JPS62127321A - Novel carbazole substituted polysiloxane - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Technical Field) The present invention is directed to a new type of polysiloxane having a carbazole group, and the solid layer having an elemental 11E4 structure formed by using this fL is For example, it can be used in electrophotographic recording materials. Accordingly, the present invention also relates to materials, especially electrically conductive layers, and electrophotographic recording materials manufactured using the V7n polysiloxane according to claims (1) to □□□. This is the target.

(Prior Art) Polymer-containing solid layers containing organic compounds are used in electrophotographic recording materials, especially in copy films or photographic offset plates. Various materials have been proposed for its creation. In this case, it is preferable to cool the photoconductive solid layer together with a photosensitive compound that has a sensitizing effect on the photoconductive solid layer. In order to impart spectral sensitivity to the base conductive compound, a spectral sensitizing organic dye, for example, can be added to the base conductive layer. This original VC layer is a sensitizing compound that should be used as a sensitizing compound.
1- forms charge carriers by absorbing the radiation irradiated on the first layer of the 9'124 layer, and with the help of the externally added 9'124 field, the above 'turquoise' Organic dyes or organic pigments that can transfer carriers to electropolymer compounds are also included in category 7). Depending on the type of this sensitizing sensitizing compound used and the field of application of the source from conductive to electrophotographic recording materials, the sensitizing effect of the sensitizing compound may be unequal or negative. It will be held in

In the case of a uniformly sensitized 24-layer injection layer, the Motoki exclusive organic compound and the sensitized photosensitive organic 1-layer are mixed with each other evenly, and in some cases, with lees aggregation, they are mixed into the intervening layer. exist(
? (Refer to specification No. 58836).

In the case of heterogeneous sensitization, the jt'4 conductive layer is composed of multiple layers, especially two layers, in the so-called m-layer structure technology, the seventh and eleventh layer containing the sensitizing sensitizing compound and its The second layer disposed on top contains a xi4 organic compound. Such a multilayer #II release of the Yuryudo River Formation is dedicated in 6 volumes in the Sei-toku Keidekitsune Publication No. 222Ll No. 408.

This known photovoltaic organic compound can be used as an organic compound, or as an organic compound when added to
An example of this is IJ-N-vinylcarbathyyl, which is highly recommended. -N-vinyllupazole transfers the fL charge together with Lewis acids, especially 2,4,7-dorini-10-9-fluorinone.
Hey °S It is convenient to use as a punishment for the former law class.
if2 L. However, in addition to poly-N-vinylcarbanol or other compounds containing carbazole groups, organic dyes or organic pigments can be added as the main component. (9), which led to the creation of optomagnetic 4
Note: The spectral sensitivity of the carbazole compound is increased and/
Alternatively, it can be used for compounds formed as charge carriers.

The prior art in this regard includes, for example, European Patent Application Publication No. tJLlbltJ88,
89, 061092, 0131215, and West German Patent Application Publication No. 321337.

However, one of the major drawbacks of poly-N-vinylcarbazole mentioned above is that it is fragile when exposed to temperature. The solid layer formed from poly-N-vinylcarbazole (note by Hirohiro Mitsuru) is hard, lacks insensitivity, and has no resistance to crack formation. It has weak adhesion to the metal that is commonly used as the Terakamoe holder of Isso's γ Koy). In order to avoid such drawbacks, various types of OT plastics are added to the Wonguanjinjie layer containing poly-N-vinylcarbazole as the main component, and the layer is bonded to a metal carrier using a plasticizer. Attempts are being made to layer them. However, both of these methods have the disadvantage that they considerably impair the customization of the electrophotographic recording materials produced by the upper BC layer. However, even if a low molecular weight carbazole group-containing compound is used as a conductive agent (for example, see West German Patent Application Publication No. 3208337),
There is an increasing demand for materials that cannot provide satisfactory photoconductive solid layers.

Based on the above, one technical problem to be solved by the present invention in this packaging is that it exhibits good contact force to the metal carrier material without compensating for the need for fancy photoelectric cables. Katora Note, Durable Photoelectric 24 Note Formation, Genden 4fi
The goal is to develop a beautiful front-to-back proboscis.

Other technical problems in history have been solved by non-invention.
``It is a combination of electronic and electronic materials that exhibits excellent photoelectric properties, especially scorchability, durability, good adhesion to metal carriers, and electronic The first step in the preparation of photographic recording materials is to develop a photoelectric solid layer.

(Summary of the Invention) The technical problem υ) above is basically solved by the novel polysiloxane of the present invention containing laterally packed carbazole groups, which are also bonded laterally to the carbazole groups. By using polysiloxane as a base TIL24 organic compound and adding an organic dye or organic pigment as a photosensitive compound that has a sensitizing effect, a second layer of siloxane can be obtained. Technical issues must also be resolved.

The subject of the invention is therefore 'c1111' for the polymer backbone.
It is a polysiloxane containing 1,000-bonded carbazole groups.

Furthermore, a conductive solid layer formed of a polysiloxane having a carbazole group located on the side thereof is also a subject of the present invention.

In the photoconductive solid layer formed from a photoconductive compound and a photosensitive compound that sensitizes the photoconductive compound, the photoelectric field compound is bonded laterally to the polymer main chain. Polysiloxane containing carbazole group 1
A photoconductive solid layer containing an organic dye or organic pigment as the sensitizing compound is also a subject of the present invention.

Furthermore, an electrophotographic recording material comprising a tetraelectric carrier and a photoconductive layer formed thereon containing the polysiloxane according to the invention is also a subject of the invention.

