JPH05100463A - Planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain a planographic printing plate having good water holding property, excellent printed picture images and high printing durability by incorporating specified nonwater-base dispersion resin particles into the surface layer and incorporating a specified binder resin. CONSTITUTION:At least one kind of nonwater-base dispersion resin particles is incorporated into the surface layer and at least one specified resin is incorporated into the binder resin in a photoconductive layer. The nonwater-base dispersion resin particles are copolymer resin particles obtd. by dispersion polymn. of unifunctional monomers which are soluble in a nonwater solvent but becomes insoluble by polymn. and contain one kind of functional group which produces one carboxyl group by decomposition. The binder resin contains >=30wt.% of the repeating unit expressed by formula I as the polymer component and having specified polar group connecting to the end of the polymer main chain. In formula I, a1 and a2 are hydrogen atoms, halogen atoms, cyano groups, or hydrocarbon groups, and R03 is a hydrocarbon group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic lithographic printing plate precursor prepared by electrophotography, and more particularly to an improvement of a photoconductive layer and a surface layer having specific properties on the photoconductive layer. The present invention relates to a lithographic printing plate precursor.

[0002]

2. Description of the Related Art At present, various types of offset master plates for direct plate making have been proposed and put into practical use. Among them, photoconductive particles such as zinc oxide and a binder resin are used on a conductive support. The photoconductor provided with a photoconductive layer containing as a main component is subjected to a normal electrophotographic process to form a highly lipophilic toner image on the photoconductor surface, and then the surface is desensitized liquid called an etchant. A technique for obtaining an offset original plate by subjecting the non-image portion to hydrophilic treatment selectively is widely used.

In order to obtain a good printed matter, first, the original image is faithfully copied to the offset original plate, the surface of the photoconductor is easily compatible with the desensitizing solution, and the non-image area is sufficiently hydrophilized. It has water resistance, and in printing, the photoconductive layer with the image does not come off, it is well compatible with fountain solution, and it is sufficiently non-image area so that stains do not occur even when the number of printed sheets increases. It is necessary to have such properties as maintaining the hydrophilicity of.

In recent years, a method of preparing a printing plate of a hydrophilic treatment type on the surface of a non-image area which is easy to make by providing a specific resin layer on an ordinary electrophotographic photosensitive member is disclosed in JP-B-45-560.
No. 6 publication. That is, a printing plate is disclosed in which a surface layer comprising a vinyl ether, a maleic anhydride copolymer, and a hydrophobic resin compatible with the vinyl ether is provided on the electrophotographic photosensitive layer. This layer is a layer that can be made hydrophilic by hydrolyzing the acid anhydride ring portion by treating the non-image portion with an alkali after forming a toner image (hydrophilizable layer). The vinyl ether-maleic anhydride copolymer used there becomes water-soluble when it is ring-opened and hydrophilized, so even if it is compatible with other hydrophobic resins, the layer is formed. However, the water resistance is extremely poor and the printing durability is at most 500-60.
The limit was 0 sheets.

Further, Japanese Patent Laid-Open Nos. 60-90343 and 60-
159756, 61-217292, etc.,
A method of providing a surface layer (hydrophilizable layer) containing a silylated polyvinyl alcohol as a main component and a crosslinking agent together is disclosed. That is, this layer is for hydrolyzing the silylated polyvinyl alcohol by hydrolyzing it in the non-image area after toner image formation. Further, in order to maintain the film strength after hydrophilization, the degree of silylation of polyvinyl alcohol is adjusted and the residual image hydroxyl groups are crosslinked with a crosslinking agent. And, it is described that, by these, the background stain property of the printed matter is improved and the number of printed sheets is improved.

However, when actually evaluated, it is still unsatisfactory especially in the background stain. Also,
Silylated polyvinyl alcohol is produced by silylating polyvinyl alcohol with a silylating agent to a desired ratio, but it is difficult to produce it stably because it is a polymer reaction. Furthermore, since the chemical structure of the hydrophilic polymer is limited, 1) chargeability and 2) quality of copied image (halftone dot reproducibility / resolution of image area, Fog in the image area, etc.), 3)
There is a problem that it is difficult to prevent the surface layer from affecting the exposure sensitivity and the like.

In order to improve the problems of the above electrophotographic lithographic printing plate precursor, the present inventors have
An electrophotographic lithographic printing plate precursor using a resin containing a functional group capable of generating a carboxyl group as a main component of the surface layer by decomposition has been proposed (JP-A-62-28345). Further, as the surface layer resin, a resin containing a functional group capable of generating a hydrophilic group upon decomposition and a compound capable of cross-linking the resin in the photosensitive layer are examined in combination, and for example, a functional group capable of generating a hydroxyl group upon decomposition. A group containing a group (JP-A-1-245970, JP-A-1-262556) and a group containing a functional group capable of generating a carboxyl group by decomposition (JP-A-1-28357, 1-2848).
No. 60), and those containing functional groups that generate a thiol group, an amino group, a phosphono group, a sulfo group and the like by decomposition (JP-A-1-304465 and 1-306855).

Further, it has been investigated to use a small amount of fine particles having a functional group capable of generating a hydrophilic group by decomposition in the surface layer and forming a higher-order network structure. For example, those containing a functional group capable of generating a carboxyl group by decomposition (JP-A-2-13965), those containing a functional group capable of generating a hydroxyl group by decomposition (JP-A-2-13966), and sulfo by decomposition. A group containing a functional group that generates a group, a phosphono group, etc. (JP-A-2-13967) is disclosed.

These binder resins or resin particles form a hydrophilic group by being hydrolyzed, hydrolyzed or photolyzed by a desensitizing liquid or immersion water used for printing. When these are used as the surface layer resin of the lithographic printing plate precursor, in any case, deterioration of electrophotographic properties (dark charge retention amount and photosensitivity) caused when the hydrophilic group itself is contained from the beginning can be avoided. The hydrophilicity of the non-image area which is hydrophilized by the desensitizing liquid is more expressed by the hydrophilic group produced by decomposition in the binder resin or resin particles in the surface layer, thereby improving the hydrophilicity of the image area. The oiliness and hydrophilicity of the non-image area become clear, the printing ink is prevented from adhering to the non-image area at the time of printing, and the surface layer has a crosslinked structure, so that the resin hydrophilized Further, it becomes water-insoluble, and due to the cross-linking effect, the hydrophilic cross-linking resin contains water and swells, water retention is created, and the hydrophilicity of the surface layer is sufficiently maintained. As a result, it becomes possible to print a large number of printed matter with clear image quality without scumming.

[0010]

The resin of the type which produces a hydrophilic group by the above decomposition reaction is decomposed by a treatment liquid to decompose a carboxyl group or a hydroxyl group masked with a protecting group in advance, thereby leaving the protecting group. It is what makes them. Therefore, this type of resin is stable and does not hydrolyze under the influence of atmospheric humidity (moisture) during storage, and the deprotection group reaction proceeds rapidly during the hydrophilization process to make it hydrophilic. It is required as an important property that a group is generated and the hydrophilicity of the non-image area can be improved.

However, when a hydrophilic group-forming functional group (protecting group) is present which does not decompose even under severe conditions such as long-term storage in a hot and humid environment and is stable, a rapid decomposition by the treatment liquid and a hydrophilic group It has been found that difficulties arise in rapid onset.

In view of the above situation, the present invention is more effective due to the hydrophilicity of the non-image area, is stable even when stored under extremely severe conditions, and is easy in a short time during the hydrophilic treatment. It is an object of the invention to provide a lithographic printing plate precursor that can exhibit hydrophilicity. That is, the object of the present invention is to obtain electrostatic properties (especially dark charge retention and photosensitivity).
A lithographic printing plate precursor that is excellent in desensitization and that reproduces a copy image that is faithful to the original image and does not generate spot stains as well as uniform stains as an offset master plate It is to be. Another object of the present invention is to provide a lithographic printing plate precursor having high printing durability, in which the hydrophilicity of the non-image area is sufficiently maintained and scumming does not occur even when the number of printed sheets is increased in printing. . Another object of the present invention is to provide a lithographic printing plate precursor having a clear and high-quality image even when the environment at the time of forming a copy image changes such as low temperature / low humidity or high temperature / high humidity. Another object of the present invention is less susceptible to the types of sensitizing dyes that can be used in combination,
An object of the present invention is to provide a lithographic printing plate precursor excellent in electrostatic characteristics even by a scanning exposure method using a semiconductor laser beam.

[0013]

SUMMARY OF THE INVENTION The present invention is directed to the above object of utilizing an electrophotographic photosensitive member comprising a conductive support, at least one photoconductive layer provided thereon, and a surface layer provided on the uppermost layer thereof. In the lithographic printing plate precursor, at least one of the following non-aqueous solvent-based dispersed resin particles [L] is contained in the surface layer, and the following resin [A] is used as the binder resin of the photoconductive layer. This is achieved by a lithographic printing plate precursor containing at least one kind.

The non-aqueous dispersion resin particle [L] is a functional group that is soluble in the non-aqueous solvent but insoluble by polymerization, and decomposes to produce at least one carboxyl group in the non-aqueous solvent. In the presence of a dispersion-stabilizing resin soluble in the solvent, which comprises at least a repeating unit containing a substituent containing a silicon atom and / or a fluorine atom, a monofunctional monomer (C) containing at least one of To
Copolymer resin particles obtained by a dispersion polymerization reaction, wherein the resin [A] has a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and has a repeating unit represented by the following general formula (I). Containing 30% by weight or more as a polymer component,
And one terminal of the polymer main chain, -PO ₃ H _2, -SO
₃ H, -COOH, -P (= O) (OH) R ₀₁ [R ₀₁ represents a hydrocarbon group or -OR ₀₂ (R ₀₂ represents a hydrocarbon group)] [-P (= O) (above-mentioned. OH) R ₀₁ is

[0015]

[Chemical 4]

Is shown. ] And a resin comprising at least one polar group selected from cyclic acid anhydride-containing groups.

[0017]

[Chemical 5]

[However, in the above formula (I), a ₁ , a
Each ₂ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₀₃ represents a hydrocarbon group. Furthermore, it is preferable that the non-aqueous solvent-based dispersed resin particles form a crosslinked structure. Furthermore, it is preferable that the dispersion stabilizing resin contains at least one polymerizable double bond group moiety represented by the following general formula (II) in the polymer chain.

[0019]

[Chemical 6]

[In the general formula (II), V ₀ is -O
-, - COO -, - OCO -, - (CH 2) p OCO
_{-, - (CH 2) p} COO -, - SO 2 -, - CONR
_{1 -, - SO 2 NR 1} -, - C 6 H 5 -, - CONHC
Represents OO- or -CONHCONH- (provided that p is
Represents an integer of 1 to 4, and R ₁ is a hydrogen atom or has 1 carbon atom.
Represents a hydrocarbon group of 18), b ₁ and b ₂ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—R ₂ or a hydrocarbon group. -COO-R ₂ (R ₂ is a hydrogen atom or a substituted also showing a substituted hydrocarbon group) represent] Furthermore, the resin (a) is the following as a copolymer component represented by the general formula (I) It is preferable to contain at least one of the aryl group-containing methacrylate components represented by the general formula (Ia) and the following general formula (Ib).

[0021]

[Chemical 7]

[In the above formulas (Ia) and (Ib), T ₁ and T ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, —COR ₀₄ or —
COOR ₀₅ (R ₀₄ and R ₀₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), L ₁ and L ₂ are each -COO-
Represents a single bond or a connecting group having 1 to 4 connecting atoms for connecting the benzene ring. The present invention utilizes an electrophotographic photoreceptor including a photoconductive layer containing a resin [A] as a binder resin and further provided with an uppermost layer (surface layer) containing non-aqueous dispersion resin particles [L]. A lithographic printing plate precursor for an electrophotographic plate making system.

After the toner image is formed according to the usual electrophotographic process (plate making), the non-image portion is contained in the uppermost layer of the non-aqueous dispersion resin particles [L] (hereinafter abbreviated as resin particles [L]). In some cases), the lipophilic surface is modified to a hydrophilic surface by a desensitizing treatment to obtain a printing original plate. Usually, in an electrophotographic photoreceptor, if one more layer (surface layer) is provided on the photoconductive layer for the purpose of improving the quality of the printed matter, the electrostatic characteristics (especially photosensitivity, residual potential, etc.) will be reduced and a faithful image will be obtained. Since the reproducibility is deteriorated, various improvements are attempted, and the influence is great.

As a result of various studies, the inventor of the present invention has made it possible to improve the electrostatic characteristics of the photoconductive layer by using the resin [A]. You can make sure that the reproducibility is not compromised.
Further, the resin particles [L] of the present invention are produced in the presence of a dispersion-stabilizing resin containing silicon atoms / fluorine atoms so that the surface layer, which is the uppermost layer, contains the specific resin particles [L]. , Compared with the conventional resin or resin particles that produce hydrophilicity, overcoming the conventional drawbacks by suppressing the necessary amount that can be efficiently used for water retention to a smaller amount, and adversely affecting the photoconductive layer. The improvement in water retention, printing durability, etc. was observed without application.

The resin particles [L] in the surface layer used in the present invention have an average particle size of 1 μm or less and a narrow distribution of particle sizes, and as the resin particles [L], It has at least two important properties. One of them is that during desensitizing treatment, a protected carboxyl group composed of a component of the monomer (C) chemically reacts with hydrolysis reaction, redox reaction, photolysis reaction, etc. to generate a carboxyl group, Converts from hydrophobic to hydrophilic properties. Further, the resin particles [L] can express hydrophilicity and at the same time,
When the resin particles [L] have a crosslinked structure, at this time, the resin particles [L] can be insoluble or slightly soluble in water and have water swelling property while having hydrophilicity.

As another one, a substituent having a strong lipophilicity,
That is, a transfer-stabilizing phenomenon occurs on the surface portion of the surface layer by binding a dispersion stabilizing resin containing at least a repeating unit containing a substituent containing at least one fluorine atom and / or silicon atom. . The fluorine atom and / or silicon atom-containing polymer as a dispersion stabilizing resin is formed by physicochemical adsorption with an insoluble component [monofunctional monomer (C)] or by the above formula (I
In the case of the dispersion-stabilizing resin containing the polymerizable double bond group portion represented by I), it is considered that both polymer components are chemically bonded.

Due to both the effects of concentrating the resin particles [L] on the surface portion and making the resin particles [L] hydrophilic by the desensitizing treatment as described above, the water retention of the non-image area of the surface layer is improved. It is fully achieved. Further, the present invention is a low-molecular-weight binder containing a specific polymer component represented by the formula (I) as a binder resin for a photoconductive layer and having the above-mentioned specific polar group bonded to at least a side chain of the polymer. It contains a polymer resin [A] having a molecular weight.

As a result, the electrostatic properties are improved, and when the photoconductive zinc oxide particles, the spectral sensitizing dye and the resin [A] are dispersed in the photoconductive layer, a specific polar group is added to the side chain of the polymer. The low-molecular-weight resin [A] bonded to the polymer adsorbs to the stoichiometric defect of the photoconductive zinc oxide, and appropriately performs the covering property and the adsorbed state to the interaction state of the zinc oxide and the dye. This is considered to be because the trap of the photoconductive zinc oxide is compensated and the humidity characteristics are dramatically improved, while the photoconductive zinc oxide is sufficiently dispersed and the aggregation is controlled.

In particular, in the case of the conventional binder resin, when the type of the spectral sensitizing dye is changed, the interaction such as adsorption is hindered, and the satisfactory electrophotographic characteristics cannot be obtained. However, when the resin [A] of the present invention is used, remarkably excellent performance can be satisfied even with a dye used for spectral sensitization for semiconductor laser light. Further, when the resin [A ′] is used, electrophotographic properties (particularly V
₁₀ , D.I. R. R. , E _1/10 ) can be improved. The reason for this is unknown, but one reason is that due to the planarity effect of the benzene ring or naphthalene ring, which is the ester component of methacrylate, the alignment of these polymer molecular chains at the zinc oxide interface in the film is properly performed. It is thought that it is due to being given.

The non-aqueous solvent-based dispersed resin particles used in the present invention will be described in more detail below. The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization. The non-aqueous solvent-based dispersed resin particles of the present invention comprise a polymer component [monomer (C) containing a monofunctional monomer (C) which contains at least one of the specific polar groups and is insoluble in the non-aqueous solvent after polymerization. And a repeating unit containing at least a fluorine atom and / or a silicon atom as a substituent, and is obtained by a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. It is a copolymer that is used.

