JPH0580573A - Planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain good water-holding property and to realize excellent printed images and high printing resistance under severe conditions by incorporating at least one kind of nonaqueous dispersion resin particles into the surface layer and incorporating at least one specified resin as a binder resin of a photoconductive layer. CONSTITUTION:The surface layer contains at least one kind of nonaqueous dispersion resin particles. The photoconductive layer contains at least one specified resin A as a binder resin. The nonaqueous dispersion resin particles are copolymer resin particles obtd. by dispersion polymn. of unifunctional monomers in a nonaqueous solvent in the presence of a dispersion stabilizer resin. The unifunctional monomers are soluble in the nonaqueous solvent but become insoluble after polymn., and these monomers contains at least one kind of functional group which produces hydroxyl by decomposition. The dispersion stabilizer resin is soluble in the solvent and contains at least a constitutional repeating unit containing a substituent having silicon atoms. The resin A has 1X10<3>-2X10<4> weight mean mol.wt. and contains the constitutional repeating unit expressed by formula I as the polymer component by >=30%.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art At present, various types of offset master plates for direct plate making have been proposed and put into practical use. Among them, photoconductive particles such as zinc oxide and a binder resin are used on a conductive support. The photoconductor provided with a photoconductive layer containing as a main component is subjected to a normal electrophotographic process to form a highly lipophilic toner image on the photoconductor surface, and then the surface is desensitized liquid called an etchant. A technique for obtaining an offset original plate by subjecting the non-image portion to hydrophilic treatment selectively is widely used. In order to obtain a good printed matter, first, the original image is faithfully copied to the offset original plate, the surface of the photoconductor is easily compatible with the desensitizing solution, and the non-image area is sufficiently hydrophilized, while at the same time being water resistant. In addition, in printing, the photoconductive layer with the image does not separate, and it has good compatibility with fountain solution, and the hydrophilicity of the non-image area is sufficient so that stains do not occur even when the number of printed sheets increases. Must be retained, and so on.

Therefore, in recent years, a method of preparing a printing plate of a hydrophilic treatment type on the surface of a non-image area, which is easy to make by providing a specific resin layer on an ordinary electrophotographic photosensitive member, has been proposed.
It is disclosed in Japanese Patent No. 5606. That is, a printing plate is disclosed in which a surface layer comprising a vinyl ether, a maleic anhydride copolymer, and a hydrophobic resin compatible with the vinyl ether is provided on the electrophotographic photosensitive layer. After forming a toner image on this layer,
It is a layer that can be hydrophilized by hydrolyzing the acid anhydride ring portion by treating the non-image area with an alkali (hydrophilizable layer). The vinyl ether-maleic anhydride copolymer used in the hydrophilizable layer (surface layer) becomes water-soluble when it is ring-opened and hydrophilized, so that it is compatible with other hydrophobic resins. Even if a layer was formed in a molten state, its water resistance was extremely poor, and its printing durability was limited to 500 to 600 sheets at most.

On the other hand, JP-A-60-90343,
JP-A-60-159756, JP-A-61-217292 and the like disclose a method of providing a surface layer (hydrophilizable layer) containing silylated polyvinyl alcohol as a main component and a crosslinking agent in combination. That is, this layer is for hydrolyzing the silylated polyvinyl alcohol by hydrolyzing it in the non-image area after toner image formation. Further, in order to maintain the film strength after hydrophilization, the degree of silylation of polyvinyl alcohol is adjusted and the residual image hydroxyl groups are crosslinked with a crosslinking agent. And, it is described that, by these, the background stain property of the printed matter is improved and the number of printed sheets is improved. However, when actually evaluated, it is still unsatisfactory, especially in the case of scumming. Further, silylated polyvinyl alcohol is produced by silylating polyvinyl alcohol with a silylating agent to a desired ratio, but it is difficult to stably produce it 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 problems of the above electrophotographic lithographic printing plate precursor, the present inventors have
An electrophotographic lithographic printing plate precursor using a resin containing a functional group capable of generating a carboxyl group as a main component of the surface layer by decomposition has been proposed (JP-A-62-28345). Further, as the surface layer resin, a resin containing a functional group capable of generating a hydrophilic group upon decomposition and a compound capable of cross-linking the resin in the photosensitive layer are examined in combination, and for example, a functional group capable of generating a hydroxyl group upon decomposition. A group containing a group (JP-A-1-245970, JP-A-1-262556) and a group containing a functional group capable of generating a carboxyl group by decomposition (JP-A-1-28357, 1-2848).
No. 60), those containing a functional group that 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).

Further, it has been investigated to use a small amount of fine particles having a functional group capable of generating a hydrophilic group by decomposition in the surface layer and forming a higher order network structure. For example, those containing a functional group capable of generating a carboxyl group by decomposition (JP-A-2-13965), those containing a functional group capable of generating a hydroxyl group by decomposition (JP-A-2-13966), and sulfo by decomposition. A group containing a functional group that generates a group, a phosphono group, etc. (JP-A-2-13967) is disclosed. These binder resins or resin particles generate 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, it is possible to avoid deterioration of electrophotographic properties (dark charge retention amount and photosensitivity) and the like that occur when the hydrophilic group itself is contained from the beginning. The hydrophilicity of the non-image area which is hydrophilized by the desensitizing solution 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 the 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 hydrophilicized resin is It becomes water insoluble, and
Due to the cross-linking effect, the hydrophilic cross-linking resin containing water 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 prints with clear image quality without background stains.

[0007]

The resin of the type which produces a hydrophilic group by the above decomposition reaction is decomposed by a treatment liquid to decompose a carboxyl group or a hydroxyl group masked with a protecting group in advance, thereby leaving the protecting group. It is what makes them. Therefore, this type of resin remains stable without being hydrolyzed under the influence of atmospheric humidity (moisture) during storage, and during the hydrophilization treatment, the deprotecting group reaction proceeds rapidly to make it hydrophilic. It is required as an important property that a group can be generated and the hydrophilicity of the non-image area can be improved. However, if a hydrophilic group-forming functional group (protective group) that stably exists without being decomposed even under severe conditions such as long-term storage in a hot and humid environment is used, rapid decomposition by the treatment liquid and rapid development of hydrophilicity will occur. It turns out that there are difficulties. In view of such a current situation, the present invention is more effective due to the hydrophilicity of the non-image area,
Another object of the present invention is to provide a lithographic printing plate precursor that is stable even when stored under extremely harsh conditions and that can easily exhibit hydrophilicity in a short time during hydrophilic treatment.

That is, the 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 obtain uniform stains as an offset original plate. Another object of the present invention is to provide a lithographic printing plate precursor that is excellent in desensitization and does not generate dot-like background stains.
Another object of the present invention is to provide a lithographic printing plate precursor having high printing durability, in which the hydrophilicity of the non-image area is sufficiently maintained and scumming does not occur even when the number of printed sheets is increased in printing. . Another object of the present invention is to provide a lithographic printing plate precursor having a clear and high-quality image even when the environment at the time of forming a copy image changes such as low temperature / low humidity or high temperature / high humidity. Another object of the present invention is to provide a lithographic printing plate precursor that is not easily affected by the types of sensitizing dyes that can be used in combination and has excellent electrostatic properties even in a scanning exposure system using a semiconductor laser beam.

[0009]

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

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

[0011]

[Chemical 4]

Is shown. ] And at least one polar group selected from acid anhydride groups.

[0013]

[Chemical 5]

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

[0015]

[Chemical 6]

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

[0017]

[Chemical 7]

[In the above formulas (Ia) and (Ib), T ₁ and T ₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, -COR ₄ or-
COOR ₅ (R ₄ and R ₅ each represent a hydrocarbon group having 1 to 10 carbon atoms), and L ₁ and L ₂ are each —COO—.
Represents a single bond or a connecting group having 1 to 4 connecting atoms for connecting the benzene ring. The present invention comprises a photoconductive layer containing a resin [A] as a binder resin, and further is obtained in the presence of a dispersion stabilizing resin containing a silicon atom and / or a fluorine atom. L] is a lithographic printing original plate for an electrophotographic plate making system using an electrophotographic photosensitive member provided with an uppermost layer (surface layer) containing L].

In the present invention, the non-aqueous dispersion resin particles [L] (hereinafter referred to as resin particles [L] containing the non-image part after forming a toner image (plate-making) in the uppermost layer according to a usual electrophotographic process are used. It may be abbreviated as []] to modify the lipophilic surface to a hydrophilic surface by a desensitizing treatment to obtain a printing original plate. Generally, in an electrophotographic photosensitive member, if a further layer (for example, a surface layer) is provided on the photoconductive layer for the purpose of improving the quality of the printed matter, electrostatic characteristics (especially photosensitivity, residual potential, etc.) are lowered, and fidelity is improved. Since various image reproducibility is deteriorated, various improvements are attempted, and the influence is great.

