JPH05100504A - Production of lithographic printing plate - Google Patents

Abstract

PURPOSE:To obtain a lithographic printing plate excellent in electrostatic characteristics by desensitizing the original plate contg. a specified nonaqueous dispersed resin grain in its surface layer and a specified binder resin in the photoconductive layer with a processing soln. contg. a specified compd. CONSTITUTION:The original plate contains, in its surface layer, a copolymer resin grain obtained by dispersion-polymerizing a monofunctional monomer having a formyl group and/or a functional group shown by formula I in a nonaqueous solvent in the presence of a dispersion stabilizing resin contg. silicon atom and/or fluorine atom. The binder resin in the photoconductive layer has 1X10<3>-2X10<4> weight average mol.wt., and contains >=30wt.% of the repeating unit shown by formula IIas the polymer component and 0.5-15wt.% of a polymer component having a polar group selected from -PO3H2, -SO3H, -COOH, -P(=O) (OH)R01 and an acid anhydride group. The photoconductive layer is desensitized by a processing soln. contg. a hydrophilic compd. having >=5.5 of the Parsons nucleophilic constant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithographic printing plate produced by an electrophotographic method, and more particularly, to improving the composition of a photoconductive layer and a surface layer having specific properties on the photoconductive layer. To improve the desensitizing method.

[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 particular, as an offset original plate, there is a big problem that scumming occurs due to insufficient desensitizing property, and in order to improve this, various studies have been made on development of a zinc oxide binder resin for improving desensitizing property. It has been done, for example, Japanese Patent Publication Sho 5
No. 0-31011, JP-A-53-54027, JP-A-54-20735, JP-A-57-202544, and JP-A-58-68046. However, even the resins that are said to be effective in improving the desensitizing property are still unsatisfactory in the background stain and the printing durability when actually evaluated. Further, it is essential to desensitize zinc oxide with a desensitizing treatment solution under acidic conditions and to use an aqueous solution containing a desensitizing agent under acidic conditions as the dampening water during printing. Therefore, when acidic paper is used as the printing paper, a problem occurs, but when neutral paper is used, the printing durability is significantly reduced. Depending on the printing ink used, dampening water interacts with the ink on the printing material to cause scumming on the printed matter or abnormal emulsification of the ink. It causes the problem of being lost. On the other hand, it is also possible to use an electrophotographic body in which an organic photoconductive compound is used as the photoconductive particles, and a photoconductive layer is provided together with a binder resin on a grained aluminum substrate.

To make an original plate of this type, a toner image is formed on the photosensitive layer by a usual electrophotographic method, and then the non-image area is dissolved and removed with a processing liquid in the same manner as described above. As a result, the non-image portion becomes an aluminum substrate and becomes hydrophilic. For example, Japanese Patent Publication No. 37-17162
Japanese Patent Publication No. 46-39405, Japanese Patent Laid-Open No. 52-2437.
JP-A-56-107246 and the like, when using a photosensitive layer in which an oxadiazole compound or an oxazole compound is bound with an alkali-soluble resin such as a styrene-maleic anhydride copolymer, or 55
-105254, JP-A-55-16125, JP-A-58-150953, JP-A-58-162961 and the like, and a photosensitive material comprising a phthalocyanine pigment or azo pigment and an alkali-soluble phenol resin. The case of using layers is known.

However, this plate-making process requires a large-scale device because the photosensitive layer in the non-image area must be dissolved and removed. Furthermore, a large amount of the photosensitive layer composition is eluted and accumulated in the processing liquid. Therefore, the durability of the treatment liquid becomes a problem, and at the same time, the problem of disposal is left as a big problem, and it is hard to say that the method is versatile.

Further, 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 photoreceptor is disclosed in Japanese Patent Publication No. 45-6606.
No. That is, a printing plate is disclosed in which a surface layer made of a vinyl ether-maleic anhydride copolymer and a hydrophobic resin compatible therewith is provided on an 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 therein becomes water-soluble when it is ring-opened and hydrophilized, so even if it is miscible with other hydrophobic resin, the layer is formed. The water resistance is extremely poor, and the printing durability is 500 at most.
The limit was ~ 600 sheets.

Further, in JP-A-60-90343, JP-A-60-159756, JP-A-61-217292, etc., a silylated polyvinyl alcohol is used as a main component, and a crosslinking agent is also used. A method of providing a surface layer (hydrophilizable layer) is shown. That is, this layer is for hydrolyzing the silylated polyvinyl alcohol by hydrolyzing it in the non-image area after toner image formation. In order to maintain the film strength after hydrophilization, the degree of silylation of polyvinyl alcohol is adjusted and the residual hydroxyl groups are crosslinked with a crosslinking agent. It is described that these improve the stain resistance of the printed matter and improve the number of printed sheets.

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 stably because it is a polymer reaction. Further, since the chemical structure of the hydrophilic polymer is limited, 1) chargeability, 2) quality of copied image (dot reproducibility / resolution of image area, There is a problem that it is difficult to prevent the surface layer from affecting the background fog in the image area), 3) exposure sensitivity, and the like.

In order to improve the above-mentioned problems of the lithographic printing plate precursor, the present inventors have previously used a resin containing a functional group capable of generating a carboxyl group by decomposition as a main component of the surface layer. The lithographic printing plate precursor used was proposed (JP-A-62-28345).

Further, as the surface layer resin, a combination of a resin containing a functional group capable of generating a hydrophilic group by decomposition and a compound capable of crosslinking the resin in the photosensitive layer is examined. Those containing a functional group to be generated (JP-A-1-245970, JP-A-1-262556), those containing a functional group to generate a carboxyl group by decomposition (JP-A-1-283527, 1-28).
4860 each), those containing a functional group which produces a thiol group, an amino group, a phosphono group, a sulfo group and the like by decomposition (JP-A-1-304465 and 1-306855).
Each publication) etc.

Further, it has been studied 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.

[0015]

However, various recent O.I. A. As for images of copy originals obtained from a device, various kinds and images of high definition have come to be used. On the other hand, it has become clear that, in the case of the original plate, a copy image with good reproducibility cannot be obtained with respect to the original document.

Furthermore, in the electrophotographic lithographic printing original plate as a digital direct lithographic printing original plate, when a scanning exposure system using a semiconductor laser beam is adopted, the time becomes longer than that of the whole surface simultaneous exposure system using visible light. In addition, since there are restrictions on the exposure intensity, electrostatic characteristics,
In particular, higher performance is required for dark charge retention characteristics and photosensitivity.

On the other hand, in the above-described known original plate, the electrophotographic characteristics are deteriorated, and the actual copy image is apt to cause the background fog, and the fine lines are skipped or the characters are blurred.
As a result, when printing as a lithographic printing plate precursor, the image quality of the printed matter deteriorates, and the effect of preventing scumming due to the hydrophilicity improvement of the non-image portion of the binder resin is lost.
That is, various O.I. A. A lithographic printing plate precursor that can be used in each case such as an image of a copy original obtained from an apparatus and an exposure method using a semiconductor laser beam is desired.

The present invention improves the above-mentioned problems of the conventional lithographic printing plate precursor. That is,
The first object of the present invention is to have excellent electrostatic characteristics (especially dark charge retention and photosensitivity), to reproduce a copy image faithful to the original image, and of course to have a uniform background stain as an offset original plate. It is an object of the present invention to provide a lithographic printing plate that is excellent in desensitizing property and does not generate a background stain.

The second object of the present invention is to provide a lithographic printing plate which is not easily affected by the type of sensitizing dye which can be used in combination and which has excellent electrostatic characteristics even in the scanning exposure system using a semiconductor laser beam.

[0020]

The object of the present invention is to provide a lithographic plate using an electrophotographic photosensitive member comprising a conductive support and at least one photoconductive layer on the conductive support, and a surface layer on the uppermost layer. In the printing plate precursor, the surface layer contains at least one of the following non-aqueous dispersion resin particles [L], and at least one of the following resin [A] as a binder resin for the photoconductive layer. The lithographic printing plate precursor containing the above is imagewise exposed to form a toner image, and the photoconductive layer in the non-image area other than the toner image area is at least the nucleophilic constant n of the person.
It is achieved by a method for producing a lithographic printing plate, which comprises a printing original plate by desensitizing with a processing liquid containing a hydrophilic compound having a value of 5.5 or more. The non-aqueous dispersion resin particles [L] contained in the surface layer of the present invention have a formyl group and / or the following general formula (I) which is soluble in the non-aqueous solvent but is insolubilized by polymerization in the non-aqueous solvent. And a monofunctional monomer [C] having at least one functional group represented by the formula (1), which is soluble in the solvent and which contains at least a repeating unit containing a substituent containing a silicon atom and / or a fluorine atom. It is a copolymer resin particle obtained by carrying out a dispersion polymerization reaction in the presence of a resin for use.

[0021]

[Chemical 5]

[However, in the above formula (I), A ₁ ,
A ₂ may be the same or different and each represents a hydrocarbon group, or A ₁ and A ₂ represent organic residues which are linked to each other to form a ring]

The resin [A] is 1 × 10 ³ to 2 × 1.
0 ⁴ has a weight average molecular weight of, and 30 wt% or more repeating units as the polymer component represented by the following general formula _{(II), -PO 3 H 2} , -SO 3 H, -COOH, -P (=
O) (OH) R ₀₁ [R ₀₁ represents a hydrocarbon group or a —OR ₀₂ group (R ₀₂ represents a hydrocarbon group)] and an acid anhydride group having at least one polar group. It is a resin containing 0.5 to 15% by weight of a combined component.