(Structure of the invention) A specific configuration of the present invention will be described below.

The novel carbazole group-containing polysiloxanes according to the invention and the novel photovoltaic injection solids Ifi formed using the same are distinguished by a very good combination of advantageous properties. It only has a deep strength that can be compared to poly N-vinylcarbasol.
It can be formed into a combustible, non-brittle material that exhibits good access to metal surfaces. Therefore, the above-mentioned polysiloxanes in stock can be used, for example, in copying technology or electronically.
It is advantageously used in the production of photoconductive layers to be used in true printing plates and electrophotographic recording materials. The polysiloxane-containing light 1! When formed by a conductive layer, its read cycle stability is also compromised by its read cycle stability, ie, not exhibiting any plate pairing despite repeated use (multiple charging and discharging cycles).

The polysiloxane of the present invention has a polysiloxane backbone chain consisting of a siloxane repeating unit (-Sl-O+), and a carbazole group is bonded to the side of its 81 atoms (-1')). The carbazole group may be substituted, but it is preferred that the polysiloxane has a non-direct carbazole group. The carbazole group can basically be bonded to the polysiloxane main chain at any position, but the carbazole group may be introduced to the polysiloxane main chain at the N atom between them, for example via an alkylene intermediate group. That's preferable.

The molecular weight of the carbazole group-containing polysiloxane according to the present invention is determined by the molecular weight of the main chain of the polysiloxane, which basically depends on whether it can be accommodated in a wide range of rotations. It is preferable to choose a thick one. Particularly suitable polysiloxanes have a 700 uniformity (number average) in the range of about 40 to about lυυ (or even more than 0), i.e., a main chain with a number average of about 40 to about 40 ILI.
IJ siloxane units or more, +: 51
Polysiloxanes that are scratched from -0→ are preferred.

The non-inventive Carleno (sol group-containing polysiloxane) which acts as the primary moiety that forms the photoconductive solid layer is actually the 81% of the polysiloxane backbone.
If all or some of the atoms are σ)9111℃
Can it combine with a residue containing carbazole? Such polysiloxanes contain at least 40% of their siloxane repeat units, preferably 8tJ-LL)(J
% is bonded with side-bonded carboxyl groups and is advantageously 0°C. The terminal groups are stored separately at 5lI of the polysiloxane main chain.
When the carbazole group of IA is not bonded to the lateral carbazole group, the other 81 atoms that do not contain a carbazole group in the siloxane main chain are generally other It is preferable to cause a reaction, for example, a crosslinking reaction, and to have a 1000-metre foil annotation.

In accordance with the present invention, a 9'Itn solid layer, etc. The 7% carbazole group-containing IJ siloxane manufactured by No. 4 is:
It may be solid at room temperature or may be highly viscous to viscous. If the degree of unity of the polysiloxane main chain forming the basis of the polysiloxane according to the invention is still low, then v
The products produced are solid at room temperature, or at least highly viscous, and as the viscosity decreases, the viscosity also decreases. Similarly, the state of the polysiloxane according to the present invention at room temperature depends on the alkylene intermediate group (spacer) present at the part where the carbazole group is bonded to the polysiloxane main chain, and the longer this alkylene intermediate group, the lower the viscosity. However, in this structure, the glass transition point of the carbazole group-containing polysiloxane of the present invention is reversed.

In the solid polysiloxane according to the invention at room temperature below 9°C, the intermediate alkylene group between the carbazole still chain group and the polysiloxane main chain is of very short chain length.

The polysiloxanes according to the invention, which are solid at room temperature (°C), form conductive solid layers that are directly transparent and non-brittle in an advantageous manner. Hey, the S of the polysiloxane main chain
Preferably, the t atom is bonded to a carno(sol)-containing side residue, but some 8 in the polysiloxane backbone is
One atom contains a carno (but not a sol group), which is generally and preferably also bonded with a group active in other reactions, such as crosslinking reactions. Original % injection prepared from polysiloxane
The polysiloxane has excellent adhesion to the metal surface, and this can be improved by reducing the number of 5t-H bonding moieties in the polysiloxane.

For example, solid polymer bond cutting is used to form a solid layer of a non-brittle material from the carboxyl group-containing polysiloxane of the present invention which is viscous or highly viscous at room temperature. Therefore, it is necessary to incorporate a highly viscous polysiloxane containing a polysiloxane or a heavy viscosity carbazole group. However, in order to form a non-brittle layer from carbazole group-containing polysiloxane with V5 or high viscosity at the lowest temperature, it is necessary to '! It is advantageous to use polynoroxanes which, in addition to the siloxane repeating units σ], also contain some siloxane repeating units υ) which provide active groups for other reactions. For example, boria 0-
Examples include a hydrogen atom, an epoxide group, an isocyanate group, an olefin, an olefin, and a similar type thereof, which are attached to the Sl atom in the main chain of 1-+j. Original'-2
Because of the formation of 4-functional solids, other active groups may be added in addition to the 4-functional solid group. is added to form one layer, and then the polysilokibane group is reacted in whole or in part while further crosslinking and bonding are carried out. In the case of viscous or highly viscous carbazole-containing polysiloxanes, where this is relevant for the formation of structured solid IT-conducting layers, the number of active groups in the layer formed from such polysiloxanes is It must be large enough to allow sufficient crosslinking and curing.

- a viscous or highly viscous polysiloxane containing carbazole groups with at least (7.5%, preferably at least 1%) of siloxane repeating levels with reactive, especially crosslinking active groups! The upper limit of the content of such active groups in the highly viscous lateral carbazole group-containing polysiloxane is that the viscosity of the lateral carbazole group is sufficient to give the layer a constant photoelectric property. The number of carbazole groups present in the polysiloxane should be determined by the number of carbazole groups present in the polysiloxane. The carbazole group-containing polysiloxane preferably contains no more than about 2 υ% of siloxane repeating units having active groups of this type.

