vacuum (10-3aug or less) in a vacuum ampoule, 2-
Dissolve N-carbazolylethyl acrylate (0.5g) in anhydrous toluene (5rLl), keep at 30°C, add catalyst solution (2-), shake vigorously for 5 minutes and keep;
Leave it for a day. This solution was poured into methanol (4 omJ) and the precipitated polymer was reprecipitated three times in a chlorobenzene-methanol system.

Yield 0.2F (40 yen) Weight average molecular weight Mw by GPC = 5. OX 10 Tg=110.3℃ GPC condition temperature: 35℃ Welding: CFCl2 Flow rate: 1mVmin Concentration: 10Tny10.5WL7ICHCt3 Injection amount: 10rn9 Standard: Polystyrene standard column: TSK G-5000H6-03000
I (8 Example 2 Synthesis of (2-N-carbazolylethyl) methacrylate N-(2-hydroxyethyl)carbazole (220,
9), hydroquinone (2.2 g), and triethylamine (200 ml) are dissolved in tetrahydrofuran (11). While stirring this under water cooling, tetrahydrofuran (500
Chloryl methacrylate R (1101) dissolved in ml) is added dropwise over 3 hours. After stirring for 1 day after the dropwise addition, the reaction solution is filtered and the solvent is distilled off. The residue is recrystallized with ethanol to obtain the desired product. 94 samples were obtained.It was further purified by silica dal chromatography (eluent: benzene).

m, p, 77℃ (literature value *77-78℃) Car C, 1,
Slm1onesc +Polymer+ 21 +
417 (1980) Aitsu Tactical Poly N-(2
- Synthesis of carbazolylethyl) methacrylate O Preparation of catalyst EtMgCt1.4 mol/l in a vacuum ampoule under high vacuum (below 10''+mnHg) - Diethyl ether solution (11 nl) of chalcone (0,35J7) (9-) was added dropwise to the solution.

0 polymerization under high vacuum (10-3 mmHg or less) in a vacuum ampoule (
2-N-carbazolylethyl) methacrylate (0,5
Dissolve g) in anhydrous toluene (5-), maintain at 30°C, add catalyst solution (2 ml), mix vigorously for 5 minutes, and leave for 1 day. This liquid was poured into methanol (40-) and the precipitated polymer was purified by reprecipitation three times in a chlorobenzene-methanol system.

Yield 0.18136chi) The IR spectrum of this polymer is shown in FIG.

Example 3 1so-poly-(2+cal/J
Zolyl-N+ethyl acrylate) has sufficient film-forming ability when applied, for example, with a chlorobenzene solution. A mixed solution of 2 g of 1so-poly-(2+carbazolyl-N+ethyl acrylate) and 2 (l) of chlorobenzene was applied onto a conductive Nesa glass (aluminum plate, etc.) and dried to produce a single layer of polymer with a thickness of 15 cm. Furthermore, on top of this a
A thin layer of −8e was vacuum-deposited to a thickness of 05 μm, and then Au was deposited to a thickness of 1000× to form an electrode.

2×105v/c on this sample side so that the Se side is positive.
While applying a constant electric field of rn, pulses of monochromatic light of 435 nm with sufficiently high intensity are irradiated from the positive side to generate carriers, and the mobility μ (v
J7sec) was measured. The result was 1.7 x 10' Vcn12/see at room temperature 25°C.

As a comparative example, the μ value measured for poly+N vinylcarbazole) was 4×10−7% m27 sec, indicating that the iio $+2−(carbazolyl-N+ethyl acrylate) had a mobility about 40 times higher.

Also, ATA is 5.7 times higher than PCEA.

Example 4 1.29 of this iso poly+2-(carbazolyl-N+ethyl acrylate) IL TNF (2,4,7-)linitrofluorenone) is dissolved in 1 OIl of chlorobenzene. This solution was applied onto an 80 μm thick aluminum foil plate using a doctor blade and heated to 40°C.
After drying for 1 hour at 40° C., vacuum drying was performed for 5 hours to obtain an electrophotographic photoreceptor with a thickness of 10 μm. This photoreceptor was manufactured using commercially available E, P, A (electro 5tatic
A corona charge of -6 kV was applied using a paper analyzer Jl Model 5P-428 (manufactured by Old Denki Co., Ltd.), and then light (white light) from a 20 Lux tungsten bulb was irradiated to examine the attenuation of the surface potential. Here, E1/2 (LlI!'8ee, half-reduced exposure amount) was selected as the photosensitivity.