The average particle diameter of the resin particles used in the present invention is preferably 2 μm or less, and preferably 0.5.
It is less than or equal to μm. And the average particle size of the particles is 0.8μ
m or less, preferably 0.5 μm or less. In the present invention, the resin particles that do not form the higher-order stitch structure or the resin particles that form the higher-order stitch structure (hereinafter simply referred to as the stitch-resin particles) are the whole surface layer composition 10
It is preferably used in an amount of 1 to 50% by weight based on 0 part by weight. If the amount of resin particles or lacquer resin particles is less than 1% by weight, the hydrophilicity of the non-image area will not be sufficient. The electrophotographic characteristics of the image are deteriorated and the copied image is deteriorated. The molecular weight of the dispersed resin particles is 10 ⁴ to 1
It is 0 ⁶ , preferably 10 ^{4 to} 5 × 10 ⁵ .

As a polymerization component in the resin particles, the proportion of the monomer (C) present is 30% by weight or more, preferably 50% by weight or more, and particularly preferably, the resin contains the monomer (C). It is composed of only the dispersion stabilizing resin. The solubility of the dispersion stabilizing resin of the present invention in the non-aqueous solvent is specifically 25 ° C. with respect to 100 parts by weight of the solvent.
In the above, it may be dissolved in at least 5% by weight. The weight average molecular weight of the dispersion stabilizing resin is 1 × 1.
0 ³ to 1 × 10 ⁵ , preferably 2 × 10 ^{3 to} 5 × 1
0 ⁴ , particularly preferably 3 × 10 ³ to 2 × 10 ⁴ .
When the weight average molecular weight of the dispersion stabilizing resin is less than 1 × 10 ³ , the generated dispersed resin particles agglomerate and fine particles having a uniform average particle diameter cannot be obtained.

On the other hand, if it exceeds 1 × 10 ⁵ , the effect of the present invention that the water retention property is improved while satisfying the electrophotographic characteristics when added to the surface layer is diminished. In the total of repeating units of the dispersion stabilizing resin of the present invention, the repeating unit having a substituent containing a fluorine atom and / or a silicon atom is preferably contained in an amount of 40% by weight or more, more preferably 60% by weight. ~ 100% by weight. When the amount of the above components of the present invention is less than 40% by weight based on the total weight, the effect of concentrating on the surface portion when the resin particles are dispersed in the surface layer decreases, and as a result, the effect of improving the water retention as the printing original plate decreases. End up.

The dispersion stabilizing resin is preferably used in an amount of 1 to 50% by weight, more preferably 5 to 25% by weight, based on the insolubilizing monomer (C). The functional group used in the present invention for decomposing to produce at least one carboxyl group (hereinafter sometimes simply referred to as a carboxyl group-forming functional group) will be described in detail. Although the carboxyl group-forming functional group of the present invention produces a carboxyl group by decomposition, the number of carboxyl groups produced from one functional group may be one or two or more. According to one preferred embodiment of the present invention, the carboxyl group generated functional group-containing resin of the general formula (IV) - is a resin containing at least one functional group represented by [COO-A _1]. Formula (IV): - In [COO-A _1], A
_{1, -CH (P 1) (P} 2), - [C (B ₁₎
(B _{2)] n - (X) m -Z,} -M (B 3) (B 4)
_{(B 5), - N =} CH-Q 1, -CO-Q 2.

[0035]

[Chemical 8]

The functional group of the general formula [-COO-A ₁ ] is one which produces a carboxyl group by decomposition and will be described in more detail below. When A ₁ is —CH (P ₁ ) (P ₂ ), P ₁ is a hydrogen atom, a —CN group, or —CF.
Represents ₃ groups, -COD ₁ group or -COOD ₁ group. However, D ₁ is an alkyl group having 1 to 6 carbon atoms: for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, an aralkyl group having a carbon number of 7 to 12 and which may be substituted: Specifically, a benzyl group, a phenethyl group, a chlorobenzyl group, a methoxybenzyl group, a chlorophenethyl group, a methylphenethyl group, etc.) or an aromatic group (for example, a phenyl group or naphthyl group which may have a substituent): , Phenyl group, chlorophenyl group, dichlorophenyl group, methylphenyl group, methoxyphenyl group, acetylphenyl group, acetamidophenyl group, methoxycarbonylphenyl group, naphthyl group, etc.).

P ₂ is --CN group, --COD ₁ group or --C
Represents an OOD ₁ group. However, D ₁ represents the same symbol as above. A ₁ is-[C (B ₁ ) (B ₂ )] _n- (X)
_{In the} case of representing _m- Z, B ₁ and B ₂ may be the same or different from each other, preferably a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (eg, methyl group). Group, ethyl group, propyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, octyl group, decyl group, hydroxyethyl group, 3-chloropropyl group, etc., and X is preferably optionally substituted phenyl. Or a naphthyl group (eg, phenyl group, methylphenyl group, chlorophenyl group, dimethylphenyl group, chloromethylphenyl group, naphthyl group, etc.), and Z is preferably a hydrogen atom or a halogen atom (eg, chlorine atom,
Fluorine atom, etc.), trihalomethyl group (eg trichloromethyl group etc.), linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (eg methyl group, chloromethyl group, dichloromethyl group, ethyl Group, propyl group, butyl group, hexyl group, tetrafluoroethyl group, octyl group, cyanoethyl group, chloroethyl group, etc.), -CN,-
NO ₂ , —SO ₂ R ₁ ′ [R ₁ ′ is an aliphatic group (for example, an alkyl group having 1 to 12 carbon atoms which may be substituted: specifically, methyl group, ethyl group, propyl group, butyl group, chloroethyl group) Group, pentyl group, octyl group, etc., having 7 to 12 carbon atoms
Optionally substituted aralkyl group: specifically, a benzyl group, a phenethyl group, a chlorobenzyl group, a methoxybenzyl group, a chlorophenethyl group, a methylphenethyl group, or the like, or an aromatic group (for example, a phenyl group which may have a substituent) Or naphthyl group: specifically, phenyl group, chlorophenyl group, dichlorophenyl group, methylphenyl group, methoxyphenyl group, acetylphenyl group, acetamidophenyl group, methoxycarbonylphenyl group, naphthyl group, etc.) ], —COOR ₂ ′ (R ₂ ′ is the above R ₁ ′
Synonymous) or _{-O-R 3 '(R 3} ' is the R ₁ '
Is synonymous with). n and m represent 0, 1 or 2.

A ₁ is -M (B ₃ ) (B ₄ ) (B ₅ ).
In the case of representing, B ₃ , B ₄ , and B ₅ may be the same or different from each other, and are preferably an aliphatic group having 1 to 18 carbon atoms which may be substituted [the aliphatic group is an alkyl group, an alkenyl group, An aralkyl group or an alicyclic group is shown, and as the substituent, for example, a halogen atom, a -CN group, an -OH group,-
O-Q '(Q' represents an alkyl group, an aralkyl group, an alicyclic group, an aryl group) and the like], and a carbon number of 6 to
18 optionally substituted aromatic groups (eg phenyl groups,
Tolyl group, chlorophenyl group, methoxyphenyl group, acetamidophenyl group, naphthyl group, etc.) or -O-
R ₄ ′ (R ₄ ′ is an optionally substituted alkyl group having 1 to 12 carbon atoms, an optionally substituted alkenyl group having 2 to 12 carbon atoms, an optionally substituted aralkyl group having 7 to 12 carbon atoms, Represents an optionally substituted alicyclic group having 5 to 18 carbon atoms and an optionally substituted aryl group having 6 to 18 carbon atoms). M represents each atom of Si, Ti, or Sn, more preferably a Si atom.

A ₁ is -N = CH-Q ₁ or -CO-Q
_{In the} case of representing ₂ , Q ₁ and Q ₂ are preferably an aliphatic group having 1 to 18 carbon atoms which may be substituted (as the aliphatic group, an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group And examples of the substituent include a halogen atom, a CN group, an alkoxy group and the like) or an optionally substituted aryl group having 6 to 18 carbon atoms (for example, a phenyl group, a methoxyphenyl group, a tolyl group, Chlorophenyl group, naphthyl group, etc.). A ₁ is

[0040]

[Chemical 9]

In the case of representing, Y ₁ represents an oxygen atom or a sulfur atom. B _6, B _7, B _8, which may be the same or different, each preferably represents a hydrogen atom, a linear or branched alkyl group (e.g. methyl substituted carbon atoms which may be 1-18, ethyl group, Propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group,
Octadecyl group, chloroethyl group, methoxyethyl group,
Methoxypropyl group etc.), optionally substituted alicyclic group (eg cyclopentyl group, cyclohexyl group etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg benzyl group, phenethyl group, chlorobenzyl group, Methoxybenzyl group etc.), optionally substituted aromatic group (eg phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group etc.) or -OR ₅ '(R ₅ '
Represents a hydrocarbon group, specifically, the above B ₆ , B ₇ , B
_The same substituents as the hydrocarbon group of ₈ are shown). p
Represents an integer of 5 or 6. A ₁ is

[0042]

[Chemical 10]

In the case of representing, Y ₂ represents an organic residue forming a cyclic imide group. Preferably, the general formula (V) represents an organic residue represented by (VI).

[0044]

[Chemical 11]

In the formula (V), B ₉ and B ₁₀ may be the same or different and each may be substituted with a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.) or a C 1-18 substituent. Alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2- (methanesulfonyl)
Ethyl group, 2- (ethoxyoxy) ethyl group, etc.], aralkyl group having 7 to 12 carbon atoms which may be substituted [for example, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, Methoxybenzyl group, chlorobenzyl group, bromobenzyl group, etc.), alkenyl group having 3 to 18 carbon atoms which may be substituted (eg, allyl group, 3-methyl-2-propenyl group, 2-hexenyl group, 4-propyl- 2-pentenyl group, 12-octadecenyl group, etc.), —S—R ₆ ′ (R ₆ ′ has the same meaning as the alkyl group, aralkyl group and alkenyl group of B ₉ or B ₁₀ ) or substituted. Good aryl groups (eg phenyl, tolyl, chlorophenyl, bromophenyl, methoxyphenyl, ethoxyphenyl, ethoxycarbo) Rufueniru group, and the like), or -NHR
₇ represents a '(R _7' represents the same content as the R ₆ '). Further, it may represent a residue forming a ring with B ₉ and B ₁₀ [for example, a 5-6 ring monocyclic ring (for example, cyclopentyl ring, cyclohexyl ring), or a 5-6 ring bicyclo ring (for example, bicycloheptane ring). , Bicycloheptin ring, bicyclooctane ring, bicyclooctene ring, etc.), and these rings may not be substituted, and as a substituent, B ₉ ,
Including the same as the contents described above in B _10].

Q represents an integer of 2 or 3. Formula (VI)
In, B _11, B ₁₂ may be the same or different, wherein B _9,
It has the same contents as B ₁₀ . Furthermore, B ₁₁ and B ₁₂
May represent an organic residue that continuously forms an aromatic ring (eg, benzene ring, naphthalene ring, etc.). In another preferable embodiment of the present invention, the compound represented by the general formula (VII) [-C
The functional group represented by O-A _2] is a resin containing at least one kind. Formula (VII) [- CO-A _2] in A ₂ is

[0047]

[Chemical 12]

Represents However, B ₁₃ , B ₁₄ , B ₁₅ ,
B ₁₆ and B ₁₇ each represent a hydrogen atom or an aliphatic group. The aliphatic group preferably has the same contents as B ₆ , B ₇ , and B ₈ . Further, B ₁₄ and B ₁₅ and B ₁₆ and B ₁₇ represent an organic residue which may be connected to each other to form a condensed ring. Preferably a 5- to 6-membered monocyclic ring (for example, cyclopentyl ring, cyclohexyl ring, etc.), 5- to 12-membered aromatic ring (for example, benzene ring, naphthalene ring, thiophene ring, pyrrole ring,
Pyran ring, quinoline ring, etc.) and the like. Furthermore, as another preferred embodiment of the present invention, the following general formula (VII
It is a resin containing at least one oxazolone ring represented by I).

[0049]

[Chemical 13]

In the general formula (VIII), B ₁₈ , B ₁₉
May be the same or different from each other, and each is a hydrogen atom,
It represents a hydrocarbon group, or B ₁₈ and B ₁₉ may together form a ring. Preferably, B ₁₈ and B ₁₉ may be the same as or different from each other, and each is a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (eg, methyl group, ethyl group, propyl group). Group, butyl group, hexyl group, 2-chloroethyl group, 2-methoxyethyl group,
2-methoxycarbonylethyl group, 3-hydroxypropyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, 4-chlorobenzyl group, 4
-Acetamidobenzyl group, phenethyl group, 4-methoxybenzyl group, etc.), optionally substituted carbon number 2 to 1
2 alkenyl groups (eg ethylene group, allyl group, isopropenyl group, butenyl group, hexenyl group, etc.), optionally substituted 5- to 7-membered alicyclic groups (eg cyclopentyl group, cyclohexyl group, chlorocyclohexyl group) Groups, etc.), optionally substituted aromatic groups (eg phenyl group, chlorophenyl group, methoxyphenyl group, acetamidophenyl group, methylphenyl group, dichlorophenyl group, nitrophenyl group, naphthyl group, butylphenyl group, dimethylphenyl group) Represents an enyl group), or B ₁₈ , B
₁₉ and together may form a ring (for example, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc.). Specific examples of the functional groups represented by formulas (IV) to (VIII) of the present invention are described below. However, the scope of the present invention is not limited to these.

[0051]

[Chemical 14]

[0052]

[Chemical 15]

[0053]

[Chemical 16]

[0054]

[Chemical 17]

[0055]

[Chemical 18]

[0056]

[Chemical 19]

[0057]

[Chemical 20]

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

The above general formulas (IV) to (VIII)
More specifically, the functional group-containing monomer (C) will be exemplified by the components represented by the following general formula (IX). However, it is not limited to these monomers (C).

[0061]

[Chemical formula 23]

In the formula (IX), X'is --O--, --CO--,
-COO -, - OCO -, - N (d 1) -CO -, - C
ON (d ₂ )-, -SO _2- , -SO ₂ N (d ₃ )-,
_{-N (d 4) SO 2,} -CH 2 COO -, - CH 2 OC
O -, - _{[C (b 1) (b 2} ) ] _l -, an aromatic group, or a heterocyclic group _{[where, d 1, d 2, d} 3, d 4 are each a hydrogen atom, a hydrocarbon group , Or-[Y 'in formula (IX)
-W], g ₁ and g ₂ may be the same or different, and are a hydrogen atom, a hydrocarbon group or -in the formula (IX).
[Y'-W], and l represents an integer of 0 to 18].
Y'represents a carbon-carbon bond which may be connected via a hetero atom connecting the bonding group X'and the bonding group [W] (as a hetero atom, an oxygen atom, a sulfur atom or a nitrogen atom is shown),
For example - _{[C (g 3) (g 4} ) ] _{-, - C 6 H 10 -} , -
_{C 6 H 4 -, - (} CH = CH) -, - O -, - S -, -
_{N (g 5) -, -} COO -, - CONH -, - SO
_{2 -, - SO 2 NH -} , - NHCOO -, - NHCON
H- or the like is a single unit or a combination of units (provided that g ₃ , g ₄ and g ₅ are the above-mentioned g ₁ and g _{2 respectively).}
Is synonymous with).

W represents a functional group represented by the formulas (IV) to (VIII). g ₁ and g ₂ are a ₁ in the formula (I),
Represents the same content as a ₂ . The monofunctional monomer containing at least one functional group selected from the group of functional groups represented by the general formulas (IV) to (VIII) used in the present invention is synthesized by a conventionally known organic synthesis reaction. can do. For example, "New Experimental Chemistry Lecture No. 14" edited by The Chemical Society of Japan
Vol. 2, Synthesis and Reactions of Organic Compounds (V) ”, page 2535 (published by Maruzen Co., Ltd.), Yoshio Iwakura: Keisuke Kurita“ Reactive Polymer ”
P. 170 (published by Kodansha), T.S. W. Greene, "P
Protective Groups in Organi
c Synthesis ”Chapter 5 (John. Wile
y & Sons, New York 1981)
J. F. W. McOmie, "Protective G
loops in Organic Chemistr
y ”Chapter 5 (Plenum Press. 1973).