As a result of various studies, the inventor of the present invention has made it possible to improve the electrostatic characteristics of the photoconductive layer by using resin [A] as one of the problems. The faithful reproducibility of the copied image can be maintained, and the resin particles [L] of the present invention are produced in the presence of a dispersion stabilizing resin containing silicon atoms / fluorine atoms. By controlling the specific resin particles [L] to the surface layer, which is the uppermost layer, to the required minimum amount capable of efficiently utilizing for water retention, the conventional defects are overcome and the photoconductive layer is adversely affected. Water retention, printing durability, etc. can be improved. 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 2 important properties. It is one of the two. One is that the hydroxyl group protected by the desensitizing solution chemically reacts to generate a hydroxyl group.

Further, when the resin particles [L] can exhibit hydrophilicity and at the same time have a crosslinked structure in the resin particles [L], at this time, the resin particles [L] have hydrophilicity and are insoluble or sparingly soluble in water. It also has water swellability. As another one,
Transferred to the surface portion of the photoconductive layer by bonding a dispersion stabilizing resin containing at least a repeating unit containing a substituent having a strong lipophilicity, that is, a substituent containing at least one fluorine atom and / or a silicon atom. This causes a concentration phenomenon. The fluorine atom and / or silicon atom-containing polymer as a dispersion stabilizing resin is formed by physicochemical adsorption with an insoluble component [monofunctional monomer (C)], or by the above formula (II). In the case of the dispersion-stabilizing resin containing a polymerizable double bond group portion represented by, both polymer components are chemically bonded. As described above, due to both effects of concentrating the resin particles [L] on the surface portion and making the resin particles [L] hydrophilic by the desensitizing treatment, sufficient water retention of the non-image area of the surface layer is achieved. Is done.

The present invention also contains, as the binder resin for the photoconductive layer, a specific polymer component represented by the formula (I) and at least one of the specific polar groups is at one end of the main chain of the polymer. A low molecular weight polymer resin [A]. This improves the electrostatic characteristics. Further, when the resin [A] contains the above-mentioned general formulas (Ia) and (Ib), it becomes even better. Further, when the photoconductive zinc oxide particles, the spectral sensitizing dye, the resin particles [L] and the resin [A] are dispersed in the photoconductive layer, a specific polar group is bonded to the side chain of the polymer. The resin [A] having a molecular weight is adsorbed on the stoichiometric defects of the photoconductive zinc oxide, and the coating property and the adsorbed state for the interaction of the zinc oxide and the dye are appropriately adjusted to thereby effect the photoconductive oxidation. It is considered that the photoconductive zinc oxide is sufficiently dispersed and the agglomeration is controlled while the zinc trap is compensated and the humidity characteristic is dramatically improved. Particularly in the case of the conventional binder resin, when the kind of the spectral sensitizing dye is changed, the interaction such as adsorption is hindered, and the satisfactory electrophotographic characteristics cannot be obtained. However, when the resin [A] of the present invention is used, remarkably excellent performance can be satisfied even with a dye used for spectral sensitization for semiconductor laser light.

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 non-aqueous solvent-based dispersed resin particles of the present invention contain at least one functional group that decomposes to generate at least one hydroxyl group, and is a monofunctional monomer (C which is insoluble in the non-aqueous solvent after polymerization). A polymer component [abbreviated as polymer component (C)] containing a repeating unit containing a fluorine atom and / or a silicon atom as at least a substituent and being soluble in the non-aqueous solvent even after polymerization. It is obtained in the presence of a dispersion stabilizing resin consisting of The molecular weight of the dispersed resin particles is 10 ⁴ to 10 ⁶ , preferably 10 ^{4 to} 5 × 10 ⁵ . The proportion of the monomer (C) as a polymerization component in the resin particles is 30% by weight or more, preferably 50% by weight or more, and particularly preferably, the resin is for stabilizing the dispersion of the monomer (C) and the monomer (C). It is composed only of resin.

The solubility of the dispersion stabilizing resin of the present invention in the non-aqueous solvent may be, specifically, at least 5% by weight in 100 parts by weight of the solvent at 25 ° C. The weight average molecular weight of the dispersion stabilizing resin is 1 × 10 ³ to 1 × 10 ⁵ , preferably 2 × 10 ³ to
It is 5 × 10 ⁴ , particularly preferably 3 × 10 ³ to 2 × 10 ⁴ . When the weight average molecular weight of the dispersion stabilizing resin is less than 1 × 10 ³ , the generated dispersed resin particles agglomerate and fine particles having a uniform average particle diameter cannot be obtained. On the other hand, when it exceeds 1 × 10 ⁵ , the effect of the present invention that the water retention is improved while satisfying the electrophotographic characteristics when added to the surface layer is diminished.

In the total of the repeating units of the dispersion stabilizing resin of the present invention, the repeating unit having a substituent containing a fluorine atom and / or a silicon atom accounts for 30% by weight of the whole.
It is preferably contained above, more preferably 5
It is 0% by weight or more. When the amount of the above components of the present invention is less than 30% by weight based on the total weight, the effect of concentrating on the surface portion when the resin particles are dispersed in the surface layer is reduced, and as a result, the effect of improving water retention as the printing original plate is weakened. I will end up. As described above, the dispersion stabilizing resin is preferably contained in an amount of 1 to 50% by weight, more preferably 5 to 25%, based on the insoluble monomer (C).
Use by weight%. The amount of the resin particles of the present invention in the surface layer is 1 to 80% by weight in 100 parts by weight of the total composition of the surface layer,
It is preferably 5 to 60% by weight.

The resin particles [L] of the present invention dispersed in the surface layer will be described in more detail below. A monomer (C) containing at least one functional group that decomposes to form at least one hydroxyl group used in the present invention (hereinafter, simply referred to as a hydroxyl group-forming functional group-containing monomer (C)). There is also). The functional group contained in the hydroxyl group-forming functional group-containing resin of the present invention produces a hydroxyl group by decomposition, and the number of hydroxyl groups produced from one functional group may be one or two or more.

According to one preferred embodiment of the present invention, the hydroxyl group-forming functional group-containing resin has the general formula (IV):
It is a resin containing at least one functional group represented by [-OL]. In the general formula (IV) [-OL],
L is _{-Si (R 1 ') (R} 2') (R 3 '), - CO-
_{Y 1, -CO-Z-Y} 2, -CH = CH-CH 3, or

[0028]

[Chemical 8]

Represents However, R ₁ ′, R ₂ ′,
R ₃ ′, R ₄ ′, R ₅ ′ and R ₆ ′ may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group or —O—R ′.
(R 'represents a hydrocarbon group), Y ₁ and Y ₂ represent a hydrocarbon group, Z represents an oxygen atom, a sulfur atom or -N.
H represents a H group, and X represents a sulfur atom or an oxygen atom.

The functional group of the above general formula [-OL] produces a hydroxyl group by decomposition, which will be described in more detail below. L is _{-S i (R 1 ') (} R 2') (R
₃ ′), R ₁ ′, R ₂ ′ _, R ₃ ′
May be the same as or different from each other, preferably a hydrogen atom, or a linear or branched alkyl group having 1 to 18 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group). , Octyl group, decyl group, dodecyl group, octadecyl group, chloroethyl group, methoxyethyl group, methoxypropyl group, etc.), optionally substituted alicyclic group (eg cyclopentyl group, cyclohexyl group, etc.), optionally substituted Aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, fluorobenzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, 3-phenylpropyl group, etc.) or optionally substituted aromatic group ( For example, phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group. Group, dichlorophenyl group), or -O-R '(R' represents a hydrocarbon group, specifically the R ₁ 'R _2', the same substituents such as hydrocarbon groups of R ₃ ' ).

When L represents --CO--Y ₁ ,
Y ₁ is preferably a linear or branched alkyl group having 1 to 6 carbon atoms which may be substituted (eg, methyl group, trichloromethyl group, trifluoromethyl group, methoxymethyl group,
Phenoxymethyl group, 2,2,2-trifluoroethyl group, t-butyl group, hexafluoro-i-propyl group, etc.), optionally substituted aralkyl group having 7 to 9 carbon atoms (for example, benzyl group, phenethyl group, Methylbenzyl group, trimethylbenzyl group, heptamethylbenzyl group,
Methoxybenzyl group, etc.), optionally substituted carbon atoms of 6 to
12 aryl groups (eg phenyl, nitrophenyl, cyanophenyl, methanesulfonylphenyl,
And a methoxyphenyl group, a butoxyphenyl group, a chlorophenyl group, a dichlorophenyl group, a trifluoromethylphenyl group and the like).

