JP2632233B2 - Lithographic printing plate - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an electrophotographic lithographic printing original plate made by electrophotography, and in particular, to a composition for forming a photoconductive layer of the lithographic printing original plate. Regarding improvement of things.

(Prior art and its problems) At present, various types of lithographic printing original plates for direct plate making have been proposed and put into practical use. Among them, conductive particles such as zinc oxide and the like on a conductive support, A photoconductor provided with a photoconductive layer containing a binder resin as a main component is subjected to a normal electrophotographic process to form a highly lipophilic toner image on the surface of the photoconductor, and then the surface is insensitive to an etchant. A technique for obtaining an offset original plate by treating with a lipophilic liquid and selectively hydrophilizing a non-image portion is widely used.

The binder resin used to form the photoconductive layer of the lithographic printing plate precursor has, first of all, excellent film forming properties of itself and excellent dispersion ability of the term conductive powder in the binder resin, The adhesion of the formed recording layer to the substrate is good, and the photoconductive layer of the recording layer has excellent charging ability,
Various electrostatic characteristics such as low dark decay, large light decay, little pre-exposure fatigue, and it is necessary to stably maintain these characteristics due to changes in humidity during imaging, and excellent imaging It is necessary to have the property.

Second, in order to obtain good printed matter from the lithographic printing plate precursor, the surface of the photoreceptor is easily compatible with the desensitizing solution, the non-image area is sufficiently hydrophilized and has water resistance. In the above, the photoconductive layer having an image is not detached, and the affinity with the dampening solution is good, and the hydrophilicity of the non-image portion is sufficiently maintained so that no stain is generated even when the number of printed sheets is large. And the like. It is already known that the ratio of zinc oxide and binder resin in the photoconductive layer affects these performances.For example, if the ratio of binder resin to zinc oxide particles in the photoconductive layer is reduced, In addition, the desensitizing property of the surface of the photoconductive layer is improved, and the background dirt is reduced. On the other hand, the internal cohesion of the photoconductive layer itself is reduced, and the printing durability is reduced due to insufficient mechanical strength. Conversely, when the ratio of the binder resin is increased, the printing durability is improved, but the background stain is increased. In particular, it is needless to say that background contamination is a phenomenon related to the quality of the desensitizing property of the photoconductive layer surface, but the desensitizing property of the photoconductive layer surface is determined by the zinc oxide in the photoconductive layer and the binder resin. It has been clarified that the ratio is not influenced only by the ratio of the binder resin, but also greatly depends on the type of the binder resin.

As long-known resins, for example, silicone resins (Japanese Patent Publication No. 34-6670), styrene-butadiene resins (Japanese Patent Publication No. 35-1960), alkyd resins, maleic acid resins,
Polyamide (JP-B-35-11219), vinyl acetate resin (JP-B-41-2425), vinyl acetate copolymer (JP-B-41
No. 2426), an acrylic resin (Japanese Patent Publication No. 35-11216), and an acrylate copolymer (for example, Japanese Patent Publication No. 35-11219).
Nos. JP-B-36-8510, JP-B-41-13946, etc.) are known. However, in an electrophotographic lithographic printing plate using these resins, 1) the affinity for the photoconductive powder is insufficient, and the dispersibility of the coating liquid is poor. Poor chargeability 3) Poor quality of image portion of copied image (particularly halftone dot reproducibility / resolution) 4) Image quality is easily affected by environment (for example, high temperature, high humidity, low temperature, low humidity) at the time of creating a copied image 5) The film strength and adhesiveness of the photosensitive layer are not sufficient, and the photosensitive layer is detached during offset printing, so that the number of printed sheets cannot be increased.

In addition, as a binder resin for a photoconductive layer, which has both electrostatic characteristics as an electrophotographic photoreceptor and printing characteristics as a printing original plate, for example, in Japanese Patent Publication No. 50-31011, (meth) acrylate monomers and obtained by copolymerizing with other monomers, consisting of a Tg10～80 ° C. of the resin ^{w1.8 × 10 4 ~10 × 10 4} , a monomer other than (meth) acrylate monomer and fumaric acid JP-A-53-54027 discloses a ternary copolymer containing a (meth) acrylate having a substituent having a carboxylic acid group at least 7 atoms away from the ester bond. In the case of using a quaternary or pentameric copolymer containing acrylic acid and hydroxyethyl (meth) acrylate, those disclosed in JP-A-54-20735 and JP-A-57-202544, In 58-68046, an alkyl group having 6 to 12 carbon atoms And substituents (meth) has been described as such as those using terpolymer containing vinyl monomer containing acrylic acid esters and carboxylic acids is effective in improving the desensitizing properties of the photoconductive layer. However, even if the resin is said to be effective in the above-mentioned electrostatic properties, moisture resistance properties and durability, it is particularly difficult to evaluate the chargeability, dark charge retention, photosensitivity electrostatic properties and light sensitivity when actually evaluated. There was a problem in the smoothness of the conductive layer and the like, which was not practically satisfactory.

Further, as a binder resin, a resin using a resin containing a functional group that generates a hydrophilic group by decomposition has been studied. For example, a resin containing a functional group that generates a hydroxyl group by decomposition (Japanese Patent Application Laid-Open No. 195684, 62-210475
And those containing a functional group that generates a carboxyl group by decomposition (Japanese Patent Application Laid-Open No. 62-212669).

These resins are hydrolyzed or hydrogenolyzed by a desensitizing solution or a fountain solution used for printing to produce a hydrophilic group, and when these are used as a binder resin of a lithographic printing plate precursor, they have a hydrophilic property. When a resin containing the group itself from the beginning is used, various problems (such as deterioration of smoothness or the amount of dark charge retention or the like) that are considered to be caused by strong interaction between the hydrophilic group and the surface of the photoconductive zinc oxide particle are considered. (E.g., deterioration of electrophotographic characteristics such as photosensitivity) can be avoided, and the hydrophilicity of the non-image area to be hydrophilized by the desensitizing solution is further enhanced by the above-mentioned hydrophilic group generated by decomposition in the resin. Therefore, the lipophilicity of the image area and the hydrophilicity of the non-image area become clear, preventing the ink from adhering to the non-image area during printing, and as a result, printing a large number of prints of clear image quality without background smear. This It has been described that is possible.

However, there is a demand for more efficient electrophotographic lithographic printing today. Specifically, it is necessary to improve the speed of plate making, the speed of etching processing, or the sharp image quality (particularly ground quality) from the start of printing. Despite the fact that obtaining printed matter (without dirt) (reducing waste paper) has become an important issue, offset masters using binder resins that generate hydrophilic groups by the above decomposition have been used. However, with respect to the problem of improving the etching processing speed or reducing the waste paper, it has not yet been said that the performance has been sufficiently achieved.

Further, a technique for incorporating hydrophilic resin particles in the photoconductive layer of a lithographic printing plate precursor is disclosed in JP-A-1232356 and JP-A-1-261657.
No. By containing the hydrophilic resin as particles in the photoconductive layer, the specific surface area becomes smaller than that existing in a molecular state, and the interaction with the zinc oxide surface is reduced, so that the hydrophilic property is maintained. Nevertheless, good printing characteristics can be obtained without inhibiting the electrophotographic characteristics. However, even if such hydrophilic resin particles are used, it is still not possible to maintain sufficiently satisfactory electrophotographic characteristics, and further improvement in printability such as generation of background stain is desired.

On the other hand, as a solution to the problems of the above-described electrostatic characteristics and background contamination of printed matter, as a binder resin for an electrophotographic photosensitive member,
The copolymer component containing an acidic group in the side chain of the polymer is 0.05 to 10
Those using weight-average molecular weight 10 ³ to 10 ⁴ of resin containing wt% (JP 63-217354), a weight average molecular weight 10 ³ to 10 ⁴ of the resin that binds an acidic group at the terminal of the polymer main chain (Japanese Patent Application Laid-Open (JP-A) No. 100554/1984), and further using a resin containing a copolymerizable component containing a curable group (Japanese Patent Application Laid-Open (JP-A) No. 1-100554).
Japanese Patent Application Sho 63-39691), which in combination with the crosslinking agent (JP-A-1-102573, Nos 2-874), those used in combination with a weight-average molecular weight ^of 10 ⁴ or more high molecular weight resins (JP 63-22
No. 0149, No. 63-220148, No. 64-564, JP-A-1-280
No. 761, No. 1-116643, No. 1-169455), heat and / or
Or those used in combination with a photocurable resin (Japanese Patent Laid-Open No. 1-10
Nos. 2573 and 2-34859) are disclosed.

However, even when these resins are used, when the photoreceptor is exposed to extremely severe conditions, it has been found that there is a problem in maintaining stable high performance and that the printability is not sufficiently satisfactory. In other words, if the charging speed is increased during the charging process, charging unevenness occurs, resulting in unevenness in a copied image, or light irradiation such as a fluorescent lamp on the surface of the photoreceptor by compensating the photoreceptor for a copying machine or the like. It has been found that when a copying operation is performed immediately after receiving the image, deterioration of a copied image (especially, reduction in image density, reduction in resolution, generation of background fog, etc.) occurs (so-called pre-exposure fatigue).

Furthermore, when used as an electrophotographic lithographic printing original plate, under the above-described conditions, the copied image becomes a deteriorated original plate, and even if it is printed as an offset master, the obtained printed matter will have reduced image quality and ground fog. This has become a serious problem that would occur.

The present invention improves the problems of the conventional electrophotographic lithographic printing plate precursor as described above.

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrophotographic lithographic printing plate precursor having improved electrostatic characteristics, especially improved charging characteristics and pre-exposure fatigue even under severe conditions during formation of a copy image.

Another object of the present invention is to provide an excellent desensitizing property, in particular, even when the printing process is accelerated from the etching process, the hydrophilicity of the non-image portion is sufficiently maintained, no background stain is generated, and high printing durability is achieved. An object of the present invention is to provide a lithographic printing plate precursor having a strong ability.

(Means for Solving the Problems) An object of the present invention is to provide an electrophotographic method comprising providing a photoconductive layer containing at least one photoconductive zinc oxide and a binder resin on a conductive support. In the lithographic printing plate precursor, the photoconductive layer contains hydrophilic resin particles having an average particle diameter equal to or smaller than the maximum particle diameter of the photoconductive zinc oxide particles, and the binder resin is a resin described below. It has been found that this is achieved by a lithographic printing plate precursor comprising at least one kind of [A] and at least one kind of resin [B].

