JPH0420970A - Electrophotographic sensitive body - Google Patents

Abstract

PURPOSE:To maintain stable and good electrostatic characteristics even in the case of the environment of a low temp. and low humidity or a high temp. and high humidity and to obtain bright and good-quality images by incorporating one kind of a resin A and one kind of a resin B into a binder resin. CONSTITUTION:The binder resin is constituted of at least the resin A of a low mol. wt. which is a graft type copolymer contg. a monofunctional macromonomer (MA) having the polyether structure expressed by formula I as a copolymer component and the resin B of a high mol. wt. consisting of a graft type copolymer contg. at least the monofunctional macromonomer (MB) and the monomer expressed by formula II. The resin A is specifically bonded with the acid group incorporated into the resin only at the terminal of the graft part. The resin A and the resin B are respectively specified in the weight average mol. wt. of the respective resins, the content of the acid group or polar group in the resins and the bond positions, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having excellent electrostatic properties, moisture resistance, and durability.

(Prior Art) Electrophotographic photoreceptors have various configurations in order to obtain predetermined characteristics or depending on the type of electrophotographic process in use.

As representative electrophotographic photoreceptors, there are photoreceptors having a photoconductive layer formed on a support and photoreceptors having an insulating layer on the surface, which are widely used. Photoreceptors comprising a support and at least one photoconductive layer are used for image formation by most common electrophotographic processes, ie, charging, image exposure and development, and optionally transfer.

Furthermore, a method of using an electrophotographic photoreceptor as an offset master plate for direct plate making is widely used.

The binder resin used to form the photoconductive layer of the electrophotographic photoreceptor has excellent film-forming properties itself and ability to disperse photoconductive powder into the binder resin, and also has excellent film-forming properties and excellent dispersion ability of the photoconductive powder into the binder resin. The photoconductive layer of the recording layer has good adhesion to the substrate, and the photoconductive layer of the recording layer has excellent charging ability, low dark decay (high light decay, low pre-exposure fatigue, and resistance to changes in humidity during imaging. Therefore, it is necessary to have various electrostatic properties such as the need to stably maintain these properties and excellent imaging performance.

Furthermore, research is being carried out on lithographic printing original plates using electrophotographic photoreceptors, and a binder resin for the photoconductive layer that has both the electrostatic properties of an electrophotographic photoreceptor and the printing properties of a printing original plate has been developed. is necessary.

However, conventionally known binder resins have particularly high chargeability and
There were problems with dark charge retention, electrostatic characteristics of photosensitivity, smoothness of the photoconductive layer, etc., and it was not practically satisfactory.

Furthermore, even in the case of a binder resin which is said to have been developed as an original plate for electrophotographic lithographic printing, when actually evaluated, there were problems with the above-mentioned electrostatic properties, scumming of printed matter, etc.

Furthermore, in order to solve these problems, a copolymer component containing an acidic group in the side chain of the polymer was used as a binder resin.
A low molecular weight resin containing 5 to 10% by weight and a low molecular weight resin that binds an acidic group to the end of the polymer main chain (PMwl).
It is disclosed in JP-A-63-217354 and JP-A-64-707 that the smoothness and electrostatic properties of the photoconductive layer can be improved by using the photoconductive layer and the image quality without background smudge can be obtained by using
61 and JP-A-2-67563.

In addition, as a binder resin, a resin containing a polymeric component containing an acidic group in the side chain of the copolymer, or bonded to the end of the main chain of the polymer, and containing a thermally and/or photocurable functional group. The technique using this is disclosed in Japanese Patent Application Laid-open No. 1-100554 and Japanese Patent Application No. 1983-3.
9690, and JP-A-1-102537 and JP-A-2-874 disclose a technique of using a resin containing an acidic group in the side chain of the copolymer or bonding to the end of the main chain of the polymer together with a crosslinking agent. disclosed, furthermore, the low molecular weight body (weight average molecular weight 10
' ~ 104) with high molecular weight (weight average molecular weight 104 or more)
A technique using a combination of resins is disclosed in Japanese Patent Application Laid-open No. 64-564,
63-220149, 63220148, JP1-280761, 1-116643 and 1
JP-A No. 1-169455 discloses a technique for using such a low molecular weight material in combination with a heat-curable and/or photo-curable resin.
The technique of using the low molecular weight substances disclosed in No. 766 and No. 2-34859 in combination with a comb-shaped polymer is disclosed in JP-A No. 2-5.
No. 3064, No. 2-56558 and patent application No. 1983-25
No. 4786, respectively. It is stated that by these techniques, the film strength of the photoconductive layer can be made sufficient and the mechanical strength can be increased without impeding the above-mentioned properties due to the use of a resin containing an acidic group at the side chain or terminal end. has been done.

(Problem to be solved by the invention) However, even when these resins are used, the environment is high temperature and
It has been found that it is still insufficient to maintain stable performance when the temperature fluctuates significantly from high temperature to low temperature and low humidity. In particular, scanning exposure methods using semiconductor laser light require longer exposure times than conventional simultaneous exposure methods using visible light across the entire surface, and there are restrictions on exposure intensity. , higher performance is required in terms of photosensitivity.

Furthermore, when a scanning exposure method using semiconductor laser light is adopted in an electrophotographic lithographic printing original plate, actual tests using a conventional photoreceptor show that the electrostatic properties described above are unsatisfactory. Especially E+/! The large difference between the
Even when printing as an offset master, serious problems such as pasting marks of the printed original appear on the printed matter.

The present invention is intended to improve the problems of conventional electrophotographic photoreceptors as described above.

An object of the present invention is to provide an electrophotographic photoreceptor that stably maintains good electrostatic properties and produces clear, high-quality images even when the environment during copy image formation changes such as low temperature and low humidity or high temperature and high humidity. It is to provide.

Another object of the present invention is to provide a CPC electrophotographic photoreceptor with excellent electrostatic properties and low environmental dependence.

Another object of the present invention is to provide an electrophotographic photoreceptor that is effective in a scanning exposure method using semiconductor laser light.

Another object of the present invention is to provide an original plate for electrophotographic planographic printing.
It has excellent electrostatic properties (particularly dark charge retention and photosensitivity), reproduces copied images that are faithful to the original, and does not cause not only uniform background smudges on the entire surface of printed matter but also dotted smudges. ,
Another object of the present invention is to provide a lithographic printing original plate which has excellent rigidity resistance and does not leave any pasting marks.

(Means for Solving the Problems) The above object is to provide an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, wherein the binder resin is a resin [A] shown below. At least one species and a tree! It has been found that this can be achieved by an electrophotographic photoreceptor characterized by containing at least one type of CB).

Resin [A]: Weight average molecular weight 1 x 103 represented by the following general formula (I)
At least one of ~2 x 104 macromonomers (MA)
Contains a species as a polymerization component, and only at one end of the polymer main chain, -potsH1 group, -3OzH group, -COQI4
Weight average molecular weight 1.
OXIO Ko~2. Graft copolymer of OXIO'.

General formula (1) [In formula (1), al and al may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -Coo-Z or Carbon number 1-8
-Coo-Z (Z is 1 carbon number
~18 hydrocarbon groups).

X is -COO--0CO-HCHtvCOO-1-(
CIlz) BOCO-1 view CHz7 (J!+, j!
g represents an integer from 1 to 3), P.

, -, coNncoo-1-
CONHCOO-Y represents a group connecting X and 10-.

[ ] represents a repeating unit, and n represents an integer of 1 to 3. When n is 2 or more, W in [ ] represents a group that forms with at least the W in the adjacent C].

(r+ and rz may be the same or different and each represents a hydrogen atom or an alkyl group).

Ro represents a hydrogen atom or a hydrocarbon group, [binder resin]
B]: at least one of the polymer components represented by the following general formulas (TVa) and (IVb), -COOII group, PO
sHi group, 5O3H group, -OH group, -PRg(R
z represents the same content as R1 above) group, -COO group, and at least one polymer component containing at least one component containing at least one polar group selected from an acid anhydride-containing group; A monofunctional macromonomer (MB) with a weight average molecule of 12 x 104 or less, which is formed by bonding a polymerizable double bond group shown in the following Funazura (III) only to one end of the main chain of the polymer it contains; A weight average molecular weight of 5 x 104 consisting of at least the following:
~lXl0' copolymer.

General formula (III) CH=C In formula (1), X is -Coo OCOCH! 0C
OCHtCOO- -O--SO□ -CONHCOO represents a hydrocarbon group).

Cl5C1 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -
coo-z, or -C00-Z+ (
Each Z+ represents a hydrogen atom or a hydrocarbon group which may be substituted.

L Ql General formula (IVb) Q In formula (IVa) or (IVb), Xl represents the same content as X in formula (II[), Ql has a carbon number of 1 to 18
represents an aliphatic group or an aromatic group having 6 to 12 carbon atoms.

dl and d8 may be the same or different from each other, and can be expressed by the formula (
Represents the same content as cl and cm in 1).

T is a hydrogen atom, a halogen atom, an alkoxy group, or C00
Zz (Zx represents an alkyl group, an aralkyl group or an aryl group).

General formula (V) CIl=C i -QX In formula (V), x2 represents the same content as Xl in formula (IVa), and QX represents ael, which represents the same content as 01 in (rVa), C2 may be the same or different, and represent the same content as 01 and C0 in formula (III).

That is, the binder resin used in the present invention is a graft copolymer containing a -functional macromonomer (MA) as a copolymerization component and having a polyether structure represented by the general formula (I). Then, a low molecular weight resin [A] bonded to an acidic group (-POJ□H), a -functional macromonomer (MB) and a -Funazura (V) at one end of the polymer main chain of the graft copolymer. and a high molecular weight resin [B] made of a graft copolymer containing at least the monomer shown below.

The conventionally known acidic group-containing binder resins mentioned above are mainly used for offset masters, and their molecular weights are large (for example, 5.
×104 or more), and these copolymers were random copolymers, and the acidic group-containing copolymer components were randomly present in the polymer main chain.

On the other hand, resin [A] used in the binder resin of the present invention
is a graft copolymer, and the acidic groups contained in the resin are not randomly present in the main chain of the polymer, but are specifically bonded only to the ends of the graft part. be.

Therefore, the part of the acidic group present at a specific position away from the main chain of the polymer adsorbs to the stoichiometric defects of the inorganic photoconductor, and the part of the main chain of the polymer covers the surface of the photoconductor. It is estimated that the coating is loose and sufficient. Due to that,
It compensates for traps in the photoconductor and improves humidity characteristics, while ensuring sufficient dispersion of the photoconductor, suppressing agglomeration, and being stable even when the environment changes significantly from high temperature/high temperature to low temperature/low humidity. It was found that high performance electrophotographic properties were maintained. And resin CB) is resin [A
] The high performance of the electrophotographic properties mentioned above can be achieved by using (
It makes the mechanical strength of the photoconductive layer sufficient, which is insufficient with resin [A] alone, without inhibiting it. This is particularly effective when using a scanning exposure method using a semiconductor laser.