According to the present invention, when constructing a VC-permeable viscous to highly viscous carbazole group-containing polysiloxane to form a highly elastic primary conductive solid layer, the active groups of the polysiloxane are
They can be reacted with each other directly, as in the case of dime bonds which can be combined, or via crosslinking agents. As a crosslinking agent,
For example, a compound having two or more olefinic bonds,
In other words, diol or polyol, diamine or polyamine, dicarboxylic acid or polycarbonate, di- or polycarbonate (7) cyclic anihydride, and the like can be considered, and the type of this bridge 41 is known. It depends on the type of active group as shown below.

In particular, the carbazole group-containing polysiloxane produced by Fuensen, which is to act as a photoconductive compound for forming the photoconductive solid layer according to the present invention, has a siloxane repeating unit represented by the following formula (1). It is advantageous to be able to do so.

1) In the above formula, R is particularly an alkyl group having 1 to 6 carbon atoms; and n means an integer of 2 or more. In the siloxane repeating unit of the general formula (1), C and R particularly mean methyl or ethyl, with methyl being preferred. The carbazole group in the siloxane line return unit of general formula (1) is advantageously unsubstituted, ie R1 and BM each represent hydrogen. Preferably, a denotes an integer in the range from 2 to 22, particularly preferably an integer in the range from 3 to 11.

The cassibazole group-containing polysiloxane according to the present invention is
Although it may be composed virtually entirely of siloxane units of general formula (1), with the exception of the terminal groups, other siloxane units, namely -i of formula (It) below VC1 Contains the 4L position in the porinloxane chain-! You can also do roto. When element 1 is a conductive compound for forming the IL-conductive solid layer according to the present invention, polysiloxane containing lateral carbazole groups is particularly suitable, and l
k is advantageous, which means that the equation (1
) consisting only of the Shiro Sensun Neregaeshi unit;
In addition to the siloxane repeating unit of the general formula (1) excluding the terminal group, it also includes other siloxane repeating units, especially those containing some units attached to the general formula side in the violet polysiloxane chain. .

R1 in the siloxane repeating unit of the general formula (
In addition to that of 1), it has the same meaning as T and means an alkyl group, especially an alkyl group having 1 to 6 carbon atoms, such as methyl or ethyl, especially methyl. It is preferable. R4 means, in the siloxane monomer units of the general formula III), residues containing crosslinkable active groups, such as vinyl groups, (meth)acrylate groups, incyanato groups or epoxy groups, and in particular hydrogen. .

Particularly preferred carbazole group-containing poly/romopuns according to the invention, excluding the terminal groups, have the general formula (1)
It contains only 70 xane repeating units, and optionally siloxane repeating units of the general formula Gl). In this preferred carbazole group-containing 70 xane, the siloxane repeating units of general formulas (1) and (il) are combined in a molar proportion of 0.4 to 12 tJ, 6 to υσ], and this yoke v5 is IJ , 8 to l: 0.2 to O
It is preferable for the length. The molar ratio of Q) is expressed by the general formula (1
) and proviso that the amount of valley repeating units is shown relative to the total amount of 70 xane repeating units. The most preferred polysiloxane of the present invention is composed of only the polysiloxane of the general formula (1) excluding the terminal groups, and the symbol n in the plate is particularly a number not exceeding 5, such as 3, 4 or 5, it includes polysiloxanes that are solid at room temperature. Furthermore, the repeating unit of general formula (1) excluding the terminal group is 80 to 99.5 moles,
- The repeating unit of Makini G[) occupies tJ, 5 to 20 mol%, and the number n in general formula (1) does not exceed 5, and R4 in general formula (11) Particularly preferred are polysiloxanes that are solid at room temperature (°C) when hydrogen is meant. Also suitable are polysiloxanes of the present invention which are viscous or partially active at room temperature and have about 80 to 99 mol% of the repeating units of the general formula (1) excluding the terminal groups, and about 20 mol% of the repeating units of the general formula (0).

Such a 1411-chain carbazole group according to the present invention is
The polysiloxanes described above are manufactured by methods which are themselves publicly available in organic chemistry. For example, H. Finkelman (
Flnkelmann) and G, Lehage (neh-
ag*) macromolecules, chemistry (Ma
krom, Ch@m, ) speed N l , 31 (19
8U) Ron Tachibana, C. Aguilera (Aguilera)
), E, Ringsdorf (Ring@dorf), A
, Schnell@r and R. Zentill, 1980 Florence, IUPAC Association Symposium on Large Molecules, Abstracts 3L16; J5 can be obtained by reacting poly(siloxane hydrogen) with N-alkenylcarbazole under reaction conditions, as shown in the article in the above Bulletin 3.557 (1982).

N-7/L'Kenilcalhasol, J, Hera (He
ifer), D. J. Lyman and W.
, A. Hev@t t's above-mentioned macromolecules, Chemistry 73.48 (1964)
The synthetic procedure presented in the paper is backtracked from a carbazole and an alkyl norogenide. This preparation procedure is illustrated by the example of poly(methyl-siloxane hydrogen) and by the reaction scheme in that volume.

In the reaction scheme HH2C-CH H,C-(r (CH2) n-2), the symbol n means an integer (alpha) as in KI'j in general formula (1) described above. Ma1ko code X is Boria 0-? Sanchu (1) / Rokibu / Repeating unit 11
The number, the symbol y, represents the number of units of the natural loxane repeating unit after the reaction of the starting materials borium and the alkenyl compound.