Resin [A]: having a weight average molecular weight of 1 × 10 ³ to 1 × 10 ⁴ , containing at least 30% by weight of a polymerization component represented by the following general formula (I), and -PO
₃ H ₂ group, -SO ₃ H group, -COOH group, R represents a hydrocarbon group or an -OR 'group (R' represents a hydrocarbon group) and a polymerization component containing at least one acidic group selected from cyclic acid anhydride-containing groups. A resin containing at least one acidic group selected from the same acidic groups as described above at one end of the polymer main chain.

General formula (I) [In the formula (I), a ₁ and a ₂ each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₁ represents a hydrocarbon group. Resin [B]: A resin having a weight average molecular weight of 3 × 10 ⁴ to 1 × 10 ⁶ and containing at least 30% by weight of a polymerization component represented by the following general formula (III).

General formula (III) [X in the formula (III) is CH _{2 n} COO−, CH _{2 m} OCO−, −
O- or (Where n and m each represent 0 or an integer of 1 to 3).

b ₁ , b ₂ and R ₂ represent the same contents as a ₁ , a ₂ and R ₁ in the formula (I). That is, in the lithographic printing plate precursor of the present invention, the hydrophilic resin is dispersed as particles in the photoconductive layer, and the binder resin is used as a polymer component of a specific repeating unit and an acidic group (hereinafter, particularly referred to in the present specification. Unless otherwise stated, the term "acidic group" shall also include a cyclic acid anhydride-containing group), and a low molecular weight resin containing a polymer component containing an acidic group at one end of the polymer main chain [ A] and a resin [B] having a medium to high molecular weight.

As described above, as a technique for containing hydrophilic resin particles in the photoconductive layer and as a binder resin for the electrophotographic photoreceptor, a resin containing an acidic group in a side chain or a resin binding an acidic group to a polymer main chain terminal is used. Although the techniques used are each known, as in the present invention, the specific resin according to the present invention, that is, the acidic group is a side chain of a polymer as a binder resin when the photoconductive layer contains hydrophilic resin particles. And the resin [A], which is simultaneously contained in the terminal of the polymer main chain, and the resin [B] having a medium to high molecular weight, surprisingly, the above problems that have not been solved only by these known techniques are solved. It has been found that the problem is solved, that is, the electrostatic characteristics (especially the charging characteristics and the pre-exposure fatigue) and the printing characteristics are dramatically improved.

In the present invention, the low-molecular-weight resin [A] is used to adsorb the spectral sensitizer to the photoconductive zinc oxide in at least a dispersion system in which the photoconductive zinc oxide, the spectral sensitizer, and the hydrophilic resin particles are present. Effectively adsorbs stoichiometric defects of zinc oxide without disturbing the surface, and makes it possible to appropriately improve the coating property of the surface of zinc oxide. It has been found that the sensitizing hardening of the sensitizer is compensated and the humidity characteristics are remarkably improved, the zinc oxide is sufficiently dispersed, and the aggregation is suppressed. And it seems that the hydrophilic resin particles according to the present invention do not inhibit the above-mentioned interaction and exhibit good printing characteristics.

Further, the resin [B] does not impair the high performance of the electrophotographic properties due to the use of the resin [A] at all, and the resin [A] alone has insufficient mechanical strength of the photoconductive layer. It is something that makes it easy.

According to the present invention, the resin [A] and the resin [B] as the binder resin of the photoconductive zinc oxide are used to specify the weight average molecular weight of each resin, the content of the acidic group in the resin, the bonding position, and the like. By doing so, in the dispersed state where the inorganic photoconductor, the spectral sensitizer, the hydrophilic resin particles and the resin coexist, the strength of each interaction can be appropriately changed, and the state can be stably maintained. It is estimated to be. By that,
It is presumed that uneven charging, in which charging characteristics are further improved, disappears and pre-exposure fatigue properties are further improved.

Further, in the present invention, the smoothness of the photoconductor surface becomes smooth. When a photoconductor having a rough surface of the photoconductive layer is used as an electrophotographic lithographic printing plate precursor, the dispersion state of the photoconductive zinc oxide particles and the above-mentioned hydrophilic resin particles and the binder resin is not appropriate, and the aggregate Since the photoconductive layer is formed in the presence of the non-image area, even if the desensitizing treatment with the desensitizing solution is performed, the non-image area is not sufficiently and sufficiently hydrophilized, causing the printing ink to adhere during printing. As a result, the background of the non-image portion of the printed matter is stained.

When the resin of the present invention is used, the interaction between the adsorption and coating of the inorganic photoconductor and the binder resin is properly performed, and the film strength of the photoconductive layer is maintained.

Furthermore, since the deterioration of image quality or the occurrence of background fogging caused by uneven charging, pre-exposure fatigue, and the like are eliminated, a very good printed image of a printed image can be obtained when used as a lithographic printing original plate.

Further, as the low molecular weight resin [A], a methacrylate component having a specific substituent having a benzene ring or a naphthalene ring and having a specific substituent represented by the following general formula (IIa) or (IIb) is used. The resin [A] containing a group-containing component and having an acidic group bonded to the terminal (hereinafter, this low-molecular-weight product is referred to as resin [A ']) is preferable.

General formula (IIa) General formula (IIb) [In the formulas (IIa) and (IIb), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, —COD ₁ or —COOD ₂ ( D ₁ and D ₂ each represent a hydrocarbon group having 1 to 10 carbon atoms).

B ₁ and B ₂ each represent a single bond or a linking group having 1 to 4 linking atoms, each linking —COO— and a benzene ring. ] Than in the case of resin [A '] is used when the resin (A) and, more electrophotographic characteristics (in particular V _10, DRR, E _1/10) improve can be achieved.

The reason for this is unknown, but one reason is that the planarization of the benzene or naphthalene ring, which is the ester component of methacrylate, causes the polymer chains to be properly aligned at the zinc oxide interface in the film. This is probably due to

The medium to high molecular weight of the resin (B) further ends -PO ₃ H ₂ group of the polymer main chain, -SO ₃ H group, -COOH group, (R ₀ represents the same content as R above) and a polymer formed by bonding at least one acidic group selected from cyclic acid anhydride-containing groups (hereinafter, this high molecular weight is referred to as resin [B ′]) ) Is preferable.

When the resin [B '] is used, the electrostatic characteristics, particularly DRR and E _1/10, are improved, and the excellent characteristics obtained by using the resin [A] are not hindered at all. It is preferable that there is almost no change even in environmental changes such as low temperature and low humidity.

 Hereinafter, the present invention will be described in more detail.

In the present invention, the hydrophilic resin particles may form a higher-order network structure.

In the present invention, the hydrophilic resin particles have the above-mentioned average particle diameter, and the resin film formed by applying a solution obtained by dissolving the resin particles in an arbitrary soluble solvent is applied to distilled water. A contact angle (measured by a goniometer) of 50 degrees or less, preferably a value of 30 degrees or less.

In the present invention, the hydrophilic resin is dispersed as particles in the photoconductive layer, and has an average particle size equal to or smaller than the largest particle of the photoconductive zinc oxide particles.

If the resin particles having a particle size larger than the zinc oxide particle size are present, the electrophotographic characteristics are deteriorated (particularly, uniform chargeability cannot be obtained). Fine lines are cut off, jump, or fogged in the non-image area.

Specifically, the hydrophilic resin particles of the present invention have a maximum particle size of 10 μm or less, preferably 5 μm or less. And the average particle diameter of the particles is 1.0 μm or less,
Preferably it is 0.5 μm or less.

The hydrophilic resin particles have a larger specific surface area as the particle diameter is smaller, and have a good effect on the above-mentioned electrophotographic properties. Although colloidal particles (0.01 μm or less) are sufficient, they are too small. If it is too long, the same harmful effects as in the case of molecular dispersion may occur, so that it is preferable to use it at 0.001 μm or more.

Further, in the present invention, as long as the hydrophilic resin particles form a higher-order network structure, they do not elute with a fountain solution at the time of printing, and have good printing characteristics even when printing a considerably large number of sheets. Can be maintained.

In the present invention, hydrophilic resin particles not forming a higher-order network structure as described above (hereinafter, simply referred to as hydrophilic resin particles) or hydrophilic resin particles forming a higher-order network structure (hereinafter, simply referred to as It is preferable to use the network hydrophilic resin particles) in an amount of 0.1 to 5% by weight based on 100 parts by weight of the photoconductive zinc oxide. When the amount of the hydrophilic resin particles or the network hydrophilic resin particles is less than 0.1% by weight, the hydrophilicity of the non-image portion is not sufficient, and when the amount is more than 5% by weight, the hydrophilicity of the non-image portion is further improved. As a result, the electrophotographic characteristics deteriorate, and the copied image deteriorates.

The hydrophilic resin particles of the present invention include synthetic hydrophilic resins and natural hydrophilic resins, and any of them can be preferably used in the present invention.

As the network hydrophilic resin particles, those obtained by modifying these are preferably used.

For example, P. Molyneax “Water-Soluble Synthetic Pol
ymers: Properties and Behavior "Vol, I and Vol.II C
RC Press.Inc. (1982), CAFinch "Chemistry and
Technology of Water-Soluble Polymers '' Plenam Pres
s (1973), Y. Nakamura "Water-soluble polymer" Chemical Industry Co. (1
968), Interfacial Chemistry Study Group, "Latest Processing and Modification Technology and Application Development of Water-Soluble Polymer Water-dispersed Resins", Management Development Center Publishing Division (1981), Davidson "Water Soluble Resin" Rei
Reference materials such as nhold (1968) are used.

Among them, synthetic hydrophilic resin, in the molecular structure,
Ether group, ethylene oxide group, -OH group, -SH group,
-COOH group, -SO ₂ H group, -SO ₃ H group, -PO ₃ H ₂ group, -CN group,
-CONH ₂ , -CHO, -SO ₂ Q ₁ , Examples thereof include those containing at least one hydrophilic group selected from a 4- to 6-membered heterocyclic ring containing at least one nitrogen atom or an organosilane group.

In the above hydrophilic group, Q ₁ is a hydrocarbon group having 1 to 6 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-bromoethyl group). Fluoroethyl group, 3-chloropropyl group, 3-methoxypropyl group, 2-methoxybutyl group,
Benzyl, phenyl, propenyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, etc.).

Q ₂ is an aliphatic group having 1 to 6 carbon atoms which may be substituted (specifically, it represents the same substituent as Q ₁ ) or —OE ₁ (E ₁
Represents the same meaning and Q _2).

Q ₃ and Q ₄ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted (specifically, the same contents as those of Q ₁ ). However, Q ₃ and
The total number of carbon atoms in Q ₄ is within 8.