The resin particles [L] of the present invention are composed of the monomer [C].
It may be polymerized together with other monomers. Any other monomer may be used as long as it can be copolymerized with the monomer [C] and the copolymer becomes an insoluble polymer in the non-aqueous solvent. Other monomers copolymerizable with these monomers include, for example, vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, aliphatic vinyl carboxylates such as allyl propionate, allyl esters and acrylic acid. , Esters or amides of unsaturated carboxylic acids such as methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc., styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, α-olefins, acrylonitrile, Examples thereof include vinyl group heterocyclic compounds such as methacrylonitrile and N-vinylpyrrolidone. These other monomers are contained in an amount of 60 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the total insoluble polymer component. If the amount of other monomer exceeds 60 parts by weight,
The effect of improving water retention as the original plate for offset printing decreases.

Next, in the non-aqueous solvent-based dispersed resin particles of the present invention, a soluble dispersion-stabilizing resin for stabilizing the resin particles in the non-aqueous solvent system will be described. The dispersion stabilizing resin for use in the present invention is characterized in that the polymer contains a substituent containing a fluorine atom and / or a silicon atom. The repeating unit having a substituent containing a fluorine atom and / or a silicon atom will be described. Examples of the chemical structure of the repeating unit include those obtained from radical addition-polymerizable monomers, those consisting of a polyester structure or those consisting of a polyether structure, and the like, in the side chains in the repeating units of these polymer structures, Any one may be used as long as it contains a fluorine atom and / or a silicon atom.

Examples of the fluorine atom-containing substituent include --C _h F _{2h + 1} (h represents an integer of 1 to 12) and-(CF
₂ ) _j CF ₂ H (j represents an integer of 1 to 11), -C ₆
H _l F _{l ′} [(l and l ′ are each an integer of 1 to 5, where l + l ′ =
5) or (l = 5-l ', l'is an integer of 1 to 5)] and the like. Examples of the substituent containing a silicon atom include -Si.
(R ₃ ) (R ₄ ) (R ₅ ), − (Si (R ₆ ) (R ₇ ) O) _k −R ₈ (k
Represents an integer of 1 to 20), a polysiloxane structure, and the like. However, R ₃ , R ₄ , and R ₅ may be the same or different, and may be an optionally substituted hydrocarbon group or -OR.
_{Represents 9} groups (R ₉ represents the same content as the hydrocarbon group of R ₃ ).

R ₃ is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, 2 -Chloroethyl group, 2-
Bromoethyl group, 2,2,2-trifluoroethyl group, 2
-Cyanoethyl group, 3,3,3-trifluoropropyl group, 2-methoxyethyl group, 3-bromopropyl group, 2
-Methoxycarbonylethyl group, 2,2,2,2 ',
2 ′, 2′-hexafluoroisopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms which may be substituted (eg,
2-methyl-1-propenyl group, 2-butenyl group, 2-
Pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4
-Methyl-2-hexenyl group, etc.), an aralkyl group having 7 to 12 carbon atoms and which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chloro) Benzyl group,
A bromobenzyl group, a methylbenzyl group, an ethylbenzyl group, a methoxybenzyl group, a dimethylbenzyl group, a dimethoxybenzyl group, etc.) and an alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, a cyclohexyl group, 2- A cyclohexyl group, a 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg,
Phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group , Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propylamidophenyl group, dodecyloylamidophenyl group, etc.).

In the —OR ₉ group, R ₉ has the same meaning as the hydrocarbon group for R ₃ above. R ₆ , R ₇ and R ₈ may be the same or different and represent the same symbol content as R ₃ , R ₄ and R ₅ . Next, specific examples of the repeating unit having a substituent containing the above fluorine atom and / or silicon atom are shown below. Here, a represents H or CH ₃ ,
Rf represents -CH ₂ C _h C _{2h + 1-} (CH ₂ ) _2- (CF ₂ ) _j CF ₂ H, and R ₁ ′, R ₂ ′ and R ₃ ′ represent C ₁ to ₁₂ alkyl groups. , R ″ represents —Si (CH ₃ ) ₃ , h represents an integer of 1 to 12, j represents an integer of 1 to 11, p represents an integer of 1 to 3, and l represents 1 to 5 Represents an integer, q represents an integer of 1 to 20, r represents an integer of 30 to 150, and t
Represents an integer of 2 to 12. However, the scope of the present invention is not limited to these.

[0069]

[Chemical formula 24]

[0070]

[Chemical 25]

[0071]

[Chemical formula 26]

[0072]

[Chemical 27]

[0073]

[Chemical 28]

[0074]

[Chemical 29]

[0075]

[Chemical 30]

Further, the dispersion stabilizing resin may contain other components in addition to the component containing a fluorine atom and / or a silicon atom. As the other component to be copolymerized, any component may be used as long as it is copolymerized with the corresponding polymer, and as the corresponding monomer, for example, α-olefins, styrenes, acrylonitrile, methacrylonitrile, Vinyl-containing heterocycles (as the heterocycle, for example, a pyran ring, a pyradrine ring, an imidazole ring, a pyridine ring, etc.),
Vinyl group-containing carboxylic acids and esters thereof (eg acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and esters thereof), vinyl group-containing carboxamides (eg acrylamide, methacrylamide, crotonic acid amide, Itaconic acid amide, itaconic acid half amide, itaconic acid diamide, etc.) and the like. In the dispersion stabilizing resin of the present invention, the content of the polymer component containing a fluorine atom and / or a silicon atom is 30 parts by weight or more, preferably 50 parts by weight or more, based on 100 parts by weight of the total polymer of the resin.

In the dispersion stabilizing resin of the present invention, the light and / or thermosetting functional group is contained in an amount of 30 parts by weight or less, preferably 20 parts by weight or less based on 100 parts by weight of the total polymer of the resin. You may. Examples of the photo- and / or thermosetting functional group to be contained include those other than the polymerizable functional group, and specific examples thereof include functional groups for forming a crosslinked structure of particles which will be described later. Furthermore, the dispersion stabilizing resin of the present invention preferably contains at least one polymerizable double bond group moiety represented by the general formula (II) in the polymer chain. The polymerizable double bond group component will be described below.

[0078]

[Chemical 31]

In the general formula (II), V ₀ is -O-,-
COO −, −OCO −, −CH ₂ OCO −, −CH ₂ COO −, −SO
_{2 -, - CONR 1 -,} - SO 2 NR 1 - or -C ₆ H ₄ - represents a. Here, R ₁ is not only a hydrogen atom, but also a preferable hydrocarbon group is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group). , Octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2
-Chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), carbon number 4 to 1
8 optionally substituted alkenyl groups (eg, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2 -Hexenyl group, 4-methyl-2-hexenyl group, etc.), and optionally substituted aralkyl groups having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2 -Naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic group having 5 to 8 carbon atoms A group (eg, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.) or a group having 6 to 12 carbon atoms Optionally aromatic group (for example, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, Decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyl A loylamidophenyl group and the like).

[0080] V ₀ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group) Group, ethoxy group, propoxy group, butoxy group, etc.) and the like. b ₁ and b ₂ are
They may be the same or different from each other, preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (eg a methyl group, an ethyl group, a propyl group, butyl). Group etc.)-COO-R ₂ or COOR ₂ via a hydrocarbon (R ₂ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, May be substituted, and specifically represents the same contents as those described for R ₁ above).

Examples of the hydrocarbon in the —COO—R ₂ group through the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like. More preferably, the general formula (II)
In, V ₀ is, -COO -, - OCO -, - CH 2 OCO
_{-, - CH 2 COO -,} - O -, - CONH -, - SO 2 NH- or -C ₆ H ₄ - represents, b _1, b _2, which may be the same or different, a hydrogen atom, a methyl group , −COOR ₂ or −
CH ₂ COOR ₂ (R ₂ is a hydrogen atom or 1 carbon atom)
To 6 alkyl groups (e.g., methyl, ethyl, propyl, butyl, hexyl, etc.). Even more preferably, one of b ₁ and b ₂ always represents a hydrogen atom.

That is, as the polymerizable double bond group component represented by the general formula (II), specifically, CH ₂ ═CH—CO—O—, CH
₂ = C (CH ₃ ) -CO-O-, C (CH ₃ ) H = CH-CO-O-, CH ₂ = C (CH
₂ COOCH ₃ ) -CO-O-, CH ₂ = C (CH ₂ COOH) -CO-O-, CH ₂
= CH-CONH-, CH ₂ = C (CH ₃ ) -CONH-, C (CH ₃ ) H = CH-CONH
-, CH ₂ = CH-O-CO-, CH ₂ = CH-CH ₂ -O-CO-, CH ₂ = CH-O
-, CH ₂ = C (COOH) -CH ₂ -CO-O-, CH ₂ = C (COOCH ₃ ) -CH _2-
CO-O-, CH ₂ = CH-C ₆ H _4- and the like can be mentioned.

The polymerizable double bond group moiety represented by the above general formula (II) is one end of the main chain of a polymer containing at least a repeating unit having a substituent containing a fluorine atom and / or a silicon atom. And are directly bonded or bonded by any linking group. Specifically as a group to be linked, it is a divalent organic residue, such as -O-, -S-,
−Nd ₁ −, −SO−, −SO ₂ −, −COO −, −OCO −, −
CONHCO -, - NHCONH -, - CONd 2 -, - SO 2 Nd 3 - and _{-Si (d 4) (d 5} ) - may be interposed selected binding groups from a divalent aliphatic group or It represents an organic residue composed of a divalent aromatic group or a combination of these divalent residues. Here, d _{1 to} d ₅ have the same contents as R ₁ in formula (II).

As the divalent aliphatic group, for example, -C (e ₈ )
_{(e 9) -, - C} (e 8) = C (e 9) -, - (C≡C) -, - C
₆ H ₁₀ −,

[0085]

[Chemical 32]

{E ₈ and e ₉ may be the same as or different from each other, and each is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or the like) or an alkyl group having 1 to 12 carbon atoms ( For example, methyl group, ethyl group,
(Propyl group, chloromethyl group, bromomethyl group, butyl group, hexyl group, octyl group, nonyl group, decyl group, etc.)
Represents. Q is -O -, - S- or -NR ₂₀ - represents,
R ₂₀ is an alkyl group having 1 to 4 carbon atoms, —CH ₂ Cl or —CH ₂
Represents Br}.

Examples of the divalent aromatic group include a benzene ring group, a naphthalene ring group and a 5- or 6-membered heterocyclic group (as a hetero atom constituting the hetero ring, selected from an oxygen atom, a sulfur atom and a nitrogen atom). Containing at least one hetero atom). These aromatic groups may have a substituent, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group). , A butyl group, a hexyl group, an octyl group, etc.) and an alkoxy group having 1 to 6 carbon atoms (eg, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.) can be mentioned as examples of the substituent.

Examples of the heterocyclic group include furan ring, thiophene ring, pyridine ring, pyrazine ring, piperazine ring, tetrahydrofuran ring, pyrrole ring, tetrahydropyran ring, 1,3-oxazoline ring and the like. The polymerizable double bond group-containing moiety as described above is specifically bonded only in the polymer chain, or the polymerizable dipolymer bond group-containing moiety is present only at one end of the main chain of the polymer chain. Examples thereof include bound polymers (hereinafter abbreviated as monofunctional polymers [M]). Specific examples of the moiety composed of the polymerizable double bond group component represented by the general formula (II) of the monofunctional polymer [M] and the organic residue linked thereto are as follows. However, it is not limited to these. However, in each of the following examples, P ₁ is —H, —CH ₃ , —CH ₂ COOCH ₃ ,
-Cl, shows -Br or -CN, P ₂ represents -H or -CH _3, X represents a -Cl or -Br, n is an integer of 2 to 12, m is an integer from 1 to 4 Indicates.

[0089]

[Chemical 33]

[0090]

[Chemical 34]

[0091]

[Chemical 35]

[0092]

[Chemical 36]

[0093]

[Chemical 37]

The monofunctional polymer [M] of the present invention can be produced by a conventionally known synthesis method. For example,
A method by an ionic polymerization method in which a monofunctional polymer [M] is obtained by reacting various reagents with the ends of a living polymer obtained by anionic polymerization or cationic polymerization,
Using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, a hydroxy group and an amino group in a molecule, a polymer having a terminal reactive group bond obtained by radical polymerization and various A polymerizable double bond group is added to a polymer obtained by reacting a reagent to obtain a monofunctional polymer [M] by a radical polymerization method or a polymer obtained by a polyaddition or polycondensation reaction in the same manner as the above radical polymerization method. Examples thereof include a method of introducing polyaddition condensation method.

Specifically, P. Dreyfuss & RP Quirk, En
cycl.Polym.Sci.Eng., 7, 551 (1987 ), PFRempp, E.Fra
nta, Adv.Polym.Sci., 58 , 1 (1984), V.Percec, Appl.P
oly.Sci., 285, 95 (1984), R. Asami, M. Takari, Makro
mol.Chem.Suppl., 12 , 163 (1985), P.Rempp.et al, Mak
romol.Chem.Suppl., 8 , 3 (1984), Yusuke Kawakami, Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 31 , 988 (1982)
, Shiro Kobayashi, Polymer, 30 , 625 (1981), Toshinobu Higashimura, Journal of Adhesion Society of Japan, 18 , 536 (1982), Koichi Ito, Polymer processing, 35 , 262 (1986), Kishiro Higashi, Takashi Tsuda , Functional materials, 19
87 , No. 10, 5, etc. and the methods described in the references and patents cited therein.

Further, in the case where the dispersed resin particles of the present invention have a nodular structure, as described above, the molecules of the polymer (C) containing the polar group-containing monofunctional monomer (C) as a polymer component are separated from each other. It is bridged and forms a higher-order rope structure, which is sparingly soluble or insoluble in water. The crosslinking of the present invention can be carried out by a conventionally known crosslinking method. That is, a method in which a polymer containing the polymer component (C) is crosslinked with various crosslinking agents or curing agents, and a polymerization reaction is carried out by incorporating at least a monomer corresponding to the polymer component (C). A method for forming an interlocking structure between molecules by allowing a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups to coexist, and the polymer component (C) and a reactive group. It can be carried out by a method such as a method of crosslinking with a polymer containing a component containing a by a polymerization reaction or a polymer reaction.

As the cross-linking agent in the above method, compounds usually used as a cross-linking agent can be mentioned. Specifically, "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko.
The compounds described in Taiseisha (1981), "Polymer Data Handbook Basic Edition" edited by The Polymer Society of Japan, Baifukan (1986), etc. can be used.

For example, an organic silane compound (eg, vinyltrimethoxysilane, vinyltributoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, and other silane coupling agents), polyisocyanate compounds (for example, toluylene diisocyanate, o-toluy) Diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, high molecular polyisocyanate, etc.), polyol-based compound (for example, 1, 4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc., polyamine compounds (eg, ethylenediamine, γ-hydroxypropyl) Pill of ethylene diamine,
Phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.),
Polyepoxy group-containing compound and epoxy resin (for example,
Kakiuchi Hiroshi, "New Epoxy Resins" Shokoido (1985), Kuniyuki Hashimoto, "Epoxy Resins", compounds described in Nikkan Kogyo Shimbun (1969), melamine resins (eg Ichiro Miwa, Hideo Matsunaga Edited by "Uria Melamine Resin"
Compounds listed in Nikkan Kogyo Shimbun (1969) and poly (meth) acrylate compounds (eg, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura “Oligomer” Kodansha (1976), Eizo Omori “ Compounds described in "Functional acrylic resin" Techno System (published in 1985) and the like are specifically mentioned, and specifically, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6
-Hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-diglycidyl ether diacrylate, oligoester acrylate and their methacrylates.

Further, a polyfunctional monomer containing two or more polymerizable functional groups coexisted by the above method [also referred to as polyfunctional monomer (D)] or a polyfunctional oligomer polymerizable functional group. Specifically, CH ₂ = CH-CH ₂ −, CH ₂ = C
OO, CH ₂ = CH −, CH ₂ = C (CH ₃ ) -CO-O−, C (CH ₃ ) H = C
H-CO-O−, CH ₂ = CH-CONH−, CH ₂ = C (CH ₃ ) -CONH−, CH
_{(CH 3) = CH-CONH} -, CH 2 = CH-O-CO-, CH 2 = C (CH 3) -
_{O-CO-, CH 2 = CH} -CH 2 -O-CO -, CH 2 = CH-NHCO-, CH 2
= CH-CH ₂ -NHCO −, CH ₂ = CH-SO ₂ −, CH ₂ = CH-CO−, CH
_{2 = CH-O -, CH} 2 = CH-S - , and the like. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, a styrene derivative such as divinylbenzene or trivinylbenzene as a monomer or oligomer having the same polymerizable functional group: polyvalent. Alcohol (eg ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 20
0, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or polyhydroxyphenols (eg hydroquinone, resorcin, catechol) And their derivatives)
Methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers: dibasic acids (eg malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) Vinyl esters, allyl esters, vinyl amides or allyl amides; polyamines (eg ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and carboxylic acids containing vinyl groups (eg methacrylic acid, acryl) Acid, crotonic acid, allyl acetic acid, etc.) and the like.