[0024]

[Chemical 6]

[However, in the above formula (II), a ₁ ,
a ₂ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group, and R ₀₃ represents a hydrocarbon. ] [-P (= O) (OH) R ₀₁ is

[0026]

[Chemical 7]

Is shown. In the present invention, the non-aqueous solvent-based dispersed resin particles may have a crosslinked structure. In addition, as the dispersion stabilizing resin in the present invention, those containing at least one polymerizable double bond group moiety represented by the following general formula (III) in the polymer chain are particularly preferable. Be done.

[0028]

[Chemical 8]

[In the general formula (III), V ₀ is -O
-, - COO -, - OCO -, - (CH 2) p OCO
_{-, - (CH 2) p} COO -, - SO 2 -, - CON
_{(R 1) -, SO 2} N (R 1) -, - C 6 H 4 -, - C
ONHCOO- or -CONHCONH- (where p represents an integer of 1 to 4 and R ₁ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms), b ₁ and b
_2, which may be the same or different, a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-R ₂ (R ₂ through -COO-R ₂ or a hydrocarbon radical is a hydrogen atom or a substituent The resin [A] is preferably represented by the following general formula (IIa) and the following general formula (IIb) as a copolymer component represented by the general formula (II). It is preferable to contain at least one of the aryl group-containing methacrylate components.

[0030]

[Chemical 9]

[However, the above formulas (IIa) and (IIb)
In, T ₁ and T ₂ are each independently a hydrogen atom,
Represents 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 -CO
A single bond connecting O- and a benzene ring or a connecting atom number 1 to
Represents 4 linking groups. The lithographic printing plate precursor of the known art as described above contains a surface layer resin that produces a hydrophilic group (for example, a hydroxyl group, a carboxyl group, etc.) upon decomposition in the surface layer, and also uses a compound that crosslinks the resin. Things to do are being tried.

In contrast, the present invention is obtained in the presence of a dispersion stabilizing resin containing a photoconductive layer containing the resin [A] as a binder resin and further containing a silicon atom and / or a fluorine atom. It is a lithographic printing plate for an electrophotographic plate making system using an electrophotographic photoreceptor provided with an uppermost layer (surface layer) containing non-aqueous dispersion resin particles. That is, insensitivity of non-aqueous dispersed resin particles (hereinafter sometimes abbreviated as resin particles [L]) contained in the uppermost layer in the non-image area after forming a toner image (plate-making) according to a usual electrophotographic process. A printing plate is obtained by modifying the lipophilic surface to a hydrophilic surface by an oiling treatment. As a result, the conventional problems can be overcome.

The resin particles [L] used in the present invention have an average particle size of 1 μm or less and a narrow particle size distribution, and the resin particles [L] have at least important properties. It has two. One of them is that when treated with a treatment liquid containing at least one nucleophilic reactive hydrophilic compound, the nucleophile is added to the terminal of the formyl group of the resin particles and / or the functional group represented by the general formula (I). A reactive hydrophilic compound is capable of undergoing an addition reaction, whereby the particles can express hydrophilicity and, at the same time, when the resin particles have a cross-linking structure, at this time, while having hydrophilicity, to water. It is insoluble or slightly soluble and has water swelling property.

Another example is a polymer (dispersion stabilizing resin) in which the resin particle [L] of the present invention contains at least a repeating unit containing a substituent containing at least one fluorine atom and / or silicon atom. It is presumed that the phenomenon of migration / concentration occurs on the surface portion of the photoconductive layer due to the combination of The polymer used as a dispersion stabilizing resin used in the synthesis of the resin particles [L] is physicochemically adsorbed with an insoluble component consisting of at least the polymer of the monomer (C), or In the case of the dispersion-stabilizing resin containing the polymerizable double bond group portion represented by the formula (III), it is considered that both polymer components are chemically bonded. As described above, the water retentivity of the non-image area of the surface layer is sufficiently achieved by both effects of concentrating the particles [L] on the surface portion and making the particles hydrophilic by the desensitizing treatment. ..

The mechanism by which the resin particles [L] of the present invention are hydrophilized by a nucleophilic reactive hydrophilic compound is represented by the following reaction formula, using the sulfite ion as the nucleophilic reactive hydrophilic compound as a representative example. It is shown in 1).

[0036]

[Chemical 10]

That is, the resin particles of the present invention have a nucleophilic reactivity such that the nucleophilic constant n of the person in the treatment liquid is 5.5 or more only when the non-image area is desensitized as a lithographic printing original plate. It is characterized by adding a hydrophilic group to the terminal by reacting with the hydrophilic compound as described above to thereby develop hydrophilicity, that is, it is rendered hydrophilic, and does not react with moisture in the atmosphere. There is no concern about storability. Since the formyl group according to the present invention is a functional group that reacts very quickly with a nucleophilic compound, it is possible to rapidly develop hydrophilicity.

If a nucleophilic reactive hydrophilic compound having a person's nucleophilic constant n of less than 5.5 is used, the hydrophilicity of the non-image area becomes insufficient. Furthermore, since the functional group represented by the general formula (I) can be converted into a formyl group by the acid treatment, the deacetalization reaction easily proceeds by the acid treatment, as shown in the reaction formula (1). It can be used similarly to the formyl group.

Further, in the present invention, the photoconductive layer contains, as a binder resin, a specific polymer component represented by the formula (II) and a polymer component containing at least one of the specific polar groups described above. And a low molecular weight polymer resin [A]. Generally, in an electrophotographic photosensitive member, if a further layer (for example, a surface layer) is provided on the photoconductive layer, electrostatic characteristics (especially photosensitivity, residual potential, etc.) are deteriorated and faithful image reproducibility is deteriorated. In addition, the effect is great as various improvements are tried.

To solve this problem, the present invention makes it possible to improve the electrostatic characteristics of the photoconductive layer by using the resin [A], and when the image is actually taken, the faithful reproducibility of the copied image is ensured. It was something that could be avoided. Furthermore, although it is usually sensitized by using a spectral sensitizing dye, these dyes sufficiently interact with the photoconductor even when the type of the spectral sensitizing dye used in the photoconductive layer of the present invention is changed. be able to.

Particularly in the case of dyes used for spectral sensitization for semiconductor laser light, this interaction is insufficient in the system of known binder resin, but in the system of the present invention, such development is not very excellent. It is a thing.

Further, as described above, the resin particles contain a polymer component containing a fluorine atom and / or a silicon atom, whereby the particles have a phenomenon of migration / concentration to the surface portion of the surface layer. And shows hydrophilicity by desensitizing treatment. Here, by using the resin particles of the present invention, a very small amount is added to produce the same effect (water retention) as that of the known technique, and the adverse effect on electrophotographic characteristics is minimized. I was able to do it.

As described above, according to the present invention, it is possible to solve the problem of excellent water retention in the non-image area after the formation of a good copy image due to the excellent electrophotographic characteristics and the desensitizing treatment after the formation of the copy image. We were able to.

The resin particles of the present invention have a maximum particle size of 2
It is not more than μm, preferably not more than 0.5 μm. The average particle size of the particles is preferably 0.8 μm or less, more preferably 0.5 μm or less. In addition,
Resin particles, the smaller the particle size, the larger the specific surface area,
The above-mentioned electrophotographic properties have a good effect, and colloidal particles (0.01 μm or less) are sufficient, but if they are too small, they resemble the case of molecular dispersion.
Since the effect of being particles for improving the water retention capacity is weakened, it is preferable to use the particles with a thickness of 0.001 μm or more.

Further, in the present invention, the resin particles are a hydrophobic polymer component, that is, a polymer component corresponding to the dispersion stabilizing resin is bonded, and the hydrophobic portion interacts with the binder resin of the surface layer. Since it is working, it does not elute with dampening water during printing due to the anchor effect of this part,
Good printing characteristics can be maintained even after printing a considerably large number of sheets.

Further, a heat and / or photocurable group may be contained as one of the polymer components as the dispersion stabilizing resin. In this case, the binder resin in the surface layer is chemically bonded to the binder resin. By doing so, the elution can be further suppressed.

Further, in the present invention, the resin particles having a crosslinked structure further suppress the elution property with water, while exhibiting the water swelling property and further improving the water retention property. In the present invention, the resin particles that do not form a crosslinked structure as described above or the resin particles that form a crosslinked structure (hereinafter simply referred to as crosslinked resin particles) are 1 to 100 parts by weight of the total composition of the surface layer. It is preferably used in an amount of 50% by weight. If the amount of resin particles or crosslinked resin particles is less than 1.0% by weight, the hydrophilicity of the non-image area will not be sufficient, and conversely, if it is more than 50% by weight, the hydrophilicity of the non-image area will be further improved, but severe. The electrophotographic characteristics under the conditions deteriorate, and the copied image deteriorates.

Further, the resin [A] contains at least one of the aryl group-containing methacrylate components represented by the following general formula (IIa) and the following general formula (IIb) as a copolymer component represented by the general formula [II]. Resin [A] containing one (hereinafter, this low molecular weight compound is referred to as resin [A '])
It is preferable that the resin [A ′] is used, and the electrophotographic characteristics (particularly V ₁₀ , DRR, E _1/10 ) can be further improved as compared with the case of the resin [A]. ..