Q ₅ , Q ₆ and Q ₇ may each be the same or different;
Represents the same content as Q ₃ and Q ₄ .

 X Represents an anion, for example, a halogen ion
(For example, chloride ion, bromine ion, iodine ion
Etc.), perchlorate ion, tetrafluoroborate ion
ON, hydroxy ion, carboxylate ion
(For example, acetonate ion, propionate ion
Etc.), sulfonate ions (for example, methanesulfone
Toion, benzenesulfonate ion, p-toluene
Sulfonate ion).

r represents 1 or 2, and when r = 1, -Q
At least one acidic group in _5~7 (-SO ₃ H, -PO
₃ H ₂ , —COOH) is contained as a substituent.

In particular, Is mentioned.

Further, the -COOH group, -SO ₂ H group, -SO ₃ H group, -PO ₃ H
_Two , Are metal salts such as alkali metals (eg, lithium, sodium, potassium, etc.), alkaline earth metals (eg, calcium, magnesium, etc.), zinc, aluminum, etc., or organic bases (eg, triethylamine, pyridine, morpholine, piperazine, etc.) ) May be formed.

Also, a 4-member containing at least one nitrogen atom as described above
Examples of the 6-membered heterocyclic ring include a pyridine ring, a piperazine ring, a pyrrole ring, an imidazole ring, a pyrazine ring, a pyrrolidine ring, a pyrroline ring, an imidazoline ring, a pyrazolidine ring, a piperazine ring, a morpholine ring, and a pyrrolidone ring. Can be These heterocycles may contain a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and the like) and a C1-C8 optionally substituted hydrocarbon group ( For example, methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-
Bromoethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-carboxyethyl group,
Carboxymethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-methanesulfonylethyl group, benzyl group, carboxybenzyl group, carboxymethylbenzyl group, phenyl group , Carboxyphenyl group, sulfophenyl group, methanesulfonylphenyl group,
Ethanesulfonylphenyl, carboxymethylphenyl, methoxyphenyl, chlorophenyl, etc.),-
An OE ₂ group (E ₂ represents the same content as the above-mentioned optionally substituted hydrocarbon group having 1 to 8 carbon atoms) or a —COOE ₃ group (E ₃ represents E
₂ represents the same content).

Examples of the organosilane group include a repeating unit represented by the following general formula (IV).

In the formula (IV), A ⁰ represents an alkyl group having 1 to 4 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 2-methoxyethyl group, -Cyanoethyl group or the like), -OE ₄ (E ₄ represents the same content as the optionally substituted alkyl group having 1 to 4 carbon atoms in A ⁰ ), or a “Z” group (Z is trimethylsiloxy,
Pentamethyldisiloxanyl, heptamethyltrisiloxanyl, nonamethyltetrasiloxanyl, bis (trimethylsiloxy) methylsiloxanyl, tris (trimethylsiloxy) siloxanyl, etc.].

W ₁ is an alkyl group having 1 to 6 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-methoxyethyl group, 2-ethoxypropyl group, 2-cyanoethyl Group, 2-hydroxyethyl group, 2-hydroxy-3-chloro-propyl group, 2-
Chloroethyl group, etc.), - OE ₅ (E ₅ represents the same content as E ₄₎ or vinyl through a divalent hydrocarbon group having 1 to 6 carbon atoms, methacryloxy, acryloxy, methacrylamide, acrylamide, It represents a group in which an unsaturated bond selected from the group consisting of styryl, allyl and the like is polymerized and binds to another repeating unit.

k is 0 or an integer of 1 to 10, indicating that the sum of the values of k is at least 2.

The hydrophilic resin of the present invention is a homopolymer or a copolymer containing a polymer component containing at least one hydrophilic group as described above in a polymer side chain, and the polymer component is used as a polymer component in the resin. 20% to 100% by weight, preferably 30% to 100% by weight.

More specifically, examples of the hydrophilic group-containing polymerization component are represented by general formula (V).

In the formula (V), X represents -COO-, -COC-, -O-, -SO
_2- , Or Represents [Where Z ₁ and Z ₂ each represent a hydrogen atom or a carbon atom 1
To 7 hydrocarbon groups (preferably, for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group,
2-hydroxyethyl group, 3-bromo-2-hydroxypropyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 3-sulfopropyl group, benzyl group, sulfobenzyl group, methoxybenzyl group , 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,
Methylbenzyl group, N, N (dihydroxyethyl) aminophenyl group, methanesulfonylphenyl group, cyanophenyl group, dicyanophenyl group, acetylphenyl group, etc.)
Wherein Z ₃ and Z ₄ may be the same or different, and represent a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or an aliphatic group having 1 to 4 carbon atoms (preferably,
For example, methyl group, ethyl group, propyl group, butyl group, etc.)
And n ₁ represents an integer of ₁ to 6. ].

W is -COO -, - OCO -, - O -, - S -, - SO 2, -NHCOO-, -NHCONH- Or a linking group formed by a combination of these linking groups.

[Wherein, l _{1 to} l ₄ may be the same or different, and each represents a hydrogen atom, a halogen atom (preferably, for example, a fluorine atom, a chlorine atom, a bromine atom, or the like) or a hydrocarbon group having 1 to 7 carbon atoms ( Preferably, for example, methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-methoxyethyl, 2-methoxycarbonylethyl, benzyl, methoxybenzyl, phenyl, methoxyphenyl, methoxy Carbonylphenyl group) or the formula (V)
Of represents W-Y] group, l ₅ to l ₇ represents the same as the contents of the above Z _1, Z _2. Y represents the hydrophilic group described above, -OH group, -SH group,
-CHO group, -CN group, -COOH group, -SO ₂ H group, -PO ₃ H ₂ group, -
₁ SO ₂ Q, Represents a 4- to 6-membered heterocyclic ring or organosilano group containing at least one nitrogen atom.

[Wherein, Q ₁ to Q ₇ represents the same as the contents of the Q ₁ to Q _7. In the formula (V), Y may be directly bonded to the polymer main chain, or X may be -O-, In this case, -Y may be directly connected to X.

e ₁ and e ₂ may be the same or different, and each represents a hydrogen atom,
Halogen atom (preferably, for example, fluorine atom, chlorine atom, bromine atom, etc.), -COOH group, -COOQ ₅ group, -CH ₂ COOQ
₅ groups (Q ₅ represents a hydrocarbon group having 1 to 7 carbon atoms, specifically, the same contents as those described above for the hydrocarbon groups of Z ₁ and Z ₂ ) or an alkyl group having 1 to 4 carbon atoms (Preferably, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.).

Hereinafter, the above-mentioned hydrophilic group-containing polymerization component will be exemplified more specifically, but the present invention is not limited thereto.

Further, in the following examples, q ₁ is -H, -CH _3, -C
l, indicates -CH ₂ COOH or -CH ₂ COOCH _3, q ₂ is -CH _3, -
COOH, shows a -CONH _2, -CONHC ₂ H ₅ or -COOCH _3, q ₃
Represents a -CH ₃ or -H, q ₄ is -H, -CH ₃ or -Cl
Are shown, q ₅ is -H, -CH _3, -CH ₂ COO, or -CH ₂ COOC,
Indicates H _3, q ₆ represents -H, a -CH ₃ or -CH ₂ COOCH _3,
r ₁ represents -H, a -CH ₃ or -C ₂ H _5, r ₂ is Wherein y ₁ is -SO ₃ H, -COOH, -CH ₂ OH or —SO ₂ H, —CONH ₂ or —SO ₂ NH ₂ , y ₂ represents —OH or —NH ₂ , J ₁ is Li, Na, K or NH (C ₂ H ₅ ) ₃ or And J ₂ represents Li, Na, K or HN (C ₂ H ₅ ) ₃ . Also, v ₁ represents an integer of ₁ to 12, v ₂ represents an integer of 1 to 4, v ₃ represents an integer of 2 to 12, v ₄ represents an integer of 1 to 11, and v ₅ represents 1
An integer of ~ 10, v ₆ is an integer of 2-10, and v ₇ is 1-4
Are respectively shown.

Other polymer components that can be copolymerized with the above-mentioned hydrophilic group-containing polymer component include, for example, those represented by the general formula (VI), and one or more of these are copolymerized. It can be polymerized.

General formula (VI) In the formula (VI), P represents the same content as X in the formula (V).

Q represents an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, octyl group, decyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, 2 -Chloroethyl group, 3-bromopropyl group, 2-methoxycarbonylethyl group, 4-methoxycarbonylbutyl group, 4-methoxybutyl group, 3-chloro-2-methoxypropyl group,
3-chloro-2-ethoxycarbonylpropyl group, 2-
A glycidylpropyl group, a 3-bromo-2-acetyloxy-propyl group, an alkenyl group having 2 to 20 carbon atoms which may be substituted (for example, a vinyl group or an allyl group), or a substituted alkenyl group having 5 to 12 carbon atoms. Alicyclic groups (eg, cyclopentyl, cyclohexyl, cyclooctyl, chlorocyclohexyl, bromocyclohexyl, 2-cyclohexylethyl, cyclohexylmethyl, etc.)
An optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl group, phenethyl group, 3-phenylpropyl group, ethyl-2-phenylethyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, Dichlorobenzyl group, bromobenzyl group, methylbenzyl group,
A dimethylbenzyl group, a trimethylbenzyl group, a methoxybenzyl group, a dimethoxybenzyl group, a trimethoxybenzyl group, a methoxycarbonylbenzyl group, an acetamidobenzyl group, and the like; an optionally substituted aryl group having 6 to 12 carbon atoms (for example, a phenyl group) , Tolyl group, xylyl group,
Mesitylene, naphthyl, chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, fluorophenyl, methoxyphenyl, chloro-
A methyl-phenyl group, a methyl-methoxy-phenyl group,
Nitrophenyl group, methoxycarbonylphenyl group, acetamidophenyl group, ethoxyphenyl group, chloronaphthyl group, ethoxycarbonylnaphthyl group, propylphenyl group, butylphenyl group, chloromethylphenyl group, methoxymethylphenyl group, N-methylaminosulfenyl Group, etc.) or a 4- to 7-membered heterocyclic ring (a heterocyclic ring other than the nitrogen-containing heterocyclic ring exhibiting hydrophilicity as described above, such as a thiophene ring, a furan ring, a pyran ring, or a benzopyran ring). , A pyrrole ring, an indole ring,
Examples include a quinoline ring, a thiazole ring, an oxazole ring, a benzothiazole ring, and the like, and these rings may contain a substituent. The substituent has the same content as Q in the above formula (VI)).

