JPH04255857A - Electrophotographic type lithographic printing original plate - Google Patents

Abstract

PURPOSE:To obtain an excellent printing picture and a plate having large plate wear by including a specified resin as a binding resin for a photoconductive layer and including a nonaqueous solvent base dispersed particle resin in a surface layer. CONSTITUTION:One of resins A as a binding resin for a photoconductive layer is included and one of nonaqueous solvent base dispersed particle resins L is included in a surface layer. The resins A have a weight average molecular weight of 1X10<3> to 2X10<4> and include a repeated unit represented by the formula as a polymer component by >=30wt% and a polymer component having at least one polar group selected from-PO3H2, -SO3H, -COOH, etc., by 0.5 to 15wt%. The nonaqueous solvent base dispersed particle resins L are a copolymer obtained by disperse polymerizing one of monofunctional monomers A which are soluble by nonaqueous solvent in nonaqueous solvent but made insoluble by polymerization and include a functional group forming a carboxyl group by decomposition in the presence of a disperse stabilizing resin soluble in nonaqueous solvent.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention is directed to plate making using an electrophotographic method.
It relates to original plates for electrophotographic lithographic printing, and is particularly
In order to provide a surface layer with specific properties on the photoconductive layer,
For improving compositions for forming surface layers of planographic printing original plates
related. [Prior Art] Currently, offset master plates for direct plate making
A wide variety of methods have been proposed and put into practical use. recent years
, providing a specific resin layer on a normal electrophotographic photoreceptor
A printing plate with hydrophilic treatment on the surface of non-image area that is easy to make plate by
The method for creating it is shown in Japanese Patent Publication No. 45-5606.
There is. That is, vinyl ether is deposited on the electrophotographic photosensitive layer.
Maleic anhydride copolymer and hydrophobic resin compatible therewith
A printing plate is disclosed which is provided with a surface layer consisting of a fat. After the toner image is formed, the non-image area of this layer is treated with alkali.
By hydrolytically opening the acid anhydride ring moiety,
It is a layer that can be made hydrated (a layer that can be made hydrophilic). used there
The vinyl ether-maleic anhydride copolymer is
Because it becomes water-soluble when it is ringed and made hydrophilic.
, even if the layer is formed in a compatible state with other hydrophobic resins.
Even if it is, its water resistance is extremely poor.
The printing durability was limited to 500 to 600 sheets at most. [0003] Furthermore, JP-A-60-90343 and JP-A-60-90343
159756, 61-217292, etc.,
The main component is silylated polyvinyl alcohol, and
Those who provide a surface layer (hydrophilic layer) using a crosslinking agent
The law is shown. That is, this layer is non-reactive after toner imaging.
In the image area, silylated polyvinyl alcohol
is hydrolyzed to make it hydrophilic. Also, hydrophilic
In order to maintain the film strength after oxidation, polyvinyl alcohol is used.
Adjust the degree of silylation and crosslink the remaining hydroxyl groups using a crosslinking agent
are doing. As a result, the background smearing properties of printed matter are improved.
It is stated that the printing quality is improved and the number of printed sheets is improved. However, when actually evaluated, it is found that
However, the level of dirt on the background is still unsatisfactory. Also,
Silylated polyvinyl alcohol is polyvinyl alcohol
is produced by silylating it to the desired ratio with a silylating agent.
However, since it is a polymer reaction, it is not possible to produce it stably.
It is difficult to Furthermore, the chemical structure of the hydrophilized polymer is limited.
Because of this, it inhibits its function as an electrophotographic photoreceptor.
1) Chargeability, 2) Quality of copied image (image area)
halftone reproducibility/resolution, background fog in non-image areas, etc.), 3)
Prevent the surface layer from affecting exposure sensitivity, etc.
There were some problems, such as difficulty. [0005] The present inventors have developed an electrophotographic planar image as described above.
In order to improve the problems of the original printing plate, first,
Generates carboxyl groups by decomposition as the main component of the surface layer
Electrophotographic lithographic printing using resin containing functional groups
Proposed the original version (Japanese Patent Application No. 1983-28345)
. Furthermore, as a surface layer resin, it becomes hydrophilic by decomposition.
A resin containing a functional group that generates a functional group and a resin in the photosensitive layer.
We are considering using a compound that crosslinks fat, for example.
Contains a functional group that generates hydroxyl groups upon decomposition
(JP-A-1-254970, JP-A-1-262556)
(No. Publication), a functional group that generates a carboxyl group upon decomposition
containing (JP-A-1-283572, JP-A-1-28
4860 publications), thiol group, amino group by decomposition
Contains functional groups that generate , phosphono groups, sulfo groups, etc.
(JP-A-1-304465, JP-A-1-306855)
Publication No.) etc. were proposed. Furthermore, hydrophilic groups are formed in the surface layer by decomposition.
Contains functional groups that generate and form a higher-order network structure
A method that uses a small amount of resin particles with a micro particle size has been investigated.
For example, functional groups that generate carboxyl groups by decomposition are
those containing functional groups (JP-A-2-13965);
Contains a functional group that generates hydroxyl groups upon decomposition
(Japanese Unexamined Patent Publication No. 2-13966), which can be easily removed by disassembly
Those containing functional groups that generate ho groups, phosphono groups, etc. (
JP-A-2-13967) and the like are disclosed. These binder resins or resin particles are insensitive.
Hydrolyzed and processed by fattening liquid or soaking water used during printing.
Those that generate hydrophilic groups through hydrogen decomposition or water decomposition, etc.
It is. These are used as surface layer resins for lithographic printing plates.
In both cases, the hydrophilic group itself is included from the beginning.
Deterioration of electrophotographic properties (dark charge retention amount and
In addition to avoiding problems such as light sensitivity), it is also hydrophilic due to the desensitizing liquid.
The hydrophilicity of the non-image area is due to the binder resin in the surface layer.
or the parent particles produced by decomposition in the resin particles.
By being more expressed by aqueous groups, the lipophilicity of the image area is improved.
The hydrophilicity of the non-image area becomes clear, making it easier to print on the non-image area during printing.
Prevents printing ink from adhering, and cross-links the inside of the surface layer.
By forming a structure, the hydrophilic resin can absorb water.
It becomes insoluble and furthermore, due to the cross-linking effect, it contains water and the parent material becomes insoluble.
The water-based cross-linked resin swells, creating water-retaining properties and forming a surface layer.
Hydrophilicity is maintained sufficiently. As a result
It becomes possible to print a large number of sheets without background smudges.
. Problem to be Solved by the Invention However, the known photoconductive
The electrophotographic lithographic printing original plate, which is composed of layers, is explained in more detail.
A detailed evaluation shows that environmental changes (high temperature/humidity or low
(temperature, low humidity), electrophotographic properties (especially charge retention in the dark,
(light sensitivity, etc.) may fluctuate, making it difficult to obtain stable and good copied images.
There were cases where it disappeared. As a result, the original version like this
When printed with a printing plate whose surface layer was desensitized,
Deterioration of printed images or reduction of scumming prevention effect.
It has become less. In addition, digital direct lithographic printing
In the electrophotographic lithographic printing original plate used as the printing original plate,
Adopts scanning exposure method using semiconductor laser light
When the
Due to the long length and restrictions on exposure intensity, electrostatic
Higher properties, especially dark charge retention properties, and photosensitivity
Performance is required. [0010] On the other hand, in the above-mentioned known original plate, the electrophotographic
The characteristics deteriorate and background fog is likely to occur in actual copied images.
In addition, skipping of thin lines and blurring of letters occur,
As a result, when printed as a lithographic printing master, the printed matter
The image quality deteriorates, and the non-image areas of the binder resin become hydrophilic.
The effect of preventing background smearing due to improved surface compatibility has disappeared. The present invention is directed to the conventional electrophotographic method as described above.
This is to improve the problems of planographic printing original plates. That is, object 1 of the present invention is to improve electrostatic properties (particularly dark charge
Excellent retention and photosensitivity), faithful reproduction of the original painting
Reproduces the image and creates a uniform background stain on the entire surface as an offset master plate.
It is non-greasy and does not cause spot stains.
An object of the present invention is to provide an excellent lithographic printing original plate. The present invention
Purpose 2 is that the environment during copy image formation is low temperature, low humidity, or
Provides clear, high-quality images even when the temperature fluctuates, such as high temperature and humidity.
An object of the present invention is to provide a lithographic printing original plate having an image. Main departure
Objective 3 of this article is the influence of the types of sensitizing dyes that can be used together.
Scanning exposure using semiconductor laser light
We aim to provide lithographic printing original plates with excellent electrostatic properties regardless of the method.
That is. [Means for Solving the Problems] The present invention has the above objects:
providing at least one photoconductive layer on the conductive support;
An electrophotographic planographic print that further has a surface layer on the top layer.
In the printing plate, the following binder resin for the photoconductive layer is used:
The surface layer further contains at least one resin [A] of
At least 1 of the following non-aqueous solvent-based dispersed resin particles [L] is added to
An original plate for electrophotographic lithographic printing characterized by containing seeds
This can be achieved by Resin [A]: having a weight average molecular weight of 1 x 103 to 2 x 104,
A repeating unit represented by the following general formula (I) as a polymer component
30% by weight or more as -PO3 H2, -SO3
H, -COOH, [Chemical 1] [R1 is a hydrocarbon group or -OR2 (R2
represents a hydrocarbon group] and an acid anhydride group
0.
Resin containing 5 to 15% by weight: General formula (I) [Formula 2] [However, in the above general formula (I), a1,
a2 is each a hydrogen atom, a halogen atom, a cyano group, or
Represents a hydrocarbon group. R3 represents a hydrocarbon group]00
14] Non-aqueous solvent-based dispersed resin particles (L):
is soluble in the non-aqueous solvent, but by polymerization
Functionality that creates carboxyl groups through decomposition and insolubilization
A small amount of monofunctional monomer (A) containing at least one group
at least one dispersion stabilizing resin soluble in the non-aqueous solvent;
copolymer obtained by dispersion polymerization reaction in the presence of
Coalescing resin particles. [0015] In the present invention, the resin [A] is generally
As a copolymer component represented by formula (I), the following general formula (I
a) and aryl group-containing represented by the following general formula (Ib)
containing at least one of the methacrylate components of
Preferably. General formula (Ia) [Chemical formula 3] General formula (Ib) [Chemical formula 4] [However, the above general formulas (Ia) and (Ib)]
, T1 and T2 are each independently a hydrogen atom,
Hydrocarbon group having 1 to 10 carbon atoms, chlorine atom, -COR4
or -COOR5 (R4 and R5 each represent the number of carbon atoms
1 to 10 hydrocarbon groups), L1 and L2
is a single bond connecting -COO- and a benzene ring, or
represents a linking group having 1 to 4 linking atoms] [0016] In the present invention, the above-mentioned non-aqueous solvent dispersion tree
Even if the fat particles form a higher-order network structure,
good. In addition, as the above-mentioned dispersion stabilizing resin in the present invention,
has a heavy group represented by the following general formula (II) in the polymer chain.
Containing at least one compoundable double bond group moiety
are particularly preferred. General formula (II) [Formula (II)] [In general formula (II), V0 is -O-
, -COO-, -OCO-, -(CH2)p -OC
O-, -(CH2)p-COO-, -SO2-,
[Chemical 6] -CONHCOO-, or -CONHCONH
- (where p represents an integer from 1 to 4, R6
represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms)
, a3 and a4 may be the same or different from each other,
Hydrogen atom, halogen atom, cyano group, hydrocarbon group, -C
OO-R7 or -COO-R7 via a hydrocarbon group (
R7 represents a hydrogen atom or an optionally substituted hydrocarbon group;
[0017] [Operation] The lithographic printing original plate of the present invention has a photoconductive layer provided thereon.
A surface layer is further provided on the top layer, and it is used for electrophotography.
After forming the image in the process, the surface of the surface layer is desensitized.
It is made hydrophilic by treatment with a liquid and used as an original plate for planographic printing.
This is an original printing plate using the same method. The photoconductive layer of the present invention comprises at least a photoconductor.
and a low amount of resin [A] consisting of a specific copolymer component.
It is characterized by containing each of them. light of the invention
The conductive layer contains at least the resin [A] as a binder resin.
The photoconductor particles are finely divided and uniformly dispersed.
Ru. Furthermore, sensitization is usually done using a spectral sensitizing dye, but this method
The types of spectral sensitizing dyes used in bright photoconductive layers vary.
These dyes interact well with the photoconductor even when
I can do business. In particular, spectral enhancement for semiconductor laser light
This interaction is not possible in known binder resin systems for pigments used for coloring.
However, in the system of the present invention, such
This is an extremely excellent product that does not cause any undesirable development. [0019] Although the details are unknown, this means that light
Conductor and spectral sensitizing dye are dispersed in the coexistence of resin [A]
Do not disturb the adsorption interaction between dye and photoconductor when
adsorbs to the photoconductor surface and maintains appropriate surface coverage.
This seems to be due to keeping it in a stable condition. These
As a result, environmental conditions such as low temperature and low humidity and high temperature and high humidity are extremely high.
Maintains good and stable electrophotographic properties even when changes occur
It is thought that this has become possible. In the present invention, a surface layer is provided as the uppermost layer on the photoconductive layer.
It is an electrophotographic photosensitive material comprising one more layer of
Improving the electrophotographic properties of the photoconductive layer as described above, that is, improving the fidelity of the photoconductive layer.
Real copy image reproducibility becomes even more important. Main departure
The surface layer of light is composed of microscopic particles with uniform particle size.
Calcium protected by reaction, redox reaction, photolysis reaction, etc.
The boxyl group undergoes a chemical reaction to produce a carboxyl group, and the
Resin particles characterized by converting from aqueous to hydrophilic [
L]. The photosensitive material of the present invention comprises such resin particles.
Contains [L], so after image formation in the electrophotographic process
In the desensitization treatment, the particles [L] develop hydrophilicity.
The non-image area of the surface layer is made hydrophilic and the ink during printing is
It has a high water retention property that does not cause water adhesion. Specifically, the resin particles of the present invention have the largest particle size.
The particle size is 2 μm or less, preferably 0.5 μm
It is as follows. And the average particle diameter of the particles is 0.8 μm
or less, preferably 0.5 μm or less. [0023] The smaller the particle diameter of the resin particles, the more
The area becomes larger, brings about the above-mentioned good effect, and the roller
Although id particles (0.01 μm or less) are sufficient,
, if it becomes too small, it will be similar to the case of molecular dispersion.
However, the effect of particles on improving water retention capacity is weakening.
Therefore, it is preferable to use a thickness of 0.001 μm or more. [0024] Furthermore, in the present invention, the resin particles are hydrophobic
The polymer component, i.e., the polymer component to which the dispersion stabilizing resin corresponds.
This hydrophobic part forms the photoconductive layer.
Because it interacts with the binder resin, this part is
Due to the Kerr effect, it will not be eluted with dampening water during printing.
, maintains good printing characteristics even after printing a large number of sheets
can do. Furthermore, in the present invention, a higher-order network structure is
If the resin particles are formed, the dissolution in water is further suppressed.
On the other hand, water swelling properties are developed, and water retention properties are also improved.
. [0026] In the present invention, the above-mentioned high-order mesh
Resin particles that do not form a structure or form a higher-order network structure
The resin particles (hereinafter simply referred to as network resin particles) are
Contained in a proportion of 10 to 90 parts by weight in the total composition of the face layer,
Preferably it is 15 to 60 parts by weight. resin particles or mesh
If the amount of resin particles is less than 10 parts by weight, the hydrophilicity of the non-image area will decrease.
If it is not sufficient, and on the other hand, it exceeds 90 parts by weight, the parent of the non-image area
Although further improvements in aqueous properties are attempted, the difference between the surface layer and the layer below it
The interfacial adhesion is reduced, and as a result, a sufficient number of prints cannot be obtained.
I can't do it anymore. Original plates for electrophotographic lithographic printing
The method involves forming a faithful copy image and desensitizing the non-image area.
It is important to achieve high water retention through the process, and the original version of the present invention
The above content will satisfy both parties.
Ru. The following describes the binder resin [A] used in the present invention.
This will be explained in more detail below. The binder resin [A] is generally
A polymer component of a specific repeating unit represented by formula (I)
30% by weight or more and 0.1 to 15% by weight of specific polar groups
It is a resin containing. General formula (I) [Formula (I), a1 and a2 are each a hydrogen atom]
R represents a halogen atom, a cyano group, or a hydrocarbon group;
3 represents a hydrocarbon group] In the resin [A], the weight average
Average molecular weight is 1 x 103 to 2 x 104, preferably 3
×103 to 1×104, and the glass of resin [A]
The transition point is preferably -20°C to 110°C, more preferably
is -10°C to 90°C. [0027] The molecular weight of resin [A] is smaller than 103.
When this happens, the film forming ability decreases and sufficient film strength cannot be maintained, resulting in
When the molecular weight is larger than 2×104, the resin of the present invention
However, photoreceptors using near-infrared to infrared spectral sensitizing dyes
under harsh conditions of high temperature, high humidity, and low temperature and low humidity.
Fluctuations in dark decay retention rate and photosensitivity become somewhat large, but stable
The effect of the present invention, in which a duplicate image can be obtained, has diminished.
Mau. Repeating unit of general formula (I) of resin [A]
The proportion of the polymer component corresponding to 30% by weight or more, preferably
Preferably 50 to 97% by weight, heavy weight containing specific polar groups.