In this case, the sign +jy is smaller than the sign X. In the case of y z In the reaction of the starting material polyxane and alkenylcarbazole, the starting material boria 0 kipun's Giraud?
A part of the 5i-H bond in the repeating unit reacts and becomes a part. [σ] The obtained carbazole group-containing poly/loxane is reacted with temperature at °C, and in the case of 5i-H#i, which exists modestly in the polysiloxane, - for example, the symbol R4 in formula (11) is 5 Other reactions Note: The structure of the building group is explained to the public, and the entire city of the above-mentioned connection is in one house.
This 1-gold 1L compound containing a group such as σ) is considered to be 1-. The production of polysiloxanes containing lucalhasol groups according to the present invention will be explained in detail by the following embodiments.

The side-chain carbazole base 1 according to the invention is provided by resiloxane as an original or proprietary compound with very good photoconductivity. Therefore, the polysiloxane according to the invention can be conveniently used in the field where poly+ N-vinylcarbazole has been used as a photoconductive compound. Conventional poly-N-vinylcarbazole is 5
5, the carbazole group-containing polysiloxane according to the present invention can be used, for example, to form a photovoltaic l-
It is advantageously used as a primary compound together with doping agents or sensitizers. Until now, it has been commonly used with poly-N-vinylcarbazole to use as a doping agent or sensitizer, which is known per se, for example an electron donor which forms a charge transfer initiation site together with the carbazole pattern. I can do it. Or Lewis acid instead of seven? lJEha21417
-Dolinitrofluorenone, 2,4,5,7-titranitrofluorenone, chloranil or tetracyanoquinone dimethane moffl can be used.

The carbazole group-containing polysiloxanes of the present inventors are useful for forming conductive solid layers that are still elastic, non-brittle.

To form this light-conducting solid layer, a solid carbazole group-containing polysiloxane is used at room temperature, and its ffl liquid is poured into it by a method known per se at 1°C. By allowing the medium to evaporate, a photoconductive solid layer is formed. 1-light conductive solid I- using viscous or highly viscous carbazole group-containing polysiloxane
In the process, depending on the VL, a film of a certain thickness is formed on the substrate together with a crosslinking agent and/or a crosslinking initiator, and then this viscous or viscous carboxy group is formed. @M The oil-filtering group VC contained in borin loxane forms a structure. The #5 company base, which is also affected by the = B1-H bond of this j- frame, is due to excessive diene or polyene.
This reacts with a 5i-H bond in a known manner as shown in the following formula, for example.

H, C-OH+CI, +CH-CH2 or in the above ae formula, U is O or an arbitrary σ) integer, and V is similarly U
meaning. As active groups in the carbazole group-containing 70 compounds of Shokosha, flJ is a residue having an olefin-i bond, and ν is a vinyl group or (methaneacryloyl). However, cross-linking of the photoconductive layer may be carried out without imposing any serious restrictions on the structure of the photoconductive layer.

For this 5MJ@, for example, heat 1 go open mother-in-law cutting or former sadaai start 4
It is also possible to simultaneously form UII11 of a predetermined component in the photoconductive layer by using a structure opening agent such as J.

The Q-siloxane according to the present invention is suitable for use in printing sheets or electrophotographic printing plates, especially electrophotographic offset printing plates, because of its excellent dependence on metal coatings. Useful for axes in layered terrain.

In addition to this, the charged 4-layer layer is made of polysiloxane containing a side chain carbazole group as a 7tt conductive compound, i.e., a compound that carries a charge under the action of an activator. In order to increase the photoconductivity, it contains an organic dye or an organic pigment which has a sensitizing effect. According to the present invention, a photosensitive compound having a sensitizing effect to form a photoconductor solid layer or a poly-N-
For sensitizing the photoconductive layer formed from vinylcarnosol or low-molecular-weight carbazole compounds, well-known and commonly used organic dyes or organic dyes can be used in principle. These include spectrally sensitizing dyes,
Namely, examples thereof include organic dyes which greatly increase the sensitivity of the photoconductive layer, as well as dyes and pigments which can form charge carriers under the action of actinic radiation. Original conductivity ratio with sensitizing effect -1
-1, that is, a photoconductive compound and a sensitizing compound having a sensitizing effect are contained in a single layer *J*, or as a sensitizing compound forming a layer, or as a sensitizing compound that is known per se. Soluble organic dyes, which are commonly used, are suitable.

On the other hand, organic pigments have photoconductive properties in which a sensitizing compound and a photoconductive compound are separated from each other and are contained in different photoconductive multilayers with sensitizing properties. used for layers. According to the invention, an organic dye or an organic preparation is added to the photoconductive solid layer in a known and customary manner for sensitizing compounds. It is generally used in an amount of about 0.5 to 101111%, based on the photoconductive compound contained in the conductive layer.

Particularly, the organic dyes to be used in the photoconductive single-uniform IX layer according to the invention, which have a sensitizing effect in one compound, include, for example, triarylmethane dyes, xanthine dyes, cyanine dyes, Examples include thiazine dyes. Representative examples include Rhodamine 7B, Rhodamine 6G, Malaquit Green, Methyl Violet, Crystal Violet, Pencal Rose, Thiocyanine, and Methylene Blue. In addition, dyes or pigments which have a sensitizing effect and have a sensitizing effect in excess of ℃ may be mentioned, such as azo dyes, phthalocyanine and isoindoline dyes. The homogeneous ratio according to the invention is reasonable and advantageous for both single-layer and heterogeneous multi-layer tt conductivity types. lU
- Dyes or pigments formed from tetracarboxylic #l derivatives are very common.