Examples of the monomers or oligomers having different polymerizable functional groups include vinyl group-containing carboxylic acids (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, arylloyl). Propionic acid, itaconiloylacetic acid, itaconiloylpropionic acid, carboxylic acid anhydride, etc.) and alcohol or amine reactants (eg allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonyl) Ester derivative or amide derivative containing vinyl group such as propionic acid (eg vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconic acid, methacryloyl) Vinyl acetate, methacryloyl propionic acid vinyl, methacryloyl propionic acid allyl, vinyl methacrylate oxycarbonyl ester, vinyl acrylate oxycarbonyl methyloxycarbonyl ethylene ester, N- allyl acrylamide, N-
Allylmethacrylamide, N-allylitaconic acid amide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (for example, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and vinyl group And a condensate with a carboxylic acid containing

The monomer or oligomer having two or more polymerizable functional groups used in the present invention is a monomer (C).
And 10 relative to the total amount of the other monomers coexisting with (C).
Polymerization is carried out using less than mol%, preferably less than 5 mol% to form a resin.

Further, in the case of forming a chemical bond by the reaction of the reactive groups between the polymers and bridging the polymers in the above-mentioned method, it is carried out in the same manner as the reaction of a normal organic low molecular compound. be able to. Specifically, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" Kodansha (Published in 1977), Ryohei Oda,
It is described in detail in books such as "Polymer Fine Chemicals" Kodansha (published in 1976). For example, polymer reactions by the combination of the functional groups of group A (hydrophilic group polymer component) and group B (polymers containing a component containing a reactive group) in the table below are generally well known. Can be mentioned as a method. R ₂₁ and R _{22 in} Table 1 are each a hydrogen atom or a hydrocarbon group having 1 to 7 carbon atoms which may be substituted (preferably, for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group). , 2-hydroxyethyl group, 3-bromo-2-hydroxypropyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 3-sulfopropyl group, benzyl group, sulfobenzyl group, methoxybenzyl group Group, carboxybenzyl group, phenyl group, sulfophenyl group, carboxyphenyl group, hydroxyphenyl group, 2-methoxyethyl group, 3-methoxypropyl group, 2-methanesulfonylethyl group, 2-cyanoethyl group, N, N ( Dichloroethyl) aminobenzyl group,
And N, N (dihydroxyethyl) aminobenzyl group, chlorobenzyl group, methylbenzyl group, N, N (dihydroxyethyl) aminophenyl group, methanesulfonylphenyl group, cyanophenyl group, dicyanophenyl group, acetylphenyl group, etc.

[0104]

[Table 1]

As described above, the class-dispersed resin particles of the present invention comprise the polymer component (C) containing a polar group and the polymer component [M] containing a repeating unit having a fluorine atom and / or silicon atom-containing substituent. It is a particle of a polymer containing and having a structure in which the intermolecular chains are highly cross-linked. In dispersion polymerization, monodisperse particles having a uniform particle size can be obtained, and fine particles having a size of 0.5 μm or less can be easily obtained. Is preferred.

The non-aqueous solvent used in the production of the non-aqueous solvent-based dispersed resin particles may be any organic solvent having a boiling point of 200 ° C. or lower, which may be used alone or in combination of two or more. Good. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ketones such as diethyl ketone, diethyl ether,
Ethers such as tetrahydrofuran and dioxane, carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate, and fatty acids having 6 to 14 carbon atoms such as hexane, octane, decane, dodecane, tridecane, cyclohexane and cyclooctane. Group hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, and halogenated hydrocarbons such as methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane and trichloroethane. However, it is not limited to the above-mentioned compound examples.

By synthesizing dispersed resin particles in these non-aqueous solvent systems by the dispersion polymerization method, the average particle size of the resin particles easily becomes 1 μm or less, and the particle size distribution is very narrow and monodisperse particles. Can be Specifically, KEJ Barrett "Dispersion Polymerization in Or
ganic Media ”John Wiley (1975), Koichiro Murata, Polymer Processing, 23 , 20 (1974), Tsunetaka Matsumoto / Toyoyoshi Tange, Japan Adhesive Association Magazine 9 , 183 (1973), Tokichi Tange, Adhesive Society of Japan 2
3 , 26 (1987), DJ Walbridge, NATO.Adv.study.Ins
t.Ser.E.No. 67, 40 (1983), British Patent No. 893429,
No. 9334038, US Pat. No. 112239
7, the same 3900412, the same 4606989 each specification,
The method is disclosed in JP-A-60-179751, JP-A-60-185963, and the like.

The dispersion resin of the present invention comprises at least one type of each of a monomer (C) and a monofunctional polymer [M],
In the case of forming a tentative structure, the polyfunctional monomer (D) is allowed to coexist as necessary. In any case, it is important that the resin synthesized from these monomers is used in the non-aqueous solvent. If it is insoluble, a desired dispersion resin can be obtained. In order to produce the dispersed resin particles used in the present invention as described above, the monomer (C), the monofunctional polymer [M], and the polyfunctional monomer (D) are generally used in a non-aqueous manner. The polymerization may be carried out by heating in a solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile or butyllithium. Specifically, a method of adding a polymerization initiator to a mixed solution of the monomer (C), the monofunctional polymer [M], and the polyfunctional monomer (D), the method described above in a non-aqueous solvent, There is a method of adding a mixture of a polymerizable compound and a polymerization initiator dropwise or optionally,
The method is not limited to these and can be produced by any method.

The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 parts by weight, relative to 100 parts by weight of the non-aqueous solvent.
˜50 parts by weight. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compounds. The polymerization temperature is 50
It is about 180 ° C, preferably 60 to 120 ° C. The reaction time is preferably 1 to 15 hours. The non-aqueous dispersion resin produced according to the present invention as described above becomes fine particles having a uniform particle size distribution. Further, other dispersion stabilizing resins may be used in combination. When another dispersion stabilizing resin is used in combination, the amount is preferably 50 parts by weight or less with respect to 100 parts by weight of the total dispersion stabilizing resin. When the amount of the other dispersion stabilizing resin exceeds 50 parts by weight, the surface concentrating property is lowered and the water retention property is deteriorated. However, if it exceeds 50 parts by weight, the surface concentrating property is improved, but the hydrophilicity of the resin particles is lowered, and the water retention property is deteriorated.

The surface layer of the photoreceptor of the present invention comprises the above resin particles uniformly dispersed in the binder resin of the matrix. The binder resin will be described in detail below.
As the binder resin for the surface layer of the present invention, all those conventionally known as binder resins can be used. Typical examples are vinyl chloride-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer, vinyl acetate copolymer, vinyl alkanoate resin, polyvinyl. Butyral, alkyd resin, epoxy ester resin, polyester resin and the like.

Specifically, Ryuji Kurita and Jiro Ishiwatari, High Polymer,
Volume 17, p. 278 (1968), Harumi Miyamoto, Hidehiko Takei, Imaging, 1973 (No. 8) p. 9, Koichi Nakamura, "Practical Technology of Binders for Recording Materials", 10th
Chapter, C.I. H. C. Published (1985), D.M. D. Tat
t, S. C. Heidecker, Tappi, 49
(No. 10), 439 (1966), E.I. S. Bal
ttazzi, R .; G. Blancloette et
al, Photo. Sci. Eng. 16 (No.
5), 354 (1972), Nguyen Chan Kae, Isamu Shimizu, Eiichi Inoue, The Electrophotographic Society Journal 18 (No. 2), 2
8 (1980), JP-B-50-31011, JP-A-53.
-54027, 54-20735, 57-2025.
44, 54-68046, and the like.

Further, the surface layer may contain a crosslinking compound and a crosslinking promoting compound. Specifically, the same compounds as the group of crosslinkable compounds used for forming the crosslinked structure with the resin particles of the present invention can be mentioned. However, when contained in the surface layer, do not inhibit the hydrophilicity after desensitization,
Also, it must be used within a range that does not adversely affect the electrophotographic characteristics of the electrophotographic photosensitive member (for example, initial potential, dark charge retention rate, photosensitivity, residual potential, etc.). Specifically, with respect to the total solid content of the surface layer forming composition, 0.0
It is preferably used in the range of 05 to 10 parts by weight.

By using these crosslinkable compounds in combination, the surface layer forms a crosslinked structure and is made to have a higher order structure, so that the film strength after desensitization of the surface layer is improved and the water retention property of the entire surface is improved. It is controlled and the water retention is improved. Furthermore, fine particles (for example, a metal oxide) other than the resin particles of the present invention are contained in the surface layer in an amount of 0.0 with respect to the total amount of the composition for forming the surface layer.
You may contain in the range of 01-5 weight part. As a result, it is possible to improve the film strength or adjust the surface smoothness due to the filler effect of adding fine particles.

Examples thereof include fillers such as silicon dioxide, zinc oxide, titanium oxide, zirconium oxide, glass particles, alumina and clay, and polymer particles such as polymethylmethacrylate, polystyrene and phenol resin. What is important in forming the surface layer is that the non-image area is sufficiently hydrophilic after the desensitizing treatment, as described above. That is, this hydrophilicity can be confirmed, for example, by measuring the contact angle with water.
The contact angle of water on the surface of the surface layer (hydrophilizable layer) before the desensitizing treatment is about 60 ° to 120 °, but it decreases to about 5 ° to 20 ° after the desensitizing treatment. And then get very wet with water. Therefore, the printing plate has an image portion made of lipophilic toner and a highly hydrophilic non-image portion formed on its surface. Therefore,
The surface layer after the desensitizing treatment may have a contact angle with water of 20 degrees or less.

The present invention is particularly excellent in that it is more hydrophilic than the conventional ones. That is, the resin particles in the present invention is decomposed by the treatment of the desensitizing liquid or the immersion water at the time of printing to generate a carboxyl group,
It develops hydrophilicity. Therefore, in the original plate of the present invention containing the resin particles in the surface layer, the lipophilicity of the image area and the hydrophilicity of the non-image area are clear due to the hydrophilicity of the non-image area which is hydrophilized by the desensitizing solution. Therefore, the printing ink is prevented from adhering to the non-image portion during printing. As a result, it becomes possible to print a large number of prints with clear image quality without background stains.

Further, in the case of the above-mentioned resin particles partially cross-linked, the solubility in water is remarkably lowered while maintaining the hydrophilicity, and the particles become hardly soluble or insoluble, and the particles themselves have a water swelling property. To have. Therefore, the hydrophilic group generated in the resin particles causes the surface of the non-image area to have hydrophilicity, and the entire surface layer contains controlled water. The effect of the present invention that the (printing ink repulsion) is further enhanced is improved, and the durability is improved.

More specifically, even if the amount of the functional groups in the resin particles is reduced, the effect of improving the hydrophilicity can be maintained unchanged, or the size of the printing machine can be increased or the printing can be performed. Even when printing conditions such as pressure fluctuations become strict, it is possible to print a large number of prints with clear image quality without background stains. In the past, only one material, such as zinc oxide, could be used because it had to have the property that photoconductivity and hydrophilization were possible in one layer, but in the printing original plate of the present invention, as described above. By forming the surface layer, the functions are separated into the photoconductive layer and the hydrophilizable layer (surface layer), so strict control during printing is significantly eased compared to the conventional system that relies on the desensitizing reaction of zinc oxide. To be done.

That is, in the conventional system using zinc oxide, a ferrocyanine compound is used as the main component of the desensitizing solution for desensitizing zinc oxide, and this compound is treated specially in order to prevent environmental pollution. What you need, and
Since the desensitized hydrophilized substance adheres to the printed matter, the amount consumed by printing many sheets at the time of printing,
It is customary to use by adding the desensitizing main agent to the immersion water for printing, but as a side effect, the usable types of color inks are limited, or it is possible to use neutral paper as the printing paper. There were problems such as difficulties. On the other hand, in the system of the present invention, since the principle of desensitization is completely different, these problems can be easily solved.

Next, the photoconductive layer of the electrophotographic photosensitive material of the present invention will be described. The photoconductive layer contains at least a photoconductor and a binder resin, and it is particularly preferable that the photoconductive layer contains at least one of the following resins [A] as the binder resin. In weight [A], the weight average molecular weight is 1 × 10.
^{3 to} 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 10 ⁴ , and the glass transition point of the resin [A] is preferably −20 ° C.
-110 degreeC, More preferably, it is -10 degreeC-90 degreeC.

If the molecular weight of the resin [A] is less than 10 ³ , the film-forming ability is deteriorated and sufficient film strength cannot be maintained. On the other hand, if the molecular weight is more than 2 × 10 ⁴ , even the resin of the present invention, In particular, in the case of photoreceptors using near-infrared to infrared spectral sensitizing dye, fluctuations in dark decay retention rate and photosensitivity under severe conditions of high temperature / high humidity, low temperature / low humidity are somewhat large, and stable copying is possible. The effect of the present invention that an image is obtained diminishes.

The proportion of the polymer component corresponding to the repeating unit of the general formula (I) of the resin [A] is 30% by weight or more, preferably 50 to 97% by weight, and a polar group is attached to one end of the polymer main chain. The proportion of the polymer component formed by bonding is 0.5 to 15% by weight, preferably 1 to 10% by weight. When the content of the polar group in the resin [A] is less than 0.5% by weight, the initial potential is low and a sufficient image density cannot be obtained. On the other hand, when the content of the polar group is more than 15% by weight, dispersibility is lowered no matter how low molecular weight the compound is, and scumming is increased when it is used as an offset master.

The low molecular weight resin [A] is represented by the above-mentioned general formula (Ia) and general formula (Ib).
Resin [A] containing a methacrylate component having a specific substituent having a benzene ring or a naphthalene ring having a specific substituent at the 2-position and / or the 2- and 6-positions
(Hereinafter, this low molecular weight compound is referred to as resin [A ']). The content of the copolymerization component of methacrylate corresponding to the repeating unit of the formula (Ia) and / or the formula (Ib) in the resin [A ′] is 30% by weight or more, preferably 50 to 97% by weight, containing a specific polar group. The proportion of the polymer component of 0.5 is 0.5 with respect to 100 parts by weight of the resin [A '].
-15% by weight, preferably 1-10% by weight.

Next, the repeating unit represented by the general formula (I), which is contained in the resin [A] in an amount of 30% by weight or more, will be further described. In the general formula (I), a ₁ and a ₂ are preferably hydrogen atom, cyano group, alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, etc.),
COO-R ₀₆ or -COO-R via a hydrocarbon group
₀₆ (R ₀₆ represents a hydrogen atom or an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group having 1 to 18 carbon atoms, which may be substituted. _It represents the same content as that described for ₀₃ ).

Examples of the hydrocarbon in the -COO-R ₀₆ group via the above hydrocarbon include a methylene group, an ethylene group, a propylene group and the like. R ₀₃ has 1 to 18 carbon atoms
An optionally substituted alkyl group (for example, a methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group , 2-methoxyethyl group, 2-ethoxyethoxy group,
3-hydroxypropyl group and the like, alkenyl group having 2 to 18 carbon atoms and optionally substituted (for example, vinyl group, allyl group, isopropenyl group, butenyl group, hexenyl group,
Heptenyl group, octenyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (benzyl group having carbon atoms,
Phenethyl group, naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.), cycloalkyl group having 5 to 8 carbon atoms which may be substituted (for example, cyclopentyl group, cyclohexyl group, Cycloheptyl group etc.), optionally substituted aryl group (eg phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, difluorophenyl group, bromophenyl) Group, chlorophenyl group, dichlorophenyl group, iodophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, cyanophenyl group, etc.) and the like.

More preferably, the copolymer component corresponding to the repeating unit of the general formula (I) is a methacrylate component containing a specific aryl group represented by the general formula (Ia) and / or the general formula (Ib). The copolymer component (resin [A ']) represented is mentioned. In formula (Ia),
Preferable T ₁ and T ₂ are, independently of each other, a hydrogen atom, a chlorine atom and a bromine atom, and a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, Ethyl group, propyl group, butyl group, etc.), aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxy) Benzyl group, chloro-methyl-benzyl group) and aryl groups (eg phenyl group,
Tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group),
And —COR ₀₄ and —COOR ₀₅ (preferable R ₀₄ and R ₀₅ include those described as the above-mentioned preferable hydrocarbon group having 1 to 10 carbon atoms).