Further, in the present invention, the surface of the photoconductive layer has smoothness. When a photoreceptor with a rough photoconductive layer surface is used as an electrophotographic lithographic printing original plate, the dispersion state of the zinc oxide particles that are the photoconductor and the binder resin is not appropriate, and aggregates may be present. Because a photoconductive layer is formed, even if desensitization treatment is performed using a desensitization treatment liquid, the non-image areas cannot be made uniformly and sufficiently hydrophilic, causing printing ink to adhere during printing, and as a result, the printed matter deteriorates. Background stains occur in non-image areas.

Furthermore, it was found that the photosensitivity was better than that of a random copolymer resin in which the polar group is contained not at the end of the graft portion but in the side chain connected to the main chain of the polymer.

Spectral sensitizing dyes, which are normally used to maintain photosensitivity in the visible to infrared light range, fully function their spectral sensitizing action when adsorbed to a photoconductor. It is assumed that the polymer-containing binder resin interacts appropriately with the photoconductor without inhibiting adsorption of the spectral sensitizing dye. This effect was particularly remarkable with cyanine dyes or phthalosoanine pigments, which are particularly effective as dyes for spectral sensitization of near-infrared to infrared light.

Even when only the low molecular weight resin [A] in the present invention is used as the binder resin, the photoconductor and the binder resin can sufficiently adsorb and coat the particle surface, which improves the smoothness of the photoconductive layer. It has good electrostatic properties, provides image quality without background smearing, and has sufficient film strength for use as a CPC photoreceptor or as an offset original plate for printing several tens of sheets. However, by coexisting resin [B] as in the present invention, the mechanical strength of the photoconductive layer, which is still insufficient with function [A] alone, is further improved without alienating the function of resin [A]. I was able to do it. Therefore, the photoreceptor of the present invention has excellent electrostatic properties even when environmental conditions vary, and
The film strength is also sufficient, and even under severe printing conditions (for example, when the printing pressure is strong with a large mill Wllfli), the film strength is 8000
It is now possible to print more than one sheet.

According to the present invention, the weight average molecular weight of the resin [A] and the resin [B] as the binder resin of the inorganic photoconductor, the content of acidic groups or polar groups in the resin, the bonding position, etc. are determined. It is presumed that this is due to the fact that the strength of the interaction between the inorganic photoconductor and the resin could be appropriately changed by changing the temperature. That is, resin [A] with stronger interaction is selectively and appropriately adsorbed to the inorganic photoconductor, while resin [B] with weaker interaction than resin [A] has a polymer in the resin. The acidic group bonded to a specific position with respect to the main chain interacts gently with the inorganic photoconductor to the extent that the electrophotographic properties are not affected, and the molecular chain length and the graft part chain length are long between the resins [B]. It is presumed that both the electrophotographic properties and the mechanical strength of the film could be significantly improved as described above by the interaction between the molecular chains of the film.

Furthermore, resin CB) has a polymer main chain at the end of the month
OxH* group, 5(hH group, -caoH5, -OH group,
Graft copolymer (OH) and at least one polar group selected from cyclic acid anhydride containing groups (
This polymer is preferably referred to as resin [B'] hereinafter.

When resin [B'] is used, the electrostatic properties, especially R, [l
and E17I@ are better, and the excellent properties achieved by using resin [A] are not hindered at all, and the effect is that there is almost no fluctuation even in Chita environmental changes such as high temperature, high temperature, low temperature and low humidity (preferable, and , the film strength is also better, and the printing durability is improved.

In the resin [A], the weight average molecular weight of the graft copolymer is lXl0" to 2x104, preferably 3XIQ'
~I
The proportion of the acidic group bonded to the end of the copolymer main chain in the copolymer is 0.5 to 15% by weight, preferably 1 to 10% by weight. Further, the glass transition point of the resin [A] is preferably -20°C to 120°C, more preferably -10°C to 90°C.

If the molecular weight of the binder resin [A] is smaller than lXl0', the film forming ability will decrease and sufficient film strength cannot be maintained, while if the molecular weight is larger than 2 x 104, even the resin of the present invention may have poor electrophotographic properties. In particular, in the case of such high molecular weight materials, if the content of acidic groups in the terminal bond exceeds 3% by weight, the deterioration of the electrophotographic properties will be significant, and the offset master When used as an adhesive, scumming becomes noticeable.

If the content of acidic groups bonded to the main chain terminal in the binder resin [A] is less than 0.5% by weight, the initial potential will be low and sufficient image density will not be obtained.

On the other hand, if the content of acidic groups is more than 15% by weight, the dispersibility decreases, film smoothness and high-temperature electrophotographic properties decrease, and furthermore, background smearing increases when used as an offset master.

The macromonomer (MA) used in the graft copolymer resin containing the macromonomer having a polyether structure of the present invention as a copolymerization component will be explained in more detail.

In the macromonomer (MA) of general formula (1), a and ag may be the same or different, and are each a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom), or a cyano group. , an alkyl group having 1 to 3 carbon atoms (e.g. methyl group, ethyl group, propyl group, etc.)
, -cooz or -CLCOOZ (Z has 1 to 1 carbon atoms
8 alkyl groups (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, etc.), aralkyl groups having 7 to 9 carbon atoms (e.g. benzyl group,
phenyl group, 3-phenylpropyl group, etc.) or optionally substituted phenyl group (e.g. phenyl group, tolyl group,
(xylyl group, methoxyphenyl group, etc.).

More preferably, either al or a2 represents a hydrogen atom.

X is preferably -COO-10CO-1-CO-1 co, coo-1-cotoco-1-CONH-5-
CONI (CONH-1P, hydrogen atom or carbon number 1
~12 hydrocarbon groups (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group) , methylbenzyl group, chlorobenzyl group, methoxybenzyl group, phenethyl group, phenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, butylphenyl group, etc.).

Y represents a group connecting X and 10- and represents a direct bond or a connecting group. Y representing a connecting group includes a divalent connecting group which may be via a hetero atom (hetero The atom is an oxygen atom, a sulfur atom, or a nitrogen atom), for example, P! 0- -S--N--COO--CONI(-1-5
0!5 (hNH--NHCOO--NHCONH-, etc., consisting of a single or a combination of bonding units (
However, fl and f□ may be the same or different and each represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom), a hydroxyl group, a cyano group, an aliphatic group having 1 to 12 carbon atoms (
For example, methyl group, ethyl group, propyl group, butyl group,
(hexyl group, octyl group, decyl group, dodecyl group, benzyl group, phenethyl group, 2-chloroethyl group, 2-cyanoethyl group, etc.), and P2 represents the same content as P1).

(However, r, ``8 may be the same or different from each other,
A hydrogen atom or an alkyl group having 1 to 8 carbon atoms (e.g.
JL4 represents an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, etc.).

[ ] represents a repeating unit sufficient to make the weight average molecular weight of the macromonomer (MA) of formula 1) IXIO' to 2X'IO', and n represents an integer from 1 to 3, provided that,
When n is 2 or more, W in () is at least the adjacent C
] represents a group different from W, and for example, the following combinations are possible (in each case below, KA3, --, and -- each represent a different group and represent the same content as W).

-x-v-o+w, -o←l.

-X-Y-0-E-W, -0)-HiJofR++-X-
Y-o-(-w+-o)-f-Ht-o)-f-ws-
0+-R.

-x -vt-o -f-11+-o) -f-L-0
3-f-11+-0 辷R1R0 represents a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, Butyl group, hexyl group, octyl group,
Decyl group, dodecyl group, tetradecyl group, octadecyl group, 2-methoxyethyl group, 3-methoxyethyl group, 2
-cyanoethyl group, 2-ethoxyethyl group, etc.), optionally substituted aralkyl groups having 7 to 9 carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group) , chlorobenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms (
(e.g., cyclopentyl group, cyclohexyl group, etc.), optionally substituted aromatic groups having 6 to 12 carbon atoms (e.g., phenyl group, tolyl group, xylyl group, naphthyl group, chlorophenyl group, bromophenyl group, alkoxyphenyl group (
Examples of alkyl groups include methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, decyl, dodecyl, etc.), acetoxyphenyl, methyl-chlorophenyl, propylphenyl, butyl phenyl group, decylphenyl group, etc.).

-Y of macromonomer (MA) in shipyard (I)
- The following examples include, but are not limited to, and in each case below, a is 1, CH, -
CH*C00CHs, -CI, -Br or -CN, b represents -H or -CHl, P represents an integer of 1 or 2, m represents an integer of 2 to 12, k is 3 or 4 represents an integer.

(A-1) a CNl=C C〇- (A-2) CHs CNl=C (A-5) (A CH2=C C0NH(CHz(GO-) (A ■ CH,=C C0NHCOO(CHz)i- (A-8) CH,=C C0NIC0NH(CHirco- (A CH2=C COO(CHthE (A If) CH,=C C0NH(C)12ru (A-12) cnz=c COO(CHzhEOCO(CH A -(A-
17) b CH2=C COO(C1l!h-Coo(CH2h) The polyether type macromonomer (MA) represented by the general formula (I) is
It can be produced by conventionally known synthesis methods. That is, it can be obtained by a method of synthesis by cationic polymerization of carboxylic acids or alcohols and epoxides or tetrahydrofurans. Specifically, P, F, Rem
pp and E.

Franta, Adv: Polym, Sci, 58.
3 (1984), R, Asami, M.

Takaki K, Kita and E, Asak
ura, Makromol, Che*.

186 +685 (1985) + R, Asami
and M, Takaki, Makromo
lChew, 5upp1. , 14. 163 (1
985), P, Rempp, P, LutzP,
Masson and E, Franta, M.
akromol, Che gu,, 5uppl.

11, 3 (1984), Takuzo Aida, Shohei Inoue, Journal of Organic Synthesis Association, 43.300 (1985), etc.

Specific examples of the macromonomer (MA) represented by general formula (1) used in the present invention are shown below, but the scope of the present invention is not limited to these.

do not have. Further, on each side, a, b, l, m, and shi represent the same contents as above.

(gate A-1) b (MA-2 (MA-3) (MA-4> (■ yo0■ (MA (MA (MA (MA) (gate A-1) The binder resin [A] of the present invention is a graft copolymer containing the macromonomer of general formula (1) described above as a copolymerization component, and other copolymerization components that have the physical properties of the binder resin described above. Any monomer may be used as long as it satisfies the above requirements and can be radically copolymerized with the macromonomer.

Preferably, the monomer represented by -Funzo (n) below is contained as a copolymer component in an amount of 20 to 95% by weight, preferably 40 to 90% by weight of the copolymer.

-Ship storage (n) b, b2 CH=C X3 1Lz In general formula (II), bl and b2 are 8 in formula (1)
1, represents the same content as a2, and more preferably represents a hydrogen atom or a methyl group.

×3 represents -000-1-〇C〇- or -O-, preferably -COO-.

R12 represents a hydrocarbon group having 1 to 18 carbon atoms.