This soluble and non-bath perylene-3,4:9゜O-
In addition to perylenetetracarboxylic anhydride, examples of tetracarboxylic acid conductors include perylenetetracarboxylic acid esters and perylenetetracarboxylic acid amides. In addition to N,N-bis(2,6-dichlorophenyl)-perylene-3,4:9,1υ-tetoccarboxylic acid diimide as a sensitizing compound of the t4-based solid j- according to the present invention, In particular, the following Q) general formula (
2), QV) and ~) Q Noberylene-3,4:9,1t
J-tetracarbo/#1 diimide vj4 ring is excessive.

(Halogen) In the general formula (2)-(g), R6 has a hydrogen atom or 1 to 611i7A, especially 2 to 3 carbon atoms, and optionally hydroxy, alkoxy, phenyl, Alternatively, cycloalkyl can be directly determined by an alkyl group, Z is a p-phenylazoanilino group, phenylnao group, or anilino group, and R6 is a hydrogen atom, an alkyl, aryl, aralkyl, or alkaryl group. , R7 is a hydrogen atom, an alkyl or an aromatic ring, r is O to 6, i, t are general formulas or q), and 10-gen dihydrogen to the aromatic ring bone, especially It means a degree of tolerance in the range of 45 to 75% of the degree of halogen substitution.

When the compound FIf-O (of the general formula 40) means a number ((range σ in the range of 2 to 4), when the symbol r or ○ is not present, R5 preferably represents a hydrogen atom.General In the formula (2), "=υ, and R5 is an alkyl group having 2 to 3 carbon atoms that can optionally be replaced with tX, e.g., t
means 10 biru, l-hydroxyfurovir, l-methoxyfurovir, l-phenylethyl or halicyclohexyethyl. Furthermore, in the sensitization of the photoconductive solid layer according to the present invention, R7 in the general formula (a) means a hydrogen atom or a lower alkyl group, such as a butyl group, and an aromatic ring The bone core is substituted with chlorine, and the degree of chlorination is about 20 to 50% of the maximum limit relative to the -j astringent aromatic ring bone core.

In addition to the electrically conductive compounds and the chemical compounds described above, the electrically conductive solid layer according to the present invention may contain components conventionally used for photovoltaic bed layers, such as binders, crosslinkers, etc. +I4
4, a reaction aid, a plasticizer, or an electron donor capable of forming a monomer with a carbazole group, such as 2,4,7-dolinitrofluorenone'&. The advantageous feature of the photoconductive solid layer according to the invention is that σ) The polysiloxane containing side chain carbazole groups to be used as the photoconductive 4a compound for its preparation can be prepared without the addition of a binder or plasticizer. It is possible to omit the combination use (even if the combination use is possible), and to produce a highly elastic, non-brittle solid m while maintaining high photoconductivity.

According to the present invention, a sensitizing compound, such as carbazole base, borishirogysan, which acts as an additive to form a homogeneous, single-layered solid layer, is used. In this case, the above components are added to the organic nutrient mixture and, if necessary, other additives and homogeneous ((mixed with 1 u), this homogeneous mixture is stratified to the desired thickness. Add a mixed bath to the mixture, place this melt on the carrier, and mix the solvent with a black number to form an upper layer with a dry line thickness of η′v u・8 to 40 μm. The thickness of this layer varies depending on the industrial operation and is preferably between 0.8 and 6 .mu.m for electrophotographic printing plates and about 5 and 25 .mu.m for copying films. To prepare a solid layer, the viscous or highly active polysiloxane of the present invention can be used in conjunction with other binders to form a photoelectric layer on a carrier. , as mentioned above in 1, thus assimilating the E-layer to the cross-linking curing of the active groups in the polysiloxane.

The photoconductive solid layer according to the invention of Idantahato is produced in a manner known per se, ie by forming a first layer of a sensitizing organic dye or organic pigment on an fs carrier.

The first F- is formed, for example, by steaming a sensitizing compound onto a carrier. However, this first
The layer formation can be carried out by dissolving the polymer in an organic, preferably readily volatile solvent, either alone or together with a binder customary for this purpose, especially a binder which can be used to customize the barrier layer. It is preferable to apply it on a carrier. Bath salt fever #! 1.The first no of this sensitizing organic dye or M machine w4 class is 0. It has a thickness of υ05 to 5 μm, in particular υ,1 to 1.5 μm. Next, on this first layer, a 21st layer is formed of a polysiloxane containing a side chain carbazole group together with other additives. This second layer is also advantageously formed by pouring the polysiloxane of the invention into a bath solution. Q) The thickness of 7j after drying is generally about 1 to 40 μm, preferably 5 to 25 μm, especially 7 to 1
The range is 5 μm. The polysiloxane of the present invention to be used for this multi-layer original 'ML24 injection layer is prepared by using the above-mentioned viscous or -viscous material in steps 1 and 5, and after layer formation, by curing the layer in step 7, /Ii is applied. It is preferable to solidify. In addition, solvents conveniently used for layer formation include those with low boiling points and easy volatility;
For example, tetrahydrofuran is preferred.

The charging conductive solid layer according to the present invention not only exhibits excellent photoconductivity equivalent to that of the conventional poly-N-vinylcarbazole base material, but also exhibits better photoconductivity than the metal surface (8). If it has good adhesion, it will be suitable for mechanical customization, especially for those with a low level of sacrificial properties. Followers also
It is also useful as an electrophotographic recording material, such as a copying sheet for copying techniques, an electrophotographic material, and a tS material.