The proportion of the combined component is 0.5 to 15% by weight, preferably
It is 1 to 10% by weight. Polar group content in resin [A]
If the amount is less than 0.5% by weight, the initial potential is low enough
image density cannot be obtained. On the other hand, the polar group content
If it is more than 15% by weight, no matter how low the molecular weight is,
However, the dispersibility decreases, and it is further used as an offset master.
smearing increases when Further, as the low molecular weight resin [A], the above-mentioned
represented by general formula (Ia) and general formula (Ib), 2
Bases with specific substituents at the 2nd and 6th positions and/or at the 2nd and 6th positions
Specific substitutions having a naphthalene ring or an unsubstituted naphthalene ring
Contains a methacrylate component with a polar group at the end
Resin [A] (hereinafter, this low molecular weight substance is referred to as resin [A])
A′]) is preferable. to resin [A']
Repeating unit of formula (Ia) and/or formula (Ib) in
The proportion of copolymerized components of methacrylate corresponding to 3
0% by weight or more, preferably 50-97% by weight, specific polarity
The proportion of the polymer component containing a functional group is resin [A'] 100
0.5 to 15% by weight, preferably 1 to 1% by weight
It is 0% by weight. Next, resin [A] contains 30% by weight or more.
further comprising a repeating unit represented by the general formula (I)
explain. In general formula (I), a1 and a2 are preferably
Preferably hydrogen atom, cyano group, alkyl having 1 to 4 carbon atoms
groups (e.g. methyl, ethyl, propyl, butyl)
), -COO-R8 or -CO via a hydrocarbon group
O-R8 (R8 is a hydrogen atom or a carbon number of 1 to 18
Alkyl group, alkenyl group, aralkyl group, alicyclic group or
represents an aryl group, which may be substituted and
Physically, it is the same as that explained for R3 below.
(represents content). -COO-R via the above hydrocarbon
Hydrocarbons in 8 groups include methylene group and ethylene group.
Examples include a carbon group, a propylene group, and the like. R3 is carbon
Number 1 to 18 optionally substituted alkyl groups (e.g.
Methyl group, ethyl group, propyl group, butyl group, pentyl group
group, hexyl group, octyl group, decyl group, dodecyl group,
tridecyl group, tetradecyl group, 2-chloroethyl group,
2-bromoethyl group, 2-cyanoethyl group, 2-hydro
xyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group
(toxy group, 3-hydroxypropyl group, etc.), carbon number 2~
18 optionally substituted alkenyl groups (e.g. vinyl group)
, allyl group, isopropenyl group, butenyl group, hexenyl group
group, heptenyl group, octenyl group, etc.), carbon number 7-1
2 optionally substituted aralkyl groups (e.g. benzyl group)
, phenethyl group, naphthylmethyl group, 2-naphthylethyl group
group, methoxybenzyl group, ethoxybenzyl group, methoxybenzyl group,
(rubenzyl group, etc.), an optionally substituted group having 5 to 8 carbon atoms,
chloroalkyl group (e.g. cyclopentyl group, cyclohexyl group)
sil group, cycloheptyl group, etc.), may be substituted
Aryl groups (e.g. phenyl, tolyl, xylyl)
, mesityl group, naphthyl group, methoxyphenyl group, etho
xyphenyl group, fluorophenyl group, difluorophenyl group
Nyl group, bromophenyl group, chlorophenyl group, dichloro group
Lophenyl group, iodophenyl group, methoxycarbonyl group
Phenyl group, ethoxycarbonylphenyl group, cyanophenyl group
phenyl group, etc.). More preferably, the repetition of general formula (I)
In the copolymer component corresponding to the unit, general formula (Ia)
and/or a specific aryl group represented by general formula (Ib)
A copolymer component represented by a methacrylate component containing
(Resin [A']) is mentioned. General formula (Ia) [Formula 3] General formula (Ib) [Formula (Ia) and (Ib), T1 and T2
are independently hydrogen atoms, hydrocarbons having 1 to 10 carbon atoms,
Base group, chlorine atom, bromine atom, -COR9 or -COO
R9 (R9 represents a hydrocarbon group having 1 to 10 carbon atoms
) represents. L1 and L2 each connect -COO- and a benzene ring.
[Formula] representing a direct bond or a connecting group having 1 to 4 connected atoms
In (Ia), as preferred T1 and T2,
In addition to each hydrogen atom, chlorine atom and bromine atom independently of each other
, the hydrocarbon group having 1 to 10 carbon atoms is preferably carbon
Number 1 to 4 alkyl groups (e.g. methyl group, ethyl group,
(ropyl group, butyl group, etc.), aralkyl group having 7 to 9 carbon atoms
(e.g. benzyl group, phenethyl group, 3-phenylpropylene group)
Pyl group, chlorobenzyl group, dichlorobenzyl group, bro
Mobenzyl group, methylbenzyl group, methoxybenzyl group
, chloro-methyl-benzyl group) and aryl group (e.g.
phenyl group, tolyl group, xylyl group, bromophenyl group
group, methoxyphenyl group, chlorophenyl group, dichloro
phenyl group), and -COR9 and -COOR9
(The preferable R9 is the one having 1 to 10 carbon atoms.
Examples of new hydrocarbon groups include those listed below.
). In formulas (Ia) and (Ib)
, L1 and L2 are -COO- and benzene, respectively.
A direct bond connecting the rings or -(CH2)n1-(n
1 represents an integer from 1 to 3), -CH2OCO-, -
CH2 CH2 OCO-, -(CH2)m1-(
m1 represents an integer of 1 or 2), -CH2 CH2
A linking group having 1 to 4 linking atoms such as O-, etc., and more
Preferably a direct bond or a linking group having 1 to 2 bonded atoms.
can be mentioned. Formula (Ia) used in the resin [A] of the present invention
) or a copolymer corresponding to the repeating unit represented by (Ib)
Specific examples of the combined components are listed below. However, within the scope of the present invention
The enclosure is not limited to this. (a-1) below
~ (a-20), n is an integer of 1 to 4, m is 0 or
is an integer of 1 to 3, p is an integer of 1 to 3, R10 to R13 are
Either -Cn H2n+1 or -(CH2)m -
C6 H5 (however, n and m are the same as above), X1
and X2 may be the same or different, hydrogen atom, -C
Represents either l, -Br, or -I. (a-1) [Formula 7] (a-2) [Formula 8] (a-3) [Formula 9] (a-4) [Formula 10] (a-5) [Formula 11] (a-6) [Formula 12] (a-7) [Formula 13] (a-8) [Formula 14] (a-9) [Formula 15] (a-10) [Formula 16] (a-11) [Formula 17] ( a-12) [Chemical formula 18] (a-13) [Chemical formula 19] (a-14) [Chemical formula 20] (a-15) [Chemical formula 21] (a-16) [Chemical formula 22] (a-17) [ [Chemical 23] (a-18) [Chemical 24] (a-19) [Chemical 25] (a-20) [Chemical 26] Next, the characteristics contained in the low molecular weight resin [A]
The following describes certain polar group-containing polymer components. The polar group
are -PO3 H2, -SO3 H, -COOH and
At least one group selected from cyclic acid anhydride-containing groups [Formula 1]
It is also preferable that the number is one type. [0034] The group [Formula 1] means that the above R1 is a hydrocarbon group or -OR2
represents a group (R2 represents a hydrocarbon group), specifically
R1 is an aliphatic group having 1 to 22 carbon atoms (e.g. methyl group,
Tyl group, propyl group, butyl group, hexyl group, octyl group
group, decyl group, dodecyl group, octadecyl group, 2-chloro
loethyl group, 2-methoxyethyl group, 3-ethoxypro
Pyr group, allyl group, crotonyl group, butenyl group, cyclo
hexyl group, benzyl group, phenethyl group, 3-phenyl group
Propyl group, methylbenzyl group, chlorobenzyl group,
(fluorobenzyl group, methoxybenzyl group, etc.) or substitution
aryl group (e.g. phenyl group, tolyl group)
, ethylphenyl group, propylphenyl group, chlorophenyls
Nyl group, fluorophenyl group, bromophenyl group, chloro
lo-methyl-phenyl group, dichlorophenyl group, methoxy
Cyphenyl group, cyanophenyl group, acetamidophenyl group
group, acetylphenyl group, butoxyphenyl group, etc.)
, and R2 has the same content as R1. [0035] Furthermore, the cyclic acid anhydride-containing group means at least
is also a group containing one cyclic acid anhydride, and contains
Examples of cyclic acid anhydrides include aliphatic dicarboxylic acid anhydrides and aromatic dicarboxylic anhydrides.
Examples include aromatic dicarboxylic acid anhydrides. aliphatic dicarbo
Examples of succinic acid anhydrides include succinic anhydride ring, glutacic anhydride ring,
acid anhydride ring, maleic acid anhydride ring, cyclopentane-
1,2-dicarboxylic anhydride ring, cyclohexane-1,
2-dicarboxylic anhydride ring, cyclohexene-1,2-
Dicarboxylic acid anhydride ring, 2,3-bicyclo[2,2,2
] Octadicarboxylic acid anhydride rings, etc., and these
The ring may include, for example, a halogen atom such as a chlorine atom or a bromine atom, or a metal atom.
Alkyl groups such as thyl group, ethyl group, butyl group, hexyl group, etc.
Groups etc. may be substituted. In addition, aromatic dicarbonate
Examples of acid anhydrides include phthalic anhydride ring, naphthalene
- dicarboxylic anhydride ring, pyridine - dicarboxylic anhydride ring
Examples include monocyclic ring, thiophene-dicarboxylic acid anhydride ring, etc.
, these rings contain halogen atoms such as chlorine atoms, bromine atoms, etc.
atom, methyl group, ethyl group, propyl group, butyl group, etc.
alkyl group, hydroxyl group, cyano group, nitro group,
Alkoxycarbonyl group (as an alkoxy group, e.g.
(methoxy group, ethoxy group, etc.) may be substituted.
stomach. The polar group-containing copolymer component of the present invention is
For example, general formula (I) [including general formulas (Ia) and (Ib)]
] Copolymerized with a monomer corresponding to the repeating unit shown in
Any vinyl compound containing the polar group to be obtained
For example, see "Polymer Data Handbook" edited by the Polymer Science Society of Japan.
Described in "Dobook [Basic Edition]" Baifukan (published in 1986), etc.
has been done. Specifically, acrylic acid, α and/or β
Substituted acrylic acid (e.g. α-acetoxy form, α-aceto
xymethyl form, α-(2-amino)methyl form, α-chloro
α-bromo, α-fluoro, α-tributyl
Lyle body, α-cyano body, β-chloro body, β-bromo body,
α-chloro-β-methoxy form, α,β-dichloro form, etc.)
, methacrylic acid, itaconic acid, itaconic acid half esters
, itaconic acid hemiamides, crotonic acid, 2-alkenyl
Carboxylic acids (e.g. 2-pentenoic acid, 2-methyl-2
-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid
senic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid
, maleic acid half esters, maleic acid half amides, vinyl
Nylbenzene carboxylic acid, vinylbenzene sulfonic acid,
Vinyl sulfonic acid, vinyl phosphonic acid, dicarboxylic acids
half-ester derivatives of vinyl or allyl groups, and
Ester derivatives of carboxylic or sulfonic acids, amino
Examples include compounds containing the polar group in the substituent of the derivative.
can be lost. Examples of copolymer components containing polar groups are as follows:
Show. Here, e1 represents H or CH3, and e2
represents H, CH3 or CH2 COOCH3,
R14 represents an alkyl group having 1 to 4 carbon atoms, and R15 represents a carbon
an alkyl group with a prime number of 1 to 6, a benzyl group or a phenyl group
, c represents an integer from 1 to 3, and d represents an integer from 2 to 11.
, e represents an integer from 1 to 11, and f represents an integer from 2 to 4.
and g represents an integer of 2 to 10. (b-1) [Formula 27] (b-2) [Formula 28] (b-3) [Formula 29] (b-4) [Formula 30] (b-5) [Formula 31] (b-6) [Chemical 32] (b-7) [Chemical 33] (b-8) [Chemical 34] (b-9) [Chemical 35] (b-10) [Chemical 36] (b-11) [Chemical 37] ( b-12) [Chemical formula 38] (b-13) [Chemical formula 39] (b-14) [Chemical formula 40] (b-15) [Chemical formula 41] (b-16) [Chemical formula 42] (b-17) [ Chemical Formula 43] (b-18) [Chemical Formula 44] (b-19) [Chemical Formula 45] (b-20) [Chemical Formula 46] (b-21) [Chemical Formula 47] (b-22) [Chemical Formula 48] (b -23) [Formula 49] (b-24) [Formula 50] (b-25) [Formula 51] (b-26) [Formula 52] (b-27) [Formula 53] (b-28) [Formula 53] (b-28) 54] (b-29) [Chemical 55] (b-30) [Chemical 56] (b-31) [Chemical 57] (b-32) [Chemical 58] (b-33) [Chemical 59] (b- 34) [Chemical 60] (b-35) [Chemical 61] (b-36) [Chemical 62] (b-37) [Chemical 63] (b-38) [Chemical 64] (b-39) [Chemical 65] ] (b-40) [Chemical 66] (b-41) [Chemical 67] (b-42) [Chemical 68] (b-43) [Chemical 69] (b-44) [Chemical 70] (b-45 ) [Chemical 71] (b-46) [Chemical 72] (b-47) [Chemical 73] (b-48) [Chemical 74] (b-49) [Chemical 75] (b-50) [Chemical 76] (b-51) [Chemical 77] (b-52) [Chemical 86] Furthermore, the low molecular weight resin [A] of the present invention ([A
']) is the general formula (I), (Ia) and
/or the monomer of (Ib) and the monomer containing the polar group
In addition, other monomers other than these can be used as copolymerization components.
May be contained. [0039] Examples of such other copolymerizable components include
For example, meta containing substituents other than those explained in general formula (I)
Acrylic esters, acrylic esters, croton
In addition to acid esters, α-olefins and carboxylic acid esters
or acrylic esters (e.g. carboxylic acids)
Acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, sodium
phthalene carboxylic acid, etc.), acrylonitrile, methacrylate
Ronitrile, vinyl ethers, itaconic acid esters
(e.g. dimethyl ester, diethyl ester, etc.),
Acrylamides, methacrylamides, styrenes (e.g.
For example, styrene, vinyltoluene, chlorostyrene, hydride
Roxystyrene, N,N-dimethylaminomethylstyrene
methoxycarbonyl styrene, methane sulfonyl styrene,
xystyrene, vinylnaphthalene, etc.), vinyl sulfone
Containing compounds, vinyl ketone-containing compounds, heterocyclic vinyls
(e.g. vinyl pyrrolidone, vinyl biridine, vinyl pyrrolidone,
midazole, vinylthiophene, vinylimidazoline,
Vinyl pyrazole, vinyl dioxane, vinyl quinoline
, vinyltetrazole, vinyloxazine, etc.).
It will be done. These other monomers account for 30% by weight in the resin [A].
It is desirable not to exceed it. Resin [A] has a weight average molecular weight of 1×10
It is a random copolymer with a low molecular weight of 3 to 2 x 104.
However, these polymerization methods are conventionally known methods, such as
Radical polymerization and ionic polymerization can be achieved by selecting polymerization conditions.
It can be easily synthesized by various methods. Polymerizing monomer
Radical polymerization reaction based on polymer, polymerization solvent, reaction setting temperature, etc.
is advantageous and preferable from the viewpoint of purification, equipment, reaction method, etc. concrete
Specifically, azobis, which is commonly known as a polymerization initiator,
Examples include system initiators and peroxides. Especially low molecular weight substances
The characteristics of the synthesis include increasing the amount of the initiator used, and
Alternatively, apply a known method such as increasing the polymerization temperature setting.
do it. Specifically, the amount of initiator used is the total monomer amount.
Range of 0.1 to 20 parts by weight per 100 parts by weight
Also, the polymerization temperature is set in the range of 30°C to 200°C. Furthermore, a method of using a chain transfer agent in combination is also known.
It is. For example, mercapto compounds, halogenated compounds
etc., in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the total monomer amount.
By using within the range of parts by weight, the desired weight average molecular weight can be adjusted.
can be adjusted. Low molecular weight resin [A] ([A'
) can be used in combination with known resins for conventional photoconductors.
It is preferable that Use of low molecular weight resins with other resins
The ratio is preferably 5-50/95-50 (weight ratio). Other resins used in combination include weight average molecular weight
amount 3×104 to 1×106, preferably 5×104
It is a medium to high molecular weight substance of ~5x105. Also, in combination
The glass transition point of the resin is -10°C to 120°C, preferably
The temperature is preferably 0°C to 90°C. For example, Ryuji Shibata, Jiro Ishiwata
, Polymer, Vol. 17, p. 278 (1968), Miyamoto
Harumi, Hidehiko Takei, Imaging, 1973 (No. 8)
) p. 9, edited by Koichi Nakamura, “Actual practice of binders for recording materials.”
Technology” Chapter 10, C. H. C. Publication (published in 1985),
D. Tatt, S. C. Heidecker
, Tappi, 49 (No. 10), 439
(1966), E. S. Baltazzi, R.