Preferably, an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group,
Butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, 2
-Methoxyethyl group, 2ethoxyethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-01. N-dimethylamino)ethyl group, 2.
3-dihydroxypropyl group, 3-carbamoylpropyl group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g., hensyl group, phenethyl group, methoxyhensyl group, ethoxyhensyl group, methylhensyl group, dimethylhensyl group) sil group, chlorohensyl group, dichlorohensyl group, dibromobenzyl group, acetoquinhenyl group, cyanobenzyl group, naphthylmethyl group, 2-naphthylethyl group, etc.), optionally substituted cyclo having 5 to 8 carbon atoms Alkyl groups (e.g. cyclopentyl group, cyclohexyl group, cyclohebutyl group, etc.), optionally substituted aryl groups (e.g. phenyl group, tolyl group, xylyl group,
Mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, chlorophenyl group, dichlorophenyl L
Bromophenyl group, dibromophenyl group, chlorobromophenyl group, acetoxyphenyl group, acetylphenyl group, chloro-methyl-phenyl group, promomethyl-
phenyl group, cyanophenyl group, methoxycarbonylphenyl group, etc.).

Furthermore, the resin of the present invention may contain monomers other than these as copolymerization components together with the macromonomer (MA) and the monomer (If) of general formula (1) described above. good.

For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyls (e.g., vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidacilline, vinylpyrazole, vinyldioxane, vinylquinoline, vinylthiazole, vinyloxazine, etc.).

However, the content of these other monomers in the copolymer does not exceed 20% by weight.

In the graft copolymer of the present invention, the macromonomer (
When the copolymerization component corresponding to MA) is 5% by weight or less,
Dispersion as a photosensitive layer coating product will not be sufficient. Moreover, if it exceeds 80% by weight, the copolymerization with -Fleet (n) will not proceed sufficiently, and in addition to the desired graft copolymer, only the monomer of general formula (■) or other monomers will be present. This is not preferable because a polymer is formed. Furthermore, when these resins are used for dispersion, aggregation with the photoconductor occurs.

The resin [A] has acidic groups (-POJ, -5038 group, -COOH group, -COOH group,
As the hydrocarbon group represented by H and R6, R1+ of 2N)
represents the same content as the hydrocarbon group.

These acidic groups may be directly bonded to the terminal of the polymer main chain or may be bonded via a linking group.

The linking group may be any bonding group, but specific examples include α1, +TT-αt (α1 and αO may be the same or different, and each may be a hydrogen atom, a halogen Atom (chlorine atom, bromine atom, etc.), OH group, -
Cyano group, alkyl group (methyl group, ethyl group, 2-chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group, hequinyl group, etc.), aralkyl group (hensyl group,
phenyl group, etc.), phenyl group, etc.), α- 1,000 CH=CH→- (α1, α4 are the same as α1, α2 α5 S--N- (α is a hydrogen atom or a hydrocarbon group) (Specifically, the hydrocarbon group includes a hydrocarbon group having 1 to 12 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hequinyl group, octyl group, denyl group, dodecyl group, 2-methoxyethyl group) group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, methylbenzyl group, chlorobenzyl group, methoxybenzyl group, phenethyl group, phenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, butylphenyl group) ))-S02
NHCONHNHCOO' N)ls
Oz-C0NHCOO-1-C0NHCONII-1 heterocycle (at least one of O, S, N, etc. as a petro atom)
Any 5- to 6-membered ring containing a species or a condensed ring thereof may be used (for example, a thiophene ring, a pyridine ring, a furan ring, an imidazole ring, a piperidine ring, a mole α6 holin ring, etc.) or -31- (α6, α7α
) may be the same or different, and are a hydrocarbon group or -0α.

(α8 is a hydrocarbon group). Examples of these hydrocarbon groups include the same ones as those listed for α) alone or a linking group constituted by a combination thereof.

Specifically, methods for producing these resins include a method using a polymerization initiator containing the acidic group or a functional group that can be converted later to replace the acidic group; A method using a chain transfer agent containing a functional group that can be converted into
It can be produced using a method of introducing the functional group by utilizing a termination reaction in an anionic polymerization method.

For example, P, Dreyfuss, R, P, Quirk.
, Encycle, Po1y+5SCj, Eng, Z,
551 (1987), V. Percec, Appl.
, Polym.

Sci, Karibeni 95 (1985), P.F., Rempp.
, E., Franta, Adv.

POIym, Sci, 53. 1 (1984),
Y, Yamashita, J, Appl.

Po1y+s, Sci, Appl, Polym, 5ys
p, 36.193 (1981), R, Asasi,
M, Takaki, Makromol, Chem.
5upp1. 12° 163 (1985), etc., by the synthesis method cited in the review.

The binder resin of the present invention may contain two or more types of resins [A] as described above.

On the other hand, the weight average molecular weight of resin [B] is 5 x 104 ~ l
x104, preferably 8 x 104 to 5 x 10S.

- The proportion of the functional macromonomer (MB) in the polymer is preferably from 1 to 70% by weight, and - the proportion of the monomer represented by shipyard (V) in the polymer is It is preferably 30 to 99% by weight.

When a polar group is bonded to the end of the main chain of the copolymer, the proportion of the polar group in the copolymer is 0.1 to 10% by weight, preferably 0.2 to 5% by weight.

The glass transition point of the resin [B] is preferably 0゛c~ll
o'c, more preferably 20°C to 90°C.

If the molecular weight of the binder resin CB) is smaller than 5XIO', sufficient film strength cannot be maintained, while if the molecular weight is larger than 1 x 106, dispersibility decreases and film smoothness deteriorates, making it difficult to reproduce copied images. The quality (particularly the reproducibility of fine lines and characters deteriorates) is deteriorated, and furthermore, when used as an offset master, background stains become significant.

-Functional macromonomer (MB) in binder resin [B]
) content is less than 1.0% by weight, the electrophotographic properties (
In particular, dark decay rate, photosensitivity) are reduced, and fluctuations in electrophotographic properties under environmental conditions become large, especially in combination with near-infrared to infrared spectral sensitizing dyes. This is thought to be due to the fact that the amount of the macromonomer that becomes the graft portion is small, resulting in a composition that is almost the same as that of conventional homopolymers or random copolymers.

- 70% car-functional macromonomer (MB) content
If it exceeds this, the copolymerizability of the macromonomer according to the present invention with monomers corresponding to other copolymerization components will not be sufficient,
Even if it is used as a binder resin, sufficient electrophotographic properties cannot be obtained.

In the oil [B] of the present invention, the -functional group macromonomer (MB) provided as a copolymerization component of the graft type copolymer resin will be explained in more detail. - The functional macromonomer (MB) has a polymerizable double bond group represented by - Funazura (Ill) and at least one of the polymer components represented by - Funazura (IVa) and (rVb). Of the polymer components containing a specific polar group (-C0OH group, OH CHO group and/or acid anhydride-containing group), at least lit is bonded to only one end of the polymer main chain, Weight average molecular weight 2×1
04 or less.

In general 2 (I[l), (rVa) and (■b),
The hydrocarbon groups contained in C5, C2, Xo, dl, d2, island, Q, and Qo each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group); It may have.

In general formula (III), Xo is -coo-1-O
CO-1CI(,0CO-2-C)I200- -0-
-3(h--CO-5, preferred hydrocarbon groups include optionally substituted alkyl groups having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, heptyl group) , hexyl group, octyl group, decyl group,
dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl, I, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), carbon number 4 to 18
an optionally substituted alganyl group (e.g., 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl L
1-hexenyl group, 2-hexenyl group, 4-methyl-
2hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., hensyl group, phenethyl group,
3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromohensyl group,
methylbenzyl group, ethylhensyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.)
, an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example,
Cyclohexyl group, 2-cyclohexylethyl group, 2-
cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group) , methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group , acetamidophenyl group, propioamidophenyl group, dobnoloylamidophenyl group, etc.).

It may have a substituent. Examples of substituents include halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy groups (e.g., methoxy group, (ethquin group, propioxy group, butoxy group, etc.).

C5 and cz may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -coo-z , or C00Z via hydrocarbon
I (Zl preferably represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, or an alicyclic group, which may be substituted, specifically represents the same content as that described for R31 above).

Examples of the hydrocarbon in the one-coo-z group via the hydrocarbon include a methylene group, an ethylene group, a propylene group, and the like.

More preferably, - for shipyard (I), xo is COO
--0CO--ClbOCO--CH2C0O--O-
-CONHCOO--CONI(CONH--CONH
- may be the same or different, and each is a hydrogen atom, a methyl group, C00Zs or -C1(zcOOZs (Zs is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group) In Cl5C!, one of them represents a hydrogen atom.

That is, the polymerizable polymerizable group represented by -Funazou (I[l) is, specifically, CH,=C1(-C-(I CfhCOOCHi CH2=C O=C-O- CH,OC1h O II l +1 CH2=C-C-0-1C) l=CH-C-0C)1.
C00I (CH2=C CHz=CH-CONH-C, etc.).

In the general formula (IVa) or (rVb), Xl is the formula (
It represents the same content as Xo in Ill). dl and d2 may be the same or different from each other, and C0 in formula (DI),
Represents the same content as C2.

Ql is an aliphatic group having 1 to 18 carbon atoms or 6 to 12 carbon atoms
represents an aromatic group.

Specifically, an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, an octyl group, a denol group,
Dodecyl group, tridecyl group, hexadesol group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2
-hydroxylethyl group, 2-methoxyethyl group, 2-
Ethoxyethyl group, 2-cyanoethyl group, 3-chloroproyl group, 2-(trimethoxysilyl)ethyl group, 2-
Tetrahydrofuryl group, 2-thienylethyl group, 2-N
, N-dimethylaminoethyl group, 2-N,N-diethylaminoethyl group, etc.), cycloalkyl group having 5 to 8 carbon atoms (
For example, cycloheptyl group, cyclohexyl group, chloronaphthyl group), optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, hensyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group) group, chlorobenzyl group, bromobenzyl group, dichlorobenzyl group, methylbenzyl group, chloro-methylhensyl group, dimethylbenzyl group, trimethylhensyl group,
aliphatic groups such as methquinohensyl groups, etc., and further carbon atoms of 6 to
12 optionally substituted aryl groups (e.g., phenyl group, tolyl group, quinryl group, chlorophenyl group, bromophenyl group, dichlorophenyl group, chloro-methyl-phenyl group, methoxyphenyl group, methoxycarbonylphenyl group, naphthyl group, Examples include aromatic groups such as chloronaphthyl group, etc.).

In formula (lVa), preferably x1 is -COO-0
CO-1CToCOOCHzOCO-1-〇-CO--
CONHCOO--CONHCONII--CONHd
A preferable example of 3, d2 is the above-mentioned C3, C! represents the same content as .

In the general formula (TVb), Qo is -CN, -CONH
a bifurcated atom (e.g. chlorine atom, bromine atom, etc.), an alkoxy group (e.g. methoxy group, ethoxy group, propioquine group, butoxy group, etc.) or -COOZz (Zz is preferably an alkyl group having 1 to 8 carbon atoms, a carbon number 7 to 12 aralkyl or aryl groups).