The reason for this is unknown, but one reason is that the arrangement of these polymer molecular chains at the zinc oxide interface in the film is due to the planarity effect of the benzene ring or naphthalene ring which is the ester component of methacrylate. Probably due to being done properly. The non-aqueous solvent-based dispersed resin particles contained in the surface layer in the present invention will be described in detail below. The resin particles of the present invention are produced by so-called non-aqueous dispersion polymerization. The monofunctional monomer [C] used in the resin particles [L] contains at least a formyl group and / or a functional group represented by the general formula [I].

[0050]

[Chemical 11]

In the above formula (I), A ₁ and A ₂ may be the same or different and each represents a hydrocarbon group, or A ₁ and A 2.
₂ represents an organic residue which is linked to each other to form a ring. A
_{When 1} and A ₂ each represent a hydrocarbon group, A ₁ and A ₂ are preferably an aliphatic group having 1 to 12 carbon atoms which may be substituted (for example, an alkyl group having 1 to 12 carbon atoms which may be substituted). : Specific examples are methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, methoxymethyl group, ethoxymethyl group, 2-hydroxyethyl group, 2- Chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-
An alkenyl group having 2 to 12 carbon atoms which may be substituted, such as a methoxyethyl group, a 2-ethoxyethyl group, a 3-hydroxypropyl group and a 3-methoxypropyl group:
Specific examples thereof include a propenyl group, a butenyl group, a hexenyl group, an octenyl group, a docenyl group and a dodecenyl group, which may have a carbon number of 7 to 12 and may be substituted; a benzyl group, a phenethyl group, 3 -Phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, methoxybenzyl group, dimethoxybenzyl group, chlorobenzyl group, bromobenzyl group, fluorobenzyl group, dichlorobenzyl group And the like, such as C 3-12 alicyclic groups that may be substituted: specific examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, and the like).

When A ₁ and A ₂ represent an organic residue which is linked to each other to form a ring, a functional group represented by formula (Ia), that is, a cyclic acetal group is preferable.

[0053]

[Chemical 12]

In the formula (Ia), A ₃ and A ₄ may be the same or different from each other, and are a hydrogen atom or a carbon number of 1 to 12
Optionally substituted hydrocarbon group or —OA ₅ group (A ₅
Represents an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, and n represents an integer of 1 to 4.

Preferred examples in which A ₃ , A ₄ and A ₅ are hydrocarbon groups of hydrocarbons 1 to 12 which may be substituted include:
Aliphatic group (specifically, the same contents as those exemplified for A ₁ and A ₂ ), aromatic group (for example, phenyl group, tolyl group,
Xylyl group, methoxyphenyl group, chlorophenyl group,
Bromophenyl group, methoxycarbonylphenyl group, dimethoxyphenyl group, chloromethylphenyl group, naphthyl group, etc.) and the like.

More preferably, the formulas (I) and (Ia) are
In the case where A _{1 to} A ₅ are aliphatic groups, the number of carbon atoms is 1 to 6
Alkyl group, alkenyl group having 3 to 6 carbon atoms, and 7 carbon atoms
An aralkyl group of 9 is preferred. Moreover, n more preferably represents an integer of 1 to 3. Examples of the copolymerization component containing a formyl group and / or a functional group represented by (I) used in the present invention include those represented by the repeating unit of the following general formula (IV).

[0057]

[Chemical 13]

[In the formula [IV], Z is -COO.
-, - OCO -, - O -, - CO -, - CONr 1 -,
-SO ₂ Nr ₁ - (r ₁ represents a hydrogen atom or a hydrocarbon group), - CONHCOO -, - CONHCONH- , C
H ₂ COO-, CH ₂ OCO- or -C ₆ H ₄ - represents a. Y is -Z- and -W ₀ - represents an organic residue or linked directly attached to. Furthermore,-[Z-Y]-

[0059]

[Chemical 14]

The part and -W ₀ may be directly connected. W ₀ represents a formyl group or a functional group represented by (I). f ₁ ,
f ₂ may be the same as or different from each other and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group or an aryl group. The general formula (IV) will be described in more detail.

Preferably, Z is --COO--, --OCO.
-, - O -, - CO -, - CONr 1 -, - SO 2 Nr
₁ - or -C ₆ H ₄ - represents a. However, r ₁ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group,
Pentyl group, hexyl group, octyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-
Methoxyethyl group, 2-hydroxyethyl group, 3-bromopropyl group, etc., and aralkyl group having 7 to 9 carbon atoms and optionally substituted (for example, benzyl group, phenethyl group, 3
-Phenylpropyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, chloro-methyl-benzyl group, dibromobenzyl group, etc.), an optionally substituted aryl group (e.g., phenyl group, tolyl group, xylyl group,
Mesityl group, methoxyphenyl group, chlorophenyl group,
Bromophenyl group, chloro-methoxy-phenyl group, etc.)
Etc.

Y represents a direct bond or an organic residue connecting -Z- and -W ₀ . When Y represents an organic residue to be linked,
The linking group, carbon atoms which may have through a heteroatom - represents a carbon bond (the hetero atom, an oxygen atom, a sulfur atom, and a nitrogen atom), for example - [C (r ₂₎
(R _{3)] -, - C 6 H 10 -} , - C 6 H 4 -, - (CH
= CH) -, - O - , - S -, - Nr 4 -, - COO
-, - CONH -, - SO 2 -, - SO 2 NH -, - N
HCOO -, - NHCONH -, - Si (r 5)
(R ₆ )-or the like, or a combination of bonding units. (However, r ₂ , r ₃ , r ₄ , r ₅ , r
₆ represents the same content as r ₁ above).

F ₁ and f ₂ may be the same or different and each is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group, a hydrocarbon group (eg, methyl group, ethyl group, propyl group, butyl group). , Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonylmethyl group, ethoxycarbonylmethyl group,
Represents an optionally substituted alkyl group having 1 to 12 carbon atoms such as butoxycarbonylmethyl group, aralkyl group such as benzyl group and phenethyl group, phenyl group, tolyl group, xylyl group, aryl group such as chlorophenyl group, etc.) .. Furthermore, the-[Z-Y] -bonding residue in formula (IV) is

[0064]

[Chemical 15]

The part and the -W ₀ part may be directly connected. Specific examples of the polymer component containing the formyl group and / or the functional group represented by the general formula (I) of the present invention are shown below. In Examples (a-1) to (a-15), a is -H or -C.
Represents H ₃ . However, the present invention is not limited to this.

[0066]

[Chemical 16]

[0067]

[Chemical 17]

[0068]

[Chemical 18]

Specific examples of the functional group represented by the general formula (Ia) of the present invention will be shown below. Examples (c'-1) to (c'-)
9), R ₁₀ and R ₁₁ represent an alkyl group having 1 to 4 carbon atoms or —CH ₂ C ₆ H ₅ , and R ₁₂ represents an alkyl group having 1 to 4 carbon atoms, —CH ₂ C ₆ H ₅ or phenyl. Represents a group. However, the scope of the present invention is not limited to these specific examples.

[0070]

[Chemical 19]

The polymer component containing the formyl group and / or the functional group of the general formula (I) in the resin particle [L] of the present invention is not limited to a total amount when the resin particle [L] is a copolymer. 30-99% by weight, especially 50-95% by weight in the copolymer
Is preferred. The molecular weight of the polymer of the resin particles is preferably 10 ³ to 10 ⁶ , particularly 5 × 10 ^{3 to} 5 × 10 ⁵ . The monofunctional monomer [C] having the formyl group and / or the functional group represented by the general formula (I) of the present invention as described above can be synthesized by a conventionally known synthesis method.

For example, as a method for synthesizing a compound containing a formyl group, edited by The Chemical Society of Japan, New Experimental Chemistry Course, Volume 14,
Pp. 636 (1978) published by Maruzen Co., Ltd. Mulle
r, "Methoden der Organisehe
n Chemie ", p. 13 (1954), Georg.
Methods described in Theme Verlag, edited by The Chemical Society of Japan, New Experimental Chemistry Lecture, Volume 19, 231 (1957) Maruzen Co., Ltd., etc.

The polymerizable functional group in the above-mentioned monomer synthesis is an ordinary polymerizable double bond group, specifically CH.
_{2 = CH-CH 2 -,} CH 2 = CH-CO-O-, CH
_{2 = CH (CH 3) -CO} -O-, CH (CH 3) = C
_{H-CO-O-, CH 2} = CH-CONH-, CH 2 =
_{C (CH 3) -CONH-, CH} 2 = C (CH 3) -C
_{ONHCOO-, CH 2 = C (CH} 3) -CONHCO
_{NH-, CH (CH 3) =} CH-CONH-, CH 2 =
_{CH-O-CO-, CH 2} = CH-C 6 H 4 -, 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 can be mentioned.

The resin particle [L] of the present invention comprises 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 or allyl esters, 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 include vinyl group-substituted heterocyclic compounds such as methacrylonitrile and N-vinylpyrrolidone.

The amount of these other monomers is 60 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the total polymer component to be insolubilized. If the amount of the other monomer exceeds 60 parts by weight, the effect of improving the water retention property 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 dispersing and 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.