The natural hydrophilic resin is described in detail in the comprehensive technical data collection of the above-mentioned water-soluble polymer water-dispersible resin (management development center publishing department). For example, lignin, starch, burlan, cellulose, alginic acid, dextran Dextrin, guar gum, gum arabic, glycogen, laminaran, lichenin, ligueran, and the like, and derivatives thereof.

As the derivative, sulfonated, carboxylated, phosphorylated, sulfoalkylated, or carboxyalkylated, alkylphosphorylated, and salts thereof are particularly preferable.

In the present invention, two or more natural hydrophilic resins may be used in combination.

In addition, among natural hydrophilic resins, glucose polymers,
And its derivatives are preferred, glucose polymers, and derivatives thereof, starch, glycogen, cellulose,
Likenin, dextran, nigeran and the like are preferred, and dextran and its derivatives are particularly preferred.

In order to make the above synthetic / natural hydrophilic resin into fine particles having the above-mentioned specific particle diameter, conventionally known dry and wet methods can be adopted. That is, the hydrophilic resin powder,
A method of directly pulverizing with a conventionally known pulverizer to obtain fine particles (for example, a method using a ball mill, a paint shaker, a jet mill, a hammer mill, or the like) and a method of forming polymer latex particles can be used. As the latter method for producing polymer latex particles, a conventionally known method for producing latex particles of a paint or a liquid developer for electrostatic photography can be used. That is, in a method of dispersing the hydrophilic resin in combination with a dispersing polymer, the hydrophilic resin and a dispersion assisting polymer (or coating polymer) are kneaded in advance to form a kneaded product, and then pulverized. It is a method of coexisting and dispersing.

Specifically, for example, Kenji Ueki's translation of paint flow and pigment dispersion, Kyoritsu Shuppan (1971), Solomon, Chemistry of Paint, Paint and Surface Coating theory and pract
ice ”, Yuji Harasaki“ Coating Engineering ”Asakura Shoten (1971
Yuji Harasaki, “Basic Science of Coatings” Maki Shoten (19
77), JP-A Nos. 62-96954, 62-115171 and 62-7
It is described in publications such as PR No.5651.

Further, a method of easily obtaining latex particles of the hydrophilic resin by a conventionally known polymerization reaction such as a suspension polymerization method and a dispersion polymerization method can also be used.

Specifically, Soichi Muroi “Chemistry of Polymer Latex” Polymer Publishing Association (1970), Taira Okuda, Hiroshi Inagaki “Synthetic Resin Emulsion” Polymer Publishing Association (1978), Soichi Muroi “Polymer Latex” It is described in books such as "Introduction" Kobunsha (1983).

In the present invention, a method of using polymer latex particles is preferable, and the average particle diameter is easily 1.0 μm by this method.
The following resin particles can be used.

By the way, in the electrophotographic lithographic printing plate precursor of the present invention, when forming a photoconductive layer, a method of dispersing a photoconductive zinc oxide in an aqueous system (for example, Japanese Patent Publication No. 51-450 and No. 47-1).
No. 8599, No. 46-41350, etc.) and a method of dispersing in a non-aqueous solvent system (for example, Japanese Patent Publication No.
-54027, 54-20735, 57-202544, 58-68
046), but if water remains in the photoconductive layer, the electrophotographic properties will be impaired. Therefore, a method of dispersing in a non-aqueous solvent system is preferred. Accordingly, in order to sufficiently disperse the latex particles of the hydrophilic resin of the present invention in the non-aqueous photoconductive layer, the latex particles are also preferably non-aqueous latex.

The non-aqueous solvent used in the non-aqueous latex may be any organic solvent having a boiling point of 200 ° C. or lower, and may be used alone or as a mixture of two or more.

Specific examples of this organic solvent include methanol, ethanol,
Alcohols such as propanol, butanol, fluorinated alcohol and benzyl alcohol; ketones such as acetone, methyl ethyl ketone, cyclohexanone and diethyl ketone; ethers such as diethyl ether, tetrahydrofuran and dioxane; methyl acetate, ethyl acetate, butyl acetate and propionic acid Carboxylic esters such as methyl,
Hexane, octane, decane, dodecane, tridecane,
C6 to C14 aliphatic hydrocarbons such as cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; methylene chloride;
Cichloroethane, tetrachloroethane, chloroform,
Halogenated hydrocarbons such as methyl chloroform, dichloropropane and trichloroethane are exemplified.

If a polymer latex is synthesized by a dispersion polymerization method in these non-aqueous solvent systems, the average particle size of the latex particles can be easily adjusted to 1
μm or less, and the distribution of the particle system is very narrow, and monodispersed particles can be obtained.

Specifically, KEJ Barrett "Dispersion Polymeriza
tion in Organic Media ”John Wiley (1975), Koichiro Murata, Polymer Processing, 23 , 20 (1974), Tsunetaka Matsumoto and Tokichi Tange, Journal of the Adhesion Society of Japan 9 , 183 (1973), Toyokichi Tange, Journal of the Japan Adhesion Association 23 , 26 (1987), DJ Walbridge, NATO, A
dv, Study.Inst.Ser.E.No.67, 40 (1983), BP893429
No., BP934038, USP 1122397, USP 3900412, US
P 4606989, JP-A-60-179951 and JP-A-60-185963 disclose the method.

Further, as the network hydrophilic resin particles, specifically, at least one structure of the repeating unit of the polymer has -O
_{H, -SH, -COOH, -SO 2} H, -SO 3 H, -CN, -CONH 2, -
CHO, -SO ₂ Q _1, Examples include those containing at least one hydrophilic group selected from an ether group, an ethylene oxide group, a heterocyclic ring forming a 4- to 6-membered ring, and an organosilane group.

In the hydrophilic group, Q ₁ is an alkyl group having 1 to 4 carbon atoms which may be substituted, (for example, a methyl group, an ethyl group,
Propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl, 3-chloropropyl, 3-methoxypropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, etc.) .

Q ₂ is an alkyl group having 1 to 4 carbon atoms which may be substituted (specifically, it represents the same substituent as Q ₁ ) or —OE ₁
(E ₁ represents the same content and Q ₁₎ representing the.

Q ₃ and Q ₄ may be the same or different, and each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be substituted (specifically, the same contents as those of Q ₁ ). However, Q ₃
And the sum of the carbon numbers of Q ₄ represents those having a total number of 6 or less.

Q ₅ , Q ₆ and Q ₇ may each be the same or different;
Represents the same content as Q ₃ and Q ₄ .

 X , r is X of the aforementioned hydrophilic resin particles. same as r
You.

Examples of the heterocyclic ring forming a 4- to 6-membered ring include, for example, a furan ring, a pyran ring, a tetrahydrofuran ring, a pyridine ring, a piperidine ring, a pyrrole ring, an imidazole ring,
Pyrazine ring, pyrrolidine ring, pyrroline ring, imidazolidine ring, imidazoline ring, pyrazolidine ring, piperazine ring, morpholine ring, pyrrolidone ring, dioxane ring, dioxolane ring, oxazoline ring, 1,3-oxazine-2-one ring, morpholinedione ring And a morpholinone ring.

These heterocycles may contain a substituent, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 3 carbon atoms which may be substituted (for example, , Methyl group, ethyl group, propyl group,
2-chloroethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, etc.), -OE
_{And two} groups (E ₂ represents the same content as the above-mentioned alkyl group which may be substituted and has 1 to 3 carbon atoms).

Examples of the organosilane group include the same as those described above for the omeganosilane group of the hydrophilic resin particles.

The network hydrophilic resin of the present invention is a homopolymer or a copolymer containing a polymer component containing at least one of the above hydrophilic groups in a polymer side chain, and is the same as in the case of the above-described hydrophilic resin. Wherein the polymerization component is a polymerization component in the resin.
20% to 100% by weight, preferably 30% to 100% by weight
Included.

The specific general formula and specific component examples of the mesh hydrophilic resin are the above-described general formula (IV) and component example (1) of the hydrophilic resin.
Same as (57).

Also, as a natural network hydrophilic resin, specifically,
Interfacial Chemistry Study Group, “Latest Processing / Modification Technology and Application Development of Water-Soluble Polymers / Water-Dispersible Resins”, Business Development Center Publishing Division (1981), Nakamura Yasuo, “Water-Soluble Polymers” 1973), RL Davidson, "Handbook of Water-S
oluble Gumsand Resins '' McGraw-Hill BOOK Company
(1980), “Encyclopedia of Polymer Science an
d Enginneering, Vol. 3, p. 69-270, John Wileyand Son
s (1985) and the like. Specifically, the same derivatives as the above-mentioned natural hydrophilic resins, and the same derivatives as the above-mentioned derivatives of the natural hydrophilic resins can be used.

The network hydrophilic resin particles of the present invention have a high-order network structure in which the polymer molecular chains of the polymer comprising the above-mentioned hydrophilic polymer component are bridged.

Thereby, the network hydrophilic resin particles become hardly soluble or insoluble in water. Specifically, the solubility of the resin in water is 80% by weight or less, preferably 50% by weight.
It is as follows.

The crosslinking of the present invention can be performed by a conventionally known crosslinking method. That is, (1) a method of crosslinking a polymer containing the hydrophilic polymerization component with various crosslinking agents or curing agents, and (2) a polymerization reaction by containing at least a monomer corresponding to the hydrophilic polymerization component. When performing the process, two polymerizable functional groups
A method of forming a network structure between molecules by coexisting a polyfunctional monomer or a polyfunctional oligomer containing at least one polymer, and (3) a method including a component containing the hydrophilic polymer component and a component containing a reactive group. It can be carried out by a method such as a method of cross-linking with the union by a polymerization reaction or a polymer reaction.

Examples of the cross-linking agent in the method (1) include compounds that are usually used as a cross-linking agent. Specifically, compounds described in Shinzo Yamashita and Tosuke Kaneko, “Handbook of Crosslinking Agents” Taiseisha (1981), edited by the Society of Polymer Science, “Basic Edition of Polymer Data Handbook”, Baifukan (1986), etc. Can be used.