[0126] formula (Ia) and (Ib), L ₁ and L ₂ is a direct bond or bond each -COO- and the benzene ring _{- (CH 2) n1 - (} n 1 represents an integer of 1 to 3 _{), - CH 2 OCO -,} - CH 2 CH 2 OCO -, -
_{(CH 2 O) m1 - (} m 1 represents an integer of 1 or 2), -
A connecting group having 1 to 4 connecting atoms such as CH ₂ CH ₂ O-, and the like, more preferably a direct bond or 1 to 2 connecting atoms.
Can be mentioned. Resin of the present invention [A]
Specific examples of the copolymerization component corresponding to the repeating unit represented by the formula (Ia) or (Ib) used in (1) are shown below.
However, the scope of the present invention is not limited to this. In the following (a-1) to (a-20), n is 1
To an integer of 4, m is 0 or an integer of 1 to 3, p is an integer of 1 to 3, and R _{10 to} R ₁₃ are all —C _n H _{2n + 1} or — (C
_{H 2) m -C 6 H 5} ( except, n, m are as defined above),
X ₁ and X ₂ may be the same or different, and are a hydrogen atom,
Represents Cl, -Br, or -I.

[0127]

[Chemical 38]

[0128]

[Chemical Formula 39]

[0129]

[Chemical 40]

[0130]

[Chemical 41]

Next, the polar group bonded to one end of the polymer main chain of the low molecular weight resin [A] will be described. Polar _{group, -PO 3 H 2, -SO 3} H, -COOH, -P (=
It is preferable that at least one selected from O) (OH) R ₀₁ and a cyclic acid anhydride-containing group.

The --P (═O) (OH) R ₀₁ group means the above R
₀₁ represents a hydrocarbon group or a —OR ₀₂ group (R ₀₂ represents a hydrocarbon group), and specifically, R ₀₁ represents an aliphatic group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, Butyl group, hexyl group, octyl group, decyl group, dodecyl group,
Octadecyl group, 2-chloroethyl group, 2-methoxyethyl group, 3-ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group Group, fluorobenzyl group, methoxybenzyl group, etc.) or optionally substituted aryl group (eg, phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro- A methyl-phenyl group,
Dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc., and R ₂ has the same content as R ₁ .

Further, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and the cyclic acid anhydride to be contained includes an aliphatic dicarboxylic acid anhydride and an aromatic dicarboxylic acid anhydride. Things can be mentioned. Examples of the aliphatic dicarboxylic acid anhydride include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-
1,2-dicarboxylic acid anhydride ring, cyclohexane-1,
2-dicarboxylic acid anhydride ring, cyclohexene-1,2-
Dicarboxylic acid anhydride ring, 2,3-bicyclo [2,2,2]
2] octadicarboxylic acid anhydride rings and the like, and these rings are, for example, halogen atoms such as chlorine atom and bromine atom,
An alkyl group such as a methyl group, an ethyl group, a butyl group and a hexyl group may be substituted.

Examples of aromatic dicarboxylic acid anhydrides include phthalic anhydride ring, naphthalene-dicarboxylic acid anhydride ring, pyridine-dicarboxylic acid anhydride ring, thiophene-dicarboxylic acid anhydride ring, and the like. These rings are
For example, chlorine atom, halogen atom such as bromine atom, alkyl group such as methyl group, ethyl group, propyl group and butyl group,
Hydroxyl group, cyano group, nitro group, alkoxycarbonyl group (as the alkoxy group, for example, methoxy group,
Ethoxy group etc.) may be substituted.

These polar groups are directly attached to the ends of the polymer main chain.
They may be bound to each other or may be bound via a linking group.
The linking group may be any bonding group, for example,
For example,-[C (d₁) (D₂)]
-(D₁, D₂May be the same or different and each
Child, halogen atom (chlorine atom, bromine atom, etc.), OH group,
Cyano group, alkyl group, (methyl group, ethyl group, 2-
Roloethyl group, 2-hydroxyethyl group, propyl group,
Butyl group, hexyl group, etc.), aralkyl group (benzyl
Group, phenethyl group, etc.), phenyl group, etc.),-(C
H (d₃) -CH (d_Four)]-(D₃, D_FourIs d₁, D
₂The same as the above), -C₆H_Ten-, -C₆H_Five,
-O-, -S-, -N (d_Five)-[D_FiveIs a hydrogen atom or
Represents a hydrocarbon group (specifically as a hydrocarbon group,
Hydrocarbon groups having a prime number of 1 to 12 (eg, methyl group, ethyl group)
Group, propyl group, butyl group, hexyl group, octyl group,
Decyl group, dodecyl group, 2-methoxyethyl group, 2-ku
Roloethyl group, 2-cyanoethyl group, benzyl group, methyl
Rubenzyl group, phenethyl group, phenyl group, tolyl group,
Chlorofer group, methoxyphenyl group, butylphenyl
Groups, etc.))], -CO-, -COO-, -O.
CO-,-(d_Five) CON-, -SO₂N (d_Five)-,
-SO₂-, -NHCONH-, -NHCOO-, -N
HSO₂-, -CONHCOO-, -CONHCONH
-, Heterocycle (O, S, N etc. are less as hetero atoms
A 5- or 6-membered ring containing one of them or a condensed ring thereof
Any of them: for example, thiophene ring, pyridine ring,
Furan ring, imidazole ring, piperidine ring, morpholine
Ring, etc.) or -Si (d ₆) (D₇)-(D
₆, D₇May be the same or different and may be a hydrocarbon group or-
Od₈(D₈Represents a hydrocarbon group). These hydrocarbons
As a base, d_FiveMake sure you list the same ones listed in
Can be used alone or in combination.
And a linking group constituted by

Further, preferably, in the binder resin [A], the copolymerization component represented by the above general formula (I) [the general formula (Ia)] is used.
Or together including] those represented by (Ib), as the polymer component to be copolymerized therewith, -PO ₃ H _2, -SO ₃
0.5 to 10% by weight of a copolymerization component containing at least one polar group selected from H, -COOH, -P (= O) (OH) R ₀₁ and a cyclic acid anhydride-containing group. However, it is preferable in terms of further improving the electrostatic characteristics.

These specific polar groups have the same contents as the polar groups bonded to one end of the polymer main chain described above.
In the resin [A], the abundance ratio of the polar group contained as a copolymer component and the polar group bonded to one end of the polymer main chain is determined by other binder resins constituting the photoconductive layer of the present invention. , The resin particles, the spectral sensitizing dye, the chemical sensitizer or other additives, and the ratio thereof is preferably adjusted arbitrarily. What is important is that the total amount of both polar groups be used within the range of 0.5 to 15% by weight.

The copolymerization component containing these polar groups is
For example, any vinyl compound containing the polar group, which is copolymerizable with the monomer corresponding to the repeating unit represented by the general formula (I) [including general formulas (Ia) and (Ib)], may be used. For example, it is described in "Polymer Data Handbook [Basic Edition]" edited by Japan Society of Polymer Science, Baifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-bromo form, α -Fluoro form, α-tributylsilyl form, α-cyano form, β-chloro form, β-bromo form, α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itacone Acid half-esters, itaconic half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-)
Hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids Examples thereof include a half-ester derivative of a vinyl group or an allyl group, an ester dielectric of these carboxylic acids or sulfonic acids, and a compound having the polar group in the substituent of an amide derivative.

Examples of the polar group-containing copolymer component are shown below. Here, e ₁ represents H or CH ₃ , e ₂ represents H, CH ₃ or CH ₂ COOCH ₃ , R ₁₄ represents an alkyl group having 1 to 4 carbon atoms, and R ₁₅ represents 1 to 6 carbon atoms. Represents an alkyl group, a benzyl group or a phenyl group, and c is 1 to
3 is an integer, d is an integer of 2 to 11, and e is 1 to
11 is an integer, f is an integer of 2 to 4, and g is 2 to
Indicates an integer of 10.

[0140]

[Chemical 42]

[0141]

[Chemical 43]

[0142]

[Chemical 44]

[0143]

[Chemical 45]

[0144]

[Chemical 46]

[0145]

[Chemical 47]

[0146]

[Chemical 48]

[0147]

[Chemical 49]

[0148]

[Chemical 50]

[0149]

[Chemical 51]

Furthermore, the low molecular weight resin [A] of the present invention
(Including [A ′]) is represented by the general formula (I) or (I
In addition to the monomer of a) and / or (Ib) and the monomer containing the polar group, another monomer other than these may be contained as a copolymerization component. Examples of such other copolymerization component include, in addition to methacrylic acid esters, acrylic acid esters, and crotonic acid esters containing a substituent other than those described in the general formula (I), α-olefins,
Vinyl carboxylates or acrylic acid esters (for example, as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid,
Benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (eg dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (eg styrene, vinyltoluene, chlorostyrene) , Hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compounds, vinylketone-containing compounds, heterocyclic vinyls (eg vinylpyrrolidone, vinylpyridine, vinylimidazole) , Vinylthiophene, vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.) and the like. .

It is desirable that these other monomers do not exceed 30% by weight in the resin [A]. In the resin [A], as a method of bonding the polar group to one end of the polymer main chain,
Conventionally known methods of reacting various reagents with the ends of living polymers obtained by anionic polymerization or cationic polymerization (methods by ionic polymerization method), polymerization initiators and / or chain transfer agents containing a specific polar group in the molecule Method of radical polymerization using (method of radical polymerization), or containing reactive group (eg amino group, halogen atom, epoxy group, acid halide, etc.) at the terminal obtained by ionic polymerization method or radical polymerization method as described above The polymer can be easily produced by a synthetic method such as a method of converting the polymer into a specific polar group of the present invention by a polymer reaction.

Specifically, P.I. Dreyfuss, R.A.
P. Quirk, Encycl. Polym, Sci.
Eng, 7 , 551 (1987), Yoshiki Nakajo, Yuya Yamashita "Dyes and Drugs", 30 , 232 (1985), Akira Ueda,
It can be produced by the methods described in the review articles such as Susumu Nagai "Science and Industry" 60 , 57 (1986) and the references cited therein.

Specifically, the chain transfer agent used is
For example, a mercapto compound containing the polar group or the reactive group (that is, a group capable of being induced to the polar group) (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid,
2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-
[N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino]
Propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-butanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-
Propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-
Mercaptoimidazole, 2-mercapto-3-pyridinol, 4- (2-meethyloxycarbonyl) phthalic anhydride, 2-mercaptoethylphosphonoic anhydride, 2
-Mercaptoethylphosphonoic anhydride monomethyl ester, or an iodinated alkyl compound containing the above polar group or substituent (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropane) Sulfonic acid).

Specific examples of the polymerization initiator containing the polar group or the specific reactive group include 4,4'-azobis (4-cyanovaleric acid) and 4,4'-azobis (4-
Cyanovaleric acid chloride), 2,2'-azobis (2-
Cyanopropanol), 2,2'-azobis (2-cyanopentanol), 2,2'-azobis [2-methyl-
N- (2-hydroxyethyl) -propioamide],
2,2'-azobis {2-methyl-N-1,1-bis (hydroxymethyl) -2-hydroxyethyl] propioamide}, 2,2'-azobis {2- [1- (2-hydroxyethyl)- 2-Imidazolin-2-yl] propane}, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2-
(4,5,6,7-tetrahydro-1H-1,3-diazopin-2-yl) propane] and the like.

Each of these chain transfer agents or polymerization initiators is added in an amount of 0.5 to 15 with respect to 100 parts by weight of all monomers.
Parts by weight, preferably 2 to 10 parts by weight. The low molecular weight resin [A] (including [A ′]) as described above is preferably used in combination with a known resin for a conventional photoconductive layer. The use ratio of the low molecular weight resin [A] and the other resin is preferably 5 to 50/95 to 50 (weight ratio).

Other resins to be used in combination include a weight average molecular weight of 3 × 10 ^{4 to} 1 to 10 ⁶ , preferably 5 × 10 ^{4 to} 5.
× 10 ^{5 is} a medium to high molecular weight substance. The glass transition point of the resin used in combination is -10 ° C to 120 ° C, preferably 0 ° C.
~ 90 ° C. For example, Ryuji Shibata and Jiro Ishiwata, Kobun, Vol. 17, p. 278 (1968), Harumi Miyamoto,
Hidehiko Takei, Imaging, 1973 (No.8) No.9
Page, edited by Koichi Nakamura, "Practical technology of binders for recording materials"
Chapter 10, C.I. H. C. Published (1985), D.M. T
att, S.A. C. Heidecker, Tappi, 4
9 (No. 10), 439 (1966), E.I. S. Ba
ltazzi R.D. G. Blanclotte eta
l, Photo. Sci. Eng. , 16 (No.
5), 354 (1972), Nguyen Chan Kay, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography, 18 (No. 2),
22 (1980), JP-B-50-51011, JP-A-5
3-54027, 54-20735, 57-202.
The materials disclosed in each publication of 544 and the like are listed.

Specifically, olefin polymers and copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl alkanoate polymers and copolymers, allyl alkanoate polymers and copolymers, styrene and Derivatives, polymers and copolymers, butadiene-styrene copolymers, isoprene-styrene copolymers, butadiene-unsaturated carboxylic acid ester copolymers, acrylonitrile copolymers, methacrylonitrile copolymers, alkyl vinyl ether copolymers Polymers, acrylic acid ester polymers and copolymers, methacrylic acid ester polymers and copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, itaconic acid diester polymers and copolymers , Maleic anhydride copolymer, acrylamide copolymer, methacrylamide Polymers, hydroxyl-modified silicone resins, polycarbonate resins, ketone resins, amide resins,
Hydroxyl and carboxyl group-modified polyester resin, butyral resin, polyvinyl acetal resin, cyclized rubber-methacrylic acid ester copolymer, cyclized rubber-acrylic acid ester copolymer, copolymer containing nitrogen atom-free heterocycle (For example, a furan ring, a tetrahydrofuran ring, a thiophene ring, a dioxane ring, a dioxofuran ring, a lactone ring, a benzofuran ring, a benzothiophene ring, a 1,3-dioxetane ring, and the like), an epoxy resin, and the like can be given.

As the medium to high molecular weight resin to be used in combination, the above-mentioned physical properties are satisfied, and the following general formula (I
A polymer containing 30 parts by weight or more of the polymer component of the repeating unit represented by II) is included.

[0159]

[Chemical 52]

[In the formula (III), V is —COO—, —O
_{CO -, - (CH 2)} h -OCO -, - (CH 2) h -
COO -, - O-or -SO ₂ - represents a. However, h is 1
In the general formula (III), f ₃ and f ₄ have the same contents as a ₁ and a ₂ in the formula (I).

R ₀₇ has the same _meaning as R ₀₃ in formula (I). A medium to high molecular weight binder resin containing a polymer component represented by the general formula (III) (hereinafter referred to as resin [B])
Examples of the resin include a random copolymer resin containing a polymer component represented by the formula (III) (JP-A-63-4981).
7, No. 63-220149, No. 63-220148, etc.), a combination resin of the random copolymer and a crosslinkable resin (JP-A-1-102573, etc.), and a graft-type copolymer (JP-A-2-102573). 53064, No. 2-56558, etc.) and the like, and those of the medium to high molecular weight compounds described in each specification.

The photoconductive compound used in the present invention may be either an inorganic compound or an organic compound. Examples of the inorganic compound used as the photoconductive compound of the present invention include conventionally known inorganic photoconductive compounds such as zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, selenium, selenium-tellurium, and lead sulfide. From a sex perspective
Zinc oxide and titanium oxide are preferred.

When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used as the photoconductive compound, 1 part of the binder resin is added to 100 parts by weight of the inorganic photoconductive compound.
It is used in a proportion of 0 to 100 parts by weight, preferably 15 to 40 parts by weight. On the other hand, as the organic compound, any of conventionally known compounds may be used, and specifically, the following two types are known as conventionally known examples as the electrophotographic lithographic printing plate precursor. First, Japanese Patent Publications 37-17162 and 6
2-51462, JP-A-52-1437, 54-198.
No. 03, No. 56-107246, No. 57-161863, etc., having a photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye, and a binding resin. JP-A-56-146145 and 60-17.
751, No. 60-17752, No. 60-17760, No. 60-254142, No. 62-54266, etc., having a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent, and a binding resin. Is. As a special case of the second example, JP-A-60-230147 and 60-23
There is also known a two-layered photoconductive layer containing a charge generating agent and a charge transporting agent in separate layers as described in JP-A No. 0148 and 60-238853. The electrophotographic lithographic printing plate precursor according to the invention may take any form of the above-mentioned two photoconductive layers. In the case of the second example, the organic photoconductive compound referred to in the present invention functions as a charge transport agent.