The fluorine atom-containing substituent is, for example,
-C_hF_{2h + 1}(H represents an integer of 1 to 12),-(CF
₂)_jCF₂H (j represents an integer of 1 to 11), -C₆
H_lF_{l '}[(L and l ′ are each an integer of 1 to 5, provided that l + l ′ =
5) or (l = 5-l ', l'is an integer of 1 to 5)] and the like.
Be done. Examples of the substituent containing a silicon atom include -Si.
(R₃) (R_Four) (R_Five), − (Si (R ₆) (R₇) O)_k-R₈(K
Represents an integer of 1 to 20), polysiloxane structure, etc.
Can be mentioned. However, R₃, R_Four, R_FiveIs the same but different
Optionally substituted hydrocarbon group or -OR
₉Group (R₉Is R₃Represents the same content as the hydrocarbon group of
Represents).

R ₃ is an optionally substituted alkyl group having 1 to 18 carbon atoms (for example, 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.

[0080]

[Chemical 20]

[0081]

[Chemical 21]

[0082]

[Chemical formula 22]

[0083]

[Chemical formula 23]

[0084]

[Chemical formula 24]

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 amount of the fluorine atom and / or silicon atom-containing polymer component 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 polymer component containing a fluorine atom and / or a silicon atom is arbitrarily adjusted. Further, in the dispersion stabilizing resin of the present invention, a photo- and / or thermosetting functional group is added to the total polymer 1 of the resin.
The content may be 30 parts by weight or less, preferably 20 parts by weight or less in 00 parts by weight. 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.

Further, the dispersion stabilizing resin of the present invention preferably contains at least one polymerizable double bond group moiety represented by the above-mentioned general formula (III) in the polymer chain. The polymerizable double bond group component will be described below.

[0088]

[Chemical 25]

In the general formula (III), 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.

In addition to hydrogen atom, R ₁ is preferably a hydrocarbon group having 1 to 18 carbon atoms which may be substituted (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.), 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 optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a 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.), alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2-cyclohexylethyl group, 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 Group, propionitrile amido phenyl group, such as dodecane white ylamide phenyl group).

[0091] 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 may be the same or different from each other, and 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 methyl group, ethyl group, propyl group, butyl group, etc.) -COO-R ₂ or COOR through the hydrocarbon
₂ (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, which may be substituted, and specifically, the above R ₁ represents the same contents as those described for _1. ).

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 compound of general formula (II
In I), V ₀ is, -COO -, - OCO -, - CH 2 OC
_{O -, - 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, methyl Group, -COOR ₂ or -CH ₂ COOR ₂ , (R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.) Represents.
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 (III), 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 = C
H-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 (III) 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, and is -O- or -S.
−, −Nq ₁ −, −SO−, −SO ₂ −, −COO −, −OCO
−, −CONHCO−, −NHCONH−, −CONq ₂ −, −SO ₂ Nq ₃
- and _{-Si (q 4) (q 5} ) - from selected linking groups may be the interposed, a divalent aliphatic group or a divalent aromatic group,
Or, it represents an organic residue constituted by a combination of these divalent residues. Here, q _{1 to} q ₅ represent the same contents as R ₁ in the formula (III). As the divalent aliphatic groups, such as _{- C (q 6) (q} 7) -, - C (q 6) = C (q 7)
−, − (C≡C) −, −C ₆ H ₁₀ −,

[0096]

[Chemical formula 26]

{Q ₆ and q ₇ may be the same 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 ₁₀ - represents,
R ₁₀ 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 heteroatom). 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 and 1,3-oxazoline ring. 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 (III) 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 is -H or -CH ₃
Is shown, X shows -Cl or -Br, n shows the integer of 2-12, m shows the integer of 1-4.

[0100]

[Chemical 27]

[0101]

[Chemical 28]

[0102]

[Chemical 29]

[0103]

[Chemical 30]

[0104]

[Chemical 31]

The dispersion stabilizing resin of the present invention preferably contains a polymerizable double bond group portion in the side chain of the polymer, and the polymer can be synthesized by a conventionally known method. For example, a method of copolymerizing a monomer containing two polymerizable double bond groups having different polymerization reactivity in a molecule,
After obtaining a polymer by copolymerizing a monofunctional monomer containing a reactive group such as a carboxyl group, a hydroxyl group, an amino group and an epoxy group in the molecule, the reactive group in the side chain of the polymer The reaction with an organic low-molecular compound containing a polymerizable double bond group containing another reactive group capable of chemically bonding with, a method of introducing by a so-called polymer reaction, etc. are mentioned as well-known methods. Be done.

As the above method, for example, JP-A-60-
The method described in Japanese Patent No. 185962 may be used. As the above method, specifically, Yoshio Iwakura, Keisuke Kurita "Reactive Polymer" Kodansha (Published in 1977), Ryohei Oda "Polymer Fine Chemical" Kodansha (Published in 1976), JP-A-6
It is described in detail in the specification etc. filed as Japanese Patent Application Laid-Open No. 1-43757 and Japanese Patent Application No. 1-149305. For example,
The polymer reaction by the combination of the functional group of group A and the functional group of group B in the following Table-1 is a commonly known method. Note that R ₂₁ and R _{22 in} Table 1 are hydrocarbon groups, and have the same contents as the hydrocarbon group for R ₁ in the above formula (III).

[0107]

[Table 1]

Further preferred as the dispersion stabilizing resin of the present invention is to contain a polymerizable double bond group moiety at one end of the main chain--
The functional polymer [M] can be produced by a conventionally known synthesis method. For example, a) a method by an ionic polymerization method in which various reagents are reacted with the ends of a living polymer obtained by anionic polymerization or cationic polymerization to obtain a monofunctional polymer [M], and b) a carboxyl group and a hydroxyl group in the molecule. Monofunctional by reacting a polymer having a terminal reactive group bond obtained by radical polymerization with various reagents using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a group or an amino group. Method by radical polymerization method for obtaining polymer [M], c) Polyaddition condensation method in which a polymerizable double bond group is introduced into the polymer obtained by polyaddition or polycondensation reaction in the same manner as the above radical polymerization method. And the like.

Specifically, P.I. Dreyfuss &
R. P. Quirk, Bncycl. Polym. Sc
i. Eng. , 7 , 551 (1987), p. F. Re
mpp, E. Franta, Adv. Polym. Sc
i. , 58 , 1 (1984), V.I. Percec, Ap
pl. Poly. Sci. , 285 , 95 (198
4), R.A. Asami, M .; Takari, Macro
mol. Chem. Suppl. , 12 , 163 (19
85), P.I. Rempp. , Et al, Macrom
ol. Chem. Suppl. , 8 , 3 (1984),
Yusuke Kawakami, Kagaku Kogyo, 38 , 56 (1987), Yuya Yamashita, Kogaku, 31 , 988 (1982), Shiro Kobayashi, Kogaku, 30 , 625 (1981), Toshinobu Higashimura, Journal of Japan Adhesion Society, 18 , 536 (1982), Koichi Ito, Polymer Processing, 35 , 262 (1986), Kishiro Azuma, Takashi Tsuda,
Functional Materials, 1987 , No. It can be synthesized according to the methods described in the review articles such as 10, 5 and the like, and the literatures and patents cited therein.

More specifically, as the method for synthesizing the monofunctional polymer [M] as described above, a polymer [M] containing a repeating unit corresponding to a radical-polymerizable monomer is disclosed in
-67563, Japanese Patent Application No. 63-64970, Japanese Patent Application Nos. 1-206989 and 1-69011, and the like, and also contains a polyester structure or a polyether structure as a repeating unit. The polymer [M] to be prepared is disclosed in Japanese Patent Application Nos. 1-56379 and 1-58989.
It can be obtained in the same manner as the methods described in the specification of the application, etc., as Nos. 1-56380.

As described above, the dispersed resin particles of the present invention contain the polar group-containing monofunctional monomer (C) containing at least a repeating unit containing a silicon atom- and / or fluorine atom-containing substituent. It is a copolymer resin particle obtained by dispersion polymerization in the presence of a dispersion stabilizing resin. Furthermore, the dispersed resin particles of the present invention have a crosslinked structure (including a higher-order network structure).
In the case of having a polymer, the polymer of the polymerizable component [abbreviated as polymer component (C)] containing the above polar group-containing monofunctional monomer (C) as a main component is bridged between the polymers. And forms a high-order mesh structure.

That is, the dispersed resin particles of the present invention are a non-aqueous latex composed of a portion insoluble in the non-aqueous dispersion solvent composed of the polymer component (C) and a polymer soluble in the solvent. In the case of having a network structure, the molecules of the polymer component (C) forming the portion insoluble in the solvent are bridged. As a result, the network resin particles become sparingly soluble or insoluble in water. Specifically, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight or less.

The crosslinking of the present invention can be carried out by a conventionally known crosslinking method. That is, (a) a method of crosslinking a polymer containing the polymer component (C) with various crosslinking agents or curing agents, and (b) containing at least a monomer corresponding to the polymer component (C). When a polymerization reaction is carried out by using a polyfunctional monomer or a polyfunctional oligomer containing two or more polymerizable functional groups, a network structure is formed between the molecules, and (c) the polymer. It can be carried out by a method such as a method in which the combined component (C) and the polymers containing the component containing a reactive group are crosslinked by a polymerization reaction or a polymer reaction. Examples of the cross-linking agent in the above method (a) include compounds that are commonly used as cross-linking agents. Specifically, the compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taisei (1981), "Polymer Data Handbook Basic Edition", Baifukan (1986), edited by The Society of Polymer Science, Japan, etc. Can be used.