．． G. Blanclotte et al., P.
hot. Sci. Eng. 16 (No. 5),
354 (1972), Nguyen Tran Khe, Isamu Shimizu,
Eiichi Inoue, Journal of the Electrophotography Society 18 (No. 2), 22 (
1980), JP 50-51011, JP 53-5
4027, 54-20735, 57-202544
Materials disclosed in each publication are listed. Specifically,
Refin polymers and copolymers, vinyl chloride copolymers, salts
Vinylidene chloride copolymer, vinyl alkanoate polymer and copolymer
Polymers, allyl alkanoate polymers and copolymers, styrene
Butadiene and its derivatives, polymers and copolymers, butadiene
Styrene copolymer, isoprene-styrene copolymer, styrene copolymer,
Tadiene-unsaturated carboxylic acid ester copolymer, acrylic
Ronitrile copolymer, methacrylonitrile copolymer,
Rukyl vinyl ether copolymer, acrylic acid ester copolymer
Polymers and copolymers, methacrylic acid ester polymers and copolymers
polymer, styrene-acrylic acid ester copolymer, styrene
Ren-methacrylic acid ester copolymer, diethyl itaconic acid
Stell polymers and copolymers, maleic anhydride copolymers,
Acrylamide copolymer, methacrylamide copolymer,
Hydroxyl modified silicone resin, polycarbonate resin, keto
resins, amide resins, hydroxyl group- and carboxyl group-modified polymers.
Lyester resin, butyral resin, polyvinyl aceter
resin, cyclized rubber-methacrylic acid ester copolymer, ring
rubber-acrylic acid ester copolymer, containing nitrogen atoms
Copolymers containing heterocycles that do not contain heterocycles (e.g.
, furan ring, tetrahydrofuran ring, thiophene ring, di
Oxane ring, dioxofuran ring, lactone ring, benzoff
Ran ring, benzothiophene ring, 1,3-dioxetane ring
etc.), epoxy resins, etc. [0044] Furthermore, as a medium to high molecular weight resin to be used in combination.
, satisfies the physical properties described above, and preferably has the following general formula (II
30 parts by weight of the repeating unit polymer component represented by I)
Examples include polymers containing the above. General formula (III) [In formula (III), V is -COO-, -OCO-, -(
CH2)h -OCO-, -(CH2)h -CO
Represents O-, -O- or -SO2-. However, h is 1~
represents an integer of 4] In general formula (III), f3 and
and f4 have the same contents as a1 and a2 in formula (I).
represent. R16 represents the same content as R3 in formula (I)
. A medium containing a polymer component represented by general formula (III)
~ High molecular weight binder resin (hereinafter referred to as resin [B]) and
For example, containing a polymer component represented by formula (III)
random copolymer resin (JP-A-63-49817,
Publications No. 63-220149 and No. 63-220148
etc.), a combination resin of the random copolymer and a crosslinkable resin (
JP-A No. 1-102573, etc.), graft copolymers (
JP 2-53064, JP 2-56558, etc.)
Examples include medium to high molecular weight substances described in the specifications of
It will be done. The photoconductor used in the present invention is an inorganic
It may be either a chemical compound or an organic compound. inorganic compound
For example, zinc oxide, titanium oxide, zinc sulfide
, cadmium sulfide, selenium, selenium-tellurium, lead sulfide, etc.
Conventionally known inorganic photoconductive compounds include
From this point of view, zinc oxide and titanium oxide are preferred. Photoconductive
Inorganic photoconductive compounds such as zinc oxide and titanium oxide
When using a compound, 100 parts by weight of the inorganic photoconductive compound
The ratio of 10 to 60 parts by weight of the above-mentioned binding resin to
, preferably in a proportion of 15 to 40 parts by weight. On the other hand, as the organic compound, conventionally known chemical compounds can be used.
Any compound may be used, specifically for electrophotographic lithographic printing.
The following two types of original plates are known as conventional examples:
There is. The first is Special Publick Publication No. 37-17162 and No. 62-51.
462, JP-A-52-2437, JP-A-54-19803,
Publications No. 56-107246 and No. 57-161863
organic photoconductive compounds, sensitizing dyes, as described in
It has a photoconductive layer mainly composed of a bonding resin.
The second is JP-A-56-146145 and JP-A-60-17751.
, 60-17752, 60-17760, 60-
254142, 62-54266, etc.
Mainly consists of charge generating agents, charge transport agents, and binding resins such as
It has a photoconductive layer. A special case of the second example
As JP 60-230147, JP 60-23014
8, as described in 60-238853 publications etc.
A charge generating agent and a charge transporting agent are contained in separate layers.
Two-layer photoconductive layers are also known. Electrophotography of the present invention
The original plate for lithographic printing can have either of the two types of photoconductive layers listed above.
You may take a stand. In the case of the second example, in the present invention
Organic photoconductive compounds act as charge transport agents
. [0047] As an organic photoconductive compound in the present invention,
(a) U.S. Patent No. 3,112,197, etc.
triazole derivatives described in (b) U.S. Pat.
Oki described in the patent specification No. 3189447 etc.
Thadiazole derivative, (c) Japanese Patent Publication No. 37-16096
Imidazole derivatives, (d
) U.S. Patent No. 3615402, U.S. Patent No. 3820989, U.S. Pat.
3542544 specifications, Japanese Patent Publication No. 45-555, No. 5
1-10983, JP 51-93224, JP 55-1
08667, 55-156953, 56-3665
6 polyarylalkane derivatives described in each publication etc.,
(e) U.S. Patent Nos. 3180729 and 4278746
Specifications of each issue, JP 55-88064, JP 55-880
65, same 49-105537, same 55-51086, same
56-80051, 56-88141, 57-
45545, 54-112637, 55-74
Pyrazoline derivatives described in 546 publications etc.
and pyrazolone derivatives, (f) U.S. Pat. No. 36154
Specification No. 04, Japanese Patent Publication No. 51-10105, No. 46-37
12, 47-28336, JP 54-8343
5, Nos. 54-110836 and 54-119925
Phenyldiamine derivatives listed in publications, etc.
(g) U.S. Patent Nos. 3,567,450 and 3,180,703
, 3240597, 3658520, 42321
03, 4175961, 4012376 specifications
, West German Patent (DAS) No. 1110518, Special Publication
1973-35702, 39-27577, JP-A-55
-144250, 56-119132, 56-22
Arylamine derivatives described in 437 publications etc.
Conductor, (h) described in US Pat. No. 3,526,501
Amino-substituted chalcone derivatives of (i) U.S. Pat.
N,N-bical basil described in specification No. 42546 etc.
derivatives, (j) as in U.S. Pat. No. 3,257,203;
The oxazole derivative described in (k) JP-A-56-
Styryl anthracene derivatives described in Publication No. 46234 etc.
Conductor, (l) Described in JP-A-54-110837, etc.
Fluorenone derivatives listed in (m) U.S. Patent No.
Specification No. 3717462, Japanese Unexamined Patent Publication No. 54-59143 (US)
Corresponding to National Patent No. 4150987), No. 55-5
2063, 55-52064, 55-46760,
Same 55-85495, Same 57-11350, Same
57-148749, 57-104144 publications etc.
Hydrazone derivatives listed in (n) US Pat.
Permit No. 4047948, No. 4047949, No. 42659
90, 4273846, 4299897, 430
Benzidine derivatives described in 6008 specifications etc., (
o) Japanese Patent Publication No. 58-190953, Japanese Patent Publication No. 59-95540
, 59-97148, 59-195658, 62
-Stilbenes described in publications such as 36674
Derivative, (p) described in Japanese Patent Publication No. 34-10966
Polyvinylcarbazole and its derivatives, (q) Special Publication
Listed in Publications No. 43-18674 and No. 43-19192
polyvinylpyrene, polyvinylanthracene, poly-
2-vinyl-4- (4'-dimethylaminophenyl
)-5-phenyloxazole, poly-3-vinyl-N
- Vinyl polymers such as ethylcarbazole, (s)
Polyacenaphthylene described in Publication No. 19193-1973,
Polyindene, copolymer of acenaphthylene and styrene, etc.
Polymer of (t) Japanese Patent Publication No. 56-13940 etc.
Pyrene-formaldehyde resin described in bromopyrene
-Formaldehyde resin, ethylcarbazole-form
Condensation resins such as aldehyde resins, (u) JP-A-56-9
Described in 0883 and 56-161550 publications
There are various triphenylmethane polymers, etc. [0048] In the present invention, an organic photoconductive compound
is limited to the compounds listed in (a) to (u).
First, all known organic photoconductive compounds are used.
be able to. These organic photoconductive compounds may
It is possible to use two or more types together. Sensitizing dye contained in the photoconductive layer of the first example
As for conventionally known sensitization used in electrophotographic photoreceptors,
Dyes can be used. These are "electronic photographs" 12
9, (1973), "Organic Synthetic Chemistry" 24 (11),
1010, (1966), etc. for example,
U.S. Patent Nos. 3,141,770 and 4,283,475
Detailed book, JP-A-48-25658, JP-A-62-7196
5 Pyrylium dyes described in each publication, etc., Applie
d Optics Supplement 3 50
(1969), described in Japanese Patent Application Laid-Open No. 50-39548, etc.
triarylmethane dye, U.S. Patent No. 359719
Cyanine dyes described in specification No. 6, etc., JP-A-60-1
No. 63047, No. 59-164588, No. 60-25
Styryl dyes described in 2517 publications etc. are advantageous.
used for. Charge generation contained in the photoconductive layer of the second example
As the agent, conventionally known organic and
Various inorganic and inorganic charge generating agents can be used. For example,
ion, selenium-tellurium, cadmium sulfide, zinc oxide, and
and the use of organic pigments shown in (1) to (9) below.
I can do that. (1) U.S. Patent No. 4,436,800, U.S. Patent No. 4
439506 specifications, JP-A-47-37543, same
58-123541, 58-192042, 58-
219263, 59-78356, 60-1797
46, 61-148453, 61-238063,
Special Publications No. 60-5941, No. 60-45664, etc.
Monoazo, bisazo, trisazo pigments etc. listed in
(2) U.S. Pat. No. 3,397,086, No. 4
666802 specifications, JP-A-51-90827, same
Metal-free or gold described in 52-55643 publications etc.
Phthalocyanine pigments such as the genus phthalocyanine, (3) Rice
National Patent No. 3371884, Japanese Patent Application Laid-open No. 47-303
Perylene pigments described in Publication No. 30, etc., (4) British Special
Specification No. 2237680, JP 47-30331
Indigo, thioindigo derivatives, (5
) British Patent No. 2237679, JP-A-47-
Quinacridone pigments described in Publication No. 30332 etc., (6
) British Patent No. 2237678, JP-A-59-
184348, 62-28738, 47-1854
4 Polycyclic quinone pigments described in various publications, (7) JP-A
Publications No. 47-30331, No. 47-18543, etc.
The bisbenzimidazole pigment described in (8) US Pat.
Permit No. 4396610, No. 4644082, etc.
Squarium salt pigment described in (9) JP-A-59-5
3850, 61-212542, etc.
durenium salt pigments, etc. These may be used alone or
can also be used in combination of two or more types. [0051] Also, a mixture of an organic photoconductive compound and a binding resin can be used.
The mixing ratio depends on the compatibility between the organic photoconductive compound and the binding resin.
The upper limit of the content of organic photoconductive compounds is determined, and this
When added in an amount exceeding
I don't like it. Low content of organic photoconductive compounds
Since the electrophotographic sensitivity decreases as the temperature increases, organic photoconductivity is
as much as possible without crystallization of the compound.
It is preferable to contain a photoconductive compound. organic light guide
The content of the electrically conductive compound is 100 parts by weight of the binding resin.
5 to 120 parts by weight of the organic photoconductive compound, preferably
is 10 to 100 parts by weight of the organic photoconductive compound. Ma
In addition, organic photoconductive compounds, singly or in combination of two or more
You may also use it as [0052] In the present invention, various pigments can be separated as necessary.
It can be used in combination as a photosensitizer. For example, Haru Miyamoto
Miyoshi, Hidehiko Takei: Imaging 1973 (No. 8) No. 1
2 pages, C. J. Young et al., RCA Review
15,469 (1954), Wataru Kiyota: Dentsu.
IEICE Journal J63-C (No. 2), 97 pages (1
980), Yuji Harasaki et al., Industrial Chemistry Journal 66, 78
and 188 pages (1963), Tadaaki Tani, Journal of the Photographic Society of Japan
35, p. 208 (1972), etc.
Bonium dyes, diphenylmethane dyes, triphenyl
Methane dyes, xanthene dyes, phthalein dyes,
Limetin dyes (e.g. oxonol dyes, merocyanine)
Pigments, cyanine pigments, rhodacyanine pigments, styryl pigments
etc.), phthalocyanine dyes (may contain metals)
) etc. More specifically, carbonium dyes,
Liphenylmethane dyes, xanthene dyes, phthalate
As a product mainly using dyes based on pigments, there is a
52, JP-A No. 50-90334, No. 50-114227
, 53-39130, 53-82353 publications,
U.S. Patent No. 3,052,540, U.S. Patent No. 4,054,45
0 Described in each specification, Japanese Patent Application Laid-open No. 16456/1983, etc.
Examples include: [0054] Oxonol dye, merocyanine dye, silver
Polymethine dyes such as anine dyes and rhodacyanine dyes
Well, F. M. Hammer “The C”
yanine DyesandRelatedC
It is possible to use the pigments described in
More specifically, U.S. Pat. No. 3,047,384;
110591, 3121008, 3125447,
3128179, 3132942, 3622,3
17 specifications, British Patent No. 1226892, British Patent No. 130
9274, 1405898 specifications, Japanese Patent Publication No. 1974-
Pigments described in 7814, 55-18892, etc.
can be mentioned. Furthermore, near-infrared light with a long wavelength of 700 nm or more
As a polymethine dye that spectrally sensitizes the infrared light region,
47-840, 47-44180, Special Publication No. 51-41
061, JP-A No. 49-5034, JP-A No. 49-45122,
57-46245, 56-35141, 57-1
57254, 61-26044, 61-27551
Publications, U.S. Patent No. 3619154, U.S. Patent No. 417595
6 Specifications, “Research Disclo
Sure” 1982, 216, pp. 117-118
Examples include those described in . Photoconductivity of the electrophotographic printing original plate of the present invention
The layer contains various publicly available materials conventionally used in electrophotographic photoreceptors.
Known additives may be included. These additives
Chemical sensitizers for improving electrophotographic sensitivity,
Various plasticizers, surfactants, etc. to improve film properties
is included. As a chemical sensitizer, for example, p-benzo
Quinone, chloranil, fluoranil, bromanil, dini
Trobenzene, anthraquinone, 2,5-dichlorobene
Zoquinone, nitrophenol, anhydrous tetrachlorphthal
Acid, 2,3-dichloro-5,6-dicyanobenzoquinone
, dinitrofluorenone, trinitrofluorenone, te
Electron-withdrawing compounds such as tracyanoethylene, JP-A-58
-65439, 58-102239, 58-12
Compounds described in 9439, 62-71965, etc.
I can list things. Examples of plasticizers include
, dimethyl phthalate, dibutyl phthalate, dioctyl
Luphthalate, triphenyl phosphate, diisobu
Thyl adipate, dimethyl sebacate, dibutyl sebacate
Butyl laurate, Methyl phthalyl ethylglyceride
Photoconductive cholate, dimethyl glycol phthalate, etc.
Can be added to improve the flexibility of the layer. These plastics
The agent should be contained within a range that does not deteriorate the electrostatic properties of the photoconductive layer.
can be done. [0057] The amount of these various additives added is particularly limited.
However, it is usually 0.0 parts by weight per 100 parts by weight of the photoconductor.
01 to 2.0 parts by weight. The thickness of the photoconductive layer is 1 to 100 μm, especially 10 μm.
~50μ is suitable. [0059] In addition, a laminated type structure of a charge generation layer and a charge transport layer may be used.
When using a photoconductive layer as a charge generation layer of a photobody, the charge
The thickness of the generation layer is 0.01-1μ, especially 0.05-0.
5μ is suitable. The photoconductive layer according to the invention can be prepared using conventionally known supports.
It can be placed on the body. Generally speaking, electrophotography
The support of the layer is preferably electrically conductive, and is preferably electrically conductive.
The carrier can be the same as before, such as metal, paper, or plastic.
Impregnating a base material such as a plastic sheet with a low-resistance substance
The back side of the substrate (with a photosensitive layer)
(the opposite side) and provides conductivity to prevent curling.
Coated with at least one layer for the purpose of
A water-resistant adhesive layer is provided on the surface of the support;
If necessary, add at least one prelayer to the surface layer of the carrier.
Those with a coating layer, and those with conductive substrates coated with Al, etc.
Plastic laminated to paper, etc. can be used.
. Specifically, examples of conductive substrates or conductive materials include:
Yukio Sakamoto, Electrophotography, 14, (No. 1), p2-1
1 (1975), Hiroyuki Moriga, “Introductory Chemistry of Special Papers” Koubun.
Kokankai (1975), M. F. Hoover,
J. Macromol. Sci. Chem. A
-4(6), pp. 1327-1417 (1970), etc.
Use what is listed. Next, the non-aqueous solvent dispersion used in the present invention
The resin particles will be explained in more detail. Resin particles of the present invention
The product is manufactured by so-called non-aqueous dispersion polymerization.
It is. First, it is soluble in nonaqueous solvents but polymerizes.
becomes insolubilized by decomposition, producing carboxyl groups
A monofunctional monomer containing at least one functional group (
A) will be explained. First, the decomposition used in the present invention
A functional group that generates at least one carboxyl group (hereinafter referred to as
Sometimes simply referred to as a carboxyl group-forming functional group.
) will be explained in detail. Carboxyl radicals of the present invention
The component functional groups produce carboxyl groups by decomposition, but
The number of carboxyl groups generated from one functional group is 1 or 2.