When L represents --CO--Z--Y ₂ , Z represents an oxygen atom, a sulfur atom or a --NH-- linking group, and Y ₂ has the same meaning as Y ₁ described above. Furthermore, L is

[0033]

[Chemical 9]

In the case of representing, X represents an oxygen atom or a sulfur atom. _{R 4 ', R 5',} R 6 ' may be the same as or different from each other, specifically mentioned R ₁
~ Indicates the same contents as ₃ . At least one functional group selected from the group of general formula [-OL] used in the present invention is used.
The seed-containing monomer [C] can be easily synthesized by a conventionally known organic synthesis reaction. For example, edited by The Chemical Society of Japan, "New Experimental Chemistry Course, Volume 14, Synthesis and Reaction of Organic Compounds [V]", page 2497 (published by Maruzen Co., Ltd.),
J. F. W. McOmie "Protective g
roups in Organic Chemistr
y ”(Plenum Press. 1973),
T. W. Greene "Protective gro
ups in Organic Synthesis "
(John Wiley & Sons-Inters
Science, 1981) and the like, and can be produced by a synthetic reaction similar to the method of introducing a protecting group into a hydroxyl group.

More specifically, the monomer (C) having a functional group of the general formula [-OL] as described above will be specifically described. For example, a compound represented by the following general formula (V) can be mentioned.

[0036]

[Chemical 10]

In the formula (V), X'is --O--, --CO--,-.
COO -, - OCO -, - N (Q 1) CO -, - CON
_{(Q 2) -, - SO} 2 -, - SO 2 N (Q 3) -, - N
_{(Q 4) SO 2 -,} - CH 2 COO -, - CH 2 OCO
-, - _{[C (g 1) (g 2} ) ] _n -, an aromatic group, or a heterocyclic group _{[where, Q 1, Q 2, Q} 3, Q 4 are each a hydrogen atom, a hydrocarbon group, Or-[Y'-O in the formula (V)
-L], g ₁ and g ₂ may be the same or different, and are a hydrogen atom, a hydrocarbon group or (Y'- in the formula (V).
O-L), and n represents an integer of 0 to 18].

Y'represents a carbon-carbon bond which may pass through a hetero atom connecting the bonding group X'and the bonding group [-OL] (the hetero atom includes an oxygen atom, a sulfur atom or a nitrogen atom). ), For example-[C (g ₃ )
(G _{4)] -, - C 6 H 10 -} , - C 6 H 4 -, - (CH
= CH) -, - O - , - S -, - N (g 5) -, - CO
O -, - CONH -, - SO 2 -, - SO 2 NH -, -
NHCOO -, - NHCONH- which has the constitution alone or in combination of binding units, such as (but g _3, g _4,
g ₅ has the same meaning as g ₁ and g ₂ ).

L has the same meaning as in formula (IV).
d ₁ and d ₂ may be the same or different, and a hydrogen atom,
A hydrocarbon group (for example, an alkyl group having 1 to 12 carbon atoms which may be substituted with -COOH or the like), -COOH or -CO
O-W [W represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aromatic group which may be substituted with a substituent containing a general formula (-OL) group. ]] Is represented.

More specifically, the following compound examples can be given as the monomer containing a functional group of the general formula [-OL]. However, Me represents a methyl group.

[0041]

[Chemical 11]

[0042]

[Chemical formula 12]

[0043]

[Chemical 13]

[0044]

[Chemical 14]

[0045]

[Chemical 15]

[0046]

[Chemical 16]

[0047]

[Chemical 17]

According to another preferred embodiment of the present invention, the hydroxyl group-forming functional group-containing resin has a functional group having at least two hydroxyl groups sterically close to each other simultaneously protected by one protecting group. Is a resin containing at least one. Examples of the functional group having in a protected form at least two hydroxyl groups sterically close to each other include, for example, the following general formula (V
Examples thereof include those represented by I), (VII), (VIII) and (IX).

[0049]

[Chemical 18]

In the formula (VI), J ₁ and J ₂ may be the same or different from each other and are a hydrogen atom, a hydrocarbon group or --O--O.
-R "(R" represents a hydrocarbon group) and U represents a carbon-carbon bond which may be bonded via a hetero atom (provided that
The number of atoms between oxygen atoms is 5 or less).

[0051]

[Chemical 19]

[0052]

[Chemical 20]

[0053]

[Chemical 21]

In the formula (IX), J ₁ and J ₂ are as defined above. J ₃ is a hydrogen atom or an aliphatic group having 1 to 8 carbon atoms (for example, an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, or a benzyl group, a phenethyl group, a methylbenzyl group, a methoxybenzyl group, a chloro group). Represents an aralkyl group such as a benzyl group).

The functional group will be described in more detail below. In formula (VI), J ₁ and J ₂ may be the same or different from each other, preferably a hydrogen atom and a carbon number of 1
To 12 optionally substituted alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, 2
-Methoxyethyl group, octyl group, etc.), aralkyl group having 7 to 9 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, methylbenzyl group, methoxybenzyl group,
Chlorobenzyl group, etc.), alicyclic group having 5 to 7 carbon atoms (eg, cyclopentyl group, cyclohexyl group, etc.), and optionally substituted aryl group (eg, phenyl group, chlorophenyl group, methoxyphenyl group, methylphenyl group, cyanophenyl group) Group or the like) or --O--R ″ ″ (R ″ ″ is J ₁ ,
J ₂ has the same meaning as the hydrocarbon group).

U represents a carbon-carbon bond which may pass through a hetero atom, and the number of atoms between oxygen atoms is within 5. As described above, at least two hydroxyl groups should be 1
The monomer (C) having a form protected with one protecting group can be synthesized by the method described in the same known technical literature as cited in the above-mentioned method of synthesizing [-OL].

More specifically, examples of the monomer containing the functional group are as follows. However, a is −
H or an -CH _3.

[0058]

[Chemical formula 22]

[0059]

[Chemical formula 23]

[0060]

[Chemical formula 24]

[0061]

[Chemical 25]

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

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

R ₃ is an optionally substituted alkyl group having 1 to 18 carbon atoms (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 above-mentioned hydrocarbon group for R ₃ . 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.

[0068]

[Chemical formula 26]

[0069]

[Chemical 27]

[0070]

[Chemical 28]

[0071]

[Chemical 29]

[0072]

[Chemical 30]

[0073]

[Chemical 31]

[0074]

[Chemical 32]

[0075]

[Chemical 33]

[0076]

[Chemical 34]

[0077]

[Chemical 35]

[0078]

[Chemical 36]

[0079]

[Chemical 37]

[0080]

[Chemical 38]

[0081]

[Chemical Formula 39]

[0082]

[Chemical 40]

Further, the dispersion stabilizing resin [P] 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 heterocycles such as pyran ring, pyradrine ring, imidazole ring, pyridine ring, etc.), vinyl group-containing carboxylic acids and their esters (eg acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid) Acid and its ester), vinyl group-containing carboxamides (for example, 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 polymer component containing a fluorine atom and / or a silicon atom is 30 parts by weight or more, preferably 50 parts by weight or more based on 100 parts by weight of the total polymer of the resin. Further, in the dispersion stabilizing resin of the present invention, the light and / or thermosetting functional group may be contained in an amount of 30 parts by weight or less, preferably 20 parts by weight or less based on 100 parts by weight of the total polymer of the resin. Good. 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 described below.

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

[0086]

[Chemical 41]

In the general formula (II), V ₀ is -O-,-
COO −, −OCO −, −CH ₂ OCO −, −CH ₂ COO −, −SO
_{2 -, - CONR 1 -,} - SO 2 NR 1 - or -C ₆ H ₄ - represents a.

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).

[0089] V ₀ is -C ₆ H ₄ - may represent a benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group) Group, ethoxy group, propoxy group, butoxy group, etc.) and the like. b ₁ and b ₂ are
They may be the same or different from each other, preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, an alkyl group having 1 to 4 carbon atoms (eg a methyl group, an ethyl group, a propyl group, butyl). Group etc.)-COO-R ₂ or COOR ₂ via a hydrocarbon (R ₂ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, May be substituted, and specifically represents the same contents as those described for R ₁ above).