For example, an organic silane compound (for example, 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's "New Epoxy Resins" Shokoido (1985), Kuniyuki Hashimoto's "Epoxy Resins", compounds described in Nikkan Kogyo Shimbun (1969), melamine resins (eg Ichiro Miwa, Hideo Matsunaga) Edited by "Uria Melamine Resin", compounds described in Nikkan Kogyo Shimbun (1969), poly (meth) acrylate compounds (for example, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura "Oligomer" Kodansha (1976) Annually), Eizo Omori "functional acrylic resin" Techno System (published in 1985) and the like, and specifically, polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6- Hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol polyacryle Door, bisphenol A-
Examples include diglycidyl ether diacrylate, oligoester acrylate, and their methacrylates.

Also, the polymerizability to be coexisted by the above method (b)
Polyfunctional monomer containing two or more functional groups [polyfunctional monomer
Also referred to as a monomer (D)] or a polyfunctional oligomer
As the polymerizable functional group, specifically, CH₂= CH-CH₂-, CH₂= CH-CO-O-,
CH₂= CH-, CH₂= C (CH₃) -CO-O-,
CH (CH₃) = CH-CO-O-, CH₂= CH-C
ONH-, CH₂= C (CH₃) -CONH-, CH
(CH₃) = CH-CONH-, CH₂= CH-O-C
O-, CH₂= C (CH₃) -O-CO-, CH₂= C
H-CH₂-O-CO-, CH₂= CH-NHCO-,
CH₂= CH-CH₂-NHCO-, CH₂= CH-S
O₂-, CH₂= CH-CO-, CH ₂= CH-O-,
CH₂= CH-S- and the like can be mentioned. Identical of these polymerizable functional groups
Monomers containing two or more
It may be an oligomer.

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, hydrinoquinone, 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 monomers or oligomers having different polymerizable functional groups include vinyl group-containing carboxylic acids (for example, 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, allylaminocarbonylpropione) Ester derivatives or amide derivatives containing vinyl groups such as acids) (eg vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, 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 the above method (c), when a chemical bond is formed by the reaction of the reactive groups between the polymers to form a bridge between the polymers, it is carried out in the same manner as the reaction of a normal organic low molecular compound. be able to. Specifically, it can be synthesized according to the same method as described in the method of synthesizing the dispersion stabilizing resin.

In dispersion polymerization, since monodisperse particles having a uniform particle size can be obtained and fine particles of 0.5 μm or less are easily obtained, polyfunctionality is used as a method for forming a network structure. The method (b) using a monomer is preferable. As described above, the network-dispersed resin particles of the present invention have a structure in which a repeating unit containing a formyl group and / or a functional group represented by the general formula (I) is contained, and the molecular chains are bridged to a higher degree. The non-aqueous solvent-soluble polymer component and the non-aqueous solvent-soluble polymer component containing at least a repeating unit having a fluorine atom and / or silicon atom-containing substituent.

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 0.8 μm or less, and the particle size distribution is very narrow and monodispersed. Can be particles.

Specifically, K. B. J. Barrett
"Dispersion Polymerization
in Organic Media "John Wil
ey (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
23 , 26 (1987), D.I. J. Walbridge
e, NATO. Adv. study. Inst. Se
r. B. No. 67, 40 (1983), British Patent No. 8
No. 93429, No. 934038, US Pat. No. 1
122397, 394012, and 4606989, JP-A-60-179751, and 60-185.
The method is disclosed in each of the 963 publications and the like.

The dispersed resin particles of the present invention include the monomer (C).
And at least one of each of the dispersion stabilizing resins, and in the case of forming a network structure, the polyfunctional monomer (D) is allowed to coexist as necessary. In any case, the important thing is If the resin particles synthesized from these monomers are insoluble in the non-aqueous solvent, desired dispersed resin particles can be obtained. More specifically, the dispersion stabilizing resin is preferably used in an amount of 1 to 50% by weight, more preferably 2 to 30% by weight, based on the insoluble monomer (C). The molecular weight of the dispersed resin particles of the present invention is 10 ³ to 10 ⁶ ,
It is preferably 5 × 10 ^{3 to} 5 × 10 ⁵ .

In order to produce the dispersion resin particles used in the present invention as described above, the monomer (C), the dispersion stabilizing resin and the polyfunctional monomer (D) are generally used in a non-aqueous solvent. Among them, heat polymerization may be carried out in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile or butyllithium. Specifically, (i) a method of adding a polymerization initiator to a mixed solution of the monomer (C), the dispersion stabilizing resin and the polyfunctional monomer (D), (ii) in a non-aqueous solvent , A method of adding the mixture of the polymerizable compound and the polymerization initiator dropwise or arbitrarily, and the like, and the method is not limited to these, and any method can be used for production.

The total amount of the polymerizable compound is about 5 to 80 parts by weight, preferably 10 parts by weight, based on 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 30
˜180 ° C., preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours. The non-aqueous dispersed resin particles produced according to the present invention as described above are fine particles having a uniform particle size distribution.

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 are decomposed by the treatment of the desensitizing solution or the soaking water at the time of printing to generate hydrophilic groups and exhibit 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 water swelling property. Like 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 sustainability is improved.

More specifically, even if the amount of the above-mentioned functional groups in the above resin particles is reduced, the effect of improving hydrophilicity can be maintained unchanged, or the size of the printing machine is increased or printing is 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 ferrocyan compound is used as the main agent of the desensitizing solution for desensitizing zinc oxide, and this compound requires special handling management 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 binder resin (A) used in the photoconductive layer of the present invention will be described in detail. In the 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 −30 ° C. to 110. C, more preferably -20 to 90 ° C. Resin [A] has a molecular weight of 1
When it is smaller than 0 ³ , the film forming ability is lowered and sufficient film strength cannot be maintained. On the other hand, when the molecular weight is larger than 2 × 10 ⁴ , even in the case of the resin of the present invention, particularly near infrared to infrared spectral sensitization is carried out. In the photoconductor using the dye, the fluctuation of the dark decay retention rate and the photosensitivity under severe conditions of high temperature / high humidity, low temperature / low humidity becomes slightly large, and the effect of the present invention that a stable copy image is obtained can be obtained. It fades.

The proportion of the polymer component corresponding to the repeating unit of the general formula (II) of the resin [A] is 30% by weight or more,
The proportion of the polymer component containing the specific polar group is preferably 0.5 to 15% by weight, and preferably 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] has a specific substituent at the 2-position and / or at the 2-position and the 6-position represented by the general formula (IIa) and the general formula (IIb). Resin [A] containing a methacrylate component having a specific substituent having a benzene ring or an unsubstituted naphthalene ring (hereinafter, this low molecular weight compound is referred to as resin [A '])
Is preferred. Formula (II in the resin [A ′]
a) and / or the proportion of the copolymerization component of methacrylate corresponding to the repeating unit of the formula (IIb) is 30% by weight or more, preferably 50 to 97% by weight, and the proportion of the specific polar group-containing polymer component is The amount is 0.5 to 15% by weight, preferably 1 to 10% by weight, based on 100 parts by weight of the resin [A '].

Next, the repeating unit represented by the general formula (II), which is contained in the resin [A] in an amount of 30% by weight or more, will be further described. In the general formula (II), 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 via a hydrocarbon group
—R ₀₆ (R ₀₆ 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, which may be substituted, and specifically, The same content as that described for R ₀₃ below is represented).

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, in the copolymer component corresponding to the repeating unit of the general formula (II),
a) and / or a copolymer component (resin [A ']) represented by a methacrylate component containing a specific aryl group represented by the general formula (IIb). In formula (IIa), preferable T ₁ and T ₂ are, independently of each other, a hydrogen atom, a chlorine atom and a bromine atom, respectively, and a carbon number of 1 to 1.
As the hydrocarbon group having 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.), aralkyl group having 7 to 9 carbon atoms (eg, benzyl group, phenethyl group, 3 -Phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl 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 (preferred R
Examples of ₀₄ and R ₀₅ include those described above as the preferable hydrocarbon group having 1 to 10 carbon atoms).

In formulas (IIa) and (IIb), L
₁ and L ₂ is a direct bond or bond each -COO- and the benzene ring _{- (CH 2) m1 - (} m 1 represents an integer of _{1~3), - CH 2 OCO -} , - CH 2 CH 2 OCO -,-
_{(CH 2 O) m2 - (} m 2 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.

Formula (II) used in the resin [A] of the present invention
Specific examples of the copolymerization component corresponding to the repeating unit represented by a) or (IIb) are shown below. However, the scope of the present invention is not limited to this. The following (d-
In 1) ~ (d-20) , n is an integer of 1 to 4, m is 0 or an integer of 1 to 3, p is an integer of 1-3, R ₁₀ ~R ₁₃ -C Both _n H _{2n + 1} or _{- (CH 2) m -C 6} H
₅ (however, n and m are the same as above), X ₁ and X ₂ may be the same or different, and a hydrogen atom, -Cl, -Br,-
Represents one of I.

[0143]

[Chemical 32]

[0144]

[Chemical 33]

[0145]

[Chemical 34]

[0146]

[Chemical 35]

Next, the polar group in the polar group-containing component of the characteristic 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 ₀₂ has the same content as R ₀₁ .

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.

The copolymerizable component containing a polar group of the resin [A] is, for example, a compound represented by the general formula (II) [the general formula (IIa),
b)], any vinyl compound containing the polar group that can be copolymerized with the monomer corresponding to the repeating unit represented by the formula (1) can be used. Basic edition] ”is described in Baifukan (published in 1986) and the like. 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 body, α-cyano body, β-chloro body,
β-bromo form, α-chloro-β-methoxy form, α, β-
Dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid 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, vinyl Benzene carboxylic acid, vinyl benzene sulfonic acid, vinyl sulfonic acid, vinyl phosphonic acid, half-ester derivative of vinyl group or allyl group of dicarboxylic acids, and ester substituents of these carboxylic or sulfonic acid, substituents of amide derivative Examples thereof include compounds having a polar group.