Examples of the organic photoconductive compound in the present invention include (a) triazole derivatives described in US Pat. No. 3,121,197 and (b) US Pat. No. 3,189,944.
Oxadiazole derivatives described in No. 7, etc., (c)
Imidazole derivatives described in JP-B-37-16096, (d) US Pat. Nos. 3,615,402 and 38,209.
89, No. 3542544, Japanese Patent Publication No. 45-55
5, JP-A-51-10983 and JP-A-51-932.
24, the same 55-108667, the same 55-156953,
Polyarylalkane derivatives described in JP-A-56-36656, (e) U.S. Pat. Nos. 3,180,729 and 4;
278746, JP-A-55-88064, JP-A-55-88065, JP-A-49-105537, and JP-A-55-5.
1086, 56-80051, 56-88141,
57-45545, 54-112637, 55-
Pyrazoline derivatives and pyrazolone derivatives described in JP-A-74546, (f) US Pat. No. 3,615,404, JP-B-51-10105, JP-A-46-3712, JP-A-47-28336, JP-A-54-83435. ,
Phenylenediamine derivatives described in JP-A-54-110836, JP-A-54-119925 and the like, (g) US Patent Nos. 3567450, 3180703 and 324059.
7, 3658520, 4232103, 4175
961, 4012376, Japanese Patent Publication No. 49-3
5702, West German Patent (DAS) 111051
No. 8, JP-B-39-27577, JP-A-55-1
44250, 56-119132, 56-2243.
7 arylamine derivatives described in each publication, (h) amino-substituted chalcone derivatives described in US Pat. No. 3,526,501, etc., (i) US Patent 354.
2546, etc., N, N-bicarbazyl derivatives, (j) US Pat. No. 3,257,203, etc., oxazole derivatives, (k) JP-A-56-462.
34, styrylanthracene derivatives,
(L) Fluorenone derivatives described in JP-A-54-110837, (m) US Pat. No. 3,717,462, JP-A-54-59143 (US Pat. No. 41.
(Corresponding to the specification of 50987), JP-A-55-5206
3, ibid 55-52064, ibid 55-46760, ibid 55
-85495, 57-11350, 57-1487.
49, 57-104144, and the like, (n) US Patent No. 404794.
8, same 4047949, same 4265990, same 4273
Nos. 846, 4299897, 4306008 and the like, and (o) JP-A-58-
190953, 59-95540, 59-9714.
8, 59-195658, 62-36674, etc., stilbene derivatives, (p) polyvinylcarbazole and its derivatives described in JP-B-34-10966, (q) JP-B-43-18674, Polyvinyl pyrene, polyvinyl anthracene, and poly-2-vinyl-4- (4 ′) described in each of the same 43-19192 publications.
Of vinyl polymers such as -dimethylaminophenyl) -5-phenyl-oxazole and poly-3-vinyl-N-ethylcarbazole; and (r) polyacenaphthylene, polyindene, acenaphthylene and styrene described in JP-B-43-19193. Polymers such as copolymers, (s) Japanese Patent Publication No. 56-
Condensed resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin described in JP 13940,
(T) JP-A-56-90833 and JP-A-56-161550
Various triphenylmethane polymers described in each publication,
and so on.

In the present invention, the organic photoconductive compound is not limited to the compounds listed in (a) to (t),
All conventionally known organic photoconductive compounds can be used. These organic photoconductive compounds may optionally be 2
It is possible to use more than one type. As the sensitizing dye contained in the photoconductive layer of the first example, conventionally known sensitizing dyes used for electrophotographic photoreceptors can be used. These are "electrophotographic" 12 9, (1973), "Synthetic Organic Chemistry" 24 (11), 1010, are described in (1966) and the like. For example, pyrilium dyes described in U.S. Pat. Nos. 31-41770, 4283475, JP-A-48-25658, JP-A-62-71965, and Applied Optics Supp.
lement 3 50 (1969), JP-A-50-3
Triarylmethane dyes described in Japanese Patent Publication No. 9548, etc.,
Cyanine dyes described in U.S. Pat. No. 3,597,196 and the like, JP-A-60-163047 and 59-1645.
88, 60-252517, etc., and the styryl dyes and the like are advantageously used.

As the charge generating agent contained in the photoconductive layer of the second example, various organic and inorganic charge generating agents known in the prior art for electrophotographic photoreceptors can be used. For example, selenium, selenium-tellurium, cadmium sulfide, zinc oxide, and the organic pigments shown in the following (1) to (9) can be used. (1) U.S. Pat. Nos. 4,436,800 and 4,439,506, JP-A-47-37543 and JP-A-58-1235.
41, the same 58-192042, the same 58-219263,
59-78356, 60-179746, 61-
Azo pigments such as monoazo, bisazo, and trisazo pigments described in JP-B Nos. 148453, 61-238063, JP-B-60-5941 and JP-B No. 60-45664, and (2) US Pat. Specification, JP-A-51-90827, JP-A-52-5564
Phthalocyanine pigments such as metal-free or metal phthalocyanines described in each of the three publications, (3) U.S. Pat. No. 3,371,884, JP-A-47
No. 30330, etc., perylene pigments,

(4) Indigo and thioindigo derivatives described in British Patent No. 2237680 and Japanese Patent Laid-Open No. 47-30331, and (5) British Patent No. 2237679 and Japanese Patent Laid-Open No. 4747.
Quinacridone pigments described in JP-A-30332, etc. (6) British Patent No. 2237678, JP-A-59
-184348, 62-28738, 47-185.
44 polycyclic quinone pigments described in each publication, (7) Bisbenzimidazole pigments described in JP-A Nos. 47-30331 and 47-18543, and (8) U.S. Pat. No. 4,396,610. Squarium salt-based pigments described in the respective specifications of JP-A-4644082, (9) JP-A-59-53850 and JP-A-61-212542.
And the azurenium salt-based pigments described in each publication and the like. These may be used alone or in combination of two or more.

The mixing ratio of the organic photoconductive compound and the binder resin determines the upper limit of the content of the organic photoconductive compound due to the compatibility between the organic photoconductive compound and the binder resin. Then, crystallization of the organic photoconductive compound occurs, which is not preferable. Since the electrophotographic sensitivity decreases as the content of the organic photoconductive compound decreases, it is preferable to include as many organic photoconductive compounds as possible within the range where crystallization of the organic photoconductive compound does not occur. The content of the organic photoconductive compound is 5 to 120 parts by weight, preferably 10 to 100 parts by weight of the organic photoconductive compound, relative to 100 parts by weight of the binding resin. The organic photoconductive compounds may be used alone or in combination of two or more.

The lithographic printing plate precursor of the present invention contains 10 to 10 parts by weight of the above-mentioned binding resin per 100 parts by weight of the photoconductive compound.
The amount used is 0 parts by weight, preferably 15 to 50 parts by weight. In the present invention, various dyes may be used together as a spectral sensitizer depending on the type of light source such as visible light exposure or semiconductor laser light exposure. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (N
o. 8) Page 12, C.I. J. Young et al .: RCA R
view 15 , p. 469 (1954), Kouhei Kiyota et al .: The Institute of Electrical Communication, J63-C (No. 2), 9
7 (1980), Yuji Harasaki et al., Journal of Industrial Chemistry, 6
6 , 78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan, 35 , 208 (1972), and other general references for carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes. , Polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain a metal), and the like.

More specifically, those mainly containing carbonium type dyes, triphenylmethane type dyes, xanthene type dyes and phthalein type dyes are described in Japanese Examined Patent Publication No. 51-4.
52, JP-A-50-90334, 50-11422.
7, JP-A-53-39130, JP-A-53-82353, US Pat. Nos. 3,052,540 and 4,054,450, and JP-A-57-16456.

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Harmmer "The Cyanin
eDyes and Related Compound
The dyes described in "ds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,110,591,
3121008, 3125447 and 312817
9, No. 3132942, No. 3622317,
British Patent Nos. 12268892, 1309274, 14
No. 05898, Japanese Patent Publications No. 48-7814, 55
The dyes described in each publication of 18892 are listed.

Furthermore, near-infrared light with a long wavelength of 700 nm or more
As polymethine dyes for spectrally sensitizing infrared light, JP-A-47-840, JP-A-47-44180 and JP-B-51-41 are known.
061, ibid 49-5034, ibid 49-45122, ibid 5
7-46245, 56-351141, 57-157.
254, 61-26044, 61-27551, U.S. Pat. Nos. 3,619,154 and 4,175,956, and "Research Disclosure".
e ", 1982, 216 , pages 117 to 118, and the like.

The photoconductor of the present invention is also excellent in that the performance thereof is hardly changed by the sensitizing dye even when various sensitizing dyes are used in combination. Furthermore, various conventionally known additives for electrophotographic photoreceptors can be used in combination, if necessary. These additives include chemical sensitizers for improving electrophotographic sensitivity, various plasticizers for improving film properties, surfactants and the like.

Examples of the chemical sensitizer include halogen, benzoquinone, chloranil, fluoranyl, bromanil,
Electron-withdrawing compounds such as dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, 2,3-dichloro-5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone and tetracyanoethylene , Hiroshi Komon et al. "Recent Development and Practical Use of Photoconductive Materials and Photoconductors" No. 4
Chapter-Chapter 6: Japan Science Information Publishing Co., Ltd. (1986)
The polyarylalkane compound, the hindered phenol compound, the p-phenylenediamine compound, etc. Moreover, JP-A-58-65439 and 58-
102239, 58-129439, 62-719.
The compounds described in each of the 65 publications and the like can also be mentioned.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methylphthalylethyl glycolate, dimethyl. Glycol phthalate or the like can be added to improve the flexibility of the photoconductive layer. These plasticizers can be contained in a range that does not deteriorate the electrostatic properties of the photoconductive layer.

The addition amount of these various additives is not particularly limited, but usually 0.0 to 100 parts by weight of the photoconductor.
It is from 01 to 2.0 parts by weight. The thickness of the photoconductive layer is 1 to 10
0 μ, particularly 10 to 50 μ is suitable. When the photoconductive layer is used as the charge generation layer of the laminated type photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is 0.01.
˜1 μ, particularly 0.05 to 0.5 μ is preferable.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally speaking, the support of the electrophotographic photosensitive layer is preferably conductive, and as the conductive support, a substrate such as metal, paper or plastic sheet is impregnated with a low resistance substance in the same manner as in the past. Those which have been subjected to a conductive treatment by, for example, those which are coated with at least one layer for the purpose of imparting conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided), and further for preventing curling, the support Having a water-resistant adhesive layer on its surface, having at least one precoat layer on the surface layer of the support, if necessary, and laminating a substrate with a conductive electroconductive plastic such as Al deposited on paper Etc. can be used.

Specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto, Electrophotography, 14, (No.
1), pp. 2-11 (published in 1975), Hiroyuki Moriga, "Introduction to Special Paper Chemistry", Polymer Publishing (1975), M.S.
F. Hoover, J .; Macromol. Sci. C
hem. A-4 (6), pp. 1273-1417 (197).
The ones described in "0 years" etc. are used. The hydrophilizable surface layer of the present invention has a thickness of 10 μm or less, and particularly preferably 0.1 to 5 μm for the Carlson process. If it is thicker than 5 μm, there may occur inconveniences such as a decrease in sensitivity of the lithographic printing plate precursor as an electrophotographic photoreceptor and an increase in residual potential.

In order to actually prepare the photoreceptor of the present invention (printing original plate), generally, an electrophotographic photosensitive layer (photoconductive layer) is first formed on a conductive support according to a conventional method. Then, on this layer, the resin particles of the present invention, the binder resin, and if necessary, the above-mentioned additives and the like are dissolved or dispersed in a volatile hydrocarbon solvent having a boiling point of 200 ° C. or less, and this is applied and dried. Thus, the surface layer can be formed and manufactured.

As the organic solvent to be used, specifically, a halogenated hydrocarbon having 1 to 3 carbon atoms such as dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, dichloropropane or trichloroethane is particularly preferable. Other chlorobenzene, toluene,
Various solvents used in the coating composition such as aromatic hydrocarbons such as xylene or benzene, ketones such as acetone or 2-butanone, ethers such as tetrahydrofuran and methylene chloride, and mixtures of the above solvents can also be used. Is.

A publicly known method can be applied to prepare a printing plate using the lithographic printing plate precursor of the present invention obtained as described above, and a copy image is formed on the electrophotographic plate having the above-mentioned structure by a conventional method. After formation, it is created by desensitizing the non-image area. That is, it is charged substantially uniformly in a dark place, and an electrostatic latent image is formed by imagewise exposure. Examples of the exposure method include scanning exposure using a semiconductor laser, a He-Ne laser, or the like, reflection image exposure using a xenon lamp, a Tigsten lamp, a fluorescent lamp, or the like as a light source, contact exposure through a transparent positive film, and the like. Next, development is performed using the above electrostatic latent image toner. As the developing method, conventionally known methods, for example, various methods such as cascade development, porcelain brush development, powder cloud development and liquid development can be used. Among them, liquid development is capable of forming a fine image and is suitable for making a printing plate. The formed toner image can be fixed by a known fixing method such as heat fixing, pressure fixing, solvent fixing and the like. With respect to the lithographic printing plate precursor having the toner image thus formed, the non-image area is then desensitized to produce a printing plate.

The desensitizing treatment used in the present invention is a method in which the resin particles of the present invention are hydrolyzed by passing them through a treatment liquid.
Examples thereof include a method of generating a carboxyl group by a method of decomposing by a redox reaction or a method of decomposing by a light irradiation treatment. A specific method of desensitizing the resin particles, that is, a method of decomposing the protected carboxyl group is arbitrarily selected depending on the decomposition reactivity of the protected carboxyl group. One of them is a method of hydrolyzing with an aqueous solution under acidic conditions of pH 1 to 6 and alkaline conditions of pH 8 to 12. Adjustment of these pHs can be easily adjusted by known compounds. Alternatively, a method by redox reaction with a reducing or oxidizing water-soluble compound is also possible, and known compounds can be used as these compounds, for example, hydrazine hydrate, zincate, lipoic acid, hydroquinones, formic acid. , Thiosulfates, hydrogen peroxide, persulfates, quinones and the like.

The treatment liquid may contain other compounds in order to accelerate the reaction or improve the storage stability of the treatment liquid. For example, 1 to 50 parts by weight of a water-soluble organic solvent may be contained in 100 parts by weight of water. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propargyl alcohol, benzyl alcohol, phenethyl alcohol, etc.),
Ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.), amides (dimethylformamide, dimethylacetamide, etc.) ), Esters (methyl acetate, ethyl acetate, ethyl formate, etc.) and the like, and these may be used alone or in combination of two or more.

The surfactant may be contained in 100 parts by weight of water in an amount of 0.1 to 20 parts by weight. Examples of the surfactant include conventionally known anionic, cationic or nonionic surfactants. For example, compounds described in Hiroshi Horiguchi "New Surfactants" Sankyo Publishing Co., Ltd. (1975), Ryohei Oda, Kazuhiro Teramura "Synthesis of Surfactants and Their Applications" Maki Shoten (1980), etc. Can be used. The scope of the present invention is not limited to the specific compound examples described above. The processing condition is a temperature of 15 ° C to 6
The immersion time at 0 ° C. is preferably 10 seconds to 5 minutes.

Furthermore, as a method of decomposing a specific functional group by irradiation with light, a process of irradiating with a "chemically active light ray" may be inserted between any of the steps after the toner image is obtained in plate making. Good. That is, after electrophotographic development, light irradiation may be performed for fixing the toner image at the time of fixing the toner image, or other conventionally known fixing methods such as heat fixing, pressure fixing,
After fixing by solvent fixing or the like, light irradiation is performed. As the “chemically actinic rays” used in the present invention,
Visible rays, ultraviolet rays, far ultraviolet rays, electron rays, X rays, γ rays, α
Any of lines and the like may be used, but ultraviolet rays are preferable. More preferably, the wavelength is from 310 nm to 500 nm
Those which can emit light rays in the range of are preferable, and generally, a high-pressure or ultra-high-pressure mercury lamp or the like is used. The light irradiation treatment is usually 10 seconds to 10 seconds from a distance of 5 cm to 50 cm.
Irradiation for 2 seconds is sufficient.

[0186]

EXAMPLES Examples of the present invention will be illustrated below, but the contents of the present invention are not limited thereto. A production example of a dispersion stabilizing resin (monofunctional polymer [M]) for resin particles and resin particles will be specifically exemplified.