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

That is, as the polymerizable double bond group component represented by the general formula (II), specifically, CH ₂ ═CH—CO—O—, CH
₂ = C (CH ₃ ) -CO-O-, C (CH ₃ ) H = CH-CO-O-, CH ₂ = C (CH
₂ COOCH ₃ ) -CO-O-, CH ₂ = C (CH ₂ COOH) -CO-O-, CH ₂
= CH-CONH-, CH ₂ = C (CH ₃ ) -CONH-, C (CH ₃ ) H = CH-CONH
-, CH ₂ = CH-O-CO-, CH ₂ = CH-CH ₂ -O-CO-, CH ₂ = CH-O
-, CH ₂ = C (COOH) -CH ₂ -CO-O-, CH ₂ = C (COOCH ₃ ) -CH _2-
CO-O-, CH ₂ = CH-C ₆ H _4- and the like can be mentioned. The polymerizable double bond group moiety represented by the above general formula (II) is directly bonded to 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. They are bound to each other or bound by any linking group. A divalent organic residue and specifically as linking to group, -O -, - S -, - Nq 1 -, - SO-,
−SO ₂ −, −COO −, −OCO −, −CONHCO−, −NHCONH
−, −CONq ₂ −, −SO ₂ Nq ₃ − and −Si (q ₄ ) (q ₅ ) −
Represents a divalent aliphatic group, a divalent aromatic group, or an organic residue composed of a combination of these divalent residues, which may have a bonding group selected from Where q
_{1 to} q ₅ represent the same contents as R ₁ in the formula (II). As the divalent aliphatic groups, such as _{- C (q 6) (q} 7)
−, −C (q ₆ ) ＝ C (q ₇ ) −, − (C≡C) −, −C ₆ H ₁₀
-,

[0092]

[Chemical 42]

{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, etc.) 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, 1,3-
Examples thereof include an oxazoline ring.

The above-mentioned polymerizable double bond group-containing moiety is specifically bonded only in the polymer chain, or a polymerizable dipolymer bond group is formed only at one end of the main chain of the polymer chain. A polymer in which the containing portion is bound (hereinafter referred to as a monofunctional polymer [M]
Abbreviated). The above monofunctional polymer [M]
Specific examples of the polymerizable double bond group component represented by the general formula (II) and a part composed of an organic residue linked thereto include the following, but are not limited to these. Absent. However, in each of the following examples, P ₁ is -H,-
CH ₃ , -CH ₂ COOCH ₃ , -Cl, -Br or -CN is shown, P
₂ represents -H or -CH ₃ , X represents -Cl or -Br,
n shows the integer of 2-12 and m shows the integer of 1-4.

[0096]

[Chemical 43]

[0097]

[Chemical 44]

[0098]

[Chemical 45]

[0099]

[Chemical 46]

[0100]

[Chemical 47]

[0101]

[Chemical 48]

The dispersion stabilizing resin of the present invention preferably contains a polymerizable double bond group moiety 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, a polymer reaction by a combination of a functional group of group A and a functional group of group B in Table 1 below is a well known method. In addition, R ₂₁ and R _{22 in} Table-1
Are each a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 7 carbon atoms (preferably, for example, a methyl group, an ethyl group,
Propyl group, butyl group, 2-chloroethyl group, 2-hydroxyethyl group, 3-bromo-2-hydroxypropyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 3-sulfopropyl group ,
Benzyl group, sulfobenzyl group, methoxybenzyl group,
Carboxybenzyl group, phenyl group, sulfophenyl group, carboxyphenyl group, hydroxyphenyl group, 2
-Methoxyethyl group, 3-methoxypropyl group, 2-methanesulfonylethyl group, 2-cyanoethyl group, N, N
(Dichloroethyl) aminobenzyl group, N, N (dihydroxyethyl) aminobenzyl group, chlorobenzyl group,
And a methylbenzyl group, N, N (dihydroxyethyl) aminophenyl group, methanesulfonylphenyl group, cyanophenyl group, dicyanophenyl group, acetylphenyl group and the like.

[0105]

[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. 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) and at least the repeating unit containing a silicon atom- and / or fluorine atom-containing substituent for stabilizing the dispersion. It is a copolymer resin particle obtained by dispersion polymerization in the presence of a resin.

Furthermore, when the dispersed resin particles of the present invention have a network structure, the polar group-containing monofunctional monomer (C) is used as a polymerizable component [abbreviated as polymer component (C)]. The polymers are bridged between polymers to form a high-order network structure. That is, the dispersed resin particle of the present invention is 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 insoluble portion 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 which are usually 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.

Polymerization of a polyfunctional monomer (also referred to as polyfunctional monomer (D)) or a polyfunctional oligomer containing two or more polymerizable functional groups which are coexistent in the above method (b). the sexual functional group, in particular _{CH 2 = CH-CH 2 -} , CH 2 = CH-CO-O-,
_{CH 2 = CH-, CH 2 =} C (CH 3) -CO-O-,
_{CH (CH 3) = CH-} CO-O-, CH 2 = CH-C
_{ONH-, CH 2 = C (CH} 3) -CONH-, CH
_{(CH 3) = CH-CONH-} , CH 2 = CH-O-C
_{O-, CH 2 = C (CH} 3) -O-CO-, CH 2 = C
_{H-CH 2 -O-CO-,} CH 2 = CH-NHCO-,
_{CH 2 = CH-CH 2 -NHCO-} , CH 2 = CH-S
_{O 2 -, CH 2 = CH} -CO-, CH 2 = CH-O-,
CH ₂ = CH-S-, and the like. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, a styrene derivative such as divinylbenzene or trivinylbenzene as a monomer or oligomer having the same polymerizable functional group: polyvalent. Alcohol (eg ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 20
0, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or polyhydroxyphenols (eg, 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 the 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, and 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 5 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, monodisperse particles having a uniform particle size are obtained, and fine particles of 0.5 μm or less are easily obtained. Therefore, as a method for forming a network structure, a polyfunctional monomer is used. The method (b) using is preferred.

As described above, the network-dispersed resin particles of the present invention contain the repeating unit containing a repeating unit containing a functional group which decomposes to form a hydroxyl group, and has a structure in which molecular chains are bridged to a higher degree. It is composed of a polymer component insoluble in an aqueous solvent and a polymer component soluble in the non-aqueous solvent, containing at least a repeating unit having a fluorine atom- and / or silicon atom-containing substituent. The non-aqueous solvent used for producing the non-aqueous solvent-based dispersed resin particles has a boiling point of 200.
Any organic solvent may be used as long as it has a temperature of not higher than 0 ° C., and it may be used alone or in combination of two or more kinds.

Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, butanol, fluorinated alcohol, benzyl alcohol, acetone,
Ketones such as methyl ethyl ketone, cyclohexanone and diethyl ketone, ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate, hexane, octane, decane, dodecane and tridecane. , Aliphatic hydrocarbons having 6 to 14 carbon atoms such as cyclohexane and cyclooctane, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, methylene chloride, dichloroethane, tetrachloroethane, chloroform, methylchloroform, dichloropropane,
Examples thereof include halogenated hydrocarbons such as 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 diameter of the resin particles easily becomes 0.8 μm or less, and the particle diameter distribution is very narrow and monodisperse particles are obtained. can do.

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 ⁴ to 10 ⁶ ,
It is preferably 10 ^{4 to} 5 × 10 ⁵ .

In order to produce the dispersed 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, relative to 100 parts by weight of the non-aqueous solvent.
˜50 parts by weight. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the polymerizable compounds. The polymerization temperature is 30
˜180 ° C., preferably 40 to 120 ° C. The reaction time is preferably 1 to 15 hours. The non-aqueous dispersion resin produced according to the present invention as described above becomes fine particles having a uniform particle size distribution. The surface layer of the photoreceptor of the present invention comprises the above resin particles uniformly dispersed in the binder resin of the matrix, and the binder resin will be described in detail below.

As the binder resin for the surface layer of the present invention, all the conventionally known 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, 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. Specific examples thereof include the same as the group of crosslinkable compounds used for forming the crosslinked structure with the resin particles of the present invention. 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 by increasing the degree of structure, the film strength after desensitization of the surface layer and the water retention of the entire surface are controlled, Water retention is improved.

Furthermore, fine particles (for example, metal oxides) other than the resin particles of the present invention are contained in the surface layer within a range of 0.001 to 5 parts by weight based on the total amount of the composition for forming a surface layer. It may be contained. 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 constructing the surface layer is that the non-image area becomes 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. For this reason,
The printing plate has an image area made of lipophilic toner and a highly hydrophilic non-image area 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 one. 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 a hydroxyl group,
It develops hydrophilicity. Therefore, in the original plate of the present invention containing the resin particles in the surface layer, the lipophilicity of the image area and the hydrophilicity of the non-image area are clear due to the hydrophilicity of the non-image area which is hydrophilized by the desensitizing solution. Therefore, the printing ink is prevented from adhering to the non-image portion during printing. As a result, it becomes possible to print a large number of prints with clear image quality without background stains.