For example, silane coupling agents such as organic silane compounds (for example, vinyltrimethoxysilane, vinylolibutoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, etc. Etc.), polyisocyanate compounds (e.g., toluylene diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, polymer polyisocyanate, etc.), polyol compounds (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxylenalkylene glycol, 1,1,1-trimethylol) Propane, etc.), polyamine-based compounds (e.g., ethylenediamine, γ-hydroxypropylated ethylenediamine, phenylenediamine hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), polyepoxy group-containing compounds and epoxy resins (e.g., "New epoxy resin" edited by Hiroshi Kakiuchi Shokodo (1985), "Epoxy resin" edited by Noriyuki Hashimoto, compounds described in Nikkan Kogyo Shimbun (1969), etc., melamine resin (for example, Ichiro Miwa, Hideo Matsunaga) Edited by "Area Metallin Resin" Compounds described in Shogaku Kogyo Shimbun (published in 1969), poly (meth) acrylate compounds (for example, Shin Ogawara, Takeo Saegusa, Toshinobu Higashimura "Oligomers" Kodansha (1976), Eizo Omori " Functional acrylic resin "Techno System (published in 1985) and the like. Specific examples include polyethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, Trimethylolpropane triacrylate, pentaerythritol polyacrylate, bisphenol A-
Diglycidyl ether diacrylate, oligoester acrylate: these methacrylates and the like.

Among the curing agents of the above method (1), examples of the curing agent for a natural hydrophilic resin such as gelatin include, for example, US Pat.
057,723, 3,671,256, 3,396,029, 4,161,4
07, 4,207,109, UK Patent No. 1,322,971
42-17112, JP-A-51-94817, JP-A-56-66841, and JP-A-5-66841
Nos. 7-207243, 59-121327, "Theory of the Photographic Process," Fourth Edition (TH James et al.), P. 94, "Polymeric amine and
Ammonium Salts "(EJ Gaters et al., P. 321) can be used.

The polymerizable functional group of the polyfunctional monomer or oligomer having two or more polymerizable functional groups in the method (2) is specifically CH ₂ CH—CH ₂ —. , CH ₂ = CH-, CH ₂ = CH-CONH-, _{CH 2 = CH-NHCO-, CH} 2 = CH-CH 2 -NHCO-, CH 2 = CH-SO
_{2 -, CH 2 = CH-} CO-, CH 2 = CH-O-, CH 2 = CH-S-,
And the like. Any monomer or oligomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, as monomers or oligomers having the same polymerizable functional group, a slurry derivative such as divinylbenzene or trivinylbenzene: a polyhydric alcohol (for example, , Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 60
0,1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane,
Pentaerythritol, etc.) or polyhydroxyphenols (eg, hydroquinone, resorcin, catechol and derivatives thereof), 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, vinylamides or allylamides:
Condensates of polyamines (eg, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) with carboxylic acids containing vinyl components (eg, methacrylic acid, acrylic acid, crotonic acid, allylacetic acid, etc.) Is mentioned.

Examples of the monomer or oligomer having a different polymerizable functional group include, for example, a carboxylic acid containing a vinyl group (for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl) Acetic acid,
Itaconiloyl propionic acid, carboxylic acid anhydride) and a reactant of an alcohol or an amine (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid,
Ester derivatives or amide derivatives containing a vinyl group such as 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc. (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, Allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyl oxycarbonyl methyl methacrylate, vinyl oxycarbonyl methyloxy carbonyl ethylene acrylate, N-allyl acrylamide, N-allyl methacrylamide, N- Allylitaconamide, methacryloylpropionic allylamide, etc.) or amino alcohols (for example, aminoethanol, 1-aminopropanol, 1- Mino butanol, 1-amino-hexanol, 2-amino butanol) and the like condensates of carboxylic acids containing vinyl groups. The monomer or oligomer having two or more polymerizable functional groups used in the present invention is polymerized using 10 mol% or less, preferably 5 mol% or less of all monomers to form a resin.

In the present invention, a polymer containing a polymerizable double bond group can also be used. Examples of the double bond group in this polymer include the same groups as described above. And
In the polymerization reaction between the polymers, it is a generally known method to carry out the reaction using the above-mentioned polymerizable polyfunctional monomer in combination.

Further, when a chemical bond is formed by the reaction of reactive groups between polymers in the above method (3) to form a bridge between the polymers, the reaction is performed in the same manner as the reaction of a general organic low-molecular compound. be able to. Specifically, it is described in detail in books such as Yoshio Iwakura, Keisuke Kurita, "Reactive Polymers" Kodansha (1977), Ryohei Oda, "Polymer Fine Chemicals" Kodansha (1976), and the like. For example, a polymer reaction is usually performed by a combination of a harmful group of Group A (hydrophilic copolymer component) and a functional group of Group B (polymers containing a component containing a reactive group) in Table A below. This is a well-known method.

As described above, the network hydrophilic resin particles of the present invention are polymer particles containing a polymer component containing a hydrophilic group, and having a structure in which the molecular chains are bridged to a higher order, for example, , LHSperling, `` Intrepenetrating Polymer Networ
ks and Related Materials "Plenum Press (1981)," Encyclopedia of Polymer Science and Engine "
ering "vol.8, p279-340 (1985), JDAnclrade,
`` Hydrogels for medical and Related Applicatio
n '', ACS.Symposium Series No. 31, American Chemical
Society, Washington DC (1976), Eizo Omori, "Development Trends of Superabsorbent Polymers and Their Applications", Techno Forum Co., Ltd., Publishing Division (1987), Masahiro Irie, "Manufacture and Application of Functional Polymer Gels""CMC Co., Ltd. (1987), Kenji Tanaka, Petrotech., 10 25 (1987), Nikkei N
ew Materials, June 1987, p57, Jun Taguchi, Kunio Ishii, "Science and Industry" 59 , 188 (1985), Fusayoshi Masuda, Functional Materials, April 1982, p36, Yoshinori Kadoma, Chemical Industry 38 , 602
(1987) or the like can be used. Examples of commercially available superabsorbent resins include Arasorp (Arakawa Chemical Industries), Wondergel (Kao Corporation), KI gel (Kuraray Isoprene), Sunwet (Sanyo Chemical Industries), Sumikagel (Sumitomo Chemical) Aqua Keep (manufactured by Iron and Steel Chemical Co., Ltd.), Lanseal (manufactured by Nippon Xlan Industry Co., Ltd.), Lion Polymer (manufactured by Lion Corporation), GP (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Arialic (manufactured by Nippon Shokubai Co., Ltd.) Chemical Co., Ltd.), Aquaprene (Meisei Chemical Co., Ltd.), CLD (Buckeye Cellulose
DWAL (manufactured by Dow Chemical), GPC (Graim
Processing), Aqualon (hercules), Magic
Water Gel (manufactured by Super Absorbent), Cecagum (manufactured by CECA), Spon Cygnus (manufactured by Kanebo Gosei Kagaku), Super Lab (manufactured by Asahi Kasei Kogyo) and the like.

Further, the particle formation of the network hydrophilic resin in the present invention is the same as the above-described particle win of the hydrophilic resin.

Next, the binder resin used in combination with the hydrophilic resin particles or the network hydrophilic resin particles will be described.

The weight average molecular weight of the resin [A] is 1 × 10 ³ to 1 × 1.
0 ^4, preferably ^{3 × 10 3 ~8 × 10 3} , the presence proportion of the copolymerizable component corresponding to a repeating unit of formula (I) is 30 wt% or more,
It is preferably from 50 to 97% by weight, and the proportion of the total amount of the acidic group-containing copolymer component and the acidic group bonded to the terminal of the main chain is as follows:
1-20% by weight is preferred. Further, the proportion of the acidic group-containing copolymer component is preferably 0.1 to 10% by weight, more preferably 0.5 to 8% by weight, and the proportion of the acidic group bonded to the main chain terminal is preferably 0.5 to 15% by weight. , More preferably 1
~ 10% by weight.

Formula (IIa) and / or Formula (II) in the resin [A ′]
The proportion of the methacrylate copolymer component corresponding to the repeating unit of b) is 30% by weight or more, preferably 50 to 97% by weight, and the proportion of the acidic group-containing copolymer component is preferably 0.1 to 10% by weight. , More preferably 0.5 to 8% by weight. The proportion of the acidic group bonded to the terminal of the polymer main chain is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight.
It is.

The glass transition point of the resin [A] is preferably -20 ° C to 110 ° C.
° C, more preferably -10 ° C to 90 ° C.

On the other hand, the weight average molecular weight of the resin [B] is 3 × 10 ⁴ -1 × 1
0 ^6, preferably from ^{5 × 10 4 ~5 × 10 5} .

The proportion of the copolymer component corresponding to the repeating unit of the formula (III) is at least 30% by weight, preferably at least 50% by weight.

The resin [B] may further contain an acidic group-containing component as a copolymer component. When the resin [B] contains the acidic group-containing copolymer component, its content is 10% by weight or less, preferably 5% by weight or less. % By weight or less.

In the resin [B '], the proportion of the acidic group bonded to the main chain terminal is preferably 0.1 to 5% by weight.

When both the acidic group-containing copolymer component and the main chain terminal are present, the total amount thereof is 0.5 to 10% by weight, preferably 0.5 to 5% by weight.

The glass transition point of the resin [B] is preferably 0 ° C to 110 ° C.
° C, more preferably 20 ° C to 90 ° C.

When the molecular weight of the binder resin [A] is smaller than 1 × 10 ³ , the film-forming ability is reduced and sufficient film strength cannot be maintained. On the other hand, when the molecular weight is larger than 1 × 10 ⁴ , even if the resin of the present invention is used. The fluctuation of electrophotographic characteristics (charging property, pre-exposure fatigue property) under severe conditions as described above is slightly increased, and the effect of the present invention that a stable copied image can be obtained is weakened.

If the total content of the acidic group in the binder resin [A] is less than 1% by weight, the initial potential is too low to obtain a sufficient image density. On the other hand, when the content of the acidic group is more than 20% by weight, the dispersibility of even a low molecular weight substance is reduced, the film smoothness and the high humidity property of electrophotographic properties are reduced, and furthermore, when used as an offset master. Background dirt increases.

When the molecular weight of the binder resin [B] is smaller than 3 × 10 ⁴ , the film strength cannot be sufficiently maintained. On the other hand, when the molecular weight is larger than 1 × 10 ⁶ , the dispersibility decreases and the film smoothness decreases. , Image quality of copied image (especially, reproducibility of fine lines and characters deteriorates)
Is worsened, and furthermore, when used as an offset master, background stain becomes remarkable.

Next, the details of the binder resin [A] and the binder resin [B] used in the present invention will be described.

The resin [A] of the present invention contains at least one kind of a repeating unit represented by the formula (I) as a polymerization component.