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.

[0153]

[Chemical 36]

[0154]

[Chemical 37]

[0155]

[Chemical 38]

[0156]

[Chemical Formula 39]

[0157]

[Chemical 40]

[0158]

[Chemical 41]

[0159]

[Chemical 42]

[0160]

[Chemical 43]

Furthermore, the low molecular weight resin [A] of the present invention
(Including [A ']) is represented by the general formula (II) or (I
In addition to the monomer of Ia) and / or (IIb) 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 (II), α-olefins, carvone Acid vinyl 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 (for example, 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,
Vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine and the like). It is desirable that these other monomers do not exceed 30% by weight in the resin [A].

The resin [A] has a weight average molecular weight of 1 × 10.
These are low molecular weight random copolymers having a molecular weight of ^{3 to} 2 × 10 ⁴ , and these polymerization methods can be easily synthesized by radical polymerization, ionic polymerization or the like by selecting the polymerization conditions in the conventionally known method. be able to. Monomers that polymerize,
The radical polymerization reaction is advantageous from the setting temperature of the polymerization solvent reaction and the like, in view of purification, apparatus reaction method and the like. In particular,
Examples of the polymerization initiator include commonly known azobis initiators and peroxides. In particular, as a characteristic of synthesizing a low molecular weight substance, a known method such as increasing the amount of the initiator used or increasing the polymerization set temperature may be applied. Specifically, the amount of the initiator used is in the range of 0.1 to 20 parts by weight with respect to the total amount of the monomers, and the set polymerization temperature is 30 ° C.
Perform at ~ 200 ° C.

Further, a method of using a chain transfer agent in combination is also known. For example, a desired weight average molecular weight can be adjusted by using a mercapto compound, a halogenated compound or the like in the range of 0.01 to 10 parts by weight with respect to the total amount of monomers.
Low molecular weight resin [A] (including [A '])
Is preferably used in combination with a known resin for the photoconductive layer described above. The use ratio of the low molecular weight resin 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 × 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, a typical one is vinyl chloride-
Vinyl acetate copolymer, styrene-butadiene copolymer,
Styrene-methacrylate copolymer, methacrylate copolymer, acrylate copolymer, vinyl acetate copolymer,
Examples thereof include polyvinyl butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin, polyester resin and the like.

Specifically, Ryuji Shibata and Jiro Ishiwata, "Polymer", Vol. 17, p. 278 (1968), Harumi Miyamoto.
Hidehiko Takei "Imaging" 1973 (No.8), page 9, Koichi Nakamura, "Practical technology of binders for insulating materials"
Chapter 10, C.I. H. C. Published (1985), D.M.
D. Tatt, S.M. C. Heidecker, Tapp
i, 49 (No. 10), 439 (1966), E.I.
S. Baltazzi, R.A. G. Blanklotte
et al, Photo. Sci. Eng. 16 (N
o. 5), 354 (1972), Nguyen Chan Kae, Isamu Shimizu, Eiichi Inoue, The Institute of Electrophotography, 18 (No.
2), 28 (1980), JP-B-50-31011, JP-A-53-54027, 54-20735, 57-57.
The materials disclosed in JP-A-202544 and JP-A-58-68046 are cited.

As a medium to high molecular weight resin, which is a preferable resin to be used in combination, the above-mentioned physical properties are satisfied, and preferably 30% by weight or more of a polymer component of a repeating unit represented by the following general formula (V) is contained. Polymers may be mentioned.

[0167]

[Chemical 44]

[In the formula (V), V is -COO-, -OC.
_{O -, - (CH 2)} q -OCO -, - (CH 2) q -C
OO -, - O- or -SO ₂ - represents a. However, q is 1
Represents an integer of 4] In the general formula (V), f ₃ and f ₄ are a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), a cyano group or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group). , Ethyl group, propyl group, butyl group, etc.).

R ₀₇ is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg, 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-ethoxyethyl group, 3-hydroxypropyl group, etc., alkenyl group having 2 to 18 carbon atoms and which may be substituted (for example, vinyl group, allyl group) , An isopropenyl group, a butenyl group, a hexenyl group, a heptenyl group, an octenyl group, etc.) and an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, naphthylmethyl group, 2-naphthylethyl group). , Methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc.),
Optionally substituted cycloalkyl group having 5 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), optionally substituted aryl group (eg, phenyl group, tolyl group, xyl 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, nitrophenyl Groups and the like).

The medium to high molecular weight binder resin [B] containing the polymer component represented by the general formula (V) is, for example, a resin of a random copolymer containing the polymer component represented by the formula (V). (Japanese Patent Laid-Open Nos. 63-49817 and 63-22014
9, 63-220148, etc.), a resin in which the random copolymer and a crosslinkable resin are used in combination (Japanese Patent Laid-Open No. 1-2117).
66, JP-A-1-102573), a copolymer containing a polymer component represented by the formula (V) and partially cross-linked in advance (JP-A-2-34860 and JP-A-2-40660), A graft-type block copolymer obtained by polymerizing a monofunctional macromonomer consisting of a polymer component of the repeating unit of (1) and a monomer corresponding to the component represented by the formula (V) (JP-A-2-53064 and JP-A-2-56558). , Ibid 3-299
57, same 3-77954, same 3-92861, same 3-5
3257 each specification) etc. are mentioned.

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 above 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 "electronic photographs" 12
9, (1973), "Synthetic Organic Chemistry" 24 (11), 1
010, (1966) and the like. For example, U.S. Pat. Nos. 31-41770 and 4283475, JP-A-48-25658, and JP-A-62-71.
Pyrylium dyes described in Japanese Patent No. 965, etc., Appli
ed Optics Supplement 3 50
(1969), triarylmethane dyes described in JP-A No. 50-39548, US Pat. No. 3,579,719.
Cyanine dyes described in Japanese Patent No. 6 and the like, JP-A-60-1
63047, ibid. 59-164588, ibid. 60-2525
The styryl dyes described in each of the 17 publications 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 and the like, (4) British Patent No. 2237680, JP-A-47.
Indigo and thioindigo derivatives described in JP-30331, etc. (5) British Patent No. 2237679, JP-A-47
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.

Further, the mixing ratio of the organic photoconductive compound and the binding resin determines the upper limit of the content of the organic photoconductive compound due to the compatibility between the organic photoconductive compound and the binding resin, and an amount exceeding this is added. 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 based on 100 parts by weight of the photoconductive compound.
It is used in a proportion of 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 JP-B-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, in the near-infrared region 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, pp. 117-118.

The photoconductor of the present invention (lithographic printing plate precursor) is excellent in that its performance 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. As these additives,
A chemical sensitizer for improving electrophotographic sensitivity, various plasticizers for improving film properties, a surfactant and the like are included. Examples of the chemical sensitizer include halogen, benzoquinone, chloranil, fluoranyl, bromanil, dinitrobenzene, anthraquinone, 2,5-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride,
Electron-withdrawing compounds such as 2,3-dichloro-5,6-dicyanobenzoquinone, dinitrofluorenone, trinitrofluorenone and tetracyanoethylene, Hiroshi Komon et al. "Recent Development and Commercialization of Photoconductive Materials and Photoconductors" Chapters 4 to 6
Chapter: Polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are the general references of the Japan Science Information Publishing Co., Ltd. (1986). Further, JP-A-58-65439 and JP-A-58-1022
39, 58-129439, 62-71965, etc., and the like.

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 and 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 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 aromatic hydrocarbons such as chlorobenzene, toluene, xylene or benzene, ketones such as acetone or 2-butanone, ethers such as tetrahydrofuran and methylene chloride, and various solvents used in the coating composition and the above solvents. Mixtures of can also be used.

A 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, the electrostatic latent image is developed with toner. As the developing method, conventionally known methods, for example, various methods such as cascade development, magnetic 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, as described above, the desensitizing of the resin particles of the present invention containing the formyl group and / or the functional group represented by the general formula (I), that is, hydrophilicity. It is achieved by the addition of. The method for desensitizing (conferring hydrophilicity) the formyl group-containing resin particles of the present invention includes a solution containing a hydrophilic group-containing compound that easily nucleophilically reacts with the formyl group (aqueous solution or water-soluble organic solvent). It is achieved by treating with a mixed solution containing).

As the hydrophilic compound which causes a nucleophilic substitution reaction on the formyl group, a nucleophilic constant n [R. G. Person, H .; Sobel,
J. Songstad, J.M. Amer. Chem. So
c. , 90 , 319 (1968)] containing a substituent having a value of 5.5 or more, and 1 in 100 parts by weight of distilled water.
A hydrophilic compound which can dissolve by weight or more can be used.

Specific compounds include, for example, hydrazine, hydroxylamine, sulfite (ammonium salt,
Sodium salt, potassium salt, zinc salt, etc.), thiosulfate, etc., and at least one polar group selected from a hydroxyl group, a carboxyl group, a sulfo group, a phosphono group, and an amino group in the molecule. Mercapto compounds,
Examples thereof include hydrazide compounds, sulfinic acid compounds, primary amine compounds, secondary amine compounds, and the like.