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

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

That is, in the conventional system using zinc oxide, a ferrocyanine compound is used as the main agent of the desensitizing solution for desensitizing zinc oxide, and this compound requires special handling management for preventing environmental pollution. What you need, and
Since the desensitized hydrophilized substance adheres to the printed matter, the amount consumed by printing many sheets at the time of printing,
It is customary to use by adding the desensitizing main agent to the immersion water for printing, but as a side effect, the usable types of color inks are limited, or it is possible to use neutral paper as the printing paper. There were problems such as difficulties.

On the other hand, in the system of the present invention, since the principle of desensitization is completely different, these problems can be easily solved. Next, the photoconductive layer of the electrophotographic photosensitive material of the present invention will be described. The photoconductive layer contains at least a photoconductor and a binder resin, and it is particularly preferable that the photoconductive layer contains at least one of the following resins [A] as the binder resin. In the resin [A], the weight average molecular weight is 1 × 10 ³ to 2 × 10 ⁴ , preferably 3 × 10 ³ to 1.
× 10 ^4, and a glass transition point of the resin (A) is preferably -30 ° C. to 110 ° C., more preferably -20 ° C. to 90
℃.

If the molecular weight of the resin [A] is less than 10 ³ , the film-forming ability will be deteriorated and sufficient film strength cannot be maintained. On the other hand, if the molecular weight is more than 2 × 10 ⁴ , the resin of the present invention will In particular, in the case of photoreceptors using near-infrared to infrared spectral sensitizing dye, fluctuations in dark decay retention rate and photosensitivity under severe conditions of high temperature / high humidity, low temperature / low humidity are somewhat large, and stable copying is possible. The effect of the present invention that an image is obtained is diminished. The proportion of the polymer component corresponding to the repeating unit of the general formula (I) of the resin [A] is 30% by weight or more, preferably 50 to 97% by weight, and the proportion of the polymer component containing a specific polar group is 0.5 to 15% by weight, preferably 1 to 10
% By weight.

The polar group content in the resin [A] is 0.5
If it is less than wt%, 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. Further, as the low molecular weight resin [A],
Specific substituents represented by the above general formulas (Ia) and (Ib) having a benzene ring or an unsubstituted naphthalene ring having a specific substituent at the 2-position and / or at the 2-position and the 6-position. Resin [A] containing a methacrylate component having (hereinafter, this low molecular weight compound is referred to as resin [A '])
Is preferred.

The content of the copolymerization component of the methacrylate corresponding to the repeating unit of the formula (Ia) and / or the formula (Ib) in the resin [A '] is 30% by weight or more, preferably 50 to 97% by weight. The proportion of the polar group-containing polymer component is 0.5 to 1 relative to 100 parts by weight of the resin [A '].
It is 5% by weight, preferably 1 to 10% by weight.

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

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

More preferably, the copolymer component corresponding to the repeating unit of the general formula (I) is a methacrylate component containing a specific aryl group represented by the general formula (Ia) and / or the general formula (Ib). The copolymer component (resin [A ']) represented is mentioned.

In the formula (Ia), preferred T ₁ and T
_{As 2} , each independently of one another, a hydrogen atom, a chlorine atom and a bromine atom, as a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms (for example, a methyl group,
Ethyl group, propyl group, butyl group, etc.), aralkyl group having 7 to 9 carbon atoms (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 (for example, phenyl group, tolyl group, xylyl group,
Bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and -COR ₀₄ and-
COOR ₀₅ (preferable R ₀₄ and R ₀₅ include those described as the above-mentioned preferable hydrocarbon group having 1 to 10 carbon atoms) can be mentioned.

[0140] formula (Ia) and (Ib), L ₁ and L ₂ is a direct bond or bond each -COO- and the benzene ring _{- (CH 2) n1 - (} n 1 represents an integer of 1 to 3 _{), - CH 2 OCO -,} - CH 2 CH 2 OCO -, -
_{(CH 2 O) m1 - (} m 1 represents an integer of 1 or 2), -
A linking group having 1 to 4 connecting atoms such as CH ₂ CH ₂ O-, etc., more preferably a direct bond or 1 to 2 connecting atoms.
There may be mentioned one linking group.

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

[0142]

[Chemical 49]

[0143]

[Chemical 50]

[0144]

[Chemical 51]

[0145]

[Chemical 52]

[0146]

[Chemical 53]

Next, the polar group bonded to one end of the polymer main chain of the low molecular weight resin [A] will be described. Polar _{group, -PO 3 H 2, -SO 3} H, -COOH, -P (=
It is preferable that at least one selected from O) (OH) R ₀₁ and a cyclic acid anhydride-containing group. -P (= O)
(OH) R ₀₁ group means that R ₀₁ is a hydrocarbon group or —OR
₀₂ group (R ₀₂ represents a hydrocarbon group), specifically R
₀₁ is an aliphatic group having 1 to 22 carbon atoms (for example, 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, fluorobenzyl group, methoxybenzyl group, etc.), or An optionally substituted aryl group (eg, phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyano group Phenyl group, acetamidophenyl group, acetylphen Group, a butoxyphenyl group and the like) and the like, R ₀₂ is the same contents as R _01.

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

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

These polar groups may be directly bonded to the ends of the polymer main chain or may be bonded via a linking group.
The linking group, but may be any binding group, for example, if specifically mentioned, - _{[C (d 1) (d 2} ) ]
-(D ₁ and d ₂ may be the same or different and each is a hydrogen atom, a halogen atom (chlorine atom, bromine atom, etc.), an OH group,
Cyano group, alkyl group, (methyl group, ethyl group, 2-chloroethyl group, 2-hydroxyethyl group, propyl group,
Butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl group, etc.),-(C
_{H (d 3) -CH (d} 4) ] - (d _3, d ₄ is d _1, d
Represents a ₂ same contents _{as), - C 6 H 10 -} , - C 6 H 5,
-O -, - S -, - N (d 5) - [d ₅ represents a hydrogen atom or a hydrocarbon group (hydrocarbon group, as specifically having 1 to 12 carbon atoms hydrocarbon group (e.g., methyl Group, ethyl group, propyl group, butyl group, hexyl group, octyl group,
Decyl group, dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group, methylbenzyl group, phenethyl group, phenyl group, tolyl group,
A chlorofer group, a methoxyphenyl group, a butylphenyl group, etc.)], -CO-, -COO-, -O.
_{CO -, - (d 5)} CON -, - SO 2 N (d 5) -,
_{-SO 2 -, - NHCONH -,} - NHCOO -, - N
HSO _2- , -CONHCOO-, -CONHCONH
-, A heterocycle (a 5- or 6-membered ring containing at least one kind of O, S, N or the like as a hetero atom, or a condensed ring thereof: a thiophene ring, a pyridine ring,
A furan ring, an imidazole ring, piperidine ring, morpholine ring and the like) or _{-Si (d 6) (d 7} ) - (d
₆ , d ₇ may be the same or different, and are a hydrocarbon group or-
It represents Od ₈ (d ₈ is a hydrocarbon group). Examples of these hydrocarbon groups include the same ones as those mentioned for d ₅ ) or the like, or a linking group constituted by a combination of these.

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

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

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

Examples of the polar group-containing copolymerization 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, g is 2 to
Indicates an integer of 10.

[0155]

[Chemical 54]

[0156]

[Chemical 55]

[0157]

[Chemical 56]

[0158]

[Chemical 57]

[0159]

[Chemical 58]

[0160]

[Chemical 59]

[0161]

[Chemical 60]

[0162]

[Chemical formula 61]

[0163]

[Chemical formula 62]

[0164]

[Chemical 63]

[0165]

[Chemical 64]

[0166]

[Chemical 65]

[0167]

[Chemical 66]

Furthermore, the low molecular weight resin [A] of the present invention
(Including [A ′]) is represented by the general formula (I) or (I
In addition to the monomer of a) and / or (Ib) and the monomer containing the polar group, another monomer other than these may be contained as a copolymerization component.

Examples of such other copolymerization component include, in addition to methacrylic acid esters, acrylic acid esters and crotonic acid esters having a substituent other than those described in the general formula (I), α-olefins. , Vinyl carboxylates or acrylic acid esters (for example, as carboxylic acid, acetic acid, propionic acid, butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (for example, Dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (for example, styrene, vinyltoluene, chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinyl chloride) Naphthalene), vinyl sulfone-containing compounds, vinyl ketones containing compounds, heterocyclic vinyl compounds (e.g., vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, vinylimidazoline,
Vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.) and the like.