Dispersion stabilizing resin (monofunctional polymer [M])
Production Example 1 of [M-1] 2,2,2,2 ′, 2 ′, 2′-hexafluoroisopropylmethacrylate 95 g, a mixed solution of 5 g of thioglycolic acid and 200 g of toluene while stirring under a nitrogen stream, The temperature was raised to 70 ° C. 1.0 g of azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and t were added to the reaction solution.
-Butyl hydroquinone 0.5g was added, temperature 100 ℃
The mixture was stirred for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of white powder. The weight average molecular weight of the polymer [M-1] was 4000.

[0188]

[Chemical 53]

Dispersion stabilizing resin (monofunctional polymer [M])
Production Example 2: [M-2] A mixed solution of 96 g of a monomer (MA-1) having the following structure, 4 g of β-mercaptopropionic acid, and 200 g of toluene was heated to a temperature of 70 ° C under a nitrogen stream. A. I. B. N.
1.0g was added and it reacted for 8 hours. Then, the reaction solution was cooled in a water bath to a temperature of 25 ° C., and 10 g of 2-hydroxyethyl methacrylate was added thereto. Dicyclohexyl carbonamide (abbreviated as D.C.C.) 15 g, 4
A mixed solution of 0.2 g of-(N, N-dimethylamino) pyridine and 50 g of methylene chloride was added dropwise with stirring over 30 minutes, and the mixture was further stirred for 4 hours. Next, 5 g of formic acid was added and after stirring for 1 hour, the precipitated insoluble material was filtered off, and the filtrate was reprecipitated in 1 liter of n-hexane. The viscous material that precipitated was collected by decantation, dissolved in 100 ml of tetrahydrofuran, the insoluble material was filtered off again, and reprecipitated in 1 liter of n-hexane. The polymer obtained by drying the precipitated viscous material had a yield of 60 g and a weight average molecular weight of 5.2 × 10 ³ .

[0190]

[Chemical 54]

Dispersion stabilizing resin (monofunctional polymer [M])
Production Example 3: [M-3] A mixed solution of 95 g of a monomer [MA-2] having the following structure, 150 g of benzotrifluoride, and 50 g of ethanol was heated to 75 ° C while stirring under a nitrogen stream. 2,4'-azobis (4-cyanovaleric acid) (abbreviation ACV) 2 g
Was added and reacted for 8 hours. After cooling, it was reprecipitated in 1 liter of methanol and the obtained polymer was dried. Next, this polymer 5
0 g and 2-hydroxyethyl methacrylate 11 g,
It was dissolved in 150 g of benzotrifluoride and the temperature was adjusted to 25 ° C. This mixture was stirred under D.I. C. C. 15g, 4-
A mixed solution of 0.1 g of (N, N-dimethylaminopyridine) and 30 g of methylene chloride was added dropwise over 30 minutes, and the mixture was stirred as it was for 4 hours. After that, 3 g of formic acid was added and the mixture was stirred for 1 hour, then the precipitated insoluble matter was filtered off, and the filtrate was added with methanol 8
It was reprecipitated in 00 ml. The precipitate was collected, dissolved in 150 g of benzotrifluoride, and reprecipitated again to obtain 30 g of a viscous material. The weight average molecular weight of the polymer [M-3] was 3.3 × 10 ⁴ .

[0192]

[Chemical 55]

Dispersion stabilizing resin (monofunctional polymer [M])
Production Examples 4 to 22: [M-4] to [M-22] In place of the monomer (MA-1) in Production Example 2, other monomers (polymer components shown in Table 2 are added). Corresponding monomer)
Each dispersion stabilizing resin [M] was produced in the same manner as in Production Example 2 except that. Each weight average molecular weight is 4 × 10 ³ ~
It was 6 × 10 ⁸ .

[0194]

[Table 2]

[0195]

[Table 3]

[0196]

[Table 4]

[0197]

[Table 5]

Dispersion stabilizing resin (monofunctional polymer [M])
Production Examples 23 to 30: [M-23] to [M-30] In Production Example 2 of the dispersion stabilizing resin, the monomer (MA-
1) and 2-hydroxyethyl methacrylate,
Instead of the compounds corresponding to each of the polymers in Table 3 below,
Other than that, each dispersion stabilizing resin [M] was manufactured by the same method. Each weight average molecular weight was 5 × 10 ^{3 to} 6 × 10 ³ .

[0199]

[Table 6]

[0200]

[Table 7]

Production Example 31 of dispersion stabilizing resin: [M-3
1] Octyl methacrylate 27 g, monomer (M
A-3) A mixed solution of 60 g of glycidyl methacrylate 3 g and 200 g of benzotrifluoride was heated to 75 ° C while stirring under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (AIBN) was added and reacted for 4 hours. I. B. N. 0.5 g was added and reacted for 4 hours. Next, 5 g of methacrylic acid, 1.0 g of N, N-dimethyldodecylamine, and 0.5 g of t-butylhydroquinone were added to this reaction mixture, and the mixture was stirred at a temperature of 110 ° C. for 8 hours. After cooling, it was reprecipitated in 2 liters of methanol to collect a slightly brownish oily substance and then dried. The yield was 73 g, and the weight average molecular weight (Mw) was 3.6 × 10 ⁴ .

[0202]

[Chemical 56]

Production Example 32 of dispersion stabilizing resin: M-32 A mixed solution of 80 g of the following monomer MA-4, 20 g of glycidyl methacrylate, 2 g of 2-mercaptoethanol and 300 g of tetrahydrofuran was stirred at a temperature of 60 under a nitrogen stream. Warmed to ° C. To this, 2,2'-mazobis (isovaleronitrile) (abbreviation: AIV.
N. ) 0.8 g was added and reacted for 4 hours. I. V.
N. 0.4 g was added and reacted for 4 hours. After cooling the reaction product to a temperature of 25 ° C., 4 g of methacrylic acid was added, and D. C. C. A mixed solution of 6 g, 0.1 g of 4- (N, N-dimethylamino) pyridine and 15 g of methylene chloride was added dropwise over 1 hour, and the mixture was stirred as it was for 3 hours. Next, 10 g of water was added, the mixture was stirred for 1 hour, the precipitated insoluble material was filtered off, and the filtrate was reprecipitated in 1 liter of methanol to collect an oily material. Further, this oily substance was mixed with benzene 150
After being dissolved in g and filtered to remove insoluble matter, it was reprecipitated again in 1 liter of methanol to collect an oily matter and dried. The yield was 56 g and the weight average molecular weight was 8 × 10 ³ .

[0204]

[Chemical 57]

Dispersion Stabilizing Resin Production Examples 33 to 39: M-
33 to M39 By performing the reaction as shown in Production Example 32, the following Table-4 was obtained.
The respective dispersion stabilizing resins were synthesized. The weight average molecular weight of each resin was in the range of 6 × 10 ^{3 to} 9 × 10 ³ .

[0206]

[Table 8]

[0207]

[Table 9]

Production Example of Resin Particles 1: [L-1] 10 g of dispersion stabilizing resin [M-32] and n-octane 2
The mixed solution (00 g) was stirred at a temperature of 60 under a nitrogen stream.
Warmed to ° C. 40 g of the following monomer [C-1],
10 g of ethylene glycol dimethacrylate, A.I.
I. V. N. A mixed solution of 0.5 g and 240 g of n-octane was added dropwise over 2 hours and the reaction was continued for 2 hours. Furthermore, A. I. V. N. 0.5 g was added and reacted for 2 hours. After cooling, a 200 mesh nylon cloth was passed through to obtain a white dispersion. The latex had an average particle size of 0.18 μm. [: CAPA-500 (Horiba, Ltd.
Particle size measurement].

[0209]

[Chemical 58]

Production Examples 2-11 of Resin Particles: [L-2]-
[L-11] Same as Production Example 1 except that the resin [M-32] and the monomer [C-1] in Production Example 1 of resin particles were replaced with the respective monomers shown in Table 5 below. To produce resin particles. The average particle size of each particle was within the range of 0.15 to 0.30.

[0211]

[Table 10]

[0212]

[Table 11]

Production Examples 13-23 of Resin Particles: [L-1
3] to [L-23] Resin particles [L-23] were prepared in the same manner as in Production Example 1 except that the polyfunctional compound shown in Table 6 below was used instead of 10 g of ethylene glycol dimethacrylate in Production Example 1 of resin particles.
-13] to [L-23] were produced. Each particle had a polymerization rate of 95 to 98% and an average particle diameter of 0.15 to 0.25 μm.

[0214]

[Table 12]

Production Example 24 of resin particles: [L-24] A mixed solution of 8 g of the dispersion stabilizing resin [P-35] and 130 g of methyl ethyl ketone was stirred at 60 ° C. under a nitrogen stream.
Warmed to. To this, 45 g of the following monomer [C-13],
5 g of diethylene glycol dimethacrylate, A.I.
I. V. N. 0.5 g and methyl ethyl ketone 15
0 g of the mixed solution was added dropwise over 1 hour, and A. I. V. N.
0.25 g was added and reacted for 2 hours. 200 after cooling
The average particle size of the dispersion obtained through the mesh nylon cloth was 0.25 μm.

[0216]

[Chemical 59]

Production Example 25 of Resin Particles: [L-25] A mixed solution of 7.5 g of the dispersion stabilizing resin M-26 and 230 g of methyl ethyl ketone was heated to 60 ° C. with stirring under a nitrogen stream. In addition to this, the monomer [C-12] 22
g, acrylamide 15 g A. I. V. N. 0.
2 g of a mixed solution of 5 g and 200 g of methyl ethyl ketone
The solution was added dropwise over a period of time, and the reaction was continued for 1 hour. Furthermore,
A. I. V. N. After adding 0.25 g and reacting for 2 hours, the mixture was cooled and passed through a 200-mesh nylon cloth, and the average particle size of the obtained dispersion was 0.25 μm.

Production Example 26 of resin particles: [L-26] 42 g of the following monomer [C-14], 8 g of ethylene glycol diacrylate, and 8 g of dispersion stabilizing resin M-27.
And 230 g of dipropyl ketone under a nitrogen stream at a temperature of 60
The mixture was added dropwise to a solution of 200 g of dipropyl ketone heated at 0 ° C over 2 hours while stirring. After reacting for 1 hour as it is,
Furthermore, A. I. V. N. 0.3 g was added and reacted for 2 hours. The average particle size of the dispersion obtained after passing through a 200-mesh nylon cloth after cooling was 0.20 μm.

[0219]

[Chemical 60]

Production Examples of Resin Particles 27-36: L-27-
L-36 In Preparation Example 26 of resin particles, the dispersion stabilizing resin M-2 was used.
Each particle was produced in the same manner as in Production Example 26 except that each dispersion stabilizing resin shown in Table 7 below was used in place of No. 7. The average particle size of each particle was in the range of 0.20 to 0.25.

[0221]

[Table 13]

Production Examples 37-42 of Resin Particles: L-37-
L-42 Resin particles in Production Example 25 were prepared using the monomer [C-12],
Acrylamide and reaction solvent: Production Example 2 except that each compound in Table 8 below was used instead of methyl ethyl ketone
Each particle was manufactured in the same manner as in 5. The average particle size of each particle was in the range of 0.15 to 0.30.

[0223]

[Table 14]

[0224]

[Table 15]

[0225]

[Table 16]

Next, a synthesis example of the binder resin [A] will be specifically illustrated. Synthesis Example of Resin [A] 1: [A-1] A mixed solution of 96 g of benzyl methacrylate, 4 g of thiosalicylic acid and 200 g of toluene was heated under a nitrogen stream at a temperature of 75.
Warmed to ° C. 1.0 g of 2,2′-azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 4 hours. Furthermore, A. I. B. N. 0.4 g was added for 2 hours, and then A. I. B. N. 0.2 g was added and stirred for 3 hours. The obtained copolymer [A-1] has the following structure,
Its weight average molecular weight was 6.8 × 10 ³ .

[0227]

[Chemical formula 61]

Synthesis Examples 2 to 13 of Resin [A]: [A-2]
~ [A-13] In Synthesis Example 1 of Resin [A], the monomers shown in Table 9 below were used in place of 96 g of benzyl methacrylate, and the other operations were performed in the same manner as in Synthesis Example 1 to obtain resins [A-13]. -2] ~ [A
-13] was synthesized. The weight average molecular weight of each resin is 6.0.
× was 10 ³ ~8 × 10 ^3.

[0229]

[Table 17]

[0230]

[Table 18]

[0231]

[Table 19]

Synthesis Examples 14 to 24 of Resin [A]: [A-1
4] to [A-24] In Synthesis Example 1 of Resin [A], instead of 96 g of benzyl methacrylate and 4 g of thiosalicylic acid, the following Table-10 is used.
Each of the resins [A-14] to [A-24] was synthesized by the same reaction as in Synthesis Example 1 except that the methacrylate and mercapto compound shown in 1 were used, and that 150 g of toluene and 50 g of isopropanol were used instead of 200 g of toluene. .. The weight average molecular weight of each obtained copolymer was 6.8 × 10 ³ .

[0233]

[Table 20]

[0234]

[Table 21]

[0235]

[Table 22]

Synthesis Example 25 of Resin [A]: [A-25] 100 g of 1-naphthyl methacrylate, 150 toluene
A mixed solution of g and 50 g of isopropanol was heated to a temperature of 80 ° C. under a nitrogen stream. 5.0 g of 4,4′-azobis (4-cyano) valeric acid (abbreviated as ACV) was added and stirred for 5 hours. Furthermore, A. C. V. 1 g was added for 2 hours, and then A. C. V. 1 g was added and stirred for 3 hours. The weight average molecular weight of the obtained polymer was 7.5 × 10 ³ .

[0237]

[Chemical formula 62]

Synthesis Example 26 of Resin [A]: [A-26] 50 g of methyl methacrylate and 150 g of methylene chloride.
The mixed solution of was cooled to -20 ° C under a nitrogen stream. 1.0 g of 10% 1,1-diphenylhexyllithium hexane solution adjusted immediately before was added, and the mixture was stirred for 5 hours. Carbon dioxide was passed under stirring at a flow rate of 10 ml / cc for 10 minutes, cooling was stopped, and the reaction mixture was allowed to stir until it reached room temperature. Next, the reaction mixture was reprecipitated in a solution of 50 cc of 1N hydrochloric acid dissolved in 1 liter of methanol, and a white powder was collected by filtration. The powder was washed with water until it became neutral, and then dried under reduced pressure. Yield 18 g, weight average molecular weight 6.
It was 5 × 10 ³ .

[0239]

[Chemical 63]

Synthesis Example 27 of Resin [A]: [A-27] 95 g of benzyl methacrylate, 4 g of thioglycolic acid
And a mixed solution of 200 g of toluene under a nitrogen stream at a temperature of 7
Warmed to 5 ° C.

A. C. V. 1.0 g was added and reacted for 6 hours, and then A. C. V. 0.4 g was added and reacted for 3 hours. The weight average molecular weight of the obtained copolymer was 7.8 × 10.
^{Was 3} .

[0242]

[Chemical 64]

Example 1 and Comparative Examples AB (Example 1) Resin [A-4] 8 g (as solid content),
32 g of resin [B-1] having the following structure (as solid content),
A mixture of 200 g of photoconductive zinc oxide, 0.017 g of the methine dye [I] having the following structure, 0.18 g of phthalic anhydride and 300 g of toluene was added to a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 1 × 10 ⁴ r.p. p. m. 15 rpm
Dispersed for minutes. This photosensitive layer-forming dispersion was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ^2, and dried at 100 ° C. for 30 seconds.

[0244]

[Chemical 65]

A toluene dispersion having the following formulation was applied on the surface of this photoreceptor by a doctor blade, dried at 100 ° C. for 20 seconds, and further heated at 120 ° C. for 1 hour to form a surface layer of about 2 μm.

Toluene Dispersion for Surface Layer Resin [B′-1] having the following structure 6 g Resin particles [L-1] 0.9 g (as solid content) Phthalic anhydride 0.01 g O-chlorophenol 0.002 g Toluene In addition, the total amount was 100 g.

[0247]

[Chemical 66]

Then, the mixture was left in the dark at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material. (Comparative Example A) The same operation as in Example 1 was carried out except that only 40 g of resin [B-1] was used in place of 8 g of resin [A-4] and 32 g of resin [B-1] in Example 1. An electrophotographic photosensitive material was produced. (Comparative Example B) Comparative Dispersion Resin Particles: LR-1 Production Example 1 of Resin Particles In Production Example 1 except that the resin having the following structure was used in place of 10 g of the dispersion stabilizing resin P-32 in L-1. It was synthesized in the same manner as 1. The average particle size of the obtained latex was 0.17 μm.