The macromonomer (MB) has the formula (IVa) and/or (
It may contain two or more kinds of polymer components shown in 8ib). When Ql is an aliphatic group, the aliphatic group having 6 to 12 carbon atoms is preferably used in an amount not exceeding 20% by weight of the total polymer component in the macromonomer (MB).

Furthermore, when X in -ship stock (lVa) is -COO-, the polymer component represented by 2 (IVa) is at least 311% of the total polymer components in the macromonomer 0'IB). It is preferable that the content is above.

Furthermore, in the macromonomer (MB), the formula (rVa
) and/or a polar group (-COO)l copolymerized as a third component with the copolymer component represented by (rVb)
As the component containing C) 10 groups, acid anhydride-containing group), any vinyl compound containing the above polar group that can be copolymerized with the above macromonomer (MB) can be used, e.g. Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g. α-acetoquine, α -acetoxymethyl form, α(2-aminomethyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α
-chloro form, β-medixy form, α, β-dichloro form, etc.)
, methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides, crotonic acid, 2-alkenylcarboxylic acids (e.g. 2-pentenoic acid, 2-methyl-
2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzene Sulfonic acid,
Vinyl sulfonic acid, vinyl phosphoric acid, dicarboxylic acids,
Examples include half-ester derivatives of vinyl or allyl groups of alcohols, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the polar group in the substituent of amide derivatives.

CH Was.

In addition, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride include aliphatic dicarboxylic acid anhydride and aromatic dicarboxylic acid anhydride. It will be done.

Examples of aliphatic diorboxylic anhydrides include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane 1,2-dicarboxylic anhydride ring, and cyclohexane-1,2-dicarboxylic anhydride ring. monocycle, cyclohexene-1,2-dicarboxylic acid anhydride ring, 2,3-bicycloC2,2,2)octanedicarboxylic acid water condensation ring, etc. These rings include, for example, chlorine atom, bromine atom, etc. may be substituted with a halogen atom, an alkyl group such as a methyl group, an ethyl group, a butyl group, or a hekynyl group.

Examples of aromatic dicarboxylic anhydrides include phthalic anhydride rings, naphthalene-dicarboxylic anhydride rings, pyridine-dicarboxylic anhydride rings, thiophene-dicarboxylic anhydride rings, etc. For example, halogen atoms such as chlorine atom and bromine atom, methyl group, ethyl group,
It may be substituted with an alkyl group such as a propyl group or a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (as an alkoxy group, for example, a methquin group, an ethoxy group, etc.).

Examples of the OH group include vinyl group- or allyl group-containing alcohols (for example, allyl alcohol, methacrylic ester, ester substituents such as acrylamide, compounds containing an -OH group in the N-substituent, etc.), hydroxyphenol, or Examples include methacrylic acid esters or amides containing a hydroxyphenyl group as a substituent.

For example, the following monomers are shown as examples,
The scope of the present invention is not limited thereto.

Here, on each side below, T1 is -Hl-CH3,
CI, -Br, -CN, -C)IzCOOC)l
z or -CH2C0OH, T2 is -H or -CH
"," indicates an integer from 2 to 18, and "kl" indicates an integer from 2 to 5.
represents an integer of 1 to 4, h represents an integer of 1 to 4, and ml represents an integer of 1 to 4.
Indicates 12 integers.

(B-1) T, (B-2) C)
I.

(B-4) GHz=C Coo (CL) JCOO)l 2 CH,=C C0NH(CHz) JCOOH (B-6) (B-7) C00(CHz)llCOO(C)Iz)-0OH (B -8) t CHz=C CO)/1((C1(z)-0CCI(CL)-+C0
0) I(B-9) z CH,=C C0NHCOO(CH,) jcOOl(C0NHCH cnzcoo.

(B (B C8z = CHCH20L; U (L; It t)
m IshiUUI+(B-18) CHz=C Coo (CHZ> j l 0COCH= CH-C
00H (B (B-20) T! (B-21) Ding, CH, = CO ■ C00 (C1lffi),, 0-P-0) 1H (B-23) t CHt O CONH (CIh); +0- P-OH H (B-24) CH2=C0 Coo(CHt)J, o-P-OC1H5H (B-26) CL=C)l-(-CL+r, 0-P-OH(B-27
) ■ CH2=CH+CHz +r+C00(Cf(z)10
-P-OHH (B-30) z cnz=c COO(C)lz)-+SOJ (B-31) Tz (B-36) (B-37) Tz CI+2 COO(CH2)h, CON (CHzCHzCooH
) 2 (B-38) T! SO,0 (B-40) Tyo0OH (B-41) (B-42) I (B Cl.

CI = CH COO(CH2)J+0H (B-44) Tz Hz=C CONH (CHz) = +0H (B-45) coz=c CH,011 COOCHzcHOH (B-46) (B-47) (B-48) T.

cHz=c C)120H CONI(CH C)1.0H (B-50) (B-51) T2 OH2 CC00(CHz) JOCO(CHz) OH (B-53) OH2 C0N)ICOO(CH2) j H ( B-56) CIl, =C C00(CH,), , C00(C)12), OH Contained as a copolymer component containing the polar group in all polymer components in the macromonomer (MB). The amount is preferably 0.5 to 50 parts by weight per 100,311 parts of the total polymer components,
More preferably, it is 1 to 40 parts by weight.

A monofunctional macromonomer (question) composed of these polar group-containing random copolymers is used as a copolymerization component of resin C.
When contained in the resin [B], the total amount of the polar group-containing components contained in all the graft parts in the resin [B]
It is preferably contained in an amount of 0.1 to 10 parts by weight per 100 parts by weight of all polymer components.

More preferably, -COOH group, -3o, H group and -P
When containing acidic groups selected from OJz groups, the total amount present in the graft portion in resin CB) is 0.1 to 5% by weight.

The macromonomer (MB) may contain other polymer components other than these. For example, monomers corresponding to other polymerizable repeating units include acrylonitrile, methacrylonitrile, and acrylamide. kind,
Methacrylamides, styrene and its derivatives (e.g. vinyltoluene, chlorostyrene, dichlorostyrene,
Bromostyrene, hydroxymethylstyrene, N, N-
dimethylaminomethylstyrene, etc.), heterocyclic vinyls (
Examples include vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.).

When these other monomers are contained, 1 to 20 parts per 100,311 parts of the total polymer components of the macromonomer (MB)
Parts by weight are preferred.

The macromonomer (MB) provided in the present invention is a random monomer consisting of at least a repeating unit represented by -shipman (TVa) and/or (IVb) and a repeating unit containing a specific polar group, as described above. It has a chemical structure in which a polymerizable double bond group represented by -shipman (In) is directly bonded to only one end of the combined main chain, or bonded by an arbitrary linking group. The linking group that connects the formula (I[l) component and the formula (~"a) or (]Vb) component or the acidic group-containing component is a carbon-carbon bond (-
Any combination of atomic groups of carbon-hetero atom bonds (hetero atoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and hetero atom-hetero atom bonds It is composed of

x More specific linking groups include +C→-R)3 [R3□, R13 are hydrogen atoms, halogen atoms (e.g.
fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (e.g. methyl group, ethyl group,
propyl group, etc.], (1--5--C--N-
--Co.

sa SOz -CON-2-30211-2-NH
COOIh4 R34 ffJ N) IcON) I-2Si (R3a, R3% are
A single linking group or two or more linking groups composed of any combination selected from atomic groups such as hydrogen atom, s represents a hydrocarbon group having the same content as Q in the above formula (IVa)] represents.

The weight average molecular weight of the macromonomer (MB) is 2 x 104
If it exceeds 100%, the copolymerizability with the hexamer represented by formula (V) decreases, which is not preferable. On the other hand, if the weight average molecular weight is too small, the effect of improving the electrophotographic properties of the photosensitive layer will be reduced, so it is preferably 1XIO3 or more.

The macromonomer (MB) used in the present invention can be produced by a conventionally known synthesis method. in particular,
Obtained by radical polymerization using a polymerization initiator and/or i1 chain transfer agent containing a reactive group such as a carboxyl group, a carboxyhalide group, a hydroxyl group, an amino group, a halogen atom, or an epoxy group in the molecule. It is synthesized by two methods, including a radical polymerization method in which an oligomer with terminal reactive groups is reacted with various reagents to form a macromonomer.

Specifically, P, Dreyfuss & R, P, Ωu
irk, EncyclePolyIl, Sci, Eng
,,l,551 (1987), P.F.,Rempp.
E, Franta, Adu, Polym, Sci,
58, l (1984), Yuji Yogami, Kagaku Kogyo Co., Ltd.
56 (1987), Yuya Yamashita, Polymer, ■, 988 (
1982), Shibe Kobayashi, Kobunshi, Betsu, 625 (1981
), Hiroshi Ito-2 polymer processing, peeling, 262 (+986)
, Raiku Shibu, Takashi Tsuda, Functional Materials, 1MLL No., 10.
It can be synthesized according to the methods described in reviews such as No. 5 and the literature and patents cited therein.

However, since the macromonomer (MB) of the present invention contains the polar group as a component of its repeating unit, it is synthesized with the following considerations in mind, for example.

As one method, for example, as shown in the following reaction formula (1), a monomer containing the polar group in the form of a protected functional group is used, and the above method is used to carry out radical polymerization and a terminal reactive group. This will introduce the following.

Reaction formula (1) % Formula % Covering group for C0OH; e.g. -C(C-Hs)
y, CHl Protecting group reaction and deprotection of the polar groups (SQ, )l group, -PO, H, group, H monomer group) randomly contained in the macromonomer (MB) provided in the present invention Reactions (eg, hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, etc.) can be carried out by conventionally known methods. Specifically, J. F. H. McOmie, “Prote.
active Gvoups in Organic C
1st try, Plenu+5Press (
(1973), T., W., Greene, “Prot.
activeGvoups in Organic 5
ynthesis, John Wiley & 5o
us (1981), Ryohei Koumaru, "Polymer Fine Chemicals", Kodansha (1976), Yoshiyu Iwakura, Keisuke Kurita, "Reactive Polymers", Mudansha (1977), Berne.
retal, J, Radiation Curing,
1986, No. 10, PLO1 JP-A-62-212
No. 669, JP-A-62-286064, JP-A-62-
210475, JP 62-195684, JP 62-258476, JP 63-260439,
Patent Application No. 1982-220510, Patent Application No. 1983-22669
It can be synthesized using the method described in No. 2, etc.

Another method is to synthesize an oligomer as described above, and then add a "specific reactive group" bonded to one end of the oligomer to the oligomer, as shown in reaction formula (II) below. This is a method of synthesis by making use of the difference in reactivity with the contained polar group and reacting with a reagent containing a polymerizable double bonding group that reacts only with "specific reactivity".