The electrophotographic recording material according to the present invention is a
It is fabricated by forming a conductive layer on a conductive carrier. As a specialized carrier for electrophotographic materials, it is possible to use, in principle, the well-known and customary Tebemata 411 carrier material for electrophotographic recording materials. Depending on the intended use, tin, lead, bismuth or similar metals are preferably vaporized on a synthetic resin sheet, preferably a sheet of polyester such as polyethylene terephthalate or polybutylene terephthalate. Conductive paper may also be used as a carrier for the photoconductive solid layer according to the invention. In addition to flat carriers, cylindrical carriers, for example metal cylinders or cylinders with a metal surface, can also be used. Photoelectric 24 according to the invention
During the preparation of the electrophotographic material, the solid layer in a is formed on the ML injection carrier in a manner known per se and commonly used.

The preferred method is original conduction! 11. At the same time as forming the garden layer tvI4, that is, a charging conductive solid layer is formed on the 411L support by pouring a bath solution.

Electrophotographic recording materials, in the known and customary manner for the preparation of such materials, have a structure between an electrically conductive carrier and a photoconductive solid layer, and also in the case of recording materials having multiple photoconductive layers, between each photoconductive layer. A barrier layer consisting of a metal oxide, such as hyaluminum acid, or a polymer such as polyamide, polyvinyl alcohol, polyacrylate, polystyrene, etc., can be provided between the secondary layers.

The present invention will be explained in more detail and concretely by way of the following examples. The units and percentages used in this example refer to one child unless otherwise specified. The volume Ii part ratio is the liter volume per ky. Carbazole described in all examples! ! The reaction for producing the converted polysiloxane is carried out in a phonetic atmosphere.

Example 1 Poly[methyl-(3-(9-carbazoyl)propyl)]
-Siloxane] Production 3.6 Miyako's poly-(methyl-siloxane water X),! −
13.68 g of 9-allylcarbazole was dissolved in 150 parts by volume of anhydrous toluene. After adding a catalytic equivalent amount of hexachloroplatinic acid (lυ% in Impropatol), the solution was heated at 80° C. for 20 hours with stirring. The reaction mixture vlJ was filtered and the resulting polymer was precipitated into ice-cold hexane. After two repetitions, a carbazole WL-substituted polysiloxane of 13.83 fi, corresponding to 86% of the theoretical violet, was obtained. This polymer, which has a glass transition temperature of 48C, can be used for various methods such as chromatographic spectroscopy, NMR spectroscopy,
Fixed by gel permeation chromatography and elemental analysis. The results of elemental analysis were as follows.

Elemental analysis CHN (C!1.H17NO8l) Theory 1st shift 71.
157 b, 41 ko, 24 (267,38)
Demonstration 10 shifts 71.5LJ 6.70
5.04 Example 2 Preparation of poly-[methyl-(6-(9-carbazoyl)hexyl)-siloxane] 3.6s of poly-(methyl-siloxane hydrogen) and 16
9-(5-hexenyllupazole) of -46 Mo was dissolved in 150 g of anhydrous toluene and reacted as described in Example 1. The reaction mixture was brought to one level, the bath medium was removed, and the residual polymer, which was viscous at room temperature, was washed multiple times with hexane.

The monocarbazole group-containing polysiloxane thus obtained, having a container capacity of 17.35 r and 94% of the theoretical amount, had a glass transition point of 8° C., and was analyzed in the same manner as in Example 1.

Elemental analysis CHN (C19)123 NO8i) Theoretical value 73
．． 74 7.49 4.53 (309,47)
Actual value 73. (J4 7.44 4.81 Example 3 Preparation of poly-[methyl-(11-(9'-carbazoyl) lantissyl-siloxane)] 3.6 poly-(methyl-siloxane hydrogen) and 21
．． 09s 9-(LL+-undecylcarbazole) was prepared as in Example 1 and dissolved in anhydrous toluene in a 15μ volume filter. Remove the solvent by pouring the reaction mixture W once,
The oily polymer was washed multiple times with hexane at room temperature.

Contains 22.17 parts, 97% of the theoretical amount.

The resulting carbazole group-containing polysiloxane having a glass transition point of -23°C was analyzed in the same manner as in Example 1.

Former system branch enemy (c24) 133 NO8i) Gon! lit
75.94 h, 763.69 (379,61J)
n'ji [llll direct 74.5L)
8.76 3.74 Example 4 Poly-[methyl-(5-(9-carbazoyl)pentyl)-ronkiben]offff13.6s of poly-(methyl-silokibun hydrogen) and 16.95i of 9-( 4-
Benzylcarbazolf was dissolved in 15 Ll parts by volume of anhydrous toluene and reacted as in Example 1, and the reaction mixture was worked up.

16.48 parts of carbazole group-containing polysiloxane, corresponding to 93% of the theoretical amount, was obtained. It was analyzed in the same manner as in Example 1. The glass transition point was 15°C.

Principal amount 1tr CHN(eta)l
heat lN08I). Buried @ admiration 73.2 7.2 4.7
(295,42) Central 6111 Hashi 72.4 7
．． 2 4.5'A Pond Examples 5 and 6 25% tetrahydrofuran solution of polysilicone with lupasol foundation prepared by Fusuya νIJ 1-4. Seven t'L were prepared. Each of these solutions was poured onto the aluminum surface coated on a polyethylene tereft sheet (to form a 65 μm thick dove) and dried by heating at 80°C for 15 minutes to obtain a 9 μm thick dry oil. The thus obtained carbazole-substituted polysiloxane layer adhered well to the aluminum surface and exhibited excellent gamma resistance. The polysiloxane layer processed in No. 4 could withstand sharp circular bending without any loss.