For example, as a mercapto compound, 2-mercaptoethanol, 2-mercaptoethylamine, N-
Methyl-2-mercaptoethylamine, N- (2-hydroxyethyl) 2-mercaptoethylamine, thioglycolic acid, thiomalic acid, thiosalicylic acid, mercaptobenzenedicarboxylic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethylphosphonic acid, mercapto Benzenesulfonic acid, 2-mercaptopropionylaminoacetic acid, 2-mercapto-1-aminoacetic acid, 1-mercaptopropionylaminoacetic acid, 1,2-dimercaptopropionylaminoacetic acid, 2,3-dihydroxypropylmercaptan, 2-methyl-2 -Mercapto-1-aminoacetic acid or the like as a sulfinic acid compound, 2-hydroxyethylsulfinic acid, 3-hydroxypropanesulfinic acid, 4-hydroxybutanesulfinic acid, carboxybenzenesulfinate , Dicarboxybenzenesulfinic acid and the like as a hydrazide compound, 2-hydrazinoethanesulfonic acid, 4-hydrazinobutanesulfonic acid, hydrazinobenzenesulfonic acid, hydrazinobenzenedisulfonic acid, hydrazinobenzoic acid, hydrazinobenzenedicarboxylic acid Etc. as primary or secondary amine compounds such as N- (2-hydroxyethyl) amine, N,
N-di (2-hydroxyethyl) amine, N, N-di (2-hydroxyethyl) ethylenediamine, tri (2
-Hydroxyethyl) ethylenediamine, N- (2,3
-Dihydroxypropyl) amine, N, N-di (2,3
-Dihydroxypropyl) amine, 2-aminopropionic acid, aminobenzoic acid, aminopyridine, aminobenzenedicarboxylic acid, 2-hydroxyethylmorpholine, 2
-Carboxyethyl morpholine, 3-carboxy piperazine etc. can be mentioned.

These nucleophilic compounds are used by being contained in the desensitizing solution. The amount of the nucleophilic compound present in these treatment liquids is 0.1 mol / liter to 10 mol / liter, preferably 0.5 mol / liter to 5 mol / liter.

Further, the pH of the treatment liquid is preferably 4 or more.
The treatment conditions are preferably a temperature of 15 ° C. to 60 ° C. and an immersion time of 10 seconds to 5 minutes. The treatment liquid may contain other compounds in addition to the nucleophilic compound and the pH adjuster described above. 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, propanol 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 above specific compound examples. The method of desensitizing the functional group-containing resin of the present invention represented by the general formula (I) is, as shown in the above reaction formula (1), a formyl group produced after a dealcoholization reaction by acid decomposition. In addition, the nucleophile is hydrophilized by nucleophilic reaction.

Since the dealcoholization reaction easily proceeds in a treatment liquid having a pH of 5 or less, a formyl group can be easily produced by treating it in a treatment liquid having a pH of 5 or less before the treatment for carrying out the nucleophilic reaction. And then hydrophilized by a nucleophilic reaction. Therefore, the planographic printing plate produced by the present invention is prepared by the desensitizing treatment as described above. Further, the hydrophilic treatment with the treatment liquid containing the nucleophilic compound can obtain the same effect even when the fountain solution at the time of printing contains the nucleophilic compound.

[0199]

EXAMPLES Examples of the present invention will be illustrated below, but the contents of the present invention are not limited thereto. The production examples of the dispersion stabilizing resin (monofunctional polymer) for resin particles and resin particles will be specifically exemplified. Production Example of Dispersion Stabilizing Resin (Monofunctional Polymer) 1: [M-
1] A mixed solution of 95 g of 2,2,2,2 ', 2', 2'-hexafluoroisopropyl methacrylate, 5 g of thioglycolic acid and 200 g of toluene was heated to 70 ° C while stirring under a nitrogen stream. 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.

[0200]

[Chemical 45]

Production Example 2 of Dispersion Stabilizing Resin (Monofunctional Polymer): [M-2] A mixed solution of 96 g of the monomer (MA-1) having the following structure, 4 g of β-mercaptopropionic acid and 200 g of toluene was added. The temperature was raised to 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 .

[0202]

[Chemical 46]

Production Example 3 of Dispersion Stabilizing Resin (Monofunctional Polymer): [M-3] A mixed solution of 95 g of the monomer [MA-2] having the following structure, 150 g of benzotrifluoride, and 50 g of ethanol was added with nitrogen. The mixture was heated to a temperature of 75 ° C while stirring under an air 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 .

[0204]

[Chemical 47]

Production Examples 4 to 22 of Dispersion Stabilizing Resin (Monofunctional Polymer): [M-4] to [M-22] Instead of the monomer (MA-1) in Production Example 2, another monomer is used. Polymer (monomer corresponding to the polymer component shown in Table 2)
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 .

[0206]

[Table 2]

[0207]

[Table 3]

[0208]

[Table 4]

[0209]

[Table 5]

Production Examples 23 to 30 of dispersion stabilizing resin (monofunctional polymer): [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 .

[0211]

[Table 6]

[0212]

[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 was 3.6 × 10 ⁴ .

[0214]

[Chemical 48]

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 under a nitrogen stream at a temperature of 60. 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 .

[0216]

[Chemical 49]

Dispersion Stabilizing Resin Production Examples 33 to 39: M-
33 to M-39 The reaction shown in Production Example 32 was carried out to give the following Table-4.
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 .

[0218]

[Table 8]

[0219]

[Table 9]

Production Example 1 of Resin Particles [L-1] A mixed solution of 10 g of the dispersion stabilizing resin [M-32] and 200 g of methyl ethyl ketone was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. In addition to this, the following monomer [C-1] 40
g, 10 g of ethylene glycol dimethacrylate, A.I.
I. V. N. 0.5 g and 240 g of methyl ethyl ketone
The mixed solution of 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. It was a latex having an average particle size of 0.20 μm. {: CAPA-500 [(manufactured by HORIBA, Ltd.)]
Particle size measurement}

[0221]

[Chemical 50]

Production Examples 2-12 of Resin Particles: [L-2]
[L-12] 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. Resin particles were manufactured in the same manner. The average particle size of each particle was within the range of 0.15 to 0.30 μm.

[0223]

[Table 10]

[0224]

[Table 11]

Production Examples 13-23 of Resin Particles: [L-1
3] to [L-23] In the same manner as in Production Example 1, except that the polyfunctional compound shown in Table 6 below was used in place of 10 g of ethylene glycol dimethacrylate in Production Example 1 of resin particles, resin particles [L −
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.

[0226]

[Table 12]

Production Example 24 of resin particles: [L-24] A mixed solution of 7.5 g of the dispersion-stabilizing resin [M-30] and 230 g of methyl ethyl ketone was stirred under a nitrogen stream while stirring.
Warmed to 0 ° C. To this, 22 g of monomer [C-1], 15 g of acrylamide, A. I. V. N. A mixed solution of 0.5 g and 200 g of methyl ethyl ketone was added dropwise over 2 hours, and the reaction was further continued for 1 hour. Furthermore, A. I. V.
N. 0.25g was added and reacted for 2 hours, then cooled to 200
The average particle size of the dispersion obtained through the mesh nylon cloth was 0.25 μm. Production Examples of Resin Particles 25 to 34: [L-25] to [L-3
4] In Production Example 3 of resin particles, a resin for stabilizing dispersion [M-3
Each particle was produced in the same manner as in Production Example 12 except that each dispersion-stabilizing resin shown in Table 7 below was used instead of [5]. The average particle size of each particle was in the range of 0.20 to 0.25.

[0228]

[Table 13]

Production Examples 35-40 of Resin Particles: [L-3
5] to [L-40] Monomer [C-1] 22 in Production Example 24 of resin particles
g, acrylamide 15 g, and reaction solvent: each particle was produced in the same manner as in Production Example 13 except that each compound shown in Table 8 below was used instead of methyl ethyl ketone. The average particle size of each particle was in the range of 0.15 to 0.30.

[0230]

[Table 14]

Next, a synthesis example of the binder resin [A] will be specifically exemplified. Synthesis Example of Binder Resin [A] 1: [A-1] A mixed solution of 95 g of benzyl methacrylate, 5 g of acrylic acid and 200 g of toluene was heated to a temperature of 90 ° C. under a nitrogen stream, and then 2,2′-azobis. 6.0 g of isobutyronitrile (abbreviation AIBN) was added and reacted for 4 hours. Furthermore, A. I. B. N. 2 g was added and reacted for 2 hours. The weight average molecular weight of the obtained copolymer [A-1] was 8
It was 500.

[0232]

[Chemical 51]

Synthesis Examples 2 to 28 of Binder Resin [A]: [A-
2] to [A-28] Resins [A-2] to [A-28] shown in Table 9 below were synthesized by operating in the same manner as the polymerization conditions of Synthesis Example 1 of Resin [A].

[0234]

[Table 15]

[0235]

[Table 16]

[0236]

[Table 17]

[0237]

[Table 18]

[0238]

[Table 19]

[0239]

[Table 20]

[0240]

[Table 21]

Example 1 and Comparative Examples AB Example 1 Resin [A-8] 8 g (as solid content), resin [B-1] 32 g (as solid content) having the following structure, photoconductive zinc oxide 200 g A methine dye [I] 0.017 having the following structure
g, a mixture of 0.18 g of phthalic anhydride and 300 g of toluene in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) 1 ×
10 ⁴ r. p. m. It was dispersed for 15 minutes at the rotation speed of. The amount of dry adhesion of this photosensitive layer-forming dispersion on a conductively treated paper is 2
Apply with a wire bar to give 5g / m ² and 100
It was dried at 30 ° C. for 30 seconds.