Reaction Formula (II) As shown in Reaction Formula (It), specific examples of combinations of specific functional groups are shown in Table A as follows. However, the present invention is not limited thereto, and the important thing is that by utilizing the reaction selectivity in ordinary organic chemical reactions, macro-septamerization can be carried out without protecting the polar groups in the oligomer. It would be good if it could be achieved.

Examples of chain transfer agents that can be used include, for example, mercapto compounds containing the polar group or a substituent that can later be induced into the polar group (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercapto compounds).
Mercaptopropionic acid, 3-mercaptobutyric acid, N-(
2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-CN-(2-mercaptoethyl)
Carbamoyl]propionic acid, 3-(N-(2-mercaptoethyl)aminocopropionic acid, N(3-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptobutanesulfonic acid, 4-mercaptobutanesulfonic acid) , 2-mercaptoethanol, 3-
Mercapto-1,2-propanediol, 1-mercapto-2propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercapto-3-imidazole, 2-mercapto-3-
pyridinol, etc.) or dusulfide compounds which are oxidized products of these mercapto compounds, or iodized alkyl compounds containing the above polar groups or substituents (e.g. iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, -Iodopropane sulfone M
etc.) etc. Preferred are mercapto compounds.

Specific reactive group-containing polymerization initiators that can be used include, for example, 2,2'-azobis(2cyatuburobanol), 2,2'-azobis(2-cyanopentanol), 4,4' -Azobis(4-cyanovaleric acid), 4
．． 4'-azobis(4-cyanovaleric acid chloride), 2
, 2'-azobis[2-(5-methyl-2-imidacillin-2-yl)propane], 2.2'-azobis(2-
(2-imidacylin-2-yl)propane], 2.2'
-azobis(2-(3,4,5,6-tetrahydropyrimidin-2-yl)propane), 2,2'-azobis(
2(1-(2-hydroxyethyl)-2-imidacillin-2-yl]propane), 2,2'-azobis[2-
methyl-N-(2-hydroxyethyl)-propionamide] or derivatives thereof.

The amount of each of these chain transfer agents or polymerization initiators is 0.1 to 15% by weight, preferably 0.5 to IO% by weight, based on 100 parts by weight of the total monomers.

Specific examples of the macromonomer (?IB) of the present invention include the following compounds. However, the scope of the present invention is not limited to these, and
In each of the following, T represents -H or CH, D represents -H, -CH5 or -CH2C0OCH3,
R41 is -CeHza-l (n is an integer of 1 to 18), Br, -CH5, -COCI (s or -COOC
H3), vl is -CN, -0COCH3, -C
ONI (z or -C, ll, vl is -CI,
-Br, -CN or -0CR, α is 2 to 18
β represents an integer of 2 to 12, T represents an integer of 2 to 4
indicates an integer.

(MB-11 (A B-2) (MB-3) (MB-4) (MB-5) (Gate B-6) (MB-7) C.O.

H (1B-9) (-B-10) (MB-14) (MB-15) I * Coo (C8 mountain 0CO (CHHz) a COOH (MB (MB (MC 00H) (: H OOH (MB (MB- 22) CH3 (MB-23) (MB-24) z ShiUUKa+ (MB-25) z OH COOR,, V Coo(CH2),, 0H (-B-26) t On the other hand, the above-mentioned macromonomer (MB) The monomer copolymerized with is represented by general formula (V). In formula (V), e
I%et may be the same or different from each other and represent the same content as C1 and C8 in formula (I[), Xt is X in formula (TVa), and Q! represent the same content as 01 in formula (TVa).

In the resin of the present invention, the composition ratio of the copolymer component having a macromonomer (MB) as a repeating unit and the copolymer component having a repeating unit of the monomer represented by the -i formula (V) is preferably 1 to 1. The weight composition ratio is 70/30 to 99 (weight composition ratio), more preferably 5 to 60/95 to 40.

In addition, in the polymer main chain, -po, u, group, -sO, H group,
Those containing no copolymerization component containing acidic groups such as C0OH group, -0)H group, and -POJJ group are preferred.

Moreover, the resin CB) of the present invention may contain monomers other than these as further copolymerization components together with the above-mentioned macromonomer (MB) and the monomer (V).

For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, heterocyclic vinyl tics, such as vinylpyrrolidone, vinylpyridine, vinylimidazole,
vinylthiophene, vinylimidacilline, vinylpyrazole, vinyldioxane, vinylquinoline, vinylthiazole, vinyloxazine, etc.).

However, the amount of these other monomers other than the macromonomer (MB) and the monomer of formula (~') in the copolymer does not exceed 20% by weight.

Furthermore, resin CB) contains at least one repeating unit represented by -Funazura (V) and at least one repeating unit represented by a macromonomer, and only at one end of the polymer main chain contains the polar group. It may be a copolymer (resin CB')) formed by combining at least one of them, or a copolymer CB' and [B'] may be used together, where the polar group is A chemical structure attached directly to one end of the polymer main chain or via an arbitrary linking group.

Bonding groups include carbon-carbon bonds (-double bonds or double bonds), carbon-hetero atom bonds (hetero atoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and hetero atoms-hetero atoms. It is composed of any combination of atomic groups of atomic bonds. For example, ÷C→-1-(CH=CH→, Rco.

(Ih□ to R34 each have the same contents as R3! to R3a above), etc., is a linking group composed of a single atomic group or a combination of two or more.

In the resin [B] used in the present invention, in order to synthesize the resin [B'] in which the polar group is bonded to the terminal of the polymer main chain, at least the above-mentioned macromonomer (MB) and - This can be achieved by concurrently using a polymerization initiator or chain transfer agent containing the polar group or a specific reactive group that can be derived therefrom in the molecule during the polymerization reaction with the monomer represented by (V).

Specifically, it can be obtained in the same manner as the method for oligomers in which one terminal reactive group is bonded to camphor in the synthesis of macromonomers.

In the electrophotographic photoreceptor of the present invention, greater mechanical strength may be desired while maintaining its excellent electrophotographic properties. For this purpose, a method of introducing a thermally and/or photocurable functional group into the main chain of the graft copolymer can be applied.

That is, in the present invention, it is preferable that the resin [A] and/or the resin CB) further contains as a copolymerization component a monomer containing at least one heat-curable and/or photo-curable functional group. The photocurable functional group appropriately crosslinks the polymers, thereby strengthening the interaction between the polymers and improving the strength of the film.

Therefore, the resin of the present invention further containing such a heat-curable and/or photo-curable functional group can prevent the interaction between the binder resin and the zinc oxide particle surface without hindering the adsorption and coating of the binder resin. This has the effect of further improving the film strength.

The heat and/or photocurable functional group of the present invention refers to a functional group that can cure a resin with at least one of heat and light.

The "thermosetting functional group (functional group that performs a thermosetting reaction)" of the present invention is, for example, "Refinement of thermosetting polymers" by Tsuyoshi Endo, J.
(C, M, C Koji, published in 1986), Hara@Yuji "Latest Binder Technology Handbook" Chapter 11-1 (General Technology Center, published in 1985), Yokiyuki Otsu "Synthesis and design of acrylic resin and development of new applications" (Chubu Management Development Center Publishing Department, 1
985), Eizo Omori “Functional Acrylic Resin” (
The functional groups cited in the review articles such as Techno System, 1985) can be used.

For example, -〇H group, -3H group, -NH, group, -NHR2,
group (R21 represents a hydrocarbon group, specifically, the formula (In
xo of ) represents the same content as 2,1 above,) CONHCHzORtx (Rat is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hequinyl group, TI Tz octyl group, etc.) -N=C=O group or -C=CH group (TI
and T each represent a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, etc.). Moreover, specifically, as the polymerizable double bond, C
H,=C)(-CH,=CH-CH2-1CH,=CH
-C-0CHz = CHCON H-1 CH.

CHt = CCON H- CHz = CHN HC0-1 CH,=CH-CH2- NHCO-1CH,=CH-5O.

CH, =CH-C0-1CH, =CH-○CH, =CH
-3- etc. can be mentioned.

Examples of the "photocurable functional group" of the present invention include Takahiro Tsunoda, "Photosensitive Tree Nj Printing Society Publishing Department (1972), Gentabe Nagamatsu, Hideo Inui, "Photosensitive Polymer" Kodansha (1977)
year) G, A, De1genne+'Encyc
1opedja of Polymer 5cienc
e and Technology.

Supplement, 'V o ] I (197
6) can be used. Specifically, addition polymerizable groups such as an allyl ester group and a vinyl ester group, a cinnamoyl group, and a duplexing group such as a maleimide ring group which may be converted into if may be mentioned.

In the present invention, in order to synthesize a resin containing a thermally and/or photocurable functional group, a nuclear thermal and/or photocurable functional group is used as a copolymer component containing a nuclear thermal and/or photocurable functional group. A monomer containing the group may be used.

When the resin of the present invention contains the thermosetting functional group,
In order to promote the crosslinking reaction in the photosensitive layer, a reaction accelerator may be added as necessary.

In the case of a reaction mode that forms a chemical bond between functional groups, examples thereof include organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, P-)luenesulfonic acid, etc.), crosslinking agents, and the like.

As a crosslinking agent, specifically, Shinzo Yamashita and Tosuke Kaneko ed.
Compounds described in "Crosslinking Agent Handbook" published by Taiseisha (1981) etc. can be used. For example, commonly used crosslinking agents such as organic silane, polyurethane, polyisocyanate, epoxy resin, melamine resin, etc. A curing agent or the like can be used.

In the case of a polymerizable reaction mode, a polymerization initiator (peroxides, azobis-based compounds, etc., preferably an azobis-based polymerization initiator), a monomer containing a polyfunctional polymerizable group (
For example, vinyl methacrylate, acrylic methacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, divinyl succinate,
divinyl adipate, diallyl succinate, 2-) tilvinyl methacrylate, divinyl hensen, etc.).

Further, in the present invention, when using a binder resin containing such a thermosetting functional group, a thermosetting treatment is performed. This heat curing treatment can be performed by tightening the drying conditions during conventional photoreceptor production. For example, 60℃~1
The treatment can be carried out at 20° C. for 5 to 120 minutes, and when the above-mentioned reaction accelerator is used in combination, the treatment can be carried out under milder conditions.

The ratio of resin CA) and resin CB) used in the present invention varies depending on the type, particle size, and surface condition of the inorganic photoconductive material used, but in general, the ratio of resin [A] and resin [B] used is 5. ~80:95-20 (weight ratio), preferably 10-60:90-40 (weight ratio).

In the present invention, resin [A] and resin [B] (
(B') can also be used in combination with other resins. Examples of such resins include alkyd resins, polybutyral resins, polyolefins, ethylene-vinyl acetate copolymers, styrene resins, styrene-butadiene resins, acrylate-butadiene resins, vinyl alkanoate resins, and the like.

If the above-mentioned other resin exceeds 30% (weight ratio) of the total binder resin amount using the resin of the present invention, the effects of the present invention (especially improvement in electrostatic properties) will be lost.