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

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

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

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

Each of these chain transfer agents or polymerization initiators is added in an amount of 0.5 to 15 with respect to 100 parts by weight of all monomers.
Parts by weight, preferably 2 to 10 parts by weight. The low molecular weight resin [A] (including [A ′]) as described above is preferably used in combination with a known resin for conventional photoconductive zinc. The use ratio of the low molecular weight resin [A] and the other resin is preferably 5 to 50/95 to 50 (weight ratio). Other resins used in combination include a weight average molecular weight of 3 × 10 ^{4 to} 1 to
10 ⁶ , preferably 5 × 10 ^{4 to} 5 × 10 ⁵ medium to high molecular weight products. The glass transition point of the resin used in combination is −
It is 10 ° C to 120 ° C, preferably 0 ° C to 90 ° C.

For example, Ryuji Shibata, Jiro Ishiwatari, Kobunshi, No.
Volume 17, pp. 278 (1968), Harumi Miyamoto, Hide Takei
Hiko, Imaging,1973(No.8) Page 9, Nakamura
Koichi, "Practical Technology of Binders for Recording Materials", 10th
Chapter, C.I. H. C. Published (1985), D.M. Tat
t, S. C. Heidecker, Tappi,49
(No. 10), 439 (1966), E.I. S. Bal
tazzi R .; G. Blanclotte eta
l, Photo. Sci. Eng. ，16(No.
5), 354 (1972), Nguyen Chan Kae, Kiyo
Yu Mizumizu, Eiichi Inoue, The Institute of Electrophotography18(No. 2),
22 (1980), JP-B-50-51011, JP-A-5
3-54027, 54-20735, 57-202.
The materials disclosed in each publication of 544 and the like are listed.

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

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

[0178]

[Chemical 67]

[In the formula (III), V is —COO—, —O
_{CO -, - (CH 2)} h -OCO -, - (CH 2) h -
COO -, - O-or -SO ₂ - represents a. However, h is 1
In the general formula (III), f ₃ and f ₄ have the same contents as a ₁ and a ₂ in the formula (I). R ₀₇ is R in formula (I)
Indicates the same content as ₀₃ . The medium to high molecular weight binder resin containing the polymer component represented by the general formula (III) (hereinafter referred to as resin [B]) is, for example, a random copolymer containing the polymer component represented by the formula (III). Polymer resins (Japanese Patent Laid-Open Nos. 63-49817, 63-220149, 63-
220148, etc.), a combination resin of the random copolymer and a crosslinkable resin (JP-A-1-102573, etc.),
Graft type copolymer (JP-A-2-53064, 2-5)
(6558, etc.) and the like, and those of medium to high molecular weight compounds described in each specification.

The photoconductive compound used in the present invention may be either an inorganic compound or an organic compound. Examples of the inorganic compound used as the photoconductive compound of the present invention include conventionally known inorganic photoconductive compounds such as zinc oxide, titanium oxide, zinc sulfide, cadmium sulfide, selenium, selenium-tellurium, and lead sulfide. From a sex perspective
Zinc oxide and titanium oxide are preferred. When an inorganic photoconductive compound such as zinc oxide or titanium oxide is used as the photoconductive compound, the binder resin is contained in an amount of 10 to 100 parts by weight, preferably 100 parts by weight of the inorganic photoconductive compound. It is used in a proportion of 15 to 40 parts by weight.

On the other hand, the organic compound may be any of the conventionally known compounds, and specifically, the following two types are known as conventionally known examples as the electrophotographic lithographic printing plate precursor. Firstly, Japanese Patent Publications 37-17162 and 62-514.
62, JP-A Nos. 52-2437, 54-19803 and 5
No. 6-107246, No. 57-161863, etc., which has a photoconductive layer mainly composed of an organic photoconductive compound, a sensitizing dye, and a binder resin. 56-146145, 60-17751,
60-177752, 60-17760, 60-2
54142, 62-54266, etc., and has a photoconductive layer mainly composed of a charge generating agent, a charge transporting agent, and a binding resin. As a special case of the second example, JP-A-60-230147 and 60-23014.
A photoconductive layer having a two-layer structure in which a charge generating agent and a charge transporting agent are contained in separate layers as described in JP-A No. 60-238853 and No. 8, is also known. 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), "Organic Synthetic 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.
02 each specification, JP-A-51-90827, 52-5
Phthalocyanine pigments such as metal-free or metal phthalocyanines described in Japanese Patent Publication No. 5643, (3) US Pat.
No. 371884, Japanese Patent Application Laid-Open No. 47-30330, and the like, perylene pigments,

(4) Indigo and thioindigo derivatives described in British Patent No. 2237680 and Japanese Patent Laid-Open No. 47-30331, and (5) British Patent No. 22376.
No. 79, Japanese Patent Application Laid-Open No. 47-30332, etc., quinacridone pigment (6) British Patent No. 223767.
No. 8, JP-A-59-184348, JP-A-62-28.
738 and 47-18544, and the like, (7) JP-A-47-30331 and JP-A-47-
No. 18543, bisbenzimidazole-based pigments, and (8) U.S. Pat. Nos. 4,396,610 and 4,644.
082 Squalium salt-based pigments described in each specification,
(9) JP-A-59-53850 and JP-A-61-212542
Examples thereof include azurenium salt-based pigments described in each publication and the like. These may be used alone or in combination of two or more.

The mixing ratio of the organic photoconductive compound and the binder resin determines the upper limit of the content of the organic photoconductive compound due to the compatibility between the organic photoconductive compound and the binder resin, and the amount of addition exceeds the upper limit. 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 1 part of the above-mentioned binding resin per 100 parts by weight of the photoconductive compound.
It is used in a proportion of 0 to 100 parts by weight, preferably 15 to 50 parts by weight.

In the present invention, various dyes can be used together as a spectral sensitizer depending on the kind 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 disclosed in Japanese Examined Patent Publication No. 51-4.
52, JP-A-50-90334, 50-11422.
7, JP-A-53-39130, JP-A-53-82353, US Pat. Nos. 3,052,540 and 4,054,450, and JP-A-57-16456.

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

[0191] 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 , pages 117 to 118, and the like.

The photoconductor of the present invention is also excellent in that its performance is unlikely to vary depending on the sensitizing dye even when various sensitizing dyes are used in combination. Furthermore, various conventionally known additives for electrophotographic photoreceptors can be used in combination, if necessary.

These additives include chemical sensitizers for improving electrophotographic sensitivity, various plasticizers for improving film properties, surfactants and the like.

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

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibutyl sebacate, butyl laurate, methylphthalylethyl glycolate 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 thickness of the hydrophilizable surface layer of the present invention is 10
.mu.m or less, especially for the Carlson process.
It is preferably 1 to 5 μm. If it is thicker than 5 μm,
There may occur inconveniences such as a decrease in sensitivity of the lithographic printing original plate as an electrophotographic photoreceptor and an increase in residual potential. In order to actually produce the photoreceptor (printing original plate) of the present invention, generally, an electrophotographic photosensitive layer (photoconductive layer) is first formed on a conductive support according to a conventional method. Then, on this layer, the resin particles of the present invention, the binder resin, and if necessary, the above-mentioned additives and the like are dissolved or dispersed in a volatile hydrocarbon solvent having a boiling point of 200 ° C. or less, and this is applied and dried. Thus, the surface layer can be formed and manufactured.

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

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

With respect to the lithographic printing original plate having the toner image thus formed, the non-image portion is subjected to a desensitizing treatment to form a printing plate. The desensitizing treatment used in the present invention hydrophilizes the protected hydroxyl group by a decomposition reaction. The decomposition reaction is arbitrarily selected depending on the reactivity of the protected hydroxyl group. Specifically, as one of them, acidic conditions of pH 1 to 6 or pH 8
The method of hydrolyzing with an aqueous solution under alkaline conditions of Nos.

The adjustment of these pHs can be easily adjusted with known compounds. Alternatively, a method by a redox reaction with a reducing or oxidizing water-soluble compound is also possible, and known compounds can be used as these compounds, for example, hydrous hydrazine, sulfite, lipoic acid, hydroquinones, formic acid, thiol. Examples thereof include sulfates, hydrogen peroxide, persulfates, quinones and the like.

The treatment liquid may contain other compounds in order to accelerate the reaction or improve the storage stability of the treatment liquid. For example, 1 to 50 parts by weight of a water-soluble organic solvent may be contained in 100 parts by weight of water. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, 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.

Further, 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 processing condition is a temperature of 15 ° C
The immersion time at 60 ° C. is preferably 10 seconds to 5 minutes. Further, as a method of decomposing a specific functional group by irradiation with light, a step of irradiating with a "chemically active light beam" may be included between any of the steps after obtaining a toner image in plate making. That is, after electrophotographic development, light irradiation may be performed for fixing when fixing a toner image, or light may be applied after fixing by other conventionally known fixing methods such as heat fixing, pressure fixing and solvent fixing. Irradiation is performed.