[0242]

[Chemical 52]

A toluene dispersion having the following formulation was coated on the surface of this photoreceptor 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'-1] 6g with the following structure Resin particles [L-1] 1.0g (as solid content) Phthalic anhydride 0.01g o-Chlorophenol 0.002g was added to toluene to make the total amount. It was 100 g. Then, the mixture was left in the dark at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

[0244]

[Chemical 53]

Comparative Example A In Example 1, 8 g of resin [A-8] and resin [B-
1] An electrophotographic photosensitive material was prepared in the same manner as in Example 1 except that 40 g of the resin [B-1] was used instead of 32 g. Comparative Example B Comparative Dispersion Resin Particles: [LR-1] In Production Example 1: [L-1] of resin particles, a resin having the following structure was used instead of 10 g of the dispersion stabilizing resin [P-32]. Was synthesized in the same manner as in Production Example 1. The average particle size of the obtained latex was 0.17 μm.

[0246]

[Chemical 54]

Comparative Photoreceptor In Example 1, 1 g of the resin particles [L-1] in the toluene dispersion for the surface layer was replaced with resin particles [LR-1] 1
An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that g (as solid content) was used. Examine the film properties (surface smoothness), electrostatic properties, desensitizing properties of the photoconductive layer (expressed by the contact angle of water of the photoconductive layer after desensitizing treatment) and printability of these photosensitive materials. It was Printability is fully automatic plate making machine EL
Developer EL on P404V (Fuji Photo Film Co., Ltd.)
Using PT, an image was formed by exposure / development treatment, and a lithographic printing plate obtained by desensitizing treatment was used for examination.
(Note that the printing machine uses Hamada Star 8 manufactured by Hamada Star Co., Ltd.
00SX type was used) The above results are summarized in Table-10.

[0248]

[Table 22]

Note 1) Smoothness of surface layer:
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 90 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 is changed to -4 by corona discharge.
After charging to 00 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 (temperature 20 ° C., 65% RH) was set to I, and the same evaluation was conducted 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 2 minutes in a desensitizing solution E-1 having the following formulation at a temperature of 30 ° C. (original plate not made into a plate: abbreviated as raw plate). These versions are Hamada Star 8005X type manufactured by Hamada Star Co., Ltd.
Print using distilled water as dampening water and print 50 times after printing.
The presence or absence of background stains on the first printed matter was visually evaluated. Desensitizing treatment liquid: E-1 Monoethanolamine 60 g Neosoap (manufactured by Matsumoto Yushi 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 11.5 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.

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 original plate). 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 develop 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-8] and resin [B-
1] 32 g, methine dye [I] 0.017 g and resin particles [L-1] 1.0 g, instead of resin [A-10] 6
g, resin [B-2] having the following structure 34.0 g, methine dye [II] having the following structure 0.020 g, and resin particles [L-2]
An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that 1.2 g was used.

[0255]

[Chemical 55]

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: -760V D. R. R. : 79% E _1/10 : 46 erg / cm ² Imaging property: Good (○) Water retention of original plate: 〃 (○) Stain of printed matter: No background stain of 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 11.5 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 11 below. Each photographic material was prepared in the same manner as in Example 1 except that (as the solid content) and 7 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.

[0259]

[Chemical 56]

[0260]

[Table 23]

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 13. As a result, the charging property, the dark charge retention rate and the photosensitivity were all excellent, and the actual copy image was high at high temperature. Even under severe conditions of humidity (30 ° C., 80% RH), a clear image was obtained with no background fog or fine line skipping. 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 12 below were used instead of the methine dye [I].

[0263]

[Table 24]

Each of the light-sensitive materials exhibited almost the same characteristics as those in Example 1 in terms of image pick-up property and printing property, showing good results. Examples 25 to 27: 6.0 g of resin [A] shown in Table 13 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. m. 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.

[0265]

[Chemical 57]

A toluene dispersion having the following formulation was applied on the surface of this photoreceptor 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 13 below 0.9 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.

[0267]

[Chemical 58]

Then, an electrophotographic light-sensitive 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-13.

[0269]

[Table 25]

In the mode of carrying out the evaluation items shown in Table 13, 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 normal humidity (20 ° C., 65%) for one day, a plate is made 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 13 for each light-sensitive material, all the performances were good, and the number of printable sheets was 5,000.

Example 28 5 g of a 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 to give a dispersion of about 0.
A 7 μm charge generation layer was formed.

[0272]

[Chemical 59]

Next, the hydrazone compound 20 of the following structural formula
g, 20 g of polycarbonate resin (manufactured by GE Corporation, trade name Lexan 121) 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.

[0274]

[Chemical 60]

Resin particles [L-27] were formed on the surface of this photoreceptor.
0.8% 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.

[0276]

[Chemical formula 61]

This photosensitive material was immersed in a desensitizing solution (E-3) prepared according to the following formulation at a temperature of 35 ° C. for 1 minute to desensitize it. Desensitizing treatment solution (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 11.
It was adjusted to 5 and the total volume was 1.0 liter. Distilled water 2
When a microliter of water droplets was placed and the contact angle with the formed water was measured with a goniometer, it was 10 ° or less. 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. Furthermore, temperature 40 ℃
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 for desensitizing treatment. 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 40 Using each of the light-sensitive materials prepared in Examples 1 to 28, an etching process was carried out as follows to prepare an offset printing original plate. After adding distilled water to 0.5 mol of the nucleophilic compound shown in Table 14 below, 100 g of an organic solvent and 6 g of Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) to make 1 liter,
The pH of each mixture was adjusted to 11.0. Desensitizing processing liquid ELP-T [manufactured by Fuji Photo Film Co., Ltd.]
Was diluted 4 times with distilled water and then immersed in the above treatment liquid at 35 ° C. for 1 minute. The obtained plate was printed under the same printing conditions as in Example 1. Each of the light-sensitive materials had good water retention and printing durability of 5,000 sheets.

[0280]

[Table 26]

[0281]

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

Claims (4)

[Claims] 1. A lithographic printing plate precursor comprising at least one photoconductive layer provided on a conductive support, and a surface layer provided on the uppermost layer of the photoconductive layer. A lithographic printing plate precursor containing at least one kind of dispersed resin particles [L] and at least one kind of resin [A] having the following content as a binder resin in the photoconductive layer is subjected to image exposure. After forming a toner image by desensitization, the photoconductive layer in the non-image area other than the toner image area is desensitized with a treatment liquid containing a hydrophilic compound having a nucleophilic constant n of at least 5.5. A method for producing a lithographic printing plate, which comprises processing to obtain a printing original plate. Non-aqueous dispersion resin particles [L]: at least one formyl group and / or a functional group represented by the following general formula (I) which is soluble in the non-aqueous solvent but is insolubilized by polymerization in the non-aqueous solvent Dispersion polymerization of a monofunctional monomer [C] having a seed 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. Copolymer resin particles obtained by reacting. [Chemical 1] [However, in the above formula (I), A ₁ and A ₂ may be the same or different and each represents a hydrocarbon group, or A ₁ and A ₂ are organic residues which are linked to each other to form a ring. Resin [A]: having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ and having a repeating unit represented by the following general formula (II) as a polymer component in an amount of 30% by weight or more, —PO ₃ H ₂ ,-
_{SO 3 H, -COOH, -P (} = O) (OH) R 01 wherein R
₀₁ represents a hydrocarbon group or a —OR ₀₂ group (R ₀₂ represents a hydrocarbon group) and a polymer component having at least one polar group selected from cyclic acid anhydride-containing groups 0.5 to 15
A resin containing 100% by weight. [Chemical 2] [However, in the formula (II), a ₁ and a ₂ are respectively
It represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₀₃ represents a hydrocarbon. ] 2. The method for producing a lithographic printing plate as claimed in claim 1, wherein the non-aqueous solvent-based dispersed resin particles form a crosslinked structure. 3. The dispersion stabilizing resin comprises a polymer chain in the polymer chain,
The method for producing a lithographic printing plate according to Claims (1) and (2), which comprises at least one polymerizable double bond group moiety represented by the following general formula (III). [Chemical 3] [In the general formula (III), V ₀ is -O-, -COO.
-, - OCO -, - ( CH 2) p OCO -, - (C
_{H 2) p COO -, -} SO 2 -, - CON (R 1) -,
_{-SO 2 N (R 1) -} , - C 6 H 4 -, - CONHCO
Represents O- or -CONHCONH- (provided that p represents an integer of 1 to 4, R ₁ represents a hydrogen atom or a carbon number of 1 to
18 hydrocarbon groups), b ₁ and b ₂ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—R ₂ or a hydrocarbon group. COO-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 (IIa) and the following general formula (IIb) as a copolymer component represented by the general formula (II), At least one is contained, The manufacturing method of the lithographic printing plate in any one of Claims (1)-(3) characterized by the above-mentioned. [Chemical 4] [However, in the above formulas (IIa) and (IIb),
T ₁ and T ₂ are each independently a hydrogen atom and a carbon number of 1 to
10 hydrocarbon groups, chlorine atom, -COR ₀₄ or -COO
R ₀₅ (R ₀₄ and R ₀₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), L ₁ and L ₂ each represent a single bond or a connecting atom number 1 to 4 which connects —COO— and the benzene ring. Represents a linking group. ]