Inorganic photoconductive materials used in the present invention include zinc oxide,
Examples include titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, tellurium selenide, lead sulfide, and the like.

The total amount of binder resin used for the inorganic photoconductive material is 10 to 100 parts by weight, preferably 15 to 50 parts by weight, per 100 parts by weight of the photoconductor.

In the present invention, various dyes can be used in combination as spectral sensitizers if necessary. For example, Harumi Miyamoto, Hidehiko Takei, Imaging 1iL1 (N[L8) p. 12, C, J
, 'loung et al., RCA Revi-ratio 469 (
1954).

Wataru Kiyota, Transactions of the Institute of Electrical Communication Engineers J 63-C (No.
2) Carbonium-based dyes diphenylmethane dyes and triphenylmethane dyes cited in reviews such as 97 (1980), Yuji Harasaki et al., Industrial Chemistry Miscellaneous 78 and 18B (1963), Tadaaki Tani 1 Journal of the Photographic Society of Japan 208 (1972), etc. , xanthine dyes, phthalein dyes, polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain metal), and the like.

More specifically, examples of those mainly using carbonium dyes, triphenylmethane dyes, xanthine dyes, and phthalein dyes include Japanese Patent Publication No. 452/1983, Japanese Patent Application Laid-open No. 90334/1983, and Japanese Patent Application Laid-Open No. 50-90334. -114227, JP 53-39130, JP 53-82353,
U.S. Patent No. 3.052.540, U.S. Patent No. 4,05
Examples thereof include those described in No. 4,450, JP-A-57-16456, and the like.

oxonol dye, merocyanine dye, cyanine dye,
Polymethine dyes such as logcyanine dyes include F, M
,Harmmar rThe Cyanine Dy
es andRelated Co@pounds J
The pigments described in U.S. Pat. No. 3.041.384 and U.S. Pat. No. 3,1 can be used.
No. 10.591, U.S. Patent No. 3.121008, U.S. Patent No. 3,125,447, U.S. Patent No. 3,128.
No. 179, U.S. Patent No. 3,132,942, U.S. Patent No. 3,622.317, British Patent No. 1,226,89
No. 2, British Patent No. 1,309,274, British Patent No. 1
, No. 405,898, Japanese Patent Publication No. 48-7814, Japanese Patent Publication No. 55-18892, and the like.

Furthermore, as a polymethine dye that spectrally sensitizes the near-infrared to infrared light region with a long wavelength of 700 nm or more, JP-A-47-840
No., JP-A No. 47-44180, JP-A No. 51-4106
No. 1, JP-A-49-5034, JP-A-49-4512
No. 2, JP-A-5746245, JP-A-56-3514
No. 1, JP-A-57-157254, JP-A-61-26
No. 044, JP-A No. 61-27551, U.S. Patent No. 3,
No. 619,154, U.S. Patent No. 4.175.956,
rResearch Disclosure J 19
1982, 216, pages 117 to 118. The photoreceptor of the present invention is excellent in that its performance does not easily vary depending on the sensitizing dye, even when various sensitizing dyes are used together. There is. Furthermore, if necessary, various conventionally known additives for electrophotographic photosensitive layers, such as chemical sensitizers, may be used in combination. Electron-accepting compounds (e.g., halogens, henzoquinone, chloranil, acid anhydrides, organic carboxylic acids, etc.) in reviews cited by Hiroshi Komon et al.
Polyarylalkane compounds, hindered phenol compounds, and p-phenylene cited in the review of ``Recent Development and Practical Application of Photoconductive Materials and Photoreceptors'' Chapters 4 to 6, published by Nihon Kagaku Information Co., Ltd. (Cl. 986) Examples include diamine compounds.

The amount of these various additives added is not particularly limited, but
Usually 0.0001 to 2.0 parts per 100 parts by weight of photoconductor.
It is 0 parts by weight.

The thickness of the photoconductive layer is preferably 1 to 100 microns, particularly 10 to 50 microns.

In addition, when a photoconductive layer is used as a charge generation layer in a laminated photoreceptor consisting of a charge generation layer and a charge transport layer, the thickness of the charge generation layer is 0.01 to 1μ, particularly 0.05 to 0.5μ. Good, suitable.

In some cases, an insulating layer is added for the purpose of protecting the photoreceptor, improving durability, dark decay characteristics, etc.

At this time, the insulating layer is set to be relatively thin, and when the photoreceptor is used in a specific electrophotographic process, the insulating layer provided is set to be relatively thick.

In the latter case, the thickness of the insulating layer is between 5 and 70μ, in particular 1
It is set from 0 to 50I.

Charge transport materials for the laminated photoreceptor include polyvinylcarbazole, oxazole dyes, birapurin dyes, triphenylmethane dyes, and the like.

The thickness of the charge transport layer is 5 to 40 μm, particularly 10 to 3 μm.
0u is preferred.

Typical resins used to form the insulating layer or charge transport layer include polystyrene resin, polyester resin, cellulose resin, polyacrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride vinyl oxide copolymer resin, Thermoplastic resins and curable resins such as polyacrylic resins, polyolefin resins, urethane resins, epoxy resins, melamine resins, and silicone resins are used as appropriate.

The photoconductive layer according to the invention can be provided on a conventionally known support. Generally speaking, the support for the electrophotographic photosensitive layer is preferably electrically conductive.As the electrically conductive support, for example, a base material such as metal, paper, or plastic sheet impregnated with a low-resistance substance is used in the same manner as in the past. those that have been subjected to conductive treatment, such as those that have been coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided) and also to prevent curling, and those that have been coated with at least one layer for the purpose of preventing curling, etc. Those with a water-resistant adhesive layer on the surface of the support, those with at least one pre-coated layer as required on the surface layer of the support, and those with a conductive plastic base coated with A1, etc., on paper. Laminated materials can be used.

Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, IT child photo, 14. (Floor 1), p2-11
(1975), Hiroyuki Moriga, “Introductory Special Paper Chemistry J Polymer Publication Society (1975), M.F., Hoover.
J, Macr.

sol, Sci, Chew, A-4(6),
Those described on pages 1327 to 1417 (1970) and the like are used.

(Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

(Synthesis example of resin [A]) Synthesis example 1 of resin [A]: (A-1) A mixture of 70 g of 26-cyclophenyl methacrylate, 1 30 g of macromonomer (MM-1) having the following structure, and 200 g of toluene was heated in a nitrogen stream. The temperature was then raised to 80°C. 4.
4'-azobis(4-cyanovaleric acid) (abbreviation ^, C, V
) and stirred for 4 hours. Furthermore, A, C, V.

Add 1.0g for 2 hours, then wash A, C, V, 0.5
g was added and stirred for 3 hours. The weight average molecular weight (abbreviation ~) of the obtained copolymer was 8.6 x 10'.

(MM-1) CH.

(A-11 CH.

CH.

Synthesis Examples 2 to 7 of Resin [A] A-2 to A-7 In Synthesis Example 1 of Resin [A], macromonomer (MM
-1) Except for replacing the macromomer shown in Table-1 below,
Resin [A] shown in Table 1 below was obtained by reacting in the same manner as in Synthesis Example 1.
were synthesized respectively. ~ of the obtained copolymer is 7.5xl
O' ~9.5 xlO' Tnia ivy.

Synthesis Example 8 of Resin [A): A mixed solution of 60 g of [A-8) Hensyl methacrylate], 40 g of a macromonomer (MM-8) having the following structure, 150 g of toluene, and 50 g of isopropyl alcohol was heated at a temperature of 80°C under a nitrogen stream. It was heated to ゛C.

5.0 g of A, C, and V were added and stirred for 4 hours. Sarani A,
C.V.

Add 1.0g for 2 hours, then add A, C, ν, 0.5
g and stirred for 3 hours.

The weight average molecular weight of the obtained copolymer was 8.3 x 10
It was 3.

(MM-8) CHz CH2=C COOCHzCl(go 10GHzCH,CI(,CH
zO1CJs~6. OX to' (A-8) -COOCHzCHzO+(CHz)40 +-ca)
Synthesis example 9 of ts resin [A]: [^-91 60 g of 2-chlorophenyl methacrylate, the following Fl,
A mixed solution of 40 g of M macromonomer 0+M-9), 4.0 g of thioglycolic acid, and 200 g of toluene was heated to 75° C. under a nitrogen stream. 2,2”-azobisisobutyronitrile (abbreviation: A, 1Bj1.) 1.5
Add g and stir for 4 hours, then add ^, r, B, N, 0.4 g
Add for 2 hours, then continue ^, 1. B, N, 0.2
g was added and stirred for 3 hours.

The weight average molecular weight of the obtained copolymer was 7.0×10
It was 3.

(MM-9) CI+! H (A-93 Ning -C00C)1. cHc11!0OC(C)1t)
ffcOO+c)IICH! Synthesis example 10-15 of 0+-CO2H resin [A]: [4-107~m
A-15] In Synthesis Example 9 of Resin [A], 4 g of each of the mercapto compounds (chain transfer agents) shown in Table 2 were used instead of 4 g of thioglycolic acid, but in the same manner as in Synthesis Example 9 above. Each resin [A] was manufactured.

Synthesis Example 16 of Surface Resin [A]: [A-16] A mixture of 60 g of 2,6-cyclophenyl methacrylate, 40 g of macromonomer (MM-9), 2 g of thioglycolic acid, 150 g of toluene, and 50 g of ethanol was heated under a nitrogen stream at temperature. It was heated to 80°C. A. Add 3g of CJ and 4
Time reaction and further A, CJ 1. Og was added and reacted for 4 hours. The weight average molecular weight of the obtained copolymer was 8.5×1
It was 03.

(A-16) N resin (Al synthesis examples 17-18: [A47)-[A
-18] Resins [A-171 and [^-181] having the following structures were respectively produced in the same manner as in Synthesis Example 9 of Resin [A].

Resin [A17] I C)l□ Resin (A-18) ~ 6.5X10" Synthesis Examples 19-24 of Resin [A): [A-191 ~ [
Resins having the following structures were produced in the same manner as in Synthesis Example 9 of A-241 Resin [A). ~ of each resin is 7.3 XIO
”~9×104.

Table: Synthesis example 1 of macromonomer (MB): 90 g of M-1 ethyl methacrylate, 10 g of 2-hydroquine ethyl methacrylate, 5 g of thioglycolic acid, and 200 g of toluene
The mixed solution was heated to 75°C while stirring under a nitrogen stream.
It was heated to 2.2'-Azobisisobutyronitrile (abbreviations a, r, B, N,)1. Og was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate and 1.0 g of N,N-dimethyldodecylamine were added to this reaction solution.
and 0.5 g of t-bunalhydroquinone, and the temperature was 1.
The mixture was stirred at 00°C for 12 hours. After cooling, this reaction solution was reprecipitated into n-hexane 21 to obtain 82 g of white powder.
The weight average molecular weight of the polymer was 3.8 XIO'.