The "chemically active rays" used in the present invention include visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays,
Either γ rays or α rays may be used, but ultraviolet rays are preferable. More preferably from wavelength 310 nm to wavelength 5
Those that can emit light in the range of 00 nm are preferable, and generally, a high-pressure or ultra-high-pressure mercury lamp or the like is used. The process of light irradiation is usually 1 from a distance of 5 cm to 50 cm.
Irradiation for 0 seconds to 10 minutes can be sufficiently performed.

[0208]

EXAMPLES Examples of the present invention will be illustrated below, but the scope of the present invention is not limited thereto. The production examples of the dispersion stabilizing resin (monofunctional polymer) for resin particles and the resin particles are specifically described below.

Production Example 1 of dispersion stabilizing resin (monofunctional polymer): [P-1] 95 g of 2,2,2,2 ', 2', 2'-hexafluoroisopropyl methacrylate, 5 g of thioglycolic acid and A mixed solution of 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 dispersion stabilizing resin [P-1] was 4000.

[0210]

[Chemical 68]

Production Example 2 of Dispersion Stabilizing Resin (Monofunctional Polymer): [P-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 dispersion stabilizing resin obtained by drying the precipitated viscous material had a yield of 60 g and a weight average molecular weight of 5.2 × 10 ³ .

[0212]

[Chemical 69]

[0213]

[Chemical 70]

Production Example 3 of Dispersion Stabilizing Resin (Monofunctional Polymer): [P-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 dispersion stabilizing resin [P-3] was 3.3 × 10 ⁴ .

[0215]

[Chemical 71]

[0216]

[Chemical 72]

Production Examples 4 to 22 of dispersion stabilizing resin (monofunctional polymer): [P-4] to [P-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 [P] 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 .

[0218]

[Table 2]

[0219]

[Table 3]

[0220]

[Table 4]

[0221]

[Table 5]

Production Examples 23 to 30 of dispersion stabilizing resin (monofunctional polymer): [P-23] to [P-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 [P] was manufactured by the same method. Each weight average molecular weight was 5 × 10 ^{3 to} 6 × 10 ³ .

[0223]

[Table 6]

[0224]

[Table 7]

[0225]

[Table 8]

Production Example 31 of dispersion stabilizing resin: [P-3
1] 37 g of octyl methacrylate, a 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 .

[0227]

[Chemical 73]

Production Example 32 of dispersion stabilizing resin: [P-3
2] 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 heated to a temperature of 60 ° C while stirring under a nitrogen stream. 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 .

[0229]

[Chemical 74]

Dispersion Stabilizing Resin Production Examples 33 to 39: [P
-33] to [P-39] By carrying out the reaction as shown in Production Example 32, 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 .

[0231]

[Table 9]

[0232]

[Table 10]

[0233]

[Table 11]

Production Example of Resin Particles 1: [L-1] 10 g of dispersion stabilizing resin [P-32] and n-octane 2
While stirring the mixed solution of 00g under a nitrogen stream, the temperature is 60 ° C.
Warmed to. To this, 50 g of the following monomer [C-1], 5 g of ethylene glycol dimethacrylate, A. I. V.
N. A mixed solution of 0.5 g and 240 g of n-octane was added dropwise over 2 hours, and the reaction was continued for 2 hours. In addition, 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. {: Measure particle size with CAPA-500 [manufactured by Horiba, Ltd.]}

[0235]

[Chemical 75]

Production Examples 2-11 of Resin Particles: [L-2]-
[L-11] Production Example 1 except that the monomer [C-1] and the dispersion stabilizing resin [P-32] in Production Example 1 of resin particles were replaced with the respective compounds shown in Table 5 below. Resin particles were produced in the same manner as in. The average particle size of each particle was within the range of 0.15 to 0.30.

[0237]

[Table 12]

[0238]

[Table 13]

Production Example 12 of resin particles: [L-12] Dispersion stabilizing resin AK-6 [manufactured by Toagosei Co., Ltd. Macromonomer: Macromonomer having dimethylsiloxane structure as repeating unit: weight average molecular weight 1.5 ×] 10 ⁴ ] 7.5
A mixed solution of g and 133 g of methyl ethyl ketone was heated to 60 ° C. with stirring under a nitrogen stream. To this, 50 g of the following monomer [C-12], 5 g of diethylene glycol dimethacrylate, A. I. V. N. A mixed solution of 0.5 g and 150 g of methyl ethyl ketone was added dropwise over 1 hour, and A. I. V. N. 0.25 g was added and reacted for 2 hours.

After cooling, the average particle size of the dispersion obtained through a 200-mesh nylon cloth was 0.18 μm.

[0241]

[Chemical 76]

Production Example 13 of Resin Particles: [L-13] A mixed solution of 7.5 g of the dispersion stabilizing resin [P-35] and 230 g of methyl ethyl ketone was heated to 60 ° C. while stirring under a nitrogen stream. In addition to this, the monomer [C-13] 35
g, acrylamide 15 g I. V. N. 0.5
g and 200 g of methyl ethyl ketone were added dropwise over 2 hours, and the reaction was continued for 1 hour. Furthermore, A.
I. V. N. After adding 0.25 g and reacting for 2 hours, the mixture was cooled and passed through a 200-mesh nylon cloth, and the average particle size of the obtained dispersion was 0.20 μm.

[0243]

[Chemical 77]

Production Example 14 of Resin Particles: [L-14] 50 g of monomer [C-14], 2 g of ethylene glycol diacrylate, 8 g of dispersion stabilizing resin [P-33] and 230 g of dipropyl ketone were used in a nitrogen stream. The solution was added dropwise to a solution of 200 g of dipropyl ketone heated to a lower temperature of 60 ° C. over 2 hours while stirring. After reacting for 1 hour as it is, A.
I. V. N. 0.3 g was added and reacted for 2 hours. The average particle size of the dispersion obtained after passing through a 200-mesh nylon cloth after cooling was 0.28 μm.

[0245]

[Chemical 78]

Production Examples 15-25 of Resin Particles: [L-1
5] to [L-25] In the same manner as in Production Example 14, except that the polyfunctional compound shown in Table 6 below was used in place of 2 g of ethylene glycol diacrylate in Production Example 14 of resin particles, −
15] to [L-25] were produced. Each particle had a polymerization rate of 95 to 98% and an average particle diameter of 0.15 to 0.25 μm.

[0247]

[Table 14]

Production Examples 26-31 of Resin Particles: [L-2
6] to [L-31] In Production Example 12 of resin particles, the dispersion stabilizing resin AK-
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 in place of No. 6. The average particle size of each particle was in the range of 0.20 to 0.25.

[0249]

[Table 15]

Production Examples 32 to 35 of Resin Particles: [L-3
2]-[L-35] In Production Example 13 of resin particles, Production Example 13 except that each compound of the following Table 8 was used in place of the monomer [C-13] acrylamide and the reaction solvent: methyl ethyl ketone.
Each particle was manufactured in the same manner as in. The average particle size of each particle was in the range of 0.15 to 0.30.

[0251]

[Table 16]

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

[0253]

[Chemical 79]

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

[0255]

[Table 17]

[0256]

[Table 18]

[0257]

[Table 19]

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

[0259]

[Table 20]

[0260]

[Table 21]

[0261]

[Table 22]

Synthesis Example 25 of resin [A]: [A-25] 1-naphthyl methacrylate 95.5 g, methacrylic acid 0.5 g, toluene 150 g and isopropanol 50.
The mixed solution of g was heated to a temperature of 80 ° C. under a nitrogen stream.
4,4'-azobis (4-cyano) valeric acid (abbreviation A.
C. V. ) 5.0 g was added and stirred for 5 hours. Furthermore, A.
C. V. 1 g was added for 2 hours, and then A. C. V. 1 g was added and stirred for 3 hours. The weight average molecular weight of the obtained polymer was 7.5 × 10 ³ .

[0263]

[Chemical 80]

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

[0265]

[Chemical 81]

Synthesis Example 27 of Resin [A]: [A-27] 95 g of benzyl methacrylate, 4 g of thioglycolic acid
And a mixed solution of 200 g of toluene under a nitrogen stream at a temperature of 7
Warmed to 5 ° C. A. C. V. 1.0 g was added and reacted for 6 hours, and then A. C. V. 0.4 g was added and reacted for 3 hours. The weight average molecular weight of the obtained copolymer was 7.8 ×.
It was 10 ³ .