Comparison 1: IJ + N-vinylcarbazole I
Similarly, the LI-rich tetrahydrofuran bath solution was poured onto the aluminum surface of a polyethylene terephthalate sheet and dried (at 80°C for 15 minutes) to form a 8 to 9 μm thick layer.
I got Zeng. When this poly-N-vinylcarbazole layer was torn apart, due to the slight bending of the polyethylene terephthalate sheet, the above layer was scattered with countless pieces at TL/I°C.The poly-N-vinylcarbazole layer was It was shown that there is no practical contact with the surface.

Example 7 Measurement of Original 11L Thickness A layer was formed with the carbazole group-containing polysiloxane prepared according to Example 1 as described in Examples 5 and 6. In addition to the carbazole-converted polysiloxane, it also contains 5 moles of trinitrofluorenone, which forms a complex with the polysiloxane (r) power/l/ hazole group, based on the total layer. The surface of this layer t is charged to 15 kV by corona discharge, and after a while the layer ft15tJ
An interference filter for a wavelength of 366 nm was used with Watt's xenon A pressure Kr, and irradiation was performed for 12 minutes. After 2 minutes of irradiation, 97.7% of the surface charge disappeared. The towel cleaning time was 743 ms.

Koden's four companies are equivalent to that of poly-N-vinylcarbazole.

Example 8 A base layer was formed as in Example 7, but in this case the carbazole group-containing polysiloxane prepared according to Example 4 was used to form a base layer, except that the carbazole groups were present throughout the layer. On the other hand, it is doped with 57% trinitrofluorenone.

When the layer charged at 8.5 kV was exposed to light for 3 minutes, 88% of the surface potential disappeared. The half-life time is 954 m in this case.
s.

And one.

Example 9 Preparation of poly-(methyl-11-(9-carbazoyl)unodecyl-siloxane-coboly(methyl-siloxane hydrogen)) 3.6 parts of poly-(methyl-siloxane hydrogen) and 17.0 parts of poly-(methyl-siloxane hydrogen).
2 parts of 9-(H)-undecylcarbathy) L/) were mixed with 150 parts of anhydrous toluene, and the reaction proceeded in the same manner as in Example 1.

The reaction mixture was made into a crosslinked film without the treatment described above, and 0.9 part of 1°21-docosadiene was added to the reaction mixture. This l'i! A film was formed from the solution and crosslinked at 12L)°C.

Example 1 A 25% tetrahydrofuran bath was prepared using the n74 carbazole group-containing monosiloxane prepared according to Example 1. A portion of this bath liquid is directly deposited on the aluminum surface coated with polyethylene terephthalate to give a dry layer thickness 'Y' after drying (15 minutes at 80°C).
IIJ μm. To the remainder of the above bath solution, 0.6% Rhodamine B was added to 4-lisiloxane. The sensitized bath solution was similarly poured onto the aluminum surface of polyethylene terephthalate to a dry thickness of 10 mm.
Form a layer of μm (7). All solid layers of carbazole-substituted polysiloxane exhibited excellent adhesion to the aluminum surface and excellent readability.

The skin formed from the carbazole polysiloxane described above was charged to a surface potential of -8.5 kVo by corona discharge, and then the plate layer was irradiated for 2 minutes with a 151 J watt xenon high-pressure lamp. The layer sensitized by Rhodamine BK has a higher 1-position drop due to this irradiation than the layer sensitized by Rhodamine BK than the layer that did not undergo this treatment. The half-life time, that is, the time required for the surface load to reduce to half the size of the original irradiated country, was a long time on the order of about 1 uou mi') seconds.

Example 11 A 25% tetrahydrofuran solution of the carbazole group-containing polysiloxane prepared according to Example 1 was added with 7.5° of N,N-bis-cyclohexyl-based on the polysiloxane.
Perylene-3,4: 9.10-tetracarboxylic acid diimide was added. Pour this solution onto the aluminum surface of a polyethylene terephthal sheet to a dry thickness of 10 μm.
A layer was formed, charged with a hexagonal potential of +8.5 V by corona discharge, and the layer was irradiated for 1 second with a 15 tJ watt xenon high-pressure lamp through a gray filter with a light density of 1. After irradiation, 65% of the human face position υ) disappeared, and the half-life time was 584 milliseconds.

Comparative Experimental Example A A photoelectric field layer was formed in the same manner as in Example 11 except that poly-N-vinylcarbazole was used instead of the carbazole group-containing polysiloxane. #Mixture of tetrahydrofuran and toluene as a solvent for liquid V@ production v! J
(6:4) was used. Photoconductivity formed from this
- showed the same level of charge as in Example 11, but it was more brittle than the layer of Example 11, and when the polyethylene terephthalate sheet was slightly bent, it broke into countless small pieces. The number of divided ponds is 1. Thus, it can be said that the poly N-vinylcarbasole layer does not actually come into contact with the aluminum surface on the polyethylene terephthalate at all.

Example 12 A 25% tetrahydrofuran m solution was prepared using the γ-carbazole group-containing polysiloxane prepared according to Example 4, and 5% of 1,6 was added to the polysiloxane.
, 7.12-tetrachloroherylene-3.4:9. IL
)-Tetracarboxylic acid diimide-bis-(n-butyl)
Benzimidazole'L'tX was added. This solution was used to form a photoelectric field layer having a dry thickness of 1 io um on an aluminum carrier at 1°C. This element [conductivity 1-] was charged as in Example 11 and irradiated with light. After irradiation, the position Q
) 75 animals disappeared and 1 lost. In this case, half-mast time is 39Ll.
One minute in Mi'J seconds.