(M-1) Synthesis example 2 of macromonomer (?IB): M-2 A mixed solution of 90 g of butyl methacrylate, 10 g of methacrylic M, 4 g of 2-mercaptoethanol, and 200 g of tetrahydrofuran was heated to a temperature of 70°C under a nitrogen stream. . A.1. 1.2 g of B and N were added and reacted for 8 hours.

The reaction solution was then cooled in a water bath to a temperature of 20°C,
10.2 g of triethylamine was added, and 14.5 g of methacrylic acid chloride was added dropwise with stirring at a temperature of 25°C or less. After the dropwise addition, the mixture was further stirred for 1 hour. Then t-
0.5 g of butylhydroquinone was added, heated to 60°C, and stirred for 4 hours. After cooling, the mixture was added dropwise to 1 liter of water with stirring for about 10 minutes), stirred as it was for 1 hour and allowed to stand, and then the water was removed by decantation. After washing twice more with water, it was dissolved in tetrahydrofuran 100I11 and reprecipitated in petroleum ether 2j2. The precipitate was collected by decantation and dried under reduced pressure. The yield of the viscous material obtained was 65g and the weight average molecular weight was 5.6X10''
'Met.

(M Macromonomer (MB) Synthesis Example 3: M-3 A mixture of 95 g of benzyl methacrylate, 5 g of 2-phosphonoethyl methacrylate, 4 g of 2-aminoethyl mercaptan, and 200 g of tetrahydrofuran was heated to a temperature of 70°C with stirring under a nitrogen stream. It was warm.

^, 1. B, N, 1.5g were added and reacted for 4 hours, and A, 1. 0.5 g of B and N were added and reacted for 4 hours. Next, this reaction solution was cooled to a temperature of 20°C, acrylic anhydride Log was added, and the mixture was stirred at a temperature of 20 to 25°C for 1 hour.

Next, add 1.0 g of t-butylhydroquinone and bring the temperature to 50.
Stirred at ~60°C for 4 hours. After cooling, add water! The reaction mixture was clarified for about 10 minutes while being stirred, and after being stirred for 1 hour, it was allowed to stand, and the water was removed by decantation. After repeating the washing with water two more times, tetrahydrofuran 100jlIi! and reprecipitated in petroleum ether 21. The precipitate was collected by decantation and dried under reduced pressure.

The yield of the obtained viscous material was 70 g, and the weight average molecular weight was 7.
It was 4 XIO'.

(M-3) Synthesis example 4 of macromonomer (MB): 95 g of M-42-chlorophenyl methacrylate, 5 g of monomer of the following structure (1), 4 g of thioglycolic acid, and 200 g of toluene.
The mixed solution was heated to a temperature of 70°C under a nitrogen stream.
Add 1.5 g of A, 1B, and N, react for 5 hours, and then add A
, 1. 0.5 g of B and N were added and reacted for 4 hours. Next, 12.4 g of glycidyl methacrylate, 1.0 g of N,N dimethyldodecylamine, and 1.5 g of butylhydroquinone were added and reacted at a temperature of 110'C for 8 hours. After cooling, the reaction mixture was mixed with 3 g of P-toluenesulfonic acid.
The mixture was added to 100 d of a 90 vol x tetrahydrofuran aqueous solution and stirred at a temperature of 30 to 35°C for 1 hour.

The above mixture was reprecipitated into a mixed solution 21 of water/ethanol ((1/3 volume)), and the precipitate was collected by decantation. This precipitate was mixed with 200+ d of tetrahydrofuran.
The powder was dissolved in and reprecipitated in n-hexane 21 to obtain 58 g of powder, which had a zero weight average molecular weight of 7.6 x 10'.

Monomer (1) H3 Hx (M CH! Synthesis example 5 of macromonomer (MB): M-52.6-cyclophenyl methacrylate) 95 g, 3- (2'
A mixed solution of 150 g of toluene and 50 g of isopropyl alcohol was heated to a temperature of 80° C. under a flow rate of 1%. 2.2'-azobis(2-cyanovaleric acid)
(Abbreviation: A, CJ,) 5.0 g was added and reacted for 5 hours, and further 1.0 g of A, C, V was added and reacted for 4 hours. After cooling, the reaction product was reprecipitated into methanol 21, filtered, and dried under reduced pressure.

The above powder 50g glycidyl methacrylate 14g 1N,
A mixture of 6 g of N-dimethyltosylamine Q, 1.0 g of t-butylhydroquinone, and 100 g of toluene was stirred at a temperature of 110° C. for 10 hours. After cooling to room temperature, the mixture was irradiated with light for 1 hour under stirring using an 80 W high-pressure mercury lamp. Thereafter, the reaction mixture was reprecipitated into 1 liter of methanol, and the powder was dried under reduced pressure using a filter. Yield 34g and weight average molecular weight? , 3 x 10'.

(M-5) Synthesis Example 1 of the resin [B] of the present invention: (B-1) 80 g of benzyl methacrylate 1 20 g of the compound (M-2) of Synthesis Example 2 of the macromonomer (MB) and 100 g of toluene
The mixed solution of g was heated to a temperature of 75°C under a nitrogen stream. 1. Add 0.8 g of 1'-azobis(cyclohexane-1-carbocyanide) (abbreviation ^, B, C, C,), react for 4 hours, and then add ^, 1. 0.5 g of B and N were added and reacted for 3 hours.

~ of the obtained copolymer is 1. It was OXIO'.

[B l〕

Synthesis example 2 of resin CB) of the present invention: (B-2) 70 g of 2-chlorophenyl methacrylate, macromonomer (question)
A mixed solution of 30 g of compound (M-1) of Synthesis Example 1, thioglycolic acid o,'yg, and 150 g of toluene was heated to a temperature of 80''C under a nitrogen stream. A, B, C, C,
0.5g was added and reacted for 5 hours, and then A, B, C, C, 0
, 3 g was added thereto, and 0.2 g of A, B, C, and C were further added and reacted for 3 hours.

~ of the obtained copolymer was 9.2 x 10'.

CB-2) Synthesis Example 3 of the resin CB) of the present invention: [B-33 60 g of methyl methacrylate, the compound of Synthesis Example 4 of macromonomer (MB): (M-4) 25 g, 15 g of methyl acrylate and 150 g of toluene The mixed solution was heated to 75° C. under a nitrogen stream. 0.5 g of A, C, and V were added and reacted for 5 hours, and 0.3 g of ^, C, and V were added and reacted for 4 hours. ~ of the obtained copolymer is 1. It was 1×104.

(B-3) Synthesis examples 4 to 11 of resin [B] of the present invention: [8-41
~ Each resin [B] was synthesized in the same manner as in Synthesis Example 1 of [B-111 Resin CB] using methacrylates and macromonomers corresponding to Table 4 below.

Synthesis Examples 12 to 19 of resin [B] of the present invention: [B-1
2] to [B49] Resin CB-2] Resin [B] shown in Table 5 below was synthesized in the same manner as in Synthesis Example 2 of Resin CB-2] by changing the methacrylate and the macromonomer mercapto compound.

The size of each resin is 9 x 104~1. It was I x 10'.

Synthesis examples 20 to 27 of resin [B] of the present invention: [B-2
01 to [11-27] Resin [B] shown in Table 6 below was synthesized in the same manner as Synthesis Example 3 of Resin [B] by changing the methacrylate, macromonomer, and azobis-based compound.

Flw- of each resin CB) is 9.5 XIO' to 1.5
It was XIO'.

Examples 1 to 2 and Comparative Examples A to D Example 1 6 g of the resin (A-8) produced in Synthesis Example 8 of Resin [A] (
34 g (as solid content) of resin (B-3) produced in Synthesis Example 3 of Resin CB] (as solid content) 200 zinc oxide
g, cyanine dye [A] with the following structure: 0.018 g,
A photosensitive layer-forming product was prepared by dispersing a mixture of 0.40 g of salicylic acid and 300 g of toluene in a ball mill for 3 hours, and this was applied to conductive-treated paper with a dry adhesion amount of 25 g/n.
Apply with a wire bar so that f
An electrophotographic light-sensitive material was prepared by drying for a second and then standing in a dark place at 20° C. and 65% RH for 24 hours.

Cyanine dye [A] Example 2 An electrophotographic light-sensitive material was produced in the same manner as in Example 1, except that 6 g of resin (A-1) was used instead of 6 g of resin (A-8) in Example 1. was created.

Comparative Example A Electrophotographic material A was produced in the same manner as in Example 1, except that 6 g of the following resin (R-1) and 34 g of the following resin (R-2) were used as the binder resin.

Resin (R-1) COOCJs Cool ~: 6.5 x 104 (weight composition ratio) Resin (
R-2) H COOC112 ~:5xio' Comparative Example B Electrophotographic exposure was carried out in the same manner as in Example 1, except that 6 g of the following resin (R-3) and 34 g of the following resin [R-4] were used as the binder resin. Material B was produced.

Resin (R-3) C00CJs (ethyl methacrylate/β-mercaptopropionic acid) charge weight ratio (9515) wt: 6×104 Resin [R-4) ~: 1.2 XIO' Film properties of these photosensitive materials ( surface smoothness), film strength,
Electrostatic properties, imaging performance, and environmental conditions at 30°C.

The electrostatic characteristics of the image pickup body at 80% RH were investigated.

Furthermore, when these photosensitive materials are used as original plates for offset masters, the photoat desensitization property (represented by the contact angle with water of the photoconductive layer after desensitization treatment) and printability (background smearing) , printing durability, etc.).

The above results are summarized in Table 7.

The implementation aspects of the evaluation items shown in Table 7 are as follows.

Note 1) Smoothness of the photoconductive layer: The obtained photosensitive material was evaluated for its smoothness (sec/cc) using Benck Smoothness Test II (manufactured by Kumagai Riko) under the condition of an air volume of 1 cc. was measured.

Note 2) Mechanical strength of the photoconductive layer: The surface of the photosensitive material obtained was tested with emery paper (11000) at a load of 60 g/cd using Hayton-14 type surface test material (manufactured by Niina Kagaku ■). The remaining film rate (%) was determined from the weight loss of the photosensitive layer by repeatedly removing abrasion powder and using it as mechanical strength.

Note 3) Electrostatic properties: In a dark room at a temperature of 20°C and 165% RH, each photosensitive material was subjected to corona discharge at -6 kV for 20 seconds using a paper analyzer (Paper Analyzer 5P-428 model manufactured by Kawaguchi Electric). After that, the surface potential was left to stand for 10 seconds, and the surface potential at this time was measured. , that is, the dark decay retention rate [DRR
(χ) was determined by (V+*o/V+o)X100(%).

After the surface of the photoconductive layer is charged to -400 nm by corona discharge, it is irradiated with monochromatic light with a wavelength of 780 nm to increase the surface potential (
V+. ) is attenuated to 1/lO, and the exposure amount E I/l@(erg/cj) is calculated from this.

In addition, the time required for the surface potential (V+) to attenuate to 1/100 is calculated from To, and the exposure amount E+z+oe (erg/
cj).