Charge amount -600v g1/2 6.5 Lux-mec Example 5 ISO poly(2+carbazolyl-N
+ ethyl acrylate) was formed to a thickness of 10 μm on an aluminum substrate to form a charge transport layer. Then the Se on this layer is 0
．． A charge generation layer was formed by vacuum evaporation to a thickness of 3 μm. The electrostatic charge amount and half-decreased exposure amount of the thus obtained laminated electrophotographic photoreceptor were measured by applying +3 kV, and the results are shown below.

Charge amount: +900v FJ172 0.5 Lux, see From this result, it was found that it had very excellent sensitivity.

Example 6 Iso poly+2-(carbazolyl-) obtained in Example 1
N+ethyl acrylate) 1g, Cu-phthalocyanine pigment (Tokyo Kasei Co., Ltd.) 0.1,9.
liogen Red 4120. C, 1,7113
Company 0B, A, S, F a) o, xg, chlorobenzene 10
．． 9 was dispersed and mixed in a Zeel mill for 10 hours.

This mixed solution was applied onto an 80 ttm thick aluminum foil plate using a doctor blade, dried at 40°C for 1 hour, and then vacuum dried at 40°C for 5 hours until the thickness was 10 μm.
An electrophotographic photoreceptor was obtained. The photosensitivity of this photoreceptor was determined in the same manner as in Example 3, and the results were as follows.

Charge amount +6kV 500V E1/2 4-OLux-see Example 7 On an aluminum foil plate with a thickness of 80 IIm, metal-free phthalocyanine pigment (Tokyo Kasei Co., Ltd.) was applied as a charge generation layer to a thickness of 0.5 μm. The iso poly+2+carbazolyl-N+ethyl acrylate-)) IJI chlorobenzene 10. obtained in Example 1 was vacuum deposited on the aluminum foil plate having the charge generation layer. ? A mixed solution was applied using a doctor blade, dried at 40°C for 1 hour, and then vacuum dried at 40°C for 5 hours to form a charge transport layer with a thickness of 10 μm. This laminated photoreceptor was tested in the same manner as in Example 3, and the results are shown below.

Charge amount -6kV -800V F'1/2 2. OLux°5llc! Example 8 A negative corona discharge was applied to the photoconductor produced in Example 6.
'f, After performing this, a positive original (an image is formed on a transparent film) with the photoreceptor surface illuminance 80 Lux.
It was exposed to light for 1 to 2 seconds, then developed using a positive two-component developer (developer for DC-15 manufactured by Sanda Kogyo Co., Ltd.), and then printed on plain paper (90 mm thick). When the image was transferred to paper and heat-fixed, it was possible to obtain a fog-free, high-contrast copy that was faithful to the original.

Example 9 bso poly+2-(carbazolyl-) obtained in Example 1
The test was carried out in the same manner as in Example 7, except that the following polymer obtained by the same reaction was used instead of N+ethyl acrylate). The results are shown below.

R charge amount E1/□ -CM -6kV 780 V
2.5 Lux・sae-CL -6kV
750V 2.3 n-0CH-
6kV 800V 2.7 II
Example 10 Poly-(2-(calczolyl-N) obtained in Example 1
+ ethyl acrylate) to prepare a photoconductive toner according to the following formulation.

The above solution was mixed in a sol mill, dried by spray drying, and pulverized to obtain a photoconductive toner having a particle size of 5 to 20 μm.

Next, 80 aluminum foil plates were prepared as a conductive substrate, and a developing container with an 80-mesh mesh screen (made of brass) installed at the bottom as a developing device was installed so that the distance between the substrate surface and the mesh screen was 1. Both were installed so as to face each other with an interval of 0 m. The developer container is filled with the photoconductive toner, and it is confirmed that no toner leaks below the mesh screen.