In the general formula (I), a ₁ and a ₂ represent a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), a cyano group or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, Butyl group). R ₁ is an alkyl group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, 2-chloroethyl, 2-
A bromoethyl group, a 2-cyanoethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 3-hydroxypropyl group, and the like, and an optionally substituted alkenyl group having 2 to 18 carbon atoms. A vinyl group, an allyl group, an isopropenyl group, a butenyl group, a hexenyl group, a heptenyl group, an octenyl group, etc., an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, a benzyl group, a phenethyl group, a naphthylmethyl group, 2-naphthylethyl group, methoxybenzyl group, ethoxybenzyl group, methylbenzyl group, etc., optionally substituted cycloalkyl group having 5-8 carbon atoms (eg, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.), substitution Optionally substituted aryl groups (eg phenyl, tolyl, xyl, mesityl, naph Tyl group, methoxyphenyl group,
Ethoxyphenyl, fluorophenyl, difluorophenyl, bromophenyl, chlorophenyl, dichlorophenyl, iodophenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, cyanophenyl, nitrophenyl, etc.) .

Further, the copolymer component preferably corresponding to the repeating unit of the general formula (I) is represented by a methacrylate component containing a specific aryl group represented by the general formula (IIa) and / or (IIb). (Resin [A ']).

In the formula (IIa), as preferred A ₁ and A ₂ , in addition to a hydrogen atom, a chlorine atom and a bromine atom, respectively, a preferred hydrocarbon group is an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group). , Propyl, butyl, etc.),
C7-C9 aralkyl group (for example, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group, etc.) and aryl groups (e.g. phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl group, chlorophenyl group, dichlorophenyl group), and the preferred hydrocarbon as -COD ₁ or -COOD ₂ (preferably D ₁ and D ₂ And those described as hydrogen groups).

In the formula (IIa), B ₁ is a single bond connecting —COO— and a benzene ring or CH ₂ n ₁ (n ₁ represents an integer of ₁ to 3), —CH ₂ OCO—, —CH ₂ CH ₂ OCO-, CH ₂ On ₂ (n ₂ is an integer of 1 or 2), - it represents a CH ₂ CH ₂ O-such as such linking atoms 1-4 linking groups.

B ₂ in formula (II b) is the same meaning as B _1.

Specific examples of the copolymer component corresponding to the repeating unit represented by the formula (IIa) or (IIb) used in the resin [A '] of the present invention are shown below. However, the scope of the present invention is not limited to this.

In each of the following examples, T ₁ and T ₂ each represent Cl, Br or I, and R ₁₁ is C _a H _{2a + 1} or A represents an integer of 1 to 4, b represents an integer of 0 or 3, and c represents an integer of 1 to 3.

The copolymerization component containing an acidic group to be copolymerized in the resin [A] of the present invention is, for example, a compound represented by the general formula (I) (the general formula (II)
a) and (IIb)) as long as it is a vinyl compound having an acidic group copolymerizable with a monomer corresponding to the repeating unit represented by (IIb). Molecular Data Handbook [Basic] "Baifukan (19
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 compound), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid semiamides, crotonic acid,
2-alkenyl carboxylic acids (eg, 2-pentenoic acid,
2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half esters, maleic acid half amides, vinyl Benzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, half-ester derivatives of vinyl or allyl groups of dicarboxylic acids, and ester derivatives of these carboxylic acids or sulfonic acids, substituents of amide derivatives. Examples include compounds containing an acidic group.

In the acidic group In the above, R represents a hydrocarbon group or an OR 'group (R' represents a hydrocarbon group), and R and R 'are preferably an aliphatic group having 1 to 22 carbon atoms (for example, a methyl group, an ethyl group, a propyl group). 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 (For example, phenyl, tolyl, ethylphenyl, propylphenyl, chlorophenyl,
Fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.).

Further, the cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and examples of the cyclic acid anhydride contained include aliphatic dicarboxylic anhydride and aromatic dicarboxylic anhydride. Can be

Examples of the aliphatic dicarboxylic anhydride include a succinic anhydride ring, a glutaconic anhydride ring, a maleic anhydride ring,
Cyclopentane-1,2-dicarboxylic anhydride ring, cyclohexane-1,2-dicarboxylic anhydride ring, cyclohexene-1,2-dicarboxylic anhydride ring, 2,3-bicyclo [2.2.
2] octanedicarboxylic anhydride rings and the like, and these rings are substituted with, for example, halogen atoms such as chlorine atom and bromine atom, and alkyl groups such as methyl group, ethyl group, butyl group and hexyl group. Is also good.

Examples of the aromatic dicarboxylic anhydride include a phthalic anhydride ring, a naphthalene-dicarboxylic anhydride ring, a pyridine-dicarboxylic anhydride ring, a thiophene-dicarboxylic anhydride ring, and the like. Is, for example, a chlorine atom, a halogen atom such as a bromine atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (for the alkoxy group, for example, Methoxy group, ethoxy group, etc.) may be substituted.

The copolymer component containing an acidic group will be exemplified. here,
P ₁ represents H or CH ₃ , P ₂ represents H, CH ₃ or CH ₂ COOCH ₃ , R ₁₂ represents an alkyl group having 1 to 4 carbon atoms, and R ₁₃ represents an alkyl group having 1 to 6 carbon atoms. , A benzyl group or a phenyl group, c represents an integer of 1-3, d represents an integer of 2-11, e represents an integer of 1-11, f represents an integer of 2-4, g Represents an integer of 2 to 10.

In the resin [A] of the present invention, at least one acidic group selected from the same acidic groups as the above-mentioned acidic groups is bonded to the terminal of the polymer main chain.

In the resin [A], the acidic group contained in the copolymer component of the polymer and the acidic group bonded to the terminal of the polymer main chain may be the same or different. In the acidic group bonded to one terminal of the polymer main chain in the resin (A), preferred acidic groups, -PO ₃ H ₂ group, -SO ₃ H group, -COOH group, A cyclic acid anhydride containing group can be mentioned.

These acidic groups may be directly bonded to the terminal of the polymer main chain, or may be bonded via a linking group. As the linking source, any bonding group may be used, but for example, if specifically mentioned, (D ₁ and d ₂ may be the same or different and each represents a hydrogen atom, a halogen atom (a chlorine atom, a bromine atom, etc.), an —OH group, a cyano group, an alkyl group (a methyl group, an ethyl group, a 2-chloroethyl group, 2-hydroxyethyl group, propyl group, butyl group, hexyl group, etc.), aralkyl group (benzyl group, phenethyl group, etc.), phenyl group, etc.), (D ₃ and d ₄ represent the same contents as d ₁ and d ₂ ), -O-, -S-, ｛D ₅ represents a hydrogen atom or a hydrocarbon group (specifically, a hydrocarbon group having 1 to 12 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group) Group, decyl group, dodecyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-cyanoethyl group,
Benzyl, methylbenzyl, chlorobenzyl, methoxybenzyl, phenethyl, phenyl, tolyl, chlorophenyl, methoxyphenyl, butylphenyl, etc.)), -CO-, -COO-, −O
CO-, _{-SO 2 -, - NHCONH -,} - NHCOO -, - NHSO 2 -, - CONHC
OO-, -CONHCONH-, a heterocyclic ring (as a hetero atom, O,
Any 5- or 6-membered ring containing at least one of S, N, and the like or a condensed ring thereof may be used. Examples thereof include a thiophene ring, a pyridine ring, a furan ring, an imidazole ring, a piperidine ring, and a morpholine ring. ) Or ｛D ₆ and d ₇ may be the same or different, and represent a hydrocarbon group or-
Od ₈ (d ₈ is a hydrocarbon group). As these hydrocarbon groups, d ₅ can be cited the same as those listed) alone linking group or the like, linking group constituted by a combination thereof.

Further, in the binder resin [A], the copolymer component represented by the above general formula (I) (including the one represented by the general formula (IIa) or (IIb)) and the copolymer component containing an acidic group In addition to the above, it is preferable to further contain 1 to 20% by weight of a copolymer component containing a heat and / or photocurable functional group from the viewpoint of obtaining higher mechanical strength.

“Thermal and / or photocurable functional group” refers to a functional group that causes a curing reaction of a resin by at least one of heat and light.

Specific examples of photocurable functional groups include Hideo Inui, Mototaro Nagamatsu, "Photosensitive Polymers" (Kodansha, published in 1977), Takahiro Kakuda, "New Photosensitive Resins" (publishing department of the Printing Society of Japan, published in 1981),
GEGreen and BPStrak, J.Macro.Sci.Reas.Macro Che
m., C21 (2), 187-273 (1981-82), CGRattey, "Ph
otopolymirization of Surface Cootings "(A. Wiley I
nterScience Pub. 1982), functional groups used in photosensitive resins and the like conventionally known as Kochi are used as photocurable resins.

Further, the “thermosetting functional group” in the present invention is a functional group other than the above-mentioned acidic group, and includes, for example, Tsuyoshi Endo, “Refinement of thermosetting polymer” (CMC Corporation, 1986), Yuji Harazaki, "Handbook of Latest Binder Technologies", Chapter II-I (Comprehensive Technology Center, published in 1985), Takayuki Otsu, "Synthesis and Design of Acrylic Resins and Development of New Applications" (Chubu Business Development Center Publishing Division,
1985), Emori Omori "Functional Acrylic Resin" (Techno System, 1985), and the like can use the functional groups of the references.

For example -OH group, -SH group, -NH ₂ group, -NHR ₃ group [R ₃ represents a hydrocarbon group, for example an optionally substituted alkyl group (e.g. methyl group having 1 to 10 carbon atoms, an ethyl group, Propyl, butyl, hexyl, octyl, decyl, 2
-Chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, etc.), C4-8 optionally substituted cycloalkyl group (e.g., cycloheptyl group, cyclohexyl group, etc.), C7-12 substituted group. Aralkyl groups (eg, benzyl group, phenethyl group, 3-phenylpropyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, etc.), and optionally substituted aryl groups (eg, phenyl group, tolyl group, xylyl group) Chlorophenyl group, bromophenyl group, methoxyphenyl group, naphthyl group, etc.) -CONHCH ₂ OR ₄ [R ₄ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, etc.)], -N =
C = O group and {D ₉ and d ₁₀ each represent a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms (eg, a methyl group, an ethyl group, etc.)} and the like. . As the polymerizable double bond group, specifically, CH ₂ 2CH—, CH ₂ CHCH—CH ₂ —, CH ₂ = CH-CONH-, _{CH 2 = CH-NHCO-, CH} 2 = CH-CH 2 -, NHCO-, CH 2 = CH-
SO _2- , CH ₂ = CH-CO-, CH ₂ = CH-O-, CH ₂ = CH-S-
And the like.