It may be more than one. According to one preferred embodiment of the invention, the cap
The ruboxyl group-forming functional group-containing monomer has the general formula (IV)
At least one functional group represented by [-COO-L3]
It is a monomer containing seeds. In general formula (IV) [-COO-L3], L3
represents [Chemical Formula 80] [Chemical Formula 81] -N=CH-Q1, [Chemical Formula 82] -NH-OH [Chemical Formula 83] or [Chemical Formula 84]. However, R17 and R18 may be the same or different.
may represent a hydrogen atom or an aliphatic group, and X3 is
Represents an aromatic group, Z is a hydrogen atom, a halogen atom, a tri-
Halomethyl group, alkyl group, -CN, -NO2, -S
O2 R17' (However, R17' represents a hydrocarbon group)
, -COOR18' (however, R18' represents a hydrocarbon group)
) or -O-R19' (where R19' is a hydrocarbon group
), and n', m' represent 0, 1 or 2
. R19, R20, R21 may be the same or different
Often, a hydrocarbon group or -O-R20' (however, R20'
represents a hydrocarbon group), M represents Si, Sn or T
represents i. Q1 and Q2 each represent a hydrocarbon group
. Y1 represents an oxygen atom or a sulfur atom, R22,
R23 and R24 may be the same or different, and each represents a hydrogen atom.
represents an aliphatic group, and p represents an integer of 5 or 6.
. Y2 represents an organic residue forming a cyclic imide group. Formula (IV) [-COO-L3]
Functional groups generate carboxyl groups by decomposition.
Yes, and will be explained in more detail below. When L3 represents [Chemical formula 80], R17 and R18 are mutually exclusive.
may be the same or different, preferably a hydrogen atom or
Straight chain or branched atom having 1 to 12 carbon atoms which may be substituted
alkyl groups (e.g. methyl, ethyl, propyl,
Lolomethyl group, dichloromethyl group, trichloromethyl group
, trifluoromethyl group, butyl group, hexyl group, octyl group
Tyl group, decyl group, hydroxyethyl group, 3-chloropropyl group
lopyl group, etc.), and X3 is preferably substituted.
phenyl group or naphthyl group (e.g. phenyl group,
Methylphenyl group, chlorophenyl group, dimethylphenyl group
chloromethylphnyl group, naphthyl group, etc.)
, Z is preferably a hydrogen atom, a halogen atom (e.g. chlorine
atom, fluorine atom, etc.), trihalomethyl group (e.g.
chloromethyl group, trifluoromethyl group, etc.), carbon number 1
~12 optionally substituted linear or branched alkyl groups
(e.g. methyl group, chloromethyl group, dichloromethyl group)
, ethyl group, propyl group, butyl group, hexyl group, tet
Lafluoroethyl group, octyl group, cyanoethyl group,
loloethyl group, etc.), -CH, -NO2, -SO2 R
17'[R17' is an aliphatic group (for example, having 1 to 12 carbon atoms)
Alkyl group that may be substituted: Specifically, methyl group,
Tyl group, propyl group, butyl group, chloroethyl group, pen
Even if substituted with 7 to 12 carbon atoms such as thyl group and octyl group
Good aralkyl groups: specifically benzyl group, phenethyl group
group, chlorobenzyl group, methoxybenzyl group, chlorobenzyl group
phenethyl group, methylphenethyl group, etc.) or aromatic group (e.g.
For example, phenyl or naphthyl groups which may contain substituents
:Specifically, phenyl group, chlorophenyl group, dichloro
Lophenyl group, methylphenyl group, methoxyphenyl group
, acetylphenyl group, acetamidophenyl group, meth
(oxycarbonylphenyl group, naphthyl group, etc.)]
, -COOR18'(R18' is synonymous with the above R17'
) or -O-R19'(R19' is the same as R17' above)
(synonymous). n', m' represent 0, 1 or 2
Was. [0065] The case where L3 described above represents [Chemical formula 80] will be explained more specifically.
Then, the following examples of substituents can be mentioned. example
For example, β, β, β-trichloroethyl group, β, β, β-trichloroethyl group,
Lifluoroethyl group, hexafluoro-i-propyl group
, -CH2-(CF2CF2)n''-H group (n
" indicates 1 to 5), 2-cyanoethyl group, 2-nito
loethyl group, 2-methanesulfonylethyl group, 2-ethyl group
sulfonylethyl group, 2-butanesulfonylethyl group
, benzenesulfonylethyl group, 4-nitrobenzene
sulfonylethyl group, 4-cyanobenzenesulfonylethyl group
group, 4-methylbenzenesulfonylethyl group, substituent
(e.g. benzyl group, meth)
xybenzyl group, trimethylbenzyl group, pentamethyl group
benzyl group, nitrobenzyl group, etc.), substituents.
phenacyl group (e.g. phenacyl group, promophenol group)
Nasyl group, etc.), phenyl group which may contain a substituent (e.g.
For example, phenyl group, nitrophenyl group, cyanophenyl group
, methanesulfonylphenyl group, trifluoromethylphenyl group
phenyl group, dinitrophenyl group, etc.). [0066] In addition, when L3 represents [Chemical formula 81], R19, R20, R
21 may be the same or different, preferably carbon
An optionally substituted aliphatic group having numbers 1 to 18 [the aliphatic group is
Alkyl group, alkenyl group, aralkyl group or alicyclic group
and the substituents include, for example, a halogen atom, a -CN group,
-OH group, -O-Q'(Q' is alkyl group, aralkyl
group, alicyclic group, aryl group), etc.],
An optionally substituted aromatic group having 6 to 18 carbon atoms (e.g.
phenyl group, tolyl group, chlorophenyl group, methoxyphene group
nyl group, acetamidophenyl group, naphthyl group, etc.) or
-O-R20'(R20' is an optionally substituted carbon number 1
~12 alkyl group, optionally substituted with 2 to 12 carbon atoms
an alkenyl group, an optionally substituted atom having 7 to 12 carbon atoms;
Ralkyl group, optionally substituted alicyclic group having 5 to 18 carbon atoms
group, an optionally substituted aryl group having 6 to 18 carbon atoms.
). [0067] M represents each atom of Si, Ti, or Sn.
However, it more preferably represents a Si atom. [0068] Also, L3 is -N=CH-Q1 or [Formula 8
2], Q1 and Q2 are preferable.
or an optionally substituted aliphatic group each having 1 to 18 carbon atoms (
Aliphatic groups include alkyl groups, alkenyl groups, and aral groups.
Indicates a kill group, an alicyclic group, and substituents include, for example, halogen.
Examples include carbon atoms, CN groups, alkoxy groups, etc.
) or an optionally substituted aryl group having 6 to 18 carbon atoms (
For example, phenyl group, methoxyphenyl group, tolyl group,
lorophenyl group, naphthyl group, etc.). [0069] When L3 represents [Chemical formula 83], Y1 is an oxygen atom or
represents a sulfur atom. R22, R23, R24 are each other
may be the same or different, preferably a hydrogen atom,
Straight chain or branched atom having 1 to 18 carbon atoms which may be substituted
alkyl groups (e.g. methyl, ethyl, propyl, butyl groups)
Tyl group, hexyl group, octyl group, decyl group, dodecyl group
group, octadecyl group, chloroethyl group, methoxyethyl group
group, methoxypropyl group, etc.), optionally substituted alicyclic group
groups (e.g. cyclobentyl group, cyclohexyl group, etc.),
An optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g.
benzyl group, phenethyl group, chlorobenzyl group, meth
xybenzyl group, etc.), optionally substituted aromatic groups (e.g.
phenyl group, naphthyl group, chlorophenyl group, tolyl group
group, methoxyphenyl group, methoxycarbonylphenyl
group, dichlorophenyl group, etc.) or -O-R21' (R2
1' represents a hydrocarbon group, specifically the above R22, R
23, showing the same substituents as the hydrocarbon group of R24)
represent p' represents an integer of 5 or 6. [0070] When L3 represents [Chemical formula 84], Y2 is a cyclic imide
Represents an organic residue forming a group. Preferably, the general formula (
V) or (VI) represents an organic residue. General formula (V) [Chemical formula 85] General formula (VI) [Chemical formula 86] In formula (V), R25 and R26 may be the same or
They may be different, each containing a hydrogen atom, a halogen atom (e.g.
chlorine atom, bromine atom, etc.), substituted with 1 to 18 carbon atoms
Good alkyl groups [e.g. methyl group, ethyl group, propylene group]
group, butyl group, hexyl group, octyl group, decyl group,
dodecyl group, hexadecyl group, octadecyl group, 2-k
loloethyl group, 2-methoxyethyl group, 2-cyanoethyl group
group, 3-chloropropyl group, 2-(methanesulfonyl group)
) ethyl group, 2-(ethoxyoxy)ethyl group, etc.], carbon
An optionally substituted aralkyl group having a prime number of 7 to 12 (e.g.
benzyl group, phenethyl group, 3-phenylpropyl group,
Methylbenzyl group, dimethylbenzyl group, methoxyben
(zyl group, chlorobenzyl group, bromobenzyl group, etc.), carbon
An optionally substituted alkenyl group having a prime number of 3 to 18 (e.g.
Allyl group, 3-methyl-2-propenyl group, 2-hexetyl group
Nyl group, 4-propyl-2-pentenyl group, 12-o
tadecenyl group, etc.), -S-R22'(R22' is the above-mentioned
R25 or R26 alkyl group, aralkyl group, alkyl group
(represents the same content as the nyl group), an optionally substituted aryl group
group (e.g. phenyl group, tolyl group, chlorophenyl group)
group, bromophenyl group, methoxyphenyl group, ethoxy
phenyl group, ethoxycarbonylphenyl group, etc.), or
-NHR23'(R23' has the same content as R22' above)
). Also, if R25 and R26 form a ring
may represent a residue [for example, a 5- to 6-membered monocyclic ring (e.g.
(e.g. cyclopentyl ring, cyclohexyl ring), or 5-
6-membered bicyclo ring (e.g. bicycloheptane ring, bicyclo ring)
Cloheptine ring, bicyclooctane ring, bicyclooctene
ring, etc.), and furthermore, these rings may be unsubstituted or substituted.
The substituents are the same as those described above for R25 and R26.
]. q represents an integer of 2 or 3. Formula (VI)
In the middle, R27 and R28 may be the same or different, and the above R27 and R28 may be the same or different.
25, represents the same content as R26. Furthermore, R2
7 and R28 represent organic residues that consecutively form an aromatic ring.
(eg, benzene ring, naphthalene ring, etc.). Another preferred embodiment of the present invention is as follows:
Functional group represented by general formula (VII) [-CO-L4]
It is a monomer containing at least one type of. In general formula (VII) [-CO-L4], L4
represents [Chemical formula 87] or [Chemical formula 88]. However, R29, R30, R31, R32, R
33 each represents a hydrogen atom or an aliphatic group. aliphatic group and
is preferably the same as R22, R23, and R24 above.
represents the content of Also, R30 and R31 and R32 and R33 are connected and condensed.
Represents an organic residue that may form a ring. Preferably 5~
6-membered monocycle (e.g. cyclopentyl ring, cyclohexy ring)
), 5- to 12-membered aromatic rings (such as benzene
ring, naphthalene ring, thiophene ring, pyrrole ring, pyran
ring, quinoline ring, etc.). Furthermore, another preferred embodiment of the present invention
Then, oxazolo represented by the following general formula (VIII)
A monomer containing at least one ring. General formula (VIII) [Chemical formula 89] In general formula (VIII), R34 and R35 are each other.
may be the same or different, and hydrogen atoms and hydrocarbons, respectively.
represents an elementary group, or R34 and R35 together form a ring
may be completed. Preferably, R34 and R35 are the same or different from each other.
Each hydrogen atom, carbon number 1 which may be substituted
~12 straight-chain or branched alkyl groups (e.g. methyl groups)
, ethyl group, propyl group, butyl group, hexyl group, 2-
Chloroethyl group, 2-methoxyethyl group, 2-methoxy
carbonylethyl group, 3-hydroxypropyl group, etc.),
An optionally substituted aralkyl group having 7 to 12 carbon atoms (
For example, benzyl group, 4-chlorobenzyl group, 4-aceto
Amidobenzyl group, phenethyl group, 4-methoxybenzyl group
), optionally substituted alkyl groups having 2 to 12 carbon atoms, etc.
Kenyl group (e.g. ethylene group, allyl group, isopropenic group)
(butenyl group, butenyl group, hexenyl group, etc.), substituted
A 5- to 7-membered alicyclic group (e.g. cyclopentyl group)
, cyclohexyl group, chlorocyclohexyl group, etc.),
Aromatic groups that may be substituted (e.g. phenyl group, chlorophyll group)
phenyl group, methoxyphenyl group, acetamidophenyl group
group, methylphenyl group, dichlorophenyl group, nitrophenyl group
phenyl group, naphthyl group, butylphenyl group, dimethylphenyl group
phenyl group, etc.), or R34 and R35 are the same
ring (e.g. tetramethylene group, pentamethylene group,
xamethylene group, etc.) may be formed. General formula (IV) used in the present invention ~(
VIII) a functional group selected from the group of functional groups represented by
The monomer containing at least one group is a conventionally known organic monomer.
Easily synthesized by synthetic reactions. For example, the Chemical Society of Japan
Edited by “New Experimental Chemistry Course Volume 14, Synthesis and Reactions of Organic Compounds”
(V)” page 2535 (published by Maruzen Co., Ltd.), Yoshio Iwakura:
Keisuke Kurita “Reactive Polymers” p. 170 (Kodansha), J
．． F. W. McOmie, “Protecti
ve Groups in Organic Chem
istry” page 183 (Pienum Pres.
s, 1973), etc.
. [0074] Also, the compound represented by the general formula (VIII)
A monomer containing a xazolone ring contains a polymerizable unsaturated bond.
Dehydration ring closure reaction of N-acyloyl-α-amino acids with
It can be manufactured by Specifically, Yoshio Iwakura:
As described in Keisuke Kurita's "Reactive Polymers" Chapter 3 (Kodansha)
It can be manufactured by a method. Other monomers copolymerizable with these monomers
For example, vinyl acetate, vinyl propionate, butylene
Fats such as vinyl acid, allyl acetate, allyl propionate, etc.
aliphatic carboxylic acid vinyl or allyl esters,
Lyric acid, methacrylic acid, crotonic acid, itaconic acid, male
Esthetics of unsaturated carboxylic acids such as inic acid, fumaric acid, etc.
compounds or amides, styrene, vinyltoluene, α-methane
Styrene derivatives such as tyrstyrene, α-olefins
, acrylonitrile, methacrylonitrile, N-vinyl
Examples include vinyl group-substituted heterocyclic compounds such as pyrrolidone.
can be lost. As mentioned above, the method for producing the desired monomer
General formulas (IV) to (VIII) used in the method
More specific about the monomer (A) containing the functional group
For example, the components of the following general formula (IX) may be mentioned.
It will be done. However, it is not limited to these monomers.
stomach. General formula (IX) [Chemical formula 90] In formula (IX), X' is -O-, -CO-, -COO-
, [Chemical formula 91] represents an aromatic group or a heterocyclic group [however, d1 , d2
, d3 and d4 are each a hydrogen atom, a hydrocarbon group, or
-[Y'-W] in formula (IX), b1, b2
may be the same or different, hydrogen atoms, hydrocarbons
represents a group or -[Y'-W] in formula (IX), l is
Indicates an integer from 0 to 18]. Y' is a bonding group X' and a bonding group [
W] may be connected through a heteroatom, which may be a carbon-carbon
Represents an elementary bond (heteroatoms include oxygen atoms and sulfur atoms)
atom, nitrogen atom), for example, [Chemical structure 92], etc., either singly or in combination.