4) Imaging performance: Each photosensitive material was left for one day and night under the following environmental conditions.

Next, the surface of the photosensitive material was charged at -3 kV, and a 45 erg
After exposure at a pitch of 25 and a scanning speed of 300 m/sec under an irradiation dose of /cj, a copy obtained by developing and fixing using ELP-T (manufactured by Fuji Photo Film ■) as a liquid developer side. Images (capri, image quality) were visually evaluated.

The environmental conditions during layer imaging were 20°C, 65% RH and 30°C, 80%.
It was carried out at RHH.

Note 5) Contact angle with water: Each photosensitive material was passed through an etching prosensor once using a solution prepared by diluting the desensitizing liquid ELP-EX (manufactured by Fuji Photo Film) twice with distilled water. After desensitizing the light guide tN surface, add 2p of distilled water to it! Place the water droplets on the
The formed contact angle with water is measured with a goniometer.

Note 6) Printing durability Each photosensitive material is plate-made under the same conditions as Note 4) above to form a toner image, desensitized under the same conditions as Note 5) above, and used as an offset master in an offset printing machine. (Oliver Model 52, manufactured by Sakurai Manufacturing Co., Ltd.), indicates the number of sheets that can be printed without causing problems with background stains in the non-image areas and image quality of the image areas (the higher the number of prints, the better the printing durability. ).

As shown in Table 7, the electrostatic properties of comparative examples using conventionally known resins showed only small changes due to changes in environmental conditions.
The values of R, R, El/l'0 and El/+1111 themselves were low. In the case of A, the mechanical properties were even more unsatisfactory than in B.

As a result, when an image was captured using a scanning exposure method using low-power semiconductor laser light, the image capture performance of the copied image was degraded.

In other words, limitations on the amount of light irradiation due to a low-output light source or potential attenuation of unexposed areas (image areas) during the exposure time due to the scanning exposure method may cause a decrease in the image quality of the actual copied image (for example, a decrease in D6, fine lines, etc.). Furthermore, as the output of semiconductor laser light becomes low and the amount of light irradiation is restricted, the residual potential after exposure becomes an important problem, and in actual imaging performance, the residual potential in non-image areas becomes It appears as a yellowtail. This is due to the electrostatic characteristics E17. . . Correspondingly, the smaller this value is, the more preferable it is, and Comparative Examples A and B are still unsatisfactory, and even in the copied images, under the actual imaging conditions, ground force blur was observed.

However, all of the photosensitive materials of the present invention had good electrostatic properties and good imaging properties. Furthermore, the film strength of the photosensitive layer of the photosensitive material of the present invention was sufficient.

Next, when the photoconductor after plate making is used as an offset master original plate, desensitization with a desensitization treatment liquid is as follows:
In all cases, the contact with water in the non-image area, which was free of burrs, was as small as 10 degrees or less, and was sufficiently hydrophilized. However, when actually printed under the printing conditions corresponding to the large-sized mark 1i4Il, Comparative Example A did not produce a clear image as an actual printed product due to the insufficient copy image after plate making and the lack of strength of the photosensitive layer. Only about 1,000 sheets of image quality could be obtained. In addition, even in Comparative Example B, which increased the strength of the photosensitive layer and improved the copied image, the reproducibility of the image was unsatisfactory.
The printing at of the printed matter deteriorated after about 00 sheets. −
In the case of the strength wood invention, 6,000 to 8,000 prints with clear image quality without background stains can be produced regardless of the environmental conditions of plate making.
I got one.

From the above, the photosensitive material of the present invention has a smoothness of the photoconductive layer of 1
1. It was good in all aspects of strength, electrostatic properties, and printability.

Examples 3 to 22 In Example 1, 6 g of resin (A-8) and resin (B-3
) 6g each of resin [A] shown in Table 8 below instead of 34g
, resin [B] were used in an amount of 34 g each, and cyanine dye [A] was used.
) Each photosensitive material was produced in the same manner as in Example 1, except that 0.018 g of cyanine dye (B) having the following structure was used instead of 0.018 g.

Cyanine dye rB) As shown in Table 8, excellent results were obtained in the present invention. Furthermore, when the resin [A] contains a methacrylate component containing a specific substituent as a polymer component, the electrostatic properties are particularly improved. In addition, we were able to print over 8,000 copies in all of the locations where we printed as off-cent master master plates.

Examples 23 to 36 In Example 1, 6 g of resin (A-8) and resin CB-3
) Instead of 34g, add 6g each of resin [A] shown in Table 9 below.
, using 34 g each of resin [B], and cyanine dye [A].
Instead of 0.018 g, a methine dye with the following structure (
C) Each photosensitive material was produced in the same manner as in Example 1 except that 0.016 g was used.

Methine dye (C) Table Each characteristic was measured in the same manner as in Example 1. The smoothness and film strength of each light-sensitive material showed properties almost equivalent to those of the sample of Example 1.

Each of the photosensitive materials of the present invention has excellent chargeability, dark charge retention, and photosensitivity, and the actual reproduced images are also produced at high temperatures (30°C).
Even under the harsh conditions of 80% RH), clear images with no soil burr were obtained. Moreover, when printed as an offset master original plate, 6000 to 8000 sheets could be printed.

Examples 37-40 As the binder resin, the resins listed in Table 10 below [A) 6.
5g and resin [B] 33.5g, zinc oxide 200g, rose bengal 0.05g, bromophenol blue 0.
03g, uranine 0.02g, phthalic anhydride 0.3g
A mixture of 240 g of toluene and 240 g of toluene was dispersed in a ball mill for 4 hours. A dry amount of 25g of this was applied to conductive treated paper.
An electrophotographic light-sensitive material was prepared by coating the film with a wire bar so that the coating composition had a temperature of /rrf, heating it at 110°C for 30 seconds, and then leaving it for 24 hours at 20°C and 65% RH.

Table 10 Electrostatic properties are measured values under the conditions of (30°C, 180% IIIH).

The photosensitive material of the present invention has chargeability, dark charge retention,
It has excellent light sensitivity, and the actual copied images can be used even in high temperature and high humidity conditions (30℃).
Even under harsh conditions (-80% RH), it provided clear images with no formation of soil pressure.

Further, when this was printed using as an original plate for an offset master, prints with clear image quality were obtained even at the number of prints shown in Table 10.

However, in terms of electrostatic properties, El/l. After the surface of the photoconductive layer was charged to -400V by corona discharge, the surface of the photoconductive layer was irradiated with visible light at an illuminance of 2.0 lux until the surface potential (V+) attenuated to 1710V. Find the time and use it to determine the exposure amount El/I. (looks/seconds) was calculated.

In addition, plate making of photosensitive materials is carried out using a fully automatic plate making machine ELP404V (
A toner image was formed using ELP-T (manufactured by Fuji Photo Film ■) as a toner.

(Effects of the Invention) According to the present invention, an electrophotographic photoreceptor having excellent electrostatic properties and mechanical strength can be obtained.

(3 others)

Claims (2)

[Claims] (1) In an electrophotographic photoreceptor having a photoconductive layer containing at least an inorganic photoconductor and a binder resin, the binder resin includes at least one of the following resins [A] and resin [B]. An electrophotographic photoreceptor comprising at least one of the following. Resin [A]: Weight average molecular weight 1×10 represented by the following general formula (I)
Contains at least one type of macromonomer (MA) of ^3 to 2 x 10^4 as a polymerization component, and -PO_3H_2 group, -SO_3H group, - only at one end of the polymer main chain.
There are COOH groups and ▲mathematical formulas, chemical formulas, tables, etc.▼{R
_1 represents a hydrocarbon group or -OR_0 (R_0 represents a hydrocarbon group) group} group, weight average molecular weight 1.0 x 10^3 formed by bonding at least one acidic group selected from
~2.0 x 10^4 graft copolymer. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. represents a hydrocarbon group, -COO-Z, or -COO-Z via a hydrocarbon group having 1 to 8 carbon atoms (Z represents a hydrocarbon group having 1 to 18 carbon atoms). X is -COO-, -OCO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ (l_1 and l_2 indicate integers from 1 to 3), -CO-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (P_1
represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms)
, -CONHCOH-, -CONHCOO-, -O-,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ or -SO_2-. Y represents a group connecting X and -O-. [ ] represents a repeating unit, and n represents an integer from 1 to 3. When n is 2 or more, W in [ ] represents a group different from at least the adjacent W in [ ]. W has ▲mathematical formula, chemical formula, table, etc.▼or ▲mathematical formula,
There are chemical formulas, tables, etc. Represents ▼ (r_1 and r_2 may be the same or different and each represents a hydrogen atom or an alkyl group). R_1_1 represents a hydrogen atom or a hydrocarbon group. [Binder resin [B]: At least one of the polymer components represented by the following general formulas (IVa) and (IVb), -COOH group, -PO_3H
_2 group, -SO_3H group, -OH group, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ Polymer component containing at least one component containing at least one polar group selected from (R_2 represents the same content as R_1 above) group, -CHO group, and cyclic acid anhydride-containing group The following general formula (III) is present only at one end of the polymer main chain containing at least one type of
A monofunctional macromonomer having a weight average molecular weight of 2×10^4 or less (MB
) and a monomer represented by the following general formula (V), a copolymer having a weight average molecular weight of 5 x 10^4 to 1 x 10^6. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (III), X_0 is -COO-, -OCO-, -C
H_2OCO-, -CH_2COO-, -O-, -SO
_2-, -CO-, -CONHCOO-, -CONHC
ONH-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R_3_1 represents a hydrogen atom or a hydrocarbon group. ). c_1 and c_2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -C
OO-Z_1 or -COO-Z_1 via hydrocarbon (
Z_1 each represents a hydrogen atom or a hydrocarbon group which may be substituted. General formula (IVa) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IVb) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In formula (IVa) or (IVb), X_1 is X in formula (III)
Represents the same content as _0. Q_1 is carbon number 1-18
represents an aliphatic group or an aromatic group having 6 to 12 carbon atoms. d_1 and d_2 may be the same or different from each other,
It represents the same content as c_1 and c_2 in formula (III). Q_0 is -CN, -CONH_2 or ▲ mathematical formula, chemical formula,
▼ represents a hydrogen atom, a halogen atom, an alkoxy group, or -COOZ_2 (Z_2 represents an alkyl group, an aralkyl group, or an aryl group). General formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (V), V_2 represents the same content as V_1 in formula (IVa), and Q_2 is the same as Q_1 in formula (IVa). represents the content of e_1 and e_2 may be the same or different, and represent the same contents as c_1 and c_2 in formula (III). (2) The resin [B] has -PO_3H_2 groups, -SO_
3H group, -COOH group, -OH group, ▲mathematical formula, chemical formula, table, etc.▼ group (R_3 is R_1 described in claim (1)
Claim (1) is a resin in which at least one polar group selected from cyclic acid anhydride-containing groups and cyclic acid anhydride-containing groups is bonded to the end of the main chain of the copolymer.
The electrophotographic photoreceptor described above.