In the present invention, as a method for causing the binder resin to contain at least one functional group selected from the group of the curable functional groups, a method of introducing a polymer into a polymer by a polymer reaction, or one or a group of such functional groups. One or more monomers contained above and the above-mentioned general formula (I) (general formula (IIa) or (IIb)
) And a monomer corresponding to the “acidic group-containing copolymer component”.

For the high-molecular reaction, conventional methods of low-molecular-weight synthesis reactions in Kochi can be used as they are, for example, “The New Experimental Chemistry Course Vol. 14, edited by The Chemical Society of Japan, Synthesis and Reaction of Organic Compounds [I]-
[V] "(published by Maruzen Co., Ltd.)," Reactive Polymers "by Yoshio Iwakura and Keisuke Kurita, and the like, and are described in detail in publicly known literature and the like.

On the other hand, the "functional group which performs light and / or heat curing reaction"
Examples of the monomer containing a functional group include a vinyl compound containing the functional group, which can be copolymerized with a monomer corresponding to the repeating unit of the general formula (I). Specific examples include compounds containing the functional group in the substituents of the same compounds as the “acidic group-containing compound” described above. An example of a repeating unit containing a “heat / photocurable functional group” will be described. Here, R ₁₁ , a, d, and e have the same contents as described above, P ₁ and P ₃ each represent H or CH ₃ , and R ₁₄ has —CH ＝ CH ₂ or —CH ₂ CH ＝ CH _2. R ₁₅ is -CH = CH ₂ , Or it indicates -CH = CHCH _3, R ₁₆ is _{-CH = CH 2, -CH 2 CH} = CH
₂ , Or Z represents S or 0, T ₃ represents OH or NH ₂ ,
h represents an integer of 1 to 11, and i represents an integer of 1 to 10.

Further, the resin [A] of the present invention is a compound represented by the above general formula (I)
Together with a monomer corresponding to the copolymer component of the general formula (IIa) and (IIb) and a monomer having an acidic group,
A monomer other than these may be contained as a copolymer component.

For example, methacrylates, acrylates containing substituents other than those described in the general formula (I),
In addition to crotonic esters, α-olefin acids, vinyl alkanoates or allyl esters (eg, alkanoic acids such as propionic acid acetate, butyric acid, valeric acid), acrylonitrile, methacrylonitrile, vinyl ethers,
Itaconic esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides, methacrylamides, styrenes (eg, styrene, vinyltoluene,
Chlorostyrene, hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene,
Methanesulfonyloxystyrene, vinylnaphthalene, etc.), heterocyclic vinyls (eg, vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene,
Vinylimidazoline, vinylpyrazole, vinyldioxane, vinylquinoline, vinyltetrazole, vinyloxazine, etc.).

In the resin [A], as a method for bonding the acidic group to one terminal of the polymer main chain, a method of reacting various reagents with the terminal of a living polymer obtained by conventionally known anionic or cationic polymerization (ionic weight Method by a radical method), a method of radical polymerization using a polymerization initiator and / or a chain transfer agent containing a specific acidic group in the molecule (a method by a radical polymerization method), or an ionic polymerization method or a radical polymerization method as described above. A polymer containing a reactive group (for example, an amino group, a halogen atom, an epoxy group, an acid halide group, etc.) at the terminal obtained by the above method is converted into a specific acidic group according to the present invention by a polymer reaction. It can be easily manufactured.

Specifically, P. Dreyfuss, RPQuirk, Encycl.Polym.Sc
Review articles such as i.Eng., 7 , 551 (1987), Yoshiki Chujo, Yuya Yamashita, "Dyes and Drugs", 30 , 232 (1985), Akira Ueda, Susumu Nagai, "Science and Industry" 60 , 57 (1986), etc. In addition, it can be produced by the method described in the cited document or the like.

Specifically, as the chain transfer agent to be used, for example, the acid group or a mercapto compound containing the above-mentioned reactive group (that is, a group which can be derived from the acid group) (eg, thioglycolic acid, thiomalic acid, thiosalicylic acid) 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptopropionic acid
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-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-
Mercaptoethanol, 1-mercapto-2-propanol, 3-mercapto-2-butanol mercaptophenol-2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 4
-(2-mercaptoethyloxycarbonyl) phthalic anhydride, 2-mercaptoethylphosphonoic acid, 2-mercaptoethylphosphonoic acid monomethyl ester, or the like, or an iodized alkyl compound containing the above polar group or substituent (for example, Iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.). Preferably, a mercapto compound is used.

Specific examples of the polymerization initiator containing the acidic 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].

These chain transfer agents or polymerization initiators are each used in an amount of 0.5 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the total monomers.

Next, a preferred embodiment of the resin [B] will be described below.

The resin [B] of the present invention contains at least one repeating unit represented by the above formula (III) as a polymerization component.

In the general formula (III), b ₁ and b ₂ represent the same contents as a ₁ and a ₂ in the general formula (I).

X is _{CH 2 n COO-, CH 2 m} OCO -, - O-, or Represents Here, n and m each represent 0 or an integer of 1 to 3. X is preferably -COO-, -OCO-, -O-, -CH
₂ COO -, - represents a CH ₂ OCO- or -O-.

R ₂ has the same contents as R _{1 in} formula (I).

The resin [B] of the present invention comprises a polymer component comprising a repeating unit represented by the formula (III) and a —COOH group, a —PO ₃ H ₂ group,
-SO ₃ H group, (R ₀ represents the same content as R) and a polymerization component containing at least one acidic group selected from acid anhydride-containing groups. The acidic group-containing copolymerization component may be any of the acidic group-containing monomers that can be polymerized with the monomer corresponding to the formula (III), and is specifically used in the resin [A] described above. Compounds similar to the monomer can be mentioned.

Furthermore, in the acidic group bonded to one terminal of the polymer main chain in the resin [B '] of the present invention, preferred -PO ₃ H ₂ group as the acidic group, -SO ₃ H group, -COOH group, Cyclic acid anhydride containing groups. Specific examples of these bonding groups to the main chain include the same examples as those of the resin [A].

In the resin [B '], the acidic group which may be contained in the copolymer component of the polymer and the acidic group bonded to the terminal of the polymer main chain may be the same or different. Specific examples of the acidic group contained in these copolymer components or at the terminal of the main chain include the same as those described for the resin [A].

Further, the resin [B] may be contained in the resin [A] as a “copolymerizable component containing a crosslinkable (crosslinkable) functional group”.
The same components may be contained, and the content is 0.1 to 20.
% By weight is preferred.

Further, the resin [B] of the present invention may contain, in addition to the polymer component represented by the general formula (III) and the acid group-containing polymer component, other polymer components polymerizable with these polymer components. Specific examples include the same compounds as those exemplified as the other polymer component in the resin [A]. However, the proportion of these other polymer components present in the resin [B] is at most 30% by weight, preferably at most 20% by weight.

In the resin [B] used in the present invention, in order to synthesize the resin [B ′] in which the acidic group is bonded to the terminal of the polymer main chain, the resin [B ′] is used during the polymerization of each monomer described above. This can be achieved by using a polymerization initiator or a chain transfer agent containing a group or a specific reactive group derivable therein in the molecule, and specifically, it can be obtained by the same method as in the synthesis of the resin [A]. . However, as is conventionally known in the polymerization reaction, the weight average molecular weight of the resin is determined by appropriately adjusting the type and amount of the polymerization initiator / chain transfer agent, the polymerization temperature, the monomer concentration, the polymerization solvent, and the like. Can be set within the range.

The ratio of the amount of the resin [A] and the amount of the resin [B] used in the present invention is 5 to 60 relative to the ratio of the resin [A] and the resin [B].
95 to 40 (weight ratio), preferably 10 to 50 to 90 to 50
(Weight ratio).

In the present invention, when the resin [A] and / or the resin [B] contains a light and / or thermosetting functional group, a crosslinking agent may be used in combination to promote crosslinking in the film. Good. As the crosslinking agent to be used, a compound usually used as a crosslinking agent can be used. Specifically, the same compounds as those used for producing the above-mentioned network hydrophilic resin particles having a higher-order network structure can be used.

The amount of the crosslinking agent used in the binder resin of the present invention is preferably 0.5 to 30% by weight, particularly preferably 1 to 10% by weight based on the total amount of the binder resin.

In the present invention, a reaction accelerator may be added to the binder resin, if necessary, in order to promote a crosslinking reaction in the photosensitive layer film.

In the case of a reaction mode in which a crosslinking reaction forms a chemical bond between functional groups, for example, an organic acid (acetic acid, propionic acid, butyric acid,
Benzenesulfonic acid, p-toluenesulfonic acid, etc.).

When the cross-linking reaction is a polymerization reaction mode, a polymerization initiator (a peroxide, an azobis-based compound is preferable, and an azobis-based polymerization initiator is preferable), a monomer containing a polyfunctional polymerizable (for example, Vinyl methacrylate, allyl methacrylate, ethylene glycol acrylate, polyethylene glycol diacrylate, divinyl succinate, divinyl adipate, diallyl succinate, 2-methyl vinyl methacrylate, divinyl benzene, etc.).

Further, in the present invention, a resin other than the resin of the present invention can be used in combination. Examples of such resins include alkyd resins, polybutyral resins, polyolefins, ethylene-vinyl acetate copolymers, styrene resins, styrene-butadiene resins, acrylate butadiene resins,
And vinyl alkanoate resins.

When the other resin exceeds 30% (weight ratio) of the total amount of the binder resin using the resin of the present invention, the effect of the present invention (especially, improvement of electrostatic characteristics) is lost.

When the binder resin of the present invention contains a light and / or thermosetting functional group in the resin [A] and / or the resin [B], the resin is crosslinked or thermoset after applying the photosensitive layer-formed product. Is done. In order to carry out crosslinking or thermal curing, for example, the drying conditions are made stricter than the drying conditions at the time of the conventional photoreceptor production. For example, the drying conditions are high temperature and / or long time. Alternatively, it is preferable to further perform a heat treatment after drying the coating solvent. For example, the treatment is performed at 60 to 120 ° C. for 5 to 120 minutes. When the above-mentioned reaction accelerator is used in combination, the treatment can be performed under milder conditions.

The inorganic photoconductive material used in the present invention is photoconductive zinc oxide, but titanium oxide, zinc sulfide, cadmium sulfide, cadmium carbonate, zinc selenide, cadmium selenide, and selenium as other inorganic light guides. Telluride, lead sulfide and the like may be used in combination.