(However, b3, b4, b5 are respectively b1,
b2). W is the formula (IV) ~ (VIII
) represents a functional group represented by a1 ′, a2 ′
may be the same or different, hydrogen atoms, halogen atoms (
(e.g. chlorine atom, bromine atom, etc.), cyano group, hydrocarbon group
(For example, methyl group, ethyl group, propyl group, butyl group,
Methoxycarbonyl group, ethoxycarbonyl group, proponent
xycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, butoxycarbonyl group,
oxycarbonyl group, methoxycarbonylmethyl group, etho
Oxycarbonylmethyl group, butoxycarbonylmethyl group
An optionally substituted alkyl group having 1 to 12 carbon atoms such as
Aralkyl groups such as ndyl group and phenethyl group, phenyl group
, tolyl group, silyl group, chlorophenyl group, etc.
group, etc.) or a substituent containing a -W group in formula (IX)
an optionally substituted alkyl group having 1 to 18 carbon atoms, alkenyl
group, aralkyl group, alicyclic group, and aromatic group. In addition, the [-X'-Y'-] bonding residue in formula (IX) is [
embedded image The moiety and -W may be directly linked. W is a notation represented by general formulas (IV) to (VIII)
Indicates the content of the issue. General formulas (IV) to (VII) of the present invention
I) to the functional group represented by [W group in formula (IX)]
A specific example will be described below. However, the scope of the present invention is
It is not limited to these. (c-1) [Chemical Formula 94] (c-2) [Chemical Formula 95] (c-3) [Chemical Formula 96] (c-4) [Chemical Formula 97] (c-5) [Chemical Formula 98] (c-6) (C-99) (c-7) (C-8) (C-9) (C-9) (C-10) (C-10) (C-11) (C-104) c-12) [Chemical formula 105] (c-13) [Chemical formula 106] (c-14) [Chemical formula 107] (c-15) [Chemical formula 108] (c-16) [Chemical formula 109] (c-17) [ Chemical Formula 110] (c-18) [Chemical Formula 111] (c-19) [Chemical Formula 112] (c-20) [Chemical Formula 113] (c-21) [Chemical Formula 114] (c-22) [Chemical Formula 115] (c -23) [Chemical formula 116] (c-24) [Chemical formula 117] (C-25) [Chemical formula 118] (c-26) [Chemical formula 119] (c-27) [Chemical formula 120] (c-28) [Chemical formula 121] (c-29) [Chemical formula 122] (c-30) [Chemical formula 123] (c-31) [Chemical formula 124] (c-32) [Chemical formula 125] (c-33) [Chemical formula 126] (c- 34) [Formula 127] (c-35) [Formula 128] (c-36) [Formula 129] (c-37) [Formula 130] (c-38) [Formula 131] (c-39) [Formula 132 ] (c-40) [Chemical Formula 133] (c-41) [Chemical Formula 134] (c-42) [Chemical Formula 135] (c-43) [Chemical Formula 136] (c-44) [Chemical Formula 137] (c-45 ) [Chemical Formula 138] (c-46) [Chemical Formula 139] (c-47) [Chemical Formula 140] (c-48) [Chemical Formula 141] (c-49) [Chemical Formula 142] (c-50) [Chemical Formula 143] (c-51) [Chemical formula 144] (c-52) [Chemical formula 145] Carboxylic acid in the resin particles [L] of the present invention
The polymer component containing a sil group-forming functional group is a resin particle [
L] is a copolymer, 10 to 9 of the total copolymer
Preferably it is 5% by weight, especially 20-90% by weight.
. [0078] The resin particles [L] of the present invention further include at least
It is characterized by being partially cross-linked. polymer
Resin particles [L] (
A resin having a crosslinked structure in the polymer) is
The carboxyl group-forming functional group that is
When generating a ruboxyl group, acidic and alkaline
Resin particles that are poorly soluble or insoluble in aqueous solutions are preferred.
Delicious. [0079] The above-mentioned protecting group-containing monomer (A) and
In addition, other copolymerizable monomers other than these may be added to the polymer composition.
It may be included as a fraction. Other monomers will be described later.
A monomer corresponding to the repeating unit of general formula (X) or
Copolymerized with a monomer corresponding to the component represented by the formula (X)
There are many things that can be mentioned. Monomer (A) as a polymerization component in the resin
The proportion of
above and contains other copolymerizable monomers,
It is at most 20% by weight or less. Insoluble in this non-aqueous solvent
The important thing about the polymerization component is that it produces carboxyl groups.
It is expressed as the contact angle with respect to distilled water as a substance after formation.
Any material that can satisfy the hydrophilicity of 50 degrees or less is sufficient. Next, the dispersion stabilizing resin of the present invention will be explained.
do. The dispersion stabilizing resin is solvated and soluble in non-aqueous solvents.
In so-called non-aqueous dispersion polymerization,
It is responsible for the dispersion stabilizing effect, specifically the solvent
At least 5 parts per 100 parts by weight at a temperature of 25°C
Any material may be used as long as it dissolves in weight%. The weight average molecular weight of the dispersion stabilizing resin is 1×
103 to 1×105, preferably 2×103
~1×105, particularly preferably 2×103
~1×104. The weight average molecular weight of the resin is 1×
If it is less than 103, the agglomeration of the generated dispersed resin particles will occur.
particles with a uniform average particle size can no longer be obtained.
Mau. On the other hand, if it exceeds 5 x 105, it will be added to the photoconductive layer.
It is said to improve water retention while satisfying electrophotographic properties when
Otherwise, the effect of the present invention will be diminished. The dispersion stabilizing resin of the present invention is compatible with the non-aqueous solvent.
Any soluble polymer may be used, but specifically,
K. E. J. Barrett “Dispers
ion Polymerization in Org
John Wiley anic
d Sons (published in 1975), R. Dowpen
co, D. P. Hart, Ind. Eng
．． Chem. Prod. Res. Develo
p. 12, (No. 1), 14 (1973), Tange
Toyoyoshi, Japan Adhesive Association Journal 23(1), 26 (1987
), D. J. Walbridge, NATO.
Adv. Study Inst. Ser. E. N
o. 67, 40 (1983), Y. Sasakian
dM. Yabuta, Proc, 10th,
Int. Conf. Org. Coat. Sc
i. Technol, 10, 263 (1984), etc.
The review article lists the cited polymers. For example, olefin polymers, modified olefins
Polymers, styrene-olefin copolymers, aliphatic carbo
vinyl ester copolymer, modified maleic anhydride copolymer
Coalescence, polyester polymer, polyether polymer, meta
Acrylate homopolymer, acrylate homopolymer, meth
Acrylate copolymer, acrylate copolymer, alkyl
resin, etc. More specifically, the dispersion stabilizing resin of the present invention
Polymer components serving as repeating units include the following:
Examples include components represented by the following general formula (X). General formula (X) [Chemical formula 146] In formula (X), X4 has the same content as V0 in formula (II)
The details are described in the explanation of V0 in formula (II).
ing. R36 is a substituted group having 1 to 22 carbon atoms.
Good alkyl groups (e.g. methyl, ethyl, propyl)
group, butyl group, pentyl group, hexyl group, octyl group,
Nonyl group, decyl group, dodecyl group, tridecyl group, tetyl group
Radecyl group, hexadecyl group, octadecyl group, dosaco
Nyl group, 2-(N,N-dimethylamino)ethyl group, 2
-(N-morpholino)ethyl group, 2-chloroethyl group,
2-bromoethyl group, 2-hydroxyethyl group, 2-bromoethyl group
Anoethyl group, 2-(α-thienyl)ethyl group, 2-carboxylic
ruboxyethyl group, 2-methoxycarbonylethyl group,
2,3-epoxypropyl group, 2,3-diacetoxypyl group
Lopyl group, 3-chloropropyl group, 4-ethoxycarbo
nylbutyl group, etc.), optionally substituted with 3 to 22 carbon atoms
Alkenyl groups (e.g. allyl, hexenyl, octene)
Nyl group, docenyl group, dodecenyl group, tridecenyl group,
octadecenyl group, oleyl group, linoleyl group, etc.), carbon
An optionally substituted aralkyl group having a prime number of 7 to 22 (e.g.
benzyl group, phenethyl group, 3-phenylpropyl group,
2-naphthylmethyl group, 2-(2'-naphthyl)ethyl
group, chlorobenzyl group, bromobenzyl group, methylbenzyl group
Zyl group, dimethylbenzyl group, trimethylbenzyl group,
Methoxybenzyl group, dimethoxybenzyl group, butylbenzyl group
carbonyl group, methoxycarbonylbenzyl group, etc.), carbon number
4 to 12 optionally substituted alicyclic groups (e.g. cyclopene
ntyl group, cyclohexyl group, cyclooctyl group, ada
mantyl group, chlorocyclohexyl group, methylcyclohexyl group
xyl group, methoxycyclohexyl group, etc.), carbon number 6 or more
22 optionally substituted aromatic groups (e.g. phenyl group,
Tolyl group, xylyl group, mesityl group, naphthyl group, amyl group
Tranyl group, chlorophenyl group, bromophenyl group, butyl group
Tylphenyl group, hexylphenyl group, octylphenyl group
group, decylphenyl group, dodecylphenyl group, methoxy
Cyphenyl group, ethoxyphenyl group, octyloxyphenyl group
phenyl group, ethoxycarbonylphenyl group, acetyl group
phenyl group, butoxycarbonylphenyl group, butylmethylene group
Ruphenyl group, N,N-dibutylaminophenyl group, N
-Methyl-N-dodecylphenyl group, thienyl group, Hira
nyl group, etc.). c1 and c2 are expressed by the formula (I
Represents the same content as a3 and a4 in I), and details
is described in the explanation of a1 and a2 in formula (I). [0087] The polymer component in the dispersion stabilizing resin of the present invention
In addition to the above-mentioned components, it contains other polymer components.
You may. Other polymer components include general formula (X)
Copolymerizable with monomers corresponding to the indicated components
Any suitable monomer may be used, for example,
α-olefins, acrylonitrile, methacrylonito
lyl, vinyl-containing heterocycles (heterocycles include pyryl,
ring, pyrodrine ring, imidazole ring, pyridine ring, etc.)
, vinyl group-containing carboxylic acids (e.g. acrylic acid, metal
tacrylic acid, crotonic acid, itaconic acid, maleic acid, etc.)
, vinyl group-containing carboxamides (e.g. acrylic
Amide, methacrylamide, crotonic acid amide, itaco
acid amide, itaconic acid hemiamide, itaconic acid diamide
etc.) etc. In the dispersion stabilizing resin of the present invention, the general formula:
The polymer component represented by (X) is 10% of the total polymer of the resin.
30 parts by weight or more, preferably 50 parts by weight or more in 0 parts by weight
It is. Furthermore, the dispersion stabilizing resin of the present invention
A polymerizable double represented by the above-mentioned general formula (II) in the child chain
Preferably, it contains at least one type of bonding group moiety.
stomach. The polymerizable double bond group portion will be explained below.
. General formula (II) [Formula 5] In general formula (II), V0 is -O-, -
COO-, -OCO-, -(CH2)p -OCO-
, -(CH2)p -COO-, -SO2 -, [Chemical 6
] -CONHCOO- or -CONHCONH-
Wasu (p represents an integer from 1 to 4). [0090] Here, R4 is a hydrogen atom or a preferable
The hydrocarbon group may be substituted with 1 to 18 carbon atoms.
alkyl groups (e.g. methyl, ethyl, propyl)
group, butyl group, heptyl group, hexyl group, octyl group,
Decyl group, dodecyl group, hexadecyl group, octadecyl group
group, 2-chloroethyl group, 2-bromoethyl group, 2-chloroethyl group,
Anoethyl group, 2-methoxycarbonylethyl group, 2-
methoxyethyl group, 3-bromopropyl group, etc.), carbon number
4 to 18 optionally substituted alkenyl groups (e.g. 2-
Methyl-1-propenyl group, 2-butenyl group, 2-pene
tenyl group, 3-methyl-2-pentenyl group, 1-pentene group
Nyl group, 1-hexenyl group, 2-hexenyl group, 4-methenyl group
methyl-2-hexenyl group, etc.), substitution with 7 to 12 carbon atoms
Aralkyl groups that may be substituted (for example, benzyl groups,
Phenethyl group, 3-phenylpropyl group, naphthylmethy
group, 2-naphthylethyl group, chlorobenzyl group, chlorobenzyl group,
mobenzyl group, methylbenzyl group, ethylbenzyl group,
Methoxybenzyl group, dimethylbenzyl group, dimethoxy
benzyl group, etc.), optionally substituted with 5 to 8 carbon atoms
Alicyclic groups (e.g. cyclohexyl group, 2-cyclohexyl group)
sylethyl group, 2-cyclopentylethyl group, etc.), or
is an optionally substituted aromatic group having 6 to 12 carbon atoms (
For example, phenyl group, naphthyl group, tolyl group, xylyl group
, propylphenyl group, butylphenyl group, octylphenyl group
phenyl group, dodecylphenyl group, methoxyphenyl group,
Ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group
Cyphenyl group, chlorophenyl group, dichlorophenyl group
, bromophenyl group, cyanophenyl group, acetylphenyl group
Nyl group, methoxycarbonylphenyl group, ethoxycal
Bonylphenyl group, butoxycarbonylphenyl group, a
Cetamidophenyl group, propioamidophenyl group,
(decoylamidophenyl group, etc.). When V0 represents the following formula, the benzene ring may have a substituent. Substituents include halogen atoms (e.g. chlorine atoms, bromine atoms)
atoms, etc.), alkyl groups (e.g., methyl group, ethyl group,
Propyl group, butyl group, chloromethyl group, methoxymethylene group
), alkoxy groups (e.g. methoxy, ethoxy, etc.),
cy group, propioxy group, butoxy group, etc.)
. [0092] a3 and a4 may be the same or different.
Preferably a hydrogen atom, a halogen atom (
For example, chlorine atom, bromine atom, etc.), cyano group, carbon number 1~
4 alkyl groups (e.g. methyl group, ethyl group, propylene group)
(butyl group, butyl group, etc.) -COO-R5 or via a hydrocarbon
COOR5 (R5 is a hydrogen atom or a carbon number of 1 to
18 alkyl groups, alkenyl groups, aralkyl groups, alicyclic groups
represents a formula group or an aryl group, which is substituted
Specifically, the one explained for R4 above.
represents the same content as ). [0093] To -COOR5 group via the above hydrocarbon
Examples of hydrocarbons include methylene groups, ethylene groups,
Examples include lopyrene group. More preferably, the general formula (
In II), V0 is -COO-, -OCO-,
-CH2 OCO-, -CH2 COO-, -O-, -
CONH-, -SO2 NH-, -CONHCOO- or
represents [Chemical formula 147], and a3 and a4 are the same as each other.
may be the same or different, hydrogen atom, methyl group, -C
OOR5 or -CH2COOR5, (R5
is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g.
Tyl group, ethyl group, propyl group, butyl group, hexyl group
etc.). Even more preferably a3 and
One of a4 always represents a hydrogen atom. That is, the polymerization represented by the general formula (II)
Specific examples of the double bonding group-containing moiety include: [Image Omitted] [Image Omitted] [Image Omitted] [Image Omitted] [0095] These polymerizable double bond group-containing moieties are
Directly bonded to the main chain of the child chain or bonded with an arbitrary linking group
It is what was done. Specifically, divalent groups are used as linking groups.
a divalent aliphatic organic residue optionally interposed with a bonding group selected from -O-, -S-,
groups or divalent aromatic groups, or divalent residues of these
Represents organic residues formed by combinations. Here, d
5 to d9 have the same content as R4 in formula (II)
represents. As the divalent aliphatic group, for example,
] {e3 and e4 may be the same or different.
hydrogen atoms, halogen atoms (for example, fluoride atoms), respectively.
(fluorine atom, chlorine atom, bromine atom, etc.) or carbon number 1 to 12
Alkyl groups (e.g. methyl, ethyl, propyl)
, chloromethyl group, bromomethyl group, butyl group, hexyl group
octyl group, octyl group, nonyl group, decyl group, etc.). Q represents -O-, -S- or -NR37-, R37
is an alkyl group having 1 to 4 carbon atoms, -CH2Cl or -C
H2 represents Br}. As the divalent aromatic group, for example, benzene
cyclic groups, naphthalene cyclic groups and 5- or 6-membered heterocyclic groups (heterocyclic groups)
Oxygen atoms, sulfur atoms as heteroatoms that make up the ring
, containing at least one heteroatom selected from nitrogen atoms.
). These aromatic groups have substituents.
For example, halogen atoms (e.g. fluorine atoms)
atom, chlorine atom, bromine atom, etc.), alkyl having 1 to 8 carbon atoms
groups (e.g. methyl, ethyl, propyl, butyl)
, hexyl group, octyl group, etc.), C1-6 alkoxy
Oxy groups (e.g. methoxy, ethoxy, propioxy)
, butoxy group, etc.) are mentioned as examples of the substituent. Examples of the heterocyclic group include a furan ring, a thiophene ring, and a pipe ring.
Lysine ring, pyrazine ring, piperazine ring, tetrahydrof
Ran ring, pyrrole ring, tetrahydropyran ring, 1,3-
Examples include oxazoline rings. The polymerizable double bond group-containing portion as described above is
, specifically randomly bonded in polymer chains, or
is bonded only to one end of the main chain of the polymer chain. Like
Alternatively, a polymerizable double bond group may be added only at one end of the main chain of the polymer chain.
A polymer to which a containing moiety is bonded (hereinafter referred to as a monofunctional polymer [
(abbreviated as M)). General formula (II) of the above monofunctional polymer [M]
) and a polymerizable double bond group-containing moiety connected to this
The following are specific examples of parts composed of organic residues:
These include, but are not limited to:
. However, in each of the following examples, P1 is -H, -CH3
, -CH2COOCH3, -Cl, -Br or -C
N, P2 represents -H or -CH3, X5
represents -Cl or -Br, and n2 represents an integer from 2 to 12.
and m2 represents an integer of 1 to 4. (d-1) [Chemical formula 152] (d-2) [Chemical formula 153] (d-3) [Chemical formula 154] (d-4) [Chemical formula 155] (d-5) [Chemical formula 156] (d-6) embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image d-12) [Chemical Formula 163] (d-13) [Chemical Formula 164] (d-14) [Chemical Formula 165] (d-15) [Chemical Formula 166] (d-16) [Chemical Formula 167] (d-17) [ (d-18) (d-18) (d-19) (d-20) (d-20) (d-21) (d-21) (d-22) (d-22) (d-22) -23) [Chemical formula 174] (d-24) [Chemical formula 175] (d-25) [Chemical formula 176] (d-26) [Chemical formula 177] (d-27) [Chemical formula 178] (d-28) [Chemical formula 178] (d-28) 179] (d-29) [Chemical formula 180] (d-30) [Chemical formula 181] Preferably, the dispersion stabilizing resin of the present invention is polymerized.
contains a double bond group moiety in the side chain of the polymer, but this
The polymer can be synthesized by conventionally known methods.
can. For example, ■ Polymerizable double bonds with different polymerization reactivity
A method of copolymerizing a monomer containing two groups in the molecule,
■Carboxyl, hydroxyl, and amino groups in the molecule
, a monofunctional monomer containing a reactive group such as an epoxy group
After copolymerizing to obtain a polymer, reactions in the side chains of this polymer occur.