[0267]

[Chemical formula 82]

Example 1 and Comparative Examples AB (Example 1) 6 g (as solid content) of resin [A-5],
34 g of resin [B-1] having the following structure (as solid content),
A mixture of 200 g of photoconductive zinc oxide, 0.017 g of the methine dye [I] having the following structure, 0.15 g of salicylic acid and 300 g of toluene was mixed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 8 × 10 ³ r.p. p. m. At 10 rpm
Dispersed for minutes. This photosensitive layer-forming dispersion was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ^2, and dried at 100 ° C. for 30 seconds.

[0269]

[Chemical 83]

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.

[0271]

[Chemical 84]

Then, an electrophotographic light-sensitive material was prepared by leaving it in the dark at 20 ° C. and 65% RH for 24 hours. (Comparative Example A) The same operation as in Example 1 was carried out except that only 40 g of resin [B-1] was used instead of 6 g of resin [A-5] and 34 g of resin [B-1] in Example 1. An electrophotographic photosensitive material was produced. (Comparative Example B) Comparative Dispersion Resin Particles: LR-1 Production Example 1 of Resin Particles In Production Example 1 except that the resin having the following structure was used in place of 10 g of the dispersion stabilizing resin P-32 in L-1. It was synthesized in the same manner as 1. The average particle size of the obtained latex was 0.17 μm.

[0273]

[Chemical 85]

Comparative Photoreceptor In Example 1, instead of 1.0 g of the resin particles [L-1] of the surface layer toluene dispersion, resin particles [LR-1] were used.
An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that 1.0 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 The printing property is a lithographic plate obtained by subjecting a fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) to the developer ELP-T to form an image by exposure and development and desensitizing. It examined using the printing plate. (Note that the printer used was a Hamada Star 800SX model manufactured by Hamada Star Co., Ltd.) The above results are summarized in Table-11.

[0275]

[Table 23]

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 100 seconds was measured, and the potential retention after dark decay for 90 seconds, that is, the dark decay retention rate [D. R. R. The (%)], (V ₁₀₀ /
It was determined by V ₁₀ ) × 100 (%).

Also, the surface of the photoconductive layer was-
After being charged to 400 V, irradiation with monochromatic light having a wavelength of 780 nm is performed, and the time until the surface potential V ₁₀ is attenuated to 1/10 is obtained, and the exposure amount E _1/10 (erg / cm ² ) is calculated from this. The condition of a temperature of 20 ° C. and 65% RH was set to I, and the same evaluation was performed under the environmental conditions of a temperature of 30 ° C. and 80% RH, and this was set to II. Note 3) Imaging: Each light-sensitive material was left for one day under the following environmental conditions. Next, it is charged at -5kV and 2.0m as a light source.
Using a W output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm), on the surface of the photosensitive material,
After speed exposure under a dose of 45 erg / cm ² at a pitch of 25 μm and a scanning speed of 330 m / sec, ELP-T (Fuji Photo Film Co., Ltd.) was used as a liquid developer.
The copied image (fog, image quality of the image) obtained by developing and fixing was visually evaluated. Note 4) Raw plate water retentivity: Each light-sensitive material itself was immersed for 3 minutes in a desensitizing solution E-1 having the following formulation (original plate not made into a plate: abbreviated as a raw plate). These plates were printed on a Hamada Star 8005X type manufactured by Hamada Star Co., Ltd. using distilled water as dampening water, and the presence or absence of background stains on the 50th printed sheet after printing was visually evaluated. Desensitizing treatment liquid: E-1 monoethanolamine 60 g Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 8 g Benzyl alcohol 100 g was diluted with distilled water to a total volume of 1.0 liter, and the pH was adjusted to 11.0 with potassium hydroxide. It was adjusted. Note 5) Stain on printed matter: E used in Note 4) at a temperature of 40 ° C. after plate-making each photosensitive material by the same operation as Note 3) above.
After immersing in the treatment liquid of -1 for 3 minutes, it was used as fountain solution E-
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 could be 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 photoconductors was subjected to a desensitizing treatment to evaluate the degree of hydrophilicity of the non-image area (water-holding capacity of the original plate). The conversion was not done enough.

Further, after the plate was actually made and then desensitized, the planographic printing plate of the present invention showed no scumming even when neutral paper was used as a printing paper, and showed a clear print quality of an image. 5,000 prints were obtained. 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 the resin particles [L] of the invention of the surface layer
Only the above exhibits sufficient hydrophilicity and does not cause ink adhesion to the non-image area. 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, 6 g of resin [A-5] and resin [B-
1] 34 g, methine dye [I] 0.017 g and resin particles [L-1] 1.0 g, instead of resin [A-19] 4
g, resin [B-2] having the following structure: 35.0 g, methine dye [II] 0.020 g having the following structure, and resin particles [L-2]
An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that 0.8 g was used.

[0281]

[Chemical formula 86]

Each property 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: -730V D. R. R. : 78% E _1/10 : 41 erg / cm ² Imaging property: Good (○) Water retention of original plate: 〃 (○) Stain of printed matter: No background stain up to 5,000 sheets E-1 used in 1
In place of the above, the desensitizing treatment liquid E-2 having the following formulation was used.

Desensitizing treatment liquid: E-2 Diethanolamine 80 g Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 8 g Methyl ethyl ketone 100 g was dissolved in distilled water to a total volume of 1.0 liter and adjusted to pH 11.5 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 14 Instead of the resin particles [L], resin [A] and resin [B] used in Example 1, 0.9 g of the resin particles [L] of the present invention shown in Table 12 below. Each photosensitive material was prepared in the same manner as in Example 1 except that (as the solid content) and 5 g of the resin [A] or 34 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.

[0285]

[Chemical 87]

[0286]

[Table 24]

With respect to each of the light-sensitive materials, the electrostatic property and the printing property were measured by operating in the same manner as in Example 1. All were excellent in chargeability, dark charge retention rate and photosensitivity, and the actual copied image was high 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 15 to 18 Photosensitive materials were prepared in the same manner as in Example 1 except that the dyes shown in Table 13 below were used instead of the methine dye [I].

[0289]

[Table 25]

[0290]

[Table 26]

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 19 to 21 Resin [A] 6.0 g shown in Table 14 below, binder resin [B-4] 34.0 g having the following structure, photoconductive zinc oxide 200 g,
A mixture of 0.03 g of uranin, 0.06 g of rose bengal, 0.02 g of tetrabromophenol blue, 0.18 g of N-hydroxymaleinimide and 300 g of toluene was dispersed in a ball mill for 6 hours. When the dispersion for forming a photosensitive layer was applied with a conductive treatment, the dry adhesion amount was 22 g / m ^2.
And a wire bar, and dried at 100 ° C. for 3 minutes to prepare an electrophotographic photosensitive material.

[0293]

[Chemical 88]

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 140 ° C. for 30 minutes to form a surface layer of about 2 μm. Toluene dispersion for surface layer Resin [B′-2] having the following structure 6 g Resin particle [L] in Table 14 below 0.9 g (as solid content) 1,2,4,5-benzenetetracarboxylic dianhydride 0.02 g Acetylacetone zirconium salt 0.0015 g was added to toluene to make the total amount 100 g.

[0295]

[Chemical 89]

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-14.

[0298]

[Table 27]

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

Example 22 5 g of bisazo pigment having the following structural formula, and tetrahydrofuran 9
5 g and resin [A-1] 0.8% by weight and resin [B-
4] A mixture of 30 g of a 4.2 wt% tetrahydrofuran solution was thoroughly pulverized with a ball mill. Then, this mixture was taken out, and 520 g of tetrahydrofuran was added with stirring. This dispersion was coated on the conductive transparent support used in Example 1 by using a wire round rod to give a dispersion of about 0.
A 7 μm charge generation layer was formed.

[0301]

[Chemical 90]

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.

[0303]

[Chemical Formula 91]

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.

[0305]

[Chemical Formula 92]

This photosensitive material was immersed in a desensitizing solution (E-3) prepared according to the following formulation at a temperature of 40 ° C. for 3 minutes 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.
The total amount was adjusted to 0 to make 1.0 liter. Distilled water 2
It was 10 ° or less when a contact angle with the formed water was measured with a goniometer by placing μ liter of water droplets.
The contact angle before the desensitizing treatment was 95 °, which clearly shows that the surface layer of the present light-sensitive material was very favorably hydrophilized. This is a fully automatic plate-making machine EL as in Example 1.
When a plate was made with P404V using an ELP-T toner, the density of the obtained master plate for offset printing was 1.0 or more, and the image quality was clear.

Further, the master plate after master making was soaked in the desensitizing solution (E-4) prepared by the following formulation for 3 minutes 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 sodium hydroxide was added thereto to adjust the pH to 12.5. 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.

[0308]

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

Claims (4)

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