Subsequently, as shown in FIG. 8, an aluminum substrate 2 is provided on the support 1, a DC bias voltage 3 of -200V is applied to the substrate 2, and a voltage is applied between the mesh screen 5 and the aluminum substrate 2. 100) (z When an AC voltage 8 of 1000 V, p was applied, the toner 6 was applied uniformly and as a very thin layer onto the aluminum substrate 2 by the coating mechanism 4. At this time, the toner 6 was applied to the aluminum substrate 2 by the stirring mechanism 7. ) The aluminum substrate 2 is triboelectrically charged in advance to have a polarity opposite to that of the aluminum substrate 2.

After that, a toner image is formed by image exposure, plain paper is placed on top of the toner image, and a negative electrode is charged from the back side of the paper to transfer the toner. When heat fixation is performed, a clear image with no background fog is obtained. Obtained.

Example 11 Synthesis of a tactical copolymer of 2-(carbazolylethyl)acrylate and methyl acrylate Preparation of O catalyst Et in a vacuum ampoule under high vacuum (below 10"" mHg)
MgC21,4moIVl, diethyl ether solution (1
ml) was added dropwise to a solution of chalcone (0.35 g) in diethyl ether (9d).

0 copolymerization in a vacuum ampoule under high vacuum (10""m Hg or less), (
2-N-carbazolylethyl)acrylate (0,5F
) and methyl acrylate (0,02,!i') were dissolved in anhydrous toluene (5 ml) and kept at 30°C.
/), shake vigorously for 5 minutes, and leave for 1 day. This solution was poured into methanol (40 mJ), and the precipitated polymer was purified by reprecipitation three times in a chlorobenzene-methanol system.

Yield 0.22 g (42 cm) Weight average molecular weight by GPC Mw = 5.5 x 10' Tg = 108.6°C GPC condition temperature: 35°C Solvent: CHCl3 Flow rate: 1 wLl/min Concentration: 10'70.5 m7 CHCt5 injection amount
= 10 ■ Standard: Polystyrene standard column: TSK G-5000H6-G-30
00H8 43 - Example 12 Copolymer of 2-(carbazolylethyl)acrylate and methyl acrylate The following copolymer was prepared in the same manner as in Example 5. The results are shown below.

nm MwX10' Charge amount
E1 no 291 9 5.5 -6kV -81
02,578224,8-6kV -8333,6

[Brief Description of the Drawings] Figure 1 shows the tactical and atactic structures of poly(2-carbazolyl(9))ethyl-44-44- Figure 2 shows the tactical-poly(2-carpaso-IJ) 9)) A diagram showing the infrared absorption spectrum of ethyl acrylate. Figure 3 is an X-ray diffraction diagram of poly(2-carbazolyl(9)) ethyl acrylate with a tactical structure and an atactic structure. A diagram showing the electric field (E) dependence of the charge mobility (μ) of poly(2-carbazolyl(9))ethyl acrylate with a tactical structure and an atactic structure. Figure 6 is a diagram showing the electric field dependence of the T0 value of tactical poly(2-carbazolyl (9)) ethyl acrylate. 8 is an infrared absorption spectrum diagram of tactical poly(2-carbazolyl(9))ethyl methacrylate, and FIG. 8 is an explanatory diagram showing the image forming method of Example 10 using the photoreceptor of the present invention.

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R is a hydrogen atom or a lower alkyl group, and Z is an alkylene group or alkyleneoxyalkylene. A stereoregular polymer characterized by having an isotactic structure. (2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼In the formula, R is a hydrogen atom or a lower alkyl group, and Z is an alkylene group or an alkyleneoxyalkylene group.At least one monomer represented by The steric monomers are sterically synthesized in the presence of (i) an organometallic compound, or (ii) a catalyst consisting of an α,β-unsaturated ketone or a combination of an α,β-unsaturated ester and an organomagnesium halide. A method for producing a stereoregular polymer comprising regular polymerization. (3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R is a hydrogen atom or a lower alkyl group, and Z is an alkylene group or alkyleneoxyalkylene. A charge transporter consisting of a stereoregular polymer with a structure.