Polymerizable duplex containing other reactive groups that can chemically bond with the group
Reacts with organic low-molecular compounds containing bonding groups, so-called
Generally, methods such as introduction by polymer reaction are well-known.
This is one of the methods that can be used. [0101] As the above method (①), for example,
Examples include the method described in Japanese Patent No. 185962. the above
■Specifically, Yoshio Iwakura and Keisuke Kurita's ``Reaction
"Polymer" Kodansha (1977), Ryohei Oda "Polymer
"Fine Chemicals" Kodansha (published in 1976), Japanese Patent Application Publication No. 1986
Publication No. 1-43757, Japanese Patent Application No. 1-149305
It is described in detail in the specification etc. filed by the applicant. For example, the functional groups of Group A and Group B in Table 1 below
Polymer reactions involving combinations of functional groups are usually well-known.
This is mentioned as a method that was adopted. In addition, R38 in Table-1,
R39 is a hydrocarbon group, and R4 in the above formula (II)
represents the same content as . [Table 1] More preferred as the dispersion stabilizing resin of the present invention
A monomer containing a polymerizable double bond group at one end of the main chain.
The functional polymer [M] can be produced by a conventionally known synthesis method.
can be built. For example, a) anionic polymerization or
is a living polymer end obtained by cationic polymerization.
A monofunctional polymer [M] is obtained by reacting various reagents at the end.
(2) method using ionic polymerization method, (b) method using carboxy in the molecule
Contains reactive groups such as hydroxyl groups, amino groups, etc.
Using a polymerization initiator and/or a chain transfer agent, radical
Polymers with terminal reactive groups bonded through polymerization and various tests
Radical polymerization to obtain a monofunctional polymer [M] by reacting a drug
By legal method, c) By polyaddition or polycondensation reaction
The obtained polymer was polymerized in the same manner as the above radical polymerization method.
Methods such as polyaddition condensation methods that introduce combinable double bond groups, etc.
Can be mentioned. Specifically, P. Dreyfuss &
R. P. Quirk, Encycle. Po
lym. Sci. Eng. , 7,551 (198
7), P. F. Rempp, E. Franta
, Adv. Polym. Sci. , 58,1(
1984), V. Percec, Appl. Po
ly. Sci. , 285, 95 (1984), R.
Asami, M. Takari, Macromo
l. Chem. Suppl. ,12,163(19
85), P. Rempp. , et al., Mac
romol. Chem. Suppl. , 8, 3(
1984), Yuji Kawakami, Chemical Industry, 38, 56 (198
7), Yuya Yamashita, Kobunshi, 31, 988 (1982),
Shiro Kobayashi, Polymers, 30, 625 (1981), Satoshi Higashimura
Nobu, Journal of Japan Adhesive Association, 18, 536 (1982), Ito.
Koichi, Polymer Processing, 35, 262 (1986), Takashi Higashi
Ro, Takashi Tsuda, Functional Materials, 1987, No. 10,5 etc.
According to the method described in the review article and the literature/patents cited therein.
can be synthesized. [0105] Synthesis method of the above monofunctional polymer [M]
More specifically, the method corresponds to radically polymerizable monomers.
The polymer [M] containing repeating units is disclosed in Japanese Patent Application Laid-Open No.
-67563 Publication, Japanese Patent Application No. 63-64970, Japanese Patent Application No. 63-64970, Japanese Patent Application No.
1-206989 and 1-69011.
It is described in the specifications, etc., and also has a polyester structure or
Polymer containing polyether structure as a repeating unit
[M] is patent application No. 1-56379, No. 1-58989,
1-56380, each listed in the application specification, etc.
obtained in the same manner as described. [0106] The dispersed resin particles of the present invention are as described above.
, the polar group-containing monofunctional monomer (A) is used for dispersion stabilization.
Copolymer resin particles obtained by dispersion polymerization in the presence of resin
It is a child. Furthermore, the dispersed resin particles of the present invention have a network structure.
When doing so, the above polar group-containing monofunctional monomer (A)
[abbreviated as polymer component (A)]
The coalescence is bridged, forming a higher-order network structure.
There is. [0107] That is, the dispersed resin particles of the present invention
a part insoluble in a non-aqueous dispersion solvent composed of body component (A)
and a polymer that is soluble in the solvent.
If it is latex and has a network structure, this solution
Molecules of polymer component (A) forming a portion insoluble in the medium
It is something that bridges the gap. This allows the carbo
After xyl group formation, network resin particles are poorly soluble in water.
Or it has become insoluble. Specifically, the resin
Solubility in water is 80% by weight or less, preferably 50% by weight
It is as follows. [0108] The crosslinking of the present invention is carried out by a conventionally known crosslinking method.
You can do this. That is, (a) the polymer component (A
) containing polymers with various crosslinking agents or curing agents.
(b) corresponding to the polymer component (A);
When carrying out a polymerization reaction by containing at least a monomer,
A polyfunctional monomer containing two or more polymerizable functional groups or
is created between molecules by coexisting polyfunctional oligomers.
A method for forming a network structure, and (c) the polymer component (A
) and a polymer containing a component containing a reactive group.
Methods such as crosslinking by reaction or polymer reaction
This can be done by The crosslinking agent used in the method (a) above is usually
Compounds used as crosslinking agents can be mentioned. Specifically, the book “Crosslinking Agent Handbook” edited by Shinzo Yamashita and Tosuke Kaneko
published by Taiseisha (1981), edited by the Society of Polymer Science, “Polymer De
Data Handbook Basic Edition” Baifukan (1986), etc.
Compounds listed can be used. For example, organic silane compounds (for example, vinyl
Nyltrimethoxysilane, vinyltributoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-methoxysilane
Lucatopropyltriethoxysilane, γ-aminopropylene
Silane coupling agents such as pyrutriethoxysilane, etc.)
, polyisocyanate compounds (e.g. toluylene diamide)
Isocyanate, o-toluylene diisocyanate, di
Phenylmethane diisocyanate, triphenylmethane
Triisocyanate, polymethylene polyphenylisocyanate
Anate, hexamethylene diisocyanate, isophoro
diisocyanate, polymer polyisocyanate, etc.),
Polyol compounds (e.g. 1,4-butanediol
, polyoxypropylene glycol, polyoxyalkyl
Ren glycol, 1,1,1-trimethylolpropane
etc.), polyamine compounds (e.g. ethylenediamine
, γ-hydroxypropylated ethylenediamine, phenyl
Diamine, hexamethylene diamine, N-aminoe
(chilpiperazine, modified aliphatic polyamines, etc.), polyethylene
Poxy group-containing compounds and epoxy resins (for example, Hiroshi Kakiuchi
Edited by "New Epoxy Resin" Shokodo (published in 1985), Hashimoto
“Epoxy Resin” edited by Kuniyuki, Nikkan Kogyo Shimbun (1969)
), melamine resins (e.g.
, Ichiro Miwa, Hideo Matsunaga (eds.) "Uria Melamine Resin"
Compounds described in Kankogyo Shinbunsha (published in 1969), etc.
), poly(meth)acrylate compounds (e.g. Taikawa
Nobu Hara, Takeo Saegusa, Toshinobu Higashimura eds. “Oligomer” Kodansha (1
(Published in 1976), Eizo Omori's "Functional Acrylic Resin" Technique
The compounds described in Nosystem (published in 1985) etc.
Specifically, polyethylene glycol diac
rylate, neopentyl glycol diacrylate, 1
, 6-hexanediol diacrylate, trimethylo
lupropane triacrylate, pentaerythritolpo
Reacrylate, bisphenol A-diglycidyl ether
Terdiacrylate, oligoester acrylate and
There are methacrylates of these. [0111] Also, in the method (b) above, polymerizable
Polyfunctional monomer containing two or more functional groups [polyfunctional monomer
polymer (D)] or polyfunctional oligomer
Specific examples of the polymerizable functional group include the following. Identicality of these polymerizable functional groups
A monomer having two or more of the same or different
The material may be an oligomer. [0112] Monomer having two or more polymerizable functional groups
Examples include monomers having the same polymerizable functional group.
Or as oligomers, divinylbenzene, trivinyl
Styrene derivatives such as benzene: Polyhydric alcohols (e.g.
, ethylene glycol, diethylene glycol, trie
tyrene glycol, polyethylene glycol #200,
#400, #600, 1,3-butylene glycol,
Opentyl glycol, dipropylene glycol, poly
propylene glycol, trimethylolpropane, tri
methylolethane, pentaerythritol, etc.), or
Polyhydroxyphenols (e.g. hydroquinone, reso-
methacrylate of lucine, catechol and their derivatives)
ethyl acid, acrylic acid or crotonic acid esters, vinyl
Ethers or allyl ethers: dibasic acids (e.g.
Ronic acid, succinic acid, glutaric acid, adipic acid, pimeline
acid, maleic acid, phthalic acid, itaconic acid, etc.)
Stelles, allyl esters, vinylamides or ants
Amides: Polyamines (e.g. ethylenediamine, 1
, 3-propylene diamine, 1,4-butylene diamine
etc.) and carboxylic acids containing vinyl groups (e.g. methacrylates)
lylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.)
Examples include condensates. [0113] Furthermore, monomers having different polymerizable functional groups
Examples of vinyl group-containing oligomers include vinyl group-containing vinyl groups.
carboxylic acids (e.g. methacrylic acid, acrylic acid, meth)
Acryloyl acetate, acryloyl acetate, methacryloyl acetate
ropionic acid, aryloylpropionic acid, itaconiroi
acetic acid, itaconylpropionic acid, carboxylic acid anhydride
reactants of alcohols or amines (e.g.
Oxycarbonylpropionic acid, allyloxycarbonyl
acetic acid, 2-allyloxycarbonylbenzoic acid, allyl
Contains vinyl groups such as aminocarbonylpropionic acid, etc.
ester derivatives or amide derivatives (e.g. methacrylate)
vinyl phosphate, vinyl acrylate, vinyl itaconate, metal
Allyl taacrylate, allyl acrylate, allyl itaconate
vinyl, methacryloyl vinyl acetate, methacryloyl propyl
vinyl ionate, allyl methacryloylpropionate, metal
Taacrylic acid vinyloxycarbonyl methyl ester, a
Vinyloxycarbonylmethyloxycarbonyl acrylate
ethylene ester, N-allylacrylamide, N-
Allyl methacrylamide, N-allyl itaconic acid amide
, methacryloylpropionate allylamide, etc.) or a
aminoalcohols (e.g. aminoethanol, 1-aminoalcohols)
Nopropanol, 1-aminobutanol, 1-aminohe
xanol, 2-aminobutanol, etc.) and vinyl groups.
Examples include condensates with carboxylic acids. Two or more polymerizable functionalities used in the present invention
The monomer or oligomer having the group is monomer (A)
and 10 relative to the total amount of other monomers coexisting with (A)
Polymerize using mol% or less, preferably 5 mol% or less, and
Forms fat. Furthermore, the reaction between polymers in the method (c) above
A chemical bond is formed through a reaction between reactive groups, creating a bridge between polymers.
When performing cross-linking, the reaction of ordinary organic low-molecular compounds and
The same can be done. Specifically, dispersion stabilizing resin
Synthesized according to the same method as described in the synthesis method of
can be done. In dispersion polymerization, the particle size of particles is uniform.
monodisperse particles with a diameter of 0.5 μm or less
Forming a network structure is preferable because it is easier to obtain microparticles.
As a method, method (c) using a polyfunctional monomer is preferred.
Delicious. As described above, the network-dispersed resin particles of the present invention are
, a repeating unit containing a protected carboxyl group and
, a polymer component soluble in the nonaqueous solvent, and a polymer component soluble in the non-aqueous solvent;
Polymer particles with a structure in which child chains are highly cross-linked
It is. [0117] Used in the production of non-aqueous solvent-based dispersed resin particles.
The non-aqueous solvent used is an organic solvent with a boiling point of 200°C or less.
Either one is fine, and it can be used alone or in combination of two or more types.
May be used in combination. Specific examples of this organic solvent include
Tanol, ethanol, propanol, butanol, fluoride
Alcohols such as alcohol, benzyl alcohol, etc.
, acetone, methyl ethyl ketone, cyclohexanone,
Ketones such as diethyl ketone, diethyl ether, tet
Ethers such as lahydrofuran and dioxane, methyl acetate
ethyl acetate, butyl acetate, methyl propionate, etc.
Carboxylic acid esters, hexane, octane, decane,
Dodecane, tridecane, cyclohexane, cycloocta
C6-14 aliphatic hydrocarbons such as benzene,
Aromatic hydrocarbons such as toluene, xylene, and chlorobenzene
elements, methylene chloride, dichloroethane, tetrachloride
loethane, chloroform, methyl chloroform, dichloro
Halogenated hydrocarbons such as lopropane and trichloroethane
etc. However, it is limited to the compound examples mentioned above.
It is not something that will be done. [0118] Dispersing resin particles in these non-aqueous solvent systems
By synthesizing with polymerization method, the average particle size of resin particles is
It easily becomes 0.8 μm or less, and the particle size distribution is
The particles can be very narrow and monodisperse. concrete
Specifically, K. E. J. Barrett “Dis
persion Polymerization in
Organic Media” John Wile
y (1975), Koichiro Murata, Polymer Processing, 23, 2
0 (1974), Tsunetaka Matsumoto, Toyokichi Tange, Japan Adhesive Association Journal
9, 183 (1973), Toyokichi Tange, Japan Adhesive Association Journal 2
3, 26 (1987), D. J. Walbridg
e, NATO. Adv. study. Inst
．． Ser. E. No. 67, 40 (1983),
British Patent Nos. 893429 and 934038,
U.S. Patent No. 1122397, U.S. Patent No. 3900412, U.S. Patent No. 46
06989 specifications, JP-A-60-179751, same
The method is disclosed in publications such as 60-185963.
There is. [0119] The dispersion resin of the present invention is composed of a monomer (A) and a dispersion resin.
It consists of at least one kind of stabilizing resin, and has a network structure.
When forming a structure, a polyfunctional monomer (D
) coexist, and in any case, the important thing is that
Even if the resin synthesized from the monomers is insoluble in the non-aqueous solvent,
For example, a desired dispersed resin can be obtained. more specifically
The dispersion stabilizing resin is added to the monomer (A) to be insolubilized.
It is preferable to use 1 to 50% by weight, more preferably
The content is usually 2 to 30% by weight. Furthermore, the dispersed resin particles of the present invention
The molecular weight is 104 to 106, preferably 104
~5×105. [0120] Dispersed resin particles used in the present invention as described above
In general, monomer (A), monomer (B
), a dispersion stabilizing resin, and a polyfunctional monomer (D).
benzoyl peroxide, azobisisobutyro in a non-aqueous solvent
Addition in the presence of a polymerization initiator such as nitrile or butyllithium
It may be thermally polymerized. Specifically, (i) monomer (A)
, monomer (B), dispersion stabilizing resin and polyfunctional monomer (
A method of adding a polymerization initiator to the mixed solution of D), (ii)
) The above polymerizable compound and polymerization initiator are mixed in a non-aqueous solvent.
There are methods such as adding the compound dropwise or optionally.
It can be manufactured using any method without limitation.
Ru. [0121] The total amount of polymerizable compounds is 100% by weight of the nonaqueous solvent.
The amount is about 5 to 80 parts by weight, preferably 10 parts by weight.
~50 parts by weight. The amount of polymerization initiator is determined by the amount of polymerizable compound
0.1 to 5% by weight of the total amount. Also, the polymerization temperature is 30
~180°C, preferably 40~120°C
Ru. The reaction time is preferably 1 to 15 hours. [0122] The non-woven fabric produced according to the present invention as described above
Water-based dispersion resin forms fine particles with uniform particle size distribution.
Ru. Surface layer containing resin particles [L] of the present invention
As for other compositions, the binder resin in the surface layer forming layer is reduced.
Any of the known surface layer resins may be used. Specifically, the same binder resin for the photoconductive layer as described above is used.
There are many examples. The amount used is 100 parts of the total composition.
It is 5 parts by weight to 90 parts by weight. Furthermore, the surface layer itself which can be made hydrophilic according to the present invention
strength, adhesion with the photoconductive layer, electrophotographic properties, etc.
For improvement, resins other than the resins of the present invention described above were added.
Alternatively, a crosslinking agent, a plasticizer, etc. may be added. rack
As a bridging agent, commonly used organic peroxides and metal sets are used.
Cross-linking agents such as Ken, organic silane, polyurethane, epoxy
A curing agent such as resin can be used. For example, Mt.
“Crosslinking Agent Handbook” edited by Fuzo Shimo and Tosuke Kaneko, published by Taiseisha (
(1981) and others. More specifically, trees
Compounds similar to those used in crosslinking fat particles [L]
can be mentioned. Furthermore, the surface layer that can be made hydrophilic is suitable for toner development.
Development characteristics during imaging, toner image adhesion or hydrophilic treatment
The surface is mechanically coated for the purpose of improving water retention etc.
It is matted or contains a matting agent in the layer.
Good too. As matting agents, silicon dioxide, zinc oxide, acid
titanium oxide, zirconium oxide, glass particles, alumina,
Fillers such as clay, polymethyl methacrylate,
Polymer particles such as polystyrene and phenolic resin
I can give an example. The thickness of the hydrophilizable surface layer of the present invention is 10
μm or less, especially for Carlson process.