Example 13 4UfJ of tetrachlorperylene-3,4:9.1 (J
-Tetrahydrocarboxylic acid diimide-bis-benzimidazole and 60% vinyl chloride/isoflobil maleate/acrylic acid co-constitutional combination (74:24
: 2) was mixed with a mixed solvent of tetrahydrofuran and toluene (3:l) and poured onto the aluminum surface coated on polyethylene terephthalate to give a thickness of about 1 μm after drying. layer was formed. Pour the carbazole group-containing polysiloxane σ) prepared according to Example 1 onto a 25% tetrahydrofuran solution, and add tetrahydrofuran'r! ! The thickness of the polysiloxane layer formed after im removal was 10 μm.

A flexible photoelectric coating with good adhesion to the carrier was obtained. The conductive layer was charged with this light to a surface potential of -8.5 kV by corona discharge, and then irradiated for 11 seconds with a 15 Ll xenon high pressure lamp using a clay filter with a light density of 1. With this irradiation, 81%
The potential disappears, and its half-life time is 0 in 238 milliseconds.
diimide-bisubenzimidazole and 'C)k+,
N-bis(phenylethyl)-perylene-3,4:9
．． 1t)-Tetracarboxylic acid diimide mixture (2:l
)' When 1 g of Y sensitizing compound was added, very good results were also obtained with T Kotogi.

Comparative Experimental Example B In the same manner as in Example 13, the top layer was made of poly-N-vinylcarbazole rather than a polysiloxane layer. This poly-N-vinylcarbazole layer was similarly dried to a thickness of 10 μm, and the thus obtained 11L4 photorecording material had photovoltaic properties equivalent to that of Example 13. However, the layers in this comparative example were thicker and less permeable, and when the polyethylene terephthalate sheet was bent, it became scattered into many small pieces.Example 14 Polyethylene terephthalate sheet coated with aluminum First, as described in Example 13, 5KN
, N-bis-(phenylethyl)-perylene-3,4:
9. Mixture of 10-tetracarboxylic acid-diimide and vinyl chloride/maleic acid ester/acrylic acid co-combination. On this first layer of sensitizing compound, a 1 μm thick solid layer of carbazole group-containing polysiloxane was applied using the solution prepared according to Example 3. Formed. 0.9 parts of 1,21-docosadiene was added to the reaction mixture prepared in Example 3, and the bath residue was poured onto the 1N to form a film.
The custom-made electrophotographic recording material produced in this way, which was crosslinked by evaporating the solvent at a temperature of 0.degree. C., was similar to Example 13σ.

Example 15 Using the same recording material as in Example 13, prepared at ℃, the recording material was used as a restoring sheet, and a repetition test was carried out at L rs. This sheet was loaded with 1g of IUIJ negative chips and exposed within 1.5 hours. During this time, acceptability, maximum wearability, clear stress, dark conductivity, and percent dropability remained unchanged.

Claims (13)

[Claims] (1) A polysiloxane characterized by containing a carbazole group bonded laterally to the polymer main chain. (2) A polysiloxane according to claim (1), which has the following general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the above formula, R^1 represents an alkyl group, R^2 and R^3 are each independently a hydrogen atom, an alkyl group, an alkoxy group,
A polysiloxane characterized by containing a siloxane repeating unit represented by an amino group, a hydroxyl group, or a halogen atom, where n is an integer of 2 or larger. (3) A polysiloxane according to claim (2), characterized in that R^1 in the siloxane repeating unit represented by the above general formula (I) is a methyl group. (4) A polysiloxane according to claim (2) or (3), in which R^2 and R^3 in the siloxane repeating unit represented by the above general formula (I) each represent a hydrogen atom. Characteristic polysiloxane. (5) A polysiloxane according to any one of claims (2) to (4), in which n in the siloxane repeating unit represented by the above general formula (I) is an integer in the range of 2 to 22. Characteristic polysiloxane. (6) A polysiloxane according to any one of claims (2) to (5), characterized in that the polysiloxane is essentially composed of repeating siloxane units represented by the above general formula (I). Siloxane. (7) A polysiloxane according to any one of claims (2) to (6), which is solid at room temperature;
A polysiloxane consisting essentially entirely of siloxane repeating units represented by the above formula (I), excluding the terminal groups, wherein n represents an integer not exceeding 5. (8) A polysiloxane according to any one of claims (2) to (6), which, in addition to the siloxane repeating unit represented by the above general formula (I), further has the following general formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the above formula, R^1 means an alkyl group, and R^4 means a crosslinkable active group). A polysiloxane characterized by containing. (9) A polysiloxane according to claim (8), characterized in that R^1 in the general formula (II) is a methyl group. (10) A polysiloxane according to claim (8) or (9), characterized in that R^4 in the siloxane repeating unit represented by the above general formula (II) is a hydrogen atom. . (11) A polysiloxane according to claim (8) or (9), in which R^4 in the siloxane repeating unit represented by the above general formula (II) is a group containing a (meth)acryloyl group. A polysiloxane characterized by: (12) A polysiloxane according to any one of claims (8) to (11), which comprises a siloxane repeating unit represented by the above general formula (I) and a siloxane repeating unit represented by the above general formula (II). mutually 80 to 99
．． A polysiloxane characterized in that it is contained in a molar ratio of 5% to 20 to 0.5%. (13) A polysiloxane according to any one of claims (8) to (12), which is viscous and oily at room temperature.