[0249]

[Chemical 67]

Comparative Photoreceptor In Example 1, resin particles [LR-1] were used instead of 0.9 g of resin particles [L-1] of the surface layer toluene dispersion.
An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that 0.9 g (as solid content) was used.

Film formation (smoothness of the surface), electrostatic characteristics, desensitizing property of the photoconductive layer (represented by contact angle of water of the photoconductive layer after desensitizing treatment) and printing of these light-sensitive materials. I investigated the sex. The printing property is a lithographic plate obtained by subjecting a fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) to the developer ELP-T to form an image by exposure and development and desensitizing. It examined using the printing plate. (Note that the printer used was a Hamada Star 800SX model manufactured by Hamada Star Co., Ltd.) The above results are summarized in Table-11.

[0252]

[Table 23]

Note 1) Smoothness of surface layer: For each light-sensitive material,
Using a Beck's smoothness tester (manufactured by Kumagai Riko Co., Ltd.), the smoothness (sec / cc) under the condition of an air capacity of 1 cc
Was measured. Note 2) Electrostatic characteristics: Corona discharge at -6 kV for 20 seconds using a paper analyzer (Kawaguchi Electric Co., Ltd. paper analyzer SP-428 type) on each light-sensitive material in a dark room at a temperature of 20 ° C and 65% RH. After that, it was left for 10 seconds and the surface potential V ₁₀ at this time was measured. Then, the potential V ₁₀₀ after standing still in the dark for 100 seconds was measured, and the potential retention after dark decay for 90 seconds, that is, the dark decay retention rate [D. R. R. The (%)], (V ₁₀₀ /
It was determined by V ₁₀ ) × 100 (%).

Also, the surface of the photoconductive layer was-
After being charged to 400 V, irradiation with monochromatic light having a wavelength of 780 nm is performed, and the time until the surface potential V ₁₀ is attenuated to 1/10 is obtained, and the exposure amount E _1/10 (erg / cm ² ) is calculated from this. The condition of temperature 20 ° C. and 65% RH was set to I, and the same evaluation was performed under the environmental conditions of temperature 30 ° C. and 80% RH, and this was set to II. Note 3) Imaging: Each light-sensitive material was left for one day under the following environmental conditions. Next, it is charged at -5kV and 2.0m as a light source.
Using a W output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm), on the surface of the photosensitive material,
After speed exposure under a dose of 45 erg / cm ² at a pitch of 25 μm and a scanning speed of 330 m / sec, ELP-T (Fuji Photo Film Co., Ltd.) was used as a liquid developer.
The copied image (fog, image quality of the image) obtained by developing and fixing was visually evaluated. Note 4) Raw plate water retentivity: Each light-sensitive material itself was immersed for 3 minutes in a desensitizing solution E-1 having the following formulation (original plate not made into a plate: abbreviated as raw plate). These plates were printed on a Hamada Star 8005X type manufactured by Hamada Star Co., Ltd. using distilled water as dampening water, and the presence or absence of background stains on the 50th printed sheet after printing was visually evaluated. Desensitizing treatment liquid: E-1 monoethanolamine 60 g Neosoap (manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) 8 g Benzyl alcohol 100 g was diluted with distilled water to a total volume of 1.0 liter, and then adjusted to pH 10.5 with potassium hydroxide. It was adjusted. Note 5) Background stain of printed matter: After making each photosensitive material by the same operation as in Note 3) above, immersing it in the processing liquid of E-1 used for Note 4) for 3 minutes, and then using E as fountain solution. A solution obtained by diluting -1 with water three times was also printed using a neutral paper as a printing paper, and the number of printed sheets until the background stain of the printed matter was visually discriminated was examined.

The surface smoothness of each photographic material was good. The electrostatic characteristics of the present invention and Comparative Example B were good, and the actual image pickup properties and the copied images were clear. However, Comparative Example A is D.I. R. R. In addition, the photosensitivity was remarkably lowered, and the image pickup property was not usable for practical use due to the lack of fine lines and characters, and the fog in the non-image area. These facts show that by using the resin [A] of the present invention as the binder resin of the photoconductive layer, excellent electrophotographic characteristics can be obtained even in the semiconductor laser light scanning exposure method.

When each of these photoreceptors was subjected to a desensitizing treatment to evaluate the degree of hydrophilicity of the non-image area (water-holding capacity of the stencil), Comparative Example B showed significant background stain due to the adhesion of printing ink. The part was not sufficiently hydrophilized. Further, after the plate was actually made and then desensitized, the planographic printing plate of the present invention showed no background stain even when neutral paper was used as the printing paper, and a printed image of clear image quality of 5 was obtained. I got a thousand.
On the other hand, in Comparative Example A, since the reproducibility of the image after plate making was insufficient, the image of the printed matter was also unsatisfactory after printing. Further, in Comparative Example B, the image after plate making was good, but the non-image area was not sufficiently desensitized, so that the printed matter had background stains from the imprinting.

This means that only the resin particles [L] of the present invention in the surface layer exhibit sufficient hydrophilicity and ink adhesion to non-image areas does not occur. As described above, the electrophotographic lithographic printing plate precursor in which the hydrophilicity of the non-image area was sufficiently advanced and the background fog did not occur was the only one of the present invention.

Example 2 In Example 1, 8 g of resin [A-4] and resin [B-
1] 32 g, methine dye [I] 0.017 g and resin particles [L-1] 0.9 g, instead of resin [A-19] 5
35 g of resin [B-2] having the following structure: 0.020 g of methine dye [II] having the following structure and resin particles [L-2] 1.
An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that 0 g was used.

[0259]

[Chemical 68]

Each characteristic was measured in the same manner as in Example 1.
The following are particularly severe environmental conditions (30 ° C, 80% R
H) shows the measurement results under. Electrostatic properties V _10: -705V D. R. R. : 79% E _1/10 : 40 erg / cm ² Imaging property: Good (○) Water retention of original plate: 〃 (○) Stain of printed matter: No background stain up to 5,000 sheets E-1 used in 1
In place of the above, the desensitizing treatment liquid E-2 having the following formulation was used.

Desensitizing treatment liquid: E-2 Diethanolamine 80 g Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 8 g Methyl ethyl ketone 100 g was dissolved in distilled water to a total volume of 1.0 liter and adjusted to pH 11.0 with potassium hydroxide. . Each of the light-sensitive materials of the present invention is excellent in chargeability, dark charge retention rate, and photosensitivity, and actual copied images and printed matter are high temperature and high humidity (30 ° C., 80% R).
Even under the harsh conditions of H), clear images were obtained with no background fog.

Examples 3 to 20 Instead of the resin particles [L], resin [A] and resin [B] used in Example 1, 0.9 g of the resin particles [L] of the present invention shown in Table 12 below. Each photosensitive material was prepared in the same manner as in Example 1 except that (as the solid content) and 6 g of the resin [A] or 33 g of the resin [B-3] having the following structure were used. The electrostatic characteristics and the printing characteristics were evaluated by operating in the same manner as in Example 1.

[0263]

[Chemical 69]

[0264]

[Table 24]

With respect to each of the light-sensitive materials, the electrostatic property and the printing property were measured by operating in the same manner as in Example 1. All were excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copied image was high in temperature and high. Even under severe conditions of humidity (30 ° C., 80% RH), a clear image free of background fog and fine line skipping was provided. When the performance of the offset lithographic original plate was evaluated by desensitizing, the water retention of the original plate was good in all cases, and 5,000 sheets could be printed even in the printing result after the actual plate making.

Examples 21 to 24 Photosensitive materials were prepared in the same manner as in Example 1 except that the dyes shown in Table 13 below were used instead of the methine dye [I].

[0267]

[Table 25]

[0268]

[Table 26]

Each of the light-sensitive materials exhibited almost the same image pick-up property and printing property as those of Example 1, showing good results.

Examples 25 to 27: 6.0 g of resin [A] shown in Table 14 below, 34.0 g of binder resin [B-4] having the following structure, 200 g of photoconductive zinc oxide,
A mixture of 0.03 g of uranine, 0.06 g of rose bengal, 0.02 g of tetrabromophenol blue, 0.20 g of maleic anhydride and 300 g of toluene was added in a homogenizer at a rotation speed of 1 × 10 ⁴ r.p.m. p. mm. Dispersed for 15 minutes. This electrophotographic photosensitive material was prepared by applying the photosensitive layer-forming dispersion to a conductive-treated paper with a wire bar so that the dry adhesion amount was 22 g / m ² and drying at 100 ° C. for 3 minutes.

[0271]

[Chemical 70]

On the surface of this photoreceptor, a toluene dispersion having the following formulation was applied with a doctor blade, dried at 100 ° C. for 20 seconds, and further heated at 120 ° C. for 1 hour to form a surface layer of about 2 μm. Toluene dispersion for surface layer Resin [B′-2] having the following structure 6 g Resin particle [L] in Table 14 below 1.0 g (as solid content) 1,2,4,5-benzenetetracarboxylic dianhydride 0.02 g Phenol 0.0015 g was added to toluene to make the total amount 100 g.

[0273]

[Chemical 71]

Then, an electrophotographic photosensitive material was prepared by leaving it in the dark at 20 ° C. and 65% RH for 24 hours. The film properties (surface smoothness) of the light-sensitive material, the imaging property, the desensitizing property of the photoconductive layer (expressed by the contact angle of the photoconductive layer after the desensitizing treatment with water) and the printability were examined. The above results are summarized in Table-14.

[0275]

[Table 27]

In the mode for carrying out the evaluation items shown in Table 14, the image pick-up performance was performed as follows, and the same operations as in Example 1 were carried out. Note) Imaging: Each photosensitive material and fully automatic plate-making machine ELP40
After leaving 4V (manufactured by Fuji Photo Film Co., Ltd.) at room temperature and humidity (20 ° C., 65%) for one day, plate making is performed to form a copy image, and the obtained copy original image (fog, image Visually observe (image quality) (this is referred to as I). The image quality II of the copied image is tested by the same method as the above I except that the platemaking is performed at high temperature and high humidity (30 ° C., 80%). As shown in Table 14 for each light-sensitive material, all the performances were good, and the number of printable sheets was 5,000.

Example 28 5 g of bisazo pigment having the following structural formula and tetrahydrofuran 9
5 g and resin [A-1] 0.8% by weight and resin [B-
4] A mixture of 30 g of a 4.2 wt% tetrahydrofuran solution was thoroughly pulverized with a ball mill. Then, this mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was coated on the conductive transparent support used in Example 1 by using a wire round rod, and the amount of about 0.
A 7 μm charge generation layer was formed.

[0278]

[Chemical 72]

Next, the hydrazone compound 20 of the following structural formula
g, 20 g of a polycarbonate resin (trade name: Lexan 121, manufactured by GE) and 160 g of tetrahydrofuran are applied on the charge generation layer using a wire round rod to form a charge transport amount of about 18 μm, and two layers are formed. An electrophotographic photosensitive member having a photosensitive layer composed of was obtained.

[0280]

[Chemical formula 73]

Resin particles [L-44] were formed on the surface of this photoreceptor.
% By weight (as solid content), 4% by weight of resin [B′-3] having the following structure, 0.01% by weight of phthalic anhydride,
And a toluene solution containing 0.005% by weight of 2-chlorophenol were coated with a doctor blade, dried at 100 ° C. for 20 seconds, and further heated at 130 ° C. for 1 hour to about 2
A μm surface layer was formed. Then in the dark at 20 ℃, 65%
An electrophotographic photosensitive material was produced by leaving it for 24 hours under the condition of RH.

[0282]

[Chemical 74]

This photosensitive material was immersed in the desensitizing solution (E-3) prepared according to the following formulation for 3 minutes to be desensitized. Desensitizing treatment liquid (E-3) Monoethanolamine 52 g Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 10 g Methylethylketone 80 g These were dissolved in distilled water to pH 10 with sodium hydroxide.
The total amount was adjusted to 0 to make 1.0 liter. Distilled water 2
It was 10 ° or less when a contact angle with the formed water was measured with a goniometer by placing μ liter of water droplets.
The contact angle before the desensitizing treatment was 95 °, which clearly shows that the surface layer of the present light-sensitive material was very favorably hydrophilized.

As in the first embodiment, this is a fully automatic plate making machine E.
When plate-making was carried out using ELP-T toner with LP404V, the density of the obtained master plate for offset printing was 1.0 or more, and the image quality was clear. Further, the master plate after master making was soaked in the desensitizing solution (E-4) prepared by the following formulation for 30 seconds and then washed with water to desensitize it. Desensitizing Treatment Liquid (E-4) Boric Acid 55 g Benzyl Alcohol 80 g These were dissolved in distilled water to a total volume of 1.0 liter, and further prepared with sodium hydroxide so that this liquid had a pH of 11.0. The contact angle of the non-image area with distilled water was 10 ° or less, and the area was sufficiently hydrophilized. When this offset printing original plate was printed by a printing machine, the printed matter after printing 5,000 sheets had no fog in the non-image area and the image was clear.

Examples 29 to 36 Examples 29 to 36 were carried out in the same manner as in Example 25 except that each compound shown in Table 15 below was used instead of 6 g of the resin [A-1] and 0.6 g of the resin particles [L-44]. A light-sensitive material was prepared in the same manner as in Example 25.

[0286]

[Table 28]

When each light-sensitive material was evaluated in the same manner as in Example 25, 5,000 prints each having a clear image with no fog in the non-image area could be obtained.

[0288]

According to the present invention, it is possible to obtain a lithographic printing plate precursor having an excellent printed image and high printing durability even under severe conditions. Further, the lithographic printing plate precursor of the present invention is effective for a scanning exposure method using a semiconductor laser beam.

[Figure 10]

Claims (4)

[Claims] 1. A lithographic printing plate precursor using an electrophotographic photosensitive member comprising a photoconductive layer of at least one layer provided on a conductive support, and a surface layer provided on the uppermost layer of the photoconductive layer. A lithographic printing plate containing at least one kind of the following non-aqueous dispersion resin particles [L] and at least one kind of the following resin [A] as a binder resin for the photoconductive layer. Original version. Non-aqueous dispersion resin particles [L]: In a non-aqueous solvent, it is soluble in the non-aqueous solvent, but is insolubilized by polymerization.
Monofunctional monomer (C) containing at least one functional group that decomposes to form at least one carboxyl group
Copolymer resin particles obtained by carrying out a dispersion polymerization reaction in the presence of a dispersion stabilizing resin soluble in the solvent, which comprises at least a repeating unit containing a substituent containing a silicon atom and / or a fluorine atom. .. Resin [A]: having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , containing a repeating unit represented by the following general formula (I) in an amount of 30% by weight or more as a polymer component, and polymer main at one end of the _{chain, -PO 3 H 2, -SO 3} H, -COO
H, -P (= O) (OH) R ₀₁ [R ₀₁ represents a hydrocarbon group or -OR ₀₂ (R ₀₂ represents a hydrocarbon group)] and at least one selected from a cyclic acid anhydride-containing group. A resin formed by combining two polar groups. [Chemical 1] [However, in the above formula (I), a ₁ and a ₂ each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₀₃ represents a hydrocarbon group. ] 2. The lithographic printing plate precursor as claimed in claim 1, wherein the non-aqueous solvent-based dispersed resin particles have a crosslinked structure. 3. The dispersion stabilizing resin comprises a polymer chain in the polymer chain,
A polymer material containing at least one polymerizable double bond group moiety represented by the following general formula (II):
And the lithographic printing plate precursor as described in 2 above. [Chemical 2] [In the general formula (II), V ₀ is -O-, -COO.
-, - OCO -, - ( CH 2) p OCO -, - (C
_{H 2) p COO -, -} SO 2 -, - CONR 1 -, - S
O ₂ NR ₁ −, —C ₆ H ₅ —, —CONHCOO—, or —CONHCONH— (where p represents an integer of 1 to 4, R ₁ represents a hydrogen atom or a hydrocarbon having 1 to 18 carbon atoms). Represents a group), b ₁ and b ₂ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—R ₂ or —C via a hydrocarbon group.
OO-R ₂ (R ₂ represents a hydrogen atom or an optionally substituted hydrocarbon group)] 4. The aryl group-containing methacrylate component represented by the following general formula (Ia) and the following general formula (Ib) as the copolymer component represented by the general formula (I), The lithographic printing plate precursor as claimed in any one of claims 1 to 3, comprising at least one. [Chemical 3] [In the above formulas (Ia) and (Ib), T ₁ and T ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, —COR ₀₄ or —COOR.
₀₅ (R ₀₄ and R ₀₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), and L ₁ and L ₂ each represent a single bond or a connecting atom number of 1 to 4 which connects —COO— and the benzene ring. Represents a linking group of. ]