It is preferably 0.1 to 5 μm. From 5μm
If it is too thick, the sensitivity of the lithographic printing original plate as an electrophotographic photoreceptor will deteriorate.
Disadvantages such as a decrease in temperature and an increase in residual potential may occur.
Ru. [0126] How to actually make the lithographic printing original plate of the present invention
Generally, first, electrophotography is performed on a conductive support using a conventional method.
A true photosensitive layer (photoconductive layer) is formed. Then on top of this layer
In addition, the resin of the present invention and, if necessary, the above-mentioned additives etc.
dissolved in a volatile hydrocarbon solvent with a boiling point of 200°C or less or
It can be manufactured by dispersing it, applying it, and drying it.
I can do that. Specifically, the organic solvent used is
dichloromethane, chloroform, 1,2-dichloroethane
ethane, tetrachloroethane, dichloropropane or trichloroethane
Halogenation with 1 to 3 carbon atoms, such as dichloroethane, etc.
Hydrocarbons are preferred. Other chlorobenzene, toluene
, aromatic hydrocarbons such as xylene or benzene,
Ketones such as acetone or 2-butanone, tetra
Ethers such as hydrofuran and methylene chloride
Various solvents and coating materials used in coating compositions, such as
Mixtures of these solvents can also be used. [0127] Lithographic printing of the present invention obtained as described above
The production of a printing plate using a master plate consists of the above-mentioned configuration.
After forming a copy image on the original plate for electrophotography by a conventional method, a non-image
It is made by desensitizing the parts. For disassembly of the present invention
The resin of the present invention containing a functional group that generates more hydrophilic groups is
The method of liposensitizing (that is, expressing hydrophilicity) is to use a treatment solution.
It can be separated by hydrolysis by passing through it or by light irradiation treatment.
There are several ways to understand this. [0128] The treatment liquid is adjusted to a predetermined pH.
It is an aqueous solution containing the agent, and the pH to be set is the same as that of the present invention.
Varies depending on the type of hydrophilic group-forming functional group, pH 1-1
Up to 3 can be used as appropriate. Furthermore, it contains other compounds.
For example, water 100% water-soluble organic solvent may be used.
It may be contained in an amount of 1 to 50 parts by weight. like this
Examples of water-soluble organic solvents include alcohols (
Methanol, ethanol, propanol, propargilia
alcohol, benzyl alcohol, phenethyl alcohol
etc.), ketones (acetone, methyl ethyl ketone, acetone),
tophenone, etc.), ethers (dioxane, trioxa
tetrahydrofuran, ethylene glycol, propylene
lene glycol, ethylene glycol monomethyl ether
Propylene glycol monomethyl ether, Tetra
hydropyran, etc.), amides (dimethylformamide,
dimethylacetamide, etc.), esters (methyl acetate,
ethyl acetate, ethyl formate, etc.), which are simple
They may be used alone or in combination of two or more. In addition, surface activity
Contains 0.1 to 20 parts by weight of a sex agent in 100 parts by weight of water.
Good too. As surfactants, conventionally known anionic,
Cationic or nonionic surfactants are listed.
It will be done. For example, Hiroshi Horiguchi "New Surfactant" Sankyo Publishing Co., Ltd.
, (published in 1975), Ryohei Oda, Kazuhiro Teramura, “Surface activity
Described in "Synthesis of Agents and Their Applications" Maki Shoten (published in 1980), etc.
Compounds can be used. The scope of the present invention is
The present invention is not limited to the specific compound examples described above. place
The conditions for dipping are a temperature of 15 to 60°C and an immersion time of 10 seconds to 5.
Minutes are preferred. [0129] Specific functional groups in the resin of the present invention can be irradiated with light.
The method of decomposition is to obtain a toner image during plate making.
The process of irradiating with "chemically active rays" during any of the following
All you have to do is take your time. That is, after electrophotographic development,
When fixing the color image, light irradiation may also be performed for fixing.
or other conventionally known fixing methods, such as heat fixing and pressure fixing.
After fixing by force fixing, solvent fixing, etc., light irradiation is performed.
It is something. [0130] "Chemically active rays" used in the present invention
Visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays,
Either γ rays or α rays may be used, but preferably ultraviolet rays are used.
Can be mentioned. More preferably wavelength 310 nm to wavelength 5
It is preferable to use one that can emit light in the range of 00 nm.
Generally, high-pressure or ultra-high-pressure mercury lamps are used.
. Light irradiation treatment is usually performed from a distance of 5cm to 50cm.
Irradiation for seconds to 10 minutes is sufficient. [Example] Examples of the present invention are illustrated below.
The contents are not limited to these. Synthesis example 1 of binder resin [A]: [A-1] Benzylmethac
95g rylate, 5g acrylic acid and 200g toluene
After heating the mixed solution of A to a temperature of 90°C under a nitrogen stream,
．． I. B. N. 6.0 g was added and reacted for 4 hours. Furthermore
A. I. B. N. 2 g was added and reacted for 2 hours. profit
The Mw of the obtained copolymer [A-1] was 8,500. Synthesis Examples 2 to 28 of Binder Resin [A]: [A-
2] to [A-28] The following procedure was performed using the same polymerization conditions as in Synthesis Example 1 of Resin [A].
Each resin [A-2] to [A-28] shown in Table 2 was synthesized. [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] Synthesis Example 29 of Binder Resin [A]: [A-29
] 95 g of 2,6-dichlorophenyl methacrylate,
5 g of lylic acid, 2 g of n-dodecyl mercaptan and toluene
200g of the mixed solution was heated to a temperature of 80°C under a nitrogen stream.
After that, A. I. B. N. Add 2g and react for 4 hours.
, then A. I. B. N. Add 0.5g and leave for 2 hours.
To A. I. B. N. Added 0.5g and reacted for 3 hours.
. After cooling, in 2 liters of a mixed solution of methanol/water (9/1)
Collect the precipitate by decantation and dry under reduced pressure.
It was dry. The yield of the waxy copolymer obtained was 78g.
The Mw was 6.3×103. Production example 1 of dispersion stabilizing resin: [P-1]
Decyl methacrylate 97g, glycidyl methacrylate
A mixed solution of 3 g of toluene and 200 g of toluene was heated under a nitrogen stream.
While stirring, the mixture was heated to a temperature of 75°C. 2,2'-azo
Bisisobutyronitrile (abbreviated as A.I.B.N.) 1.
0g was added and stirred for 4 hours, and further A. I. B. N. 0
．． 5 g was added and stirred for 4 hours. Then add this reaction mixture to
5g of methacrylic acid, N,N-dimethyldodecylamine
Add 1.0g and 0.5g of t-butylhydroquinone,
The mixture was stirred at a temperature of 110°C for 8 hours. After cooling, methanol
After re-sedimenting in 2 liters of water and collecting the slightly brownish oil, dry it.
It was dry. Yield: 73g, weight average molecular weight (Mw): 3.6×
It was 104. [P-1] [Chemical formula 183] Production example 2 of dispersion stabilizing resin: [P-2] 2
- 100 g of ethylhexyl methacrylate, 1 part of toluene
A mixed solution of 50g and 50g of isopropanol was heated with nitrogen.
The mixture was heated to a temperature of 75° C. while stirring under a stream of air. 2,2'-
Azobis (4-cyanovaleric acid) (abbreviation A.C.V.)
2g of A. was added and reacted for 4 hours, and then A. C. V. 0.8
g was added and reacted for 4 hours. After cooling, in 2 liters of methanol
The oil was collected and dried. 50 g of the obtained oil, 2-hydroxyethyl
6 g of chill methacrylate, 150 g of tetrahydrofuran
Dissolve the mixture of
Imide (D.C.C.) 8g, 4-(N,N-dimethylene)
0.2 g of pyridine and 20 g of methylene chloride.
The mixed solution was added dropwise at a temperature of 25 to 30°C, and then left as it was for 4 hours.
Stir for hours. Next, add 5 g of formic acid to this reaction mixture and
Stir for hours. After filtering out the precipitated insoluble matter, the filtrate is filtered.
It was reprecipitated into 1 liter of tanol and the oily substance was collected by filtration. Furthermore, this
Dissolve the oil in 200g of tetrahydrofuran and remove the insoluble matter.
After filtering, reprecipitate again in 1000 ml of methanol to obtain an oily
The material was collected and dried. Yield 32g, Mw 4.2×1
It was 04. [P-2] [Chemical formula 184] Production example 3 of dispersion stabilizing resin: [P-3]
96 g of thyl methacrylate, 4 g of thioglycolic acid and
A mixed solution of 200 g of toluene was stirred under a nitrogen atmosphere.
Then, the mixture was heated to a temperature of 70°C. A. I. B. N. 1.0
g was added and reacted for 8 hours. Next, add glycidium to this reaction solution.
8 g of methacrylate, N,N-dimethyldodecylamide
Add 1.0 g of chlorine and 0.5 g of t-butylhydroquinone.
Then, the mixture was stirred at a temperature of 100°C for 12 hours. After cooling this
The reaction solution was reprecipitated into 2 liters of methanol, and 82 g of oil was obtained.
Obtained. The number average molecular weight of the polymer was 5,600. [P-3]
[Chemical formula 185] Production example 4 of dispersion stabilizing resin: [P-4]n
-butyl methacrylate 107g, β-mercaptopro
A mixed solution of 4 g of pionic acid and 200 g of toluene was mixed with nitrogen
The mixture was heated to 70°C while stirring under a stream of air. A.
I. B. N. 1 g was added and reacted for 6 hours. This anti
After cooling the reaction mixture and setting the temperature to 25°C, the 2-hydrohydride
10g of roxyethyl methacrylate and dicarboxyl
Carbondiimide (D.C.C.) 8g, 4-(N,
0.2 g of N-dimethylamino)pyridine and methylene chloride
Add 20g of the mixed solution dropwise at a temperature of 25 to 30°C, and
The mixture was stirred as it was for 4 hours. Then add 5 formic acid to this reaction mixture.
g and stirred for 1 hour. After filtering out the precipitated insoluble matter
, reprecipitate the filtrate in 1000 ml of methanol and filter the oily substance.
collected. Furthermore, this oil was diluted with 200% tetrahydrofuran.
After filtering off the insoluble matter, add 2000ml of methanol again.
The oil was collected and dried. Yield 68g
Mw was 6.6×103. [P-4] [Chemical formula 186] Production examples 5 to 12 of dispersion stabilizing resin: [P-
5] to [P-12] In Production Example 4, 100 g of n-butyl methacrylate
Except that the monomer group corresponding to Table 3 below was used instead of
Each resin was produced in the same manner as in Production Example 4. M of each resin
w was in the range of 5.5 x 103 to 7 x 103. [Table 7] Production examples 13 to 16 of dispersion stabilizing resin: [P
-13] to [P-16] In Production Example 4, the substitute for 2-hydroxy methacrylate
Except for using the compounds corresponding to Table 4 below,
Each resin was produced in the same manner as in Example 4. Mw of each resin
was in the range of 6 x 103 to 7 x 103. [Table 8] Production example 1 of resin particles: [L-1] Dispersion stability
Resin [P-1] 8.0g (as solid content), the following structure
35 g of synthetic monomer (M-1), 1 methyl methacrylate
5g, diethylene glycol dimethacrylate 1.0g
A mixed solution of 250 g of n-heptane was stirred under a nitrogen stream.
The temperature was raised to 60° C. while stirring. 2,2'-Azobis
(isovaleronitrile) (abbreviation A.I.V.N.) 0
．． 3 g was added and reacted for 6 hours. Initiator (A.I.V.N.
．． ) After 20 minutes of addition, the homogeneous solution started to become cloudy and the reaction temperature
The temperature rose to 90°C. After cooling, 200 mesh knife
A white dispersion was obtained through a cotton cloth. Average particle size 0.25
It was latex of μm. (Monomer M-1) [Chemical formula 1
87] Production examples 2 to 11 of resin particles: [L-2] to
[L-11] In Production Example 1 of resin particles, instead of monomer M-1
Proceed as in Production Example 1 except for replacing the monomers in Table 5 below.
Resin particles were produced. [Table 9] [Table 10] [0143] Production example 12 of resin particles: [L-12] Below
Monomer [M-12] 30g, AB-6 (Toagosei Co., Ltd.)
Manufactured by: Monofunctional macromolecule consisting of butyl acrylate units
Nomer) 5g, ethylene glycol diallylate 3g
, a mixed solution of 80 g of ethyl acetate and 70 g of n-hexane
was heated to 60° C. under a nitrogen stream. A. I. V.
N. Add 0.05g and react for 4 hours to form a white dispersion.
I got it. After cooling, pass through 200 mesh nylon cloth.
The average particle size of the resulting dispersion was 0.35 μm. (Monomer M-12) [Chemical formula 188] Production examples 13 to 23 of resin particles: [L-13
] ~ [L-23] 6 g of each dispersion stabilizing resin [P] in Table 6 below (solid content and
) and 100 g of methyl ethyl ketone in a nitrogen solution.
The mixture was heated to 60° C. while stirring under a stream of bare air. This solution
30g of each monomer (M) in Table 6 below, ethylene glycol
Cold dimethacrylate 5g, A. I. V. N. 0
．． A mixed solution of 3g and 150g of methyl ethyl ketone was added to 1
It dripped in time. After stirring for 1 hour, A. I. V.
N. 0.2g was added and reacted for 3 hours. 200 mesh after cooling
A white dispersion was obtained through a nylon cloth. obtained
The average particle size of each latex is 0.20μm ~ 0.30μm
It was within the range of m. [Table 11] [Table 12] Example 1 and Comparative Example A Example 1 Resin [A-3] 6g (as solid content), a tree with the following structure
Fat [B-1] 34g (as solid content), photoconductive oxidation
200g of zinc, heptamethine cyanine dye with the following structure [
I] 0.15g, phthalic anhydride 0.05g and toluene
Add 300g of the mixture to a homogenizer (Nippon Seiki Co., Ltd.).
) in 6×103 r. p. m. 15 minutes at the rotation speed of
Dispersed between. The obtained dispersion for forming a photosensitive layer is subjected to conductive treatment.
wire so that the dry adhesion amount is 18g/m2 on the paper.
The coating was applied using a heating bar and dried at 110°C for 1 minute. Resin [B-1] [Chemical formula 189] On this photoreceptor, four layers of resin particles [L-5]
Amount % (as solid content), resin [C-1] double with the following structure
Amount % and 1,4-xylylene diisocyanate 0.5 weight
Drop a toluene dispersion containing % on the photosensitive layer.
After coating with a blade, heat at 120℃ for 1 hour to reduce the thickness to about 2μm.
A surface layer was formed. Then, in the dark at 20℃, 65%
The electrophotographic effect is improved by leaving it for 24 hours under RH conditions.
We created optical materials. Resin [C-1] [Chemical formula 190] Comparative example A A resin [R-
1] 4% by weight, resin [C-1] 2% by weight and 1,4-key
Tolu containing 0.5% by weight of silylene diisocyanate
An electrophotographic solution was applied in the same manner as in Example 1, and an electrophotographic effect was applied.
We created optical materials. Resin [R-1] [Chemical formula 191] Comparative example B Conditions for producing the photoconductive layer of the electrophotographic photoreceptor of Example 1
, instead of resin [A-1] and resin [B-1]
, Example except that 40 g of resin [R-2] having the following structure was used.
An electrophotographic light-sensitive material was prepared in the same manner as in Example 1. resin
[R-2] [Chemical formula 192] Film properties (surface smoothness) of these photosensitive materials
), electrostatic properties, imaging performance, and environmental conditions at 30°C and 80% R.
The imaging performance when set to H was investigated. Furthermore, these photosensitive materials
Photoconductive layer when used as an offset master master
desensitization property (contact of photoconductive layer with water after desensitization treatment)
(represented by corners) and printability (scumming, printing durability, etc.)
. The above results are summarized in Table 7. [Table 13] [0150] The implementation of the evaluation items listed in Table 7 is as follows.
It is as below. Note 1) Smoothness of photoconductive layer: obtained feeling
Optical materials were tested using a Bekk smoothness tester (manufactured by Kumagai Riko Co., Ltd.).
The smoothness (sec.
/cc) was measured. Note 2) Electrostatic properties: Temperature 20°C, 65%
A paper analyzer (
Kawaguchi Electric Co., Ltd. Paper Analyzer-SP-428
After corona discharge for 20 seconds at -6 kV using
It was left for 10 seconds and the surface potential at this time was measured as V10.
. Then, the potential V after leaving it for 180 seconds in the dark
190 and the potential after dark decaying for 180 seconds.
Retention property, that is, dark decay retention rate [DRR (%)] [(
V190/V10)×100(%)]. Also
, the photoconductive layer surface was charged to -400V by corona discharge.
After that, the surface potential (
Find the time it takes for V10) to decay to 1/10, and calculate this
Calculate the exposure amount E1/10 (erg/cm2) from
do. Note 3) Imaging properties: Each photosensitive material was
It was left for one day and night under environmental conditions. Next, it is charged with -5kV and exposed to light.
Gallium-aluminum-hybrid with 2.8 mW output as a source.
Using an elementary semiconductor laser (oscillation wavelength 780 nm),
Pitch under irradiation dose of 64erg/cm2 on optical material surface
25μm and scanning speed 300m/sec
ELP-T (Fuji Photo) as a liquid developer after speed exposure
By developing and fixing the image using film (manufactured by Film Co., Ltd.)
Visually evaluate the obtained copy image (fogging, image quality).
Ta. The environmental conditions during imaging were 20°C, 65% RH, and 30°C, 8
It was carried out at 0% RH. Note 4) Water retention: Electronic copying without plate making
A photosensitive material is treated with a desensitizing treatment liquid (E) prepared according to the following formulation.
-1), and was immersed in this solution for 3 minutes and then washed with water. Desensitizing treatment liquid (E-1) Diethanolamine
6
0g Neo Soap (manufactured by Takemoto Yushi Co., Ltd.)
15g
benzyl alcohol
100g
Dissolve this in distilled water to make a total volume of 1.0 liters, then add water
The pH was adjusted to 11.0 with potassium oxide. Desensitization treatment
This plate was printed using an offset printing machine (Sakurai Seisakusho).
Oliver Co., Ltd. Model 52) to check the level of scumming on printed matter.
was visually evaluated. Note 5) Printing durability Each photosensitive material was plate-made under the same conditions as in Note 3) above, and the toner was
An image is formed and desensitized under the same conditions as 4) above.
Print this as an offset master under the same conditions as 4) above.
However, there are problems with background stains in non-image areas of printed matter and image quality in image areas.
Indicates the number of pages that can be printed without causing
, indicating good printing durability). Electrostatic properties of the photosensitive material of the present invention and Comparative Example A
and imaging performance showed good results even when environmental conditions changed.
. However, conventional resins are not used as binder resins for photoconductive layers.
Comparative Example B, which had
The reproduced images obtained were also unsatisfactory. In addition, desensitization
Degree of hydrophilicity after processing as an offset master master plate
Upon investigation, it was found that the original plate of the present invention and Comparative Example B were
The material is sufficiently hydrophilized and stains from the printing ink are visible.
It showed good water retention. However, Comparative Example A is slightly contaminated.
The occurrence of this was observed. Actual plate making to form a copy image
The original plate was desensitized and printed in the same way.
, No background stains in non-image areas from the start of printing, and the print image quality is also good.
Only the original plate of the present invention gave good printed matter.
. In other words, Comparative Example A has insufficient water-retaining ability;
Comparative Example B is due to deterioration of copy image quality due to deterioration of electrophotographic characteristics.
However, good printed matter could not be obtained. As above,
Only the photosensitive material of the present invention has excellent electrophotographic properties and printing characteristics.
You can obtain something that has a certain character. Example 2 4,4'-bis(diethyl acetate) was used as an organic photoconductive substance.
5 g of (mino)-2,2'-dimethyltriphenylmethane,
Resin [A-1] 1g (as solid content), a tree with the following structure
Fat [B-2] 3g, spectral sensitizing dye (II) of the following structural formula
40mg, anilide compound with the following structural formula as a chemical sensitizer
0.2 g of substance (A) was mixed with 30 ml of methylene chloride.
Dissolved in a mixture of 30 ml of ethylene chloride and photosensitive solution.
And so. Resin [B-2] [Chemical formula 193] This photosensitive liquid was passed through a wire round rod.
A conductive transparent support (100 μm polyethylene
Vapor-deposited film of indium oxide on terephthalate support
have Approximately 4 μm when coated on surface resistance (103 Ω)
An organic thin film having a photosensitive layer was obtained. This electrophotographic photoreceptor
3% by weight (solid content) of resin particles [L-2]
), 2% by weight of resin [C-2] with the following structure, phthalic anhydride
0.1% by weight of acid and 0.01% by weight of 2-chlorophenol
% toluene dispersion liquid with a doctor blade.
After coating, dry at 100℃ for 20 seconds, and then dry at 130℃ for 1
A surface layer of approximately 2 μm was formed by heating for a period of time. Then
Leave in the dark at 20°C and 65% RH for 24 hours.
As a result, an electrophotographic light-sensitive material was prepared. Resin [C-2] [Chemical formula 194] Insensitive resin prepared from this photosensitive material according to the following formulation
The sample was immersed in a chemical treatment solution (E-2) for 3 minutes to be desensitized. Desensitizing treatment liquid (E-2) Nucor B4SN (Nippon Nyukazai Co., Ltd.)
) 10g methyl ethyl
ketones
Dissolve 100g of these in distilled water,
The pH was adjusted to 10.5 with sodium oxide, and the total volume was 1. 0
It was set as liter. Place a drop of 2 μl of distilled water on this and shape it.
The contact angle with water was measured using a goniometer.
The angle was less than 10°. The contact angle before desensitization treatment was 88°, which clearly shows that
, the surface layer of this photosensitive material was very well hydrophilized.
. In addition, this desensitized original plate was used in Note 4 of Example 1.
When printing under the following conditions and looking at the background stains on the printed matter, no stains were observed.
I couldn't. [0160] On the other hand, this electrophotographic light-sensitive material
Fully automatic plate making machine ELP404V (Tomi
The toner image is shaped by making a plate using
This is offset by desensitization treatment under the same conditions as above.
As a master, an offset printing machine (Sakurai Seisakusho Co., Ltd.)
(Manufacturer, Model 52) and printed on high-quality paper. print non-
Print without causing background smudges in the image area or problems with the image quality of the image area.
The number of sheets that could be printed was 8,000. Furthermore, this photosensitive material
(45℃, 75%RH) for 3 weeks.
After that, the same process was performed, but there was no difference at all from before.
It was. [0161] The method for measuring the evaluation items of the electrostatic properties described above is
It is as follows. In a dark room at a temperature of 20°C and 65% RH.
, paper analyzer (Kawaguchi Electric Co., Ltd.) for each photosensitive material.
-6 using a manufactured paper analyzer SP-428 model)
After corona discharge for 20 seconds at kV, leave it for 10 seconds.
, the surface potential V10 at this time was measured. then continue as is
Measure the potential V70 after leaving it for 60 seconds in the dark.
The ability to retain the potential after dark decay for seconds, that is, the dark decay retention rate
[D. R. R. (%)], (V70/V10) x 10
It was calculated as 0 (%). In addition, the surface of the photoconductive layer is
After being charged to -400V, the surface of the photoconductive layer was illuminated with an illuminance of 2.
Irradiated with visible light of 0 lux, the surface potential (V10) was 1
Find the time until it decays to /10 or E1/100.
Therefore, from now on, the exposure amount will be E1/10 or E1/100 (L).
x seconds). Example 3 5 g of bisazo pigment with the following structure, 95 g of tetrahydrofuran
g and resin [A-1] 0.8% by weight and resin [B-1]
Mixture of 30 g of 4.2% by weight tetrahydrofuran solution
was thoroughly ground in a ball mill. Then this mixture
was taken out, and 520 g of tetrahydrofuran was added while stirring.
I got it. This dispersion was carried out using a wire round rod.
Approximately 0.7
A charge generation layer with a thickness of μm was formed. (bisazo pigment)
[0163] Next, hydrazone compound 20 of the following structural formula
g, polycarbonate resin (manufactured by GE, trade name: Lexan)
121) Mixing of 20g and 160g of tetrahydrofuran
Pour the solution above the charge generation layer using a wire round rod.
A charge transport layer of about 18 μm was formed by coating on top of the 2
An electrophotographic photoreceptor having a photosensitive layer consisting of layers was obtained. (Hydrazone compound) [Chemical formula 196] On this photoreceptor, the surface layer used in Example 2 was
In the forming dispersion, 3% by weight of resin particles [L-2]
Except that 3% by weight of resin particles [L-23] was used instead.
A surface layer was formed in the same manner as in Example 2, and an electrophotographic photosensitive material was prepared.
A sample was prepared. [0165] The photosensitive material produced in this way was
-6kV with analyzer (Kawaguchi Electric, SP-428)
charged, initial potential (V0), dark charge retention rate (D.R.
R. ) and light attenuation exposure (E1/10) were measured.
, each V0 = -560V, D. R. R. =85%
And E1/10=9.8 [lux・sec]
Ta. [0166] Furthermore, in the same manner as in Example 1, a fully automatic manufacturing process was carried out.
Plate making using ELP-T toner with a printing machine ELP404V.
The resulting master plate for offset printing
The density was 1.0 or more and the image quality was clear. [0167] Furthermore, a desensitizing treatment liquid prepared according to the following formulation
During (E-3), apply this master plate after plate making for 30 seconds.
After soaking, it was washed with water and subjected to a desensitizing treatment. Desensitizing treatment liquid (E-3) Monoethanolamine
60g
benzyl alcohol
100g this
Dissolve them in distilled water, make a total volume of 1.0 liters, and add water.
Adjust the pH of this solution to 11.0 with sodium oxide.
It was adjusted. The contact angle of the non-image area with distilled water is 10° or less.
It was sufficiently hydrophilized. This original plate for offset printing
When printed on a printing machine, the printed matter after printing 8,000 sheets was non-standard.
There was no fog in the image area and the image was clear. Example 4 X-type metal-free phthalocia as an organic photoconductive compound
Nin (manufactured by Dainippon Ink Co., Ltd.)
　　　　　　　　　　　　　　　　　　　　　　　　　
... 1.9 parts additive
As shown below, thiobarbituric acid below compounds
　　　　　　　　　　　　　　　　　　　　　　　　　
...0.15 parts
197] Resin [A-2]
... 2
Part Resin [B-1]
... 1
5 parts Tetrahydrofuran/Cyclohexane (8 parts
/2) Weight ratio mixed solution
　　　　　　　　　　　　　　　　　　　　　　　　　
...100 copies, 500ml
Place it in a glass container with the glass beads and apply the paint shade.
After dispersion for 60 minutes in a car (manufactured by Toyo Seiki Co., Ltd.),
The lath beads were separated by filtration to obtain a photoconductive layer dispersion. Next
The dry adhesion amount of the photoconductive layer dispersion was
Apply with a wire bar so that it is 10g/m2,
It was dried at 10°C for 1 minute. [0169] Next, a composition with the following formulation is applied onto this photoreceptor.
, in a paint shaker with glass beads for 5 minutes.
After dispersion, filter through 200 mesh nylon cloth.
The dispersion was applied as a surface layer and heated at 100°C for 30 seconds.
It was dried and further heated at 120°C for 2 hours. Composition for surface layer Resin particles [L-17]
　　　　　　　　　　　　　　　　　　　　　　　　　
Part 4 Colloidal Silica
　　　　　　　　　　　　　　　　　　　　　　　　　
0.5 part Resin with the following structure [B-3
]
2 parts Phthalic anhydride
　　　　　　　　　　　　　　　　　　　　　　　　　
0.1 part Torue
hmm
100 parts resin [
B-3] [Chemical formula 198] This was further heated in the dark under the conditions of (20°C, 65% RH).
The mixture was left standing for 4 hours to produce an electrophotographic light-sensitive material. Electrostatic properties of the photosensitive material thus obtained
, imaging performance, and printability were examined in the same manner as in Example 1.
Beta. Electrostatic properties (20℃, 65
%RH) (30℃, 80%RH) V10
(-V) -555V
-540V
D. R. R (%) 83%
80%
E1/10 (erg/cm2)
32
35 Imaging performance is
The image quality was clear and good, with no background stains in non-image areas. or
Preservation as a desensitized offset master plate
Water-based has no scumming, and the printing durability of the original plate after plate making is 8.
000 sheets was good. Example 5 Resin [A-3] 8g, resin [B-1] 28g, zinc oxide
200g, uranine 0.02g, rose bengal 0.0
4g, bromophenol blue 0.03g, anhydrous phthalate
Homogenize a mixture of 0.40 g of acid and 300 g of toluene.
In iser, 1 x 104 r. p. m. for 5 minutes at a rotation speed of
Dispersed. The dry adhesion amount was 18 on conductive treated paper.
g/m2 with a wire bar and heated to 110℃.
and dried for 30 minutes. On this photoreceptor,
The composition for the surface layer was applied in the same manner as in Example 2, and
A secondary photographic material was prepared. [0172] Electrostatic properties, imaging properties, and printing of this photosensitive material
The properties were examined in the same manner as in Example 2. This photosensitive material
The initial potential (V0
)-580V, dark charge retention rate (D.R.R.) 85%
, and light attenuation exposure amount (E1/10) 15.0 [ lu
x·sec] were obtained. Furthermore, this is carried out in Example 2.
The master plate for offset printing obtained by making a plate in the same manner as
The rate density was 1.0 or higher and the image quality was clear. [0173] Furthermore, this master plate after plate making is used for actual production.
Using the desensitizing treatment liquid (E-2) used in Example 2,
After soaking in this solution for 0 seconds, wash with water and apply desensitization treatment.
Ta. Contact angle of the non-image area of the obtained printing master plate with distilled water
was sufficiently hydrophilized at an angle of 10° or less. Then this off
Seto printing original plate, treatment liquid (E-2) 50 times with distilled water
Printed on a printing machine using a diluted solution as soaking water.
However, after printing 10,000 sheets, the printed matter has fog in the non-image area.
The image was clear. Examples 6 to 15 In Example 1, 6 g of the photoconductive layer resin [A-3] and
In place of 3% by weight of resin particles [L-5] in the surface layer, use the following table.
6g (as solid content) of each resin [A] of -8, resin particles
Example 1 except that 3% by weight (as solid content) was used.
Each electrophotographic light-sensitive material was produced in the same manner. [Table 14] [0175] This was plate-made using the same device as in Example 1.
The density of the obtained offset printing master plate
was 1.0 or more, and the image quality was clear. In addition, desensitizing treatment
After 10,000 sheets were printed, the results were as follows:
There was no fog in the non-image area, and the image was clear. Examples 16 to 23 In Example 5, the resin [A-3] in the photoconductive layer and the
Instead of resin particles [L-2] in the surface layer, the following Table-9
Example except that resin [A] and resin particles [L] were used respectively.
Each lithographic printing original plate was prepared in the same manner as in Step 5. [Table 15] After making a plate for each photoreceptor, use a processing solution with the following formulation.
It was immersed in the liquid for 3 minutes to make it desensitized. Resin particle desensitization liquid
: Diethanolamine
8
0g Nucor BSN (Nippon Nyukazai Co., Ltd.
)) 6g
benzyl alcohol
100g in distilled water
After dissolving and bringing the total volume to 1 liter, pip with potassium hydroxide.
Aqueous solution adjusted to H10.5. These are the same as in Example 5.
When printed in different ways, each original plate is clear with no background smudges.
More than 8,000 prints of good image quality were obtained for each. Effect of the invention: According to the present invention, under severe conditions,
An electrophotographic lithographic plate with excellent print images and high printing durability
An original printing plate can be obtained. In addition, the lithographic stamp of the present invention
The original printing plate is made by scanning exposure using semiconductor laser light.
Effective for optical methods. [C78]

Claims (4)

[Claims] 1. An electrophotographic lithographic printing original plate comprising at least one photoconductive layer on a conductive support and a surface layer as the uppermost layer, as a binder resin for the photoconductive layer. , an original plate for electrophotographic planographic printing, characterized in that it contains at least one kind of resin [A] shown below, and further contains at least one kind of non-aqueous solvent-based dispersed resin particles shown below in the surface layer. Resin [A]: has a weight average molecular weight of 1 x 103 to 2 x 104, contains 30% by weight or more of repeating units represented by the following general formula (I) as a polymer component, and -PO3 H2
, -SO3H, -COOH, [Formula 1] [R1 represents a hydrocarbon group or -OR2 (R2 represents a hydrocarbon group)] and an acid anhydride group. Polymer component 0.5-15
Resin containing % by weight: General formula (I) [In the above general formula (I), a1 and a2 each represent a hydrogen atom, a halogen atom, a cyano group, or a hydrocarbon group. R3 represents a hydrocarbon group] Non-aqueous solvent-based dispersed resin particles (L): A functional group that generates carboxyl groups by decomposition, which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization. Copolymer resin particles obtained by subjecting at least one monofunctional monomer (A) containing at least one group to a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. 2. The resin [A] is one of the aryl group-containing methacrylate components represented by the following general formula (Ia) and the following general formula (Ib) as the copolymer component represented by the general formula (I). The original plate for electrophotographic lithographic printing according to claim 1 or 2, characterized in that it contains at least one of the following. General formula (Ia) [Chemical formula 3] General formula (Ib) [Chemical formula 4] [However, in the above general formulas (Ia) and (Ib), T
1 and T2 each independently have a hydrogen atom and a carbon number of 1
~10 hydrocarbon groups, chlorine atoms, -COR4 or -C
OOR5 (R4 and R5 each have 1 to 10 carbon atoms
(represents a hydrocarbon group), and L1 and L2 each represent a single bond or a linking group having 1 to 4 linking atoms that connects -COO- and the benzene ring] 3. The original plate for electrophotographic planographic printing according to claim 1 or claim 2, wherein the non-aqueous solvent-based dispersed resin particles form a high-order network structure. 4. Claim 1, wherein the dispersion stabilizing resin contains at least one kind of polymerizable double bond group moiety represented by the following general formula (II) in the polymer chain. An original plate for electrophotographic planographic printing. General formula (II) [Formula (II)] [In general formula (II), V0 is -O-, -CO
O-, -OCO-, -(CH2)p -OCO-, -
(CH2) p -COO-, -SO2 -, [Chemical 6] -CONHCOO-, or -CONHCONH- (where p represents an integer of 1 to 4, and R4 is a hydrogen atom or a carbon number of 1 to 18 (represents a hydrocarbon group), a3
, a4 may be the same or different, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R
6 or -COO-R6 (R6
represents a hydrogen atom or a hydrocarbon group that may be substituted]