In the present invention, the total amount of the binder resin used for the photoconductive zinc oxide is 100 parts by weight of the photoconductor, a proportion of the binder resin is 10 to 100 parts by weight, preferably a proportion of 15 to 50 parts by weight. Used in.

In the present invention, various dyes can be used as spectral sensitizers as needed. For example, Harumiya Miyamoto, Hidehiko Takei, Imaging 1973 (No.8), page 12, CJ Young et al., RC
A Review 15, 469 (1954), Kohei Kiyota, IEICE Transactions J 63-C (No.2), 97 (1980), Yuji Harasaki et al., Industrial Chemistry Magazine 66 78 and 188 (1963), Tadaaki Tani , Journal of the Japan Society of photographic Science and Technology 35, 208 (1972) carbonium-based dyes of review references such as,
Diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes, polymethine dyes (eg, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain metals), etc. No.

More specifically, those using mainly carbonium dyes, triphenylmethane dyes, xanthene dyes, and phthalein dyes are described in JP-B-51-452,
-90334, JP-A-50-114227, JP-A-53-39130,
JP-A-53-82353, U.S. Pat. No. 3,052,540, U.S. Pat. No. 4,054,450, and JP-A-57-16456 are examples.

Oxonol dyes, merocyanine dyes, cyanine dyes, polymethine dyes such as rhodacyanine dyes, F.
M. Harmmar `` The Cyanine Dyes and Related Compound
s '' and the like can be used, and more specifically, U.S. Pat.No. 3,047,384, U.S. Pat.No.3,110,591,
U.S. Patent No.3,121,008, U.S. Patent No.3,125,447, U.S. Patent No.3,128,179, U.S. Patent No.3,132,942, U.S. Patent No.3,622,317, U.K. Patent No.1,226,892, U.K. Patent No.1,
No. 309,274, British Patent No. 1,405,898, JP-B-48-7814
And JP-B-55-18892.

Further, as a polymethine dye for spectrally sensitizing the near infrared to infrared light region having a long wavelength of 700 nm or more, JP-A-47-840, JP-A-47-44180, JP-B-51-41061, 1949-5034
No., JP-A-49-45122, JP-A-57-46245, JP-A-56
No. -35141, JP-A-57-157254, JP-A-61-26044,
JP-A-61-27551, U.S. Pat.No. 3,619,154, U.S. Pat.No.4,175,956, `` Research Disclosure '' 1982, 21
6, pages 117 to 118 and the like. The photoreceptor of the present invention is excellent in that even when various sensitizing dyes are used in combination, the performance is hardly changed by the sensitizing dye. Furthermore, various conventionally known additives for an electrophotographic photosensitive layer such as a chemical sensitizer can be used in combination, if necessary.
For example, the review mentioned above: Imaging 1973 (No. 8) No. 12
"Recent development and commercialization of photoconductive materials and photoreceptors", e.g., electron accepting compounds (e.g., halogen, benzoquinone, chloranil, acid anhydride, organic carboxylic acid, etc.) and Hiroshi Komon, which are described in pages and other reviews. Chapters 4 to 6 include polyarylalkane compounds, hindered phenol compounds, p-phenylenediamine compounds, and the like, which are reviewed in Japanese Science Information Co., Ltd., Publishing Division (1986).

The amounts of these various additives are not particularly limited, but are usually 0.0001 to 2.0 parts by weight based on 100 parts by weight of the photoconductor.

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

When a photoconductive layer is used as the charge generation layer of the photoreceptor having the charge generation layer and the charge transport layer, the thickness of the charge generation layer is preferably 0.01 to 1 μm, particularly preferably 0.05 to 0.5 μm.

In some cases, an insulating layer is provided for the main purpose of protecting the photoreceptor, improving durability, and improving dark attenuation characteristics. At this time, the insulating layer is set relatively thin, and the insulating layer provided when the photoconductor is used in a specific electrophotographic process is set relatively thick.

In the latter case, the thickness of the insulating layer is between 5 and 70 μm, especially 10
Set to ~ 50μ.

Examples of the charge transport material of the laminated photoreceptor include polyvinyl carbazole, oxazole dyes, pyrazoline dyes, and triphenylmethane dyes. The thickness of the charge transport layer is preferably 5 to 40 μm, particularly preferably 10 to 30 μm.

Typical examples of the resin used for forming the insulating layer or the charge transport layer include polystyrene resin, polyester resin, cellulose resin, polyether resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, A thermoplastic resin of a polyacryl resin, a polyolefin resin, a urethane resin, an epoxy resin, a melamine resin, a silicone resin, and a curable resin are appropriately used.

The photoconductive layer according to the present invention can be provided on a conventionally known support. Generally, the support of the electrophotographic photosensitive layer is preferably conductive. As the conductive support, a base material such as a metal, paper, or a plastic sheet is impregnated with a low-resistance substance in the same manner as in the related art. A substrate that has been subjected to a conductive treatment, for example, by applying a conductivity to the back surface of the substrate (the surface opposite to the surface on which the photosensitive layer is provided), and further coated with at least one layer for the purpose of preventing curling and the like. A substrate provided with a water-resistant adhesive layer on its surface, a substrate provided with at least one or more precoat layers as necessary on the surface layer of the support, or a substrate conductive plastic on which Al or the like is deposited is laminated on paper. Can be used.

Specifically, as an example of a conductive substrate or a conductive material, Yukio Sakamoto, Electrophotography, 14, (No. 1), p2-11 (197)
5), Hiroyuki Moriga, “Introduction to Special Paper Chemistry,” Polymer Publishing Association (1
975), MF Hoover, J. Macromol. Sci. Chem. A-4 (6),
Those described in pages 1327 to 1417 (1970) and the like are used.

A known method can be applied to manufacture a lithographic printing plate using the electrophotographic lithographic printing plate precursor of the present invention. That is, it is charged substantially uniformly in a dark place, and forms an electrostatic latent image by image exposure. Exposure methods include semiconductor laser, He
-Scanning exposure with Ne laser or xenon lamp,
Reflection image exposure using a tungsten lamp, a fluorescent lamp or the like as a light source, contact exposure through a transparent positive film, and the like can be mentioned. Next, the electrostatic latent image is developed with toner. As a development method, conventionally known methods, for example, cascade development,
Various methods such as magnetic brush development, powder cloud development, and liquid development can be used. Among them, liquid development is capable of forming a fine image and is suitable for producing a printing plate. The formed toner image can be fixed by a known fixing method, for example, heat fixing, pressure fixing, solvent fixing and the like.

The printing plate having the toner image thus formed is then subjected to a hydrophilic treatment of a non-image portion by a conventional method. A so-called desensitizing solution is usually used for the hydrophilization treatment. Conventionally, as this kind of desensitizing treatment solution, a cyanide-containing treatment solution containing ferrocyanate and ferricyanate as main components, an ammine cobalt complex, phytic acid and derivatives thereof, and a cyan-free treatment containing guanidine derivatives as main components Liquids, treatment liquids containing an inorganic or organic acid which forms a chelate with zinc ions as a main component, treatment liquids containing a water-soluble polymer, and the like are known.

For example, as a cyanide-containing treatment solution,
Nos. 9045, 46-39403, JP-A-52-76101, 57-10
Nos. 7889 and 54-117201.

As a phytic acid-based compound-containing treatment solution, JP-A-53-
83807, 53-83805, 53-102102, 53-1097
No. 01, No. 53-127003, No. 54-2803, No. 54-44901 and the like.

JP-A-53-104301, JP-A-53-140103 and JP-A-54-18304 disclose processing solutions containing metal complex compounds such as cobalt complexes.
And JP-B-43-28404.

As the treatment liquid containing an inorganic or organic acid, Japanese Patent Publication No. 39-1307
No. 02, No. 40-10308, No. 43-28408, No. 40-26124
And JP-A-51-118501.

As a guanidine compound-containing treatment solution, JP-A-56-11
No. 1695 and the like.

Examples of the processing solution containing a water-soluble polymer include JP-A-52-12.
No. 6302, No. 52-134501, No. 53-49506, No. 53-5502
Nos. 53-104302, JP-B-38-9665, 39-22263
And Nos. 40-763, 40-2202, and JP-A-49-36402.

In any of the above desensitizing solutions, zinc oxide in the surface layer, which is a photoconductive layer, is ionized into zinc ions, and this ion undergoes a chelation reaction with a compound that forms a chelate in the desensitizing solution. Is believed to form zinc chelates, which are deposited in the surface layer and become hydrophilic.

Therefore, the printing original plate of the present invention is a printing plate that can be printed by performing a desensitization treatment using a desensitization treatment liquid.

Preferred embodiments of the present invention can be described below.

(1) A lithographic printing plate precursor, wherein the hydrophilic resin particles form a high-order network structure.

(2) In the resin [A], as a copolymer component represented by the general formula (I), at least one of aryl group-containing methacrylate components represented by the following general formulas (IIa) and (IIb): A lithographic printing plate precursor comprising:

General formula (IIa) General formula (IIb) [In formulas (IIa) and (IIb), A ₁ and A ₂ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom,
A bromine atom, -COD ₁ or -COOD ₂ (D ₁ and D ₂ each represents a hydrocarbon having 1 to 10 carbon atoms) represent.

B ₁ and B ₂ each represent a single bond or a linking group having 1 to 4 linking atoms, each linking —COO— and a benzene ring. (3) The resin [B] contains 30% by weight or more of the copolymer component represented by the above general formula (III), and contains -COOH group, -PO ₃ H
₂ groups, -SO ₃ H group, (R ₀ represents the same content as R above) and a random copolymer containing at least one copolymer component containing at least one acidic group selected from acid anhydride-containing groups in an amount of 10% by weight or more. A lithographic printing original plate characterized by the following:

(4) The resin [B] is characterized in that at least one acidic group selected from the same acidic groups as the acidic groups described in (3) above is bonded to one end of the polymer main chain. A lithographic printing plate.

(Example) Production example 1 of hydrophilic resin particles 1: A mixed solution of 95 g of L-1 dodecyl methacrylate, 5 g of acrylic acid and 200 g of toluene was heated to 70 ° C. while stirring under a nitrogen stream. 1.5 g of 2,2-azobis (isobutyronitrile) (abbreviation: AIBN) was added thereto and reacted for 8 hours. 12 g of glycidyl methacrylate, t-
1 g of butylhydroquinone and 0.8 g of N, N-dimethyldodecylamine were added and reacted at 100 ° C. for 15 hours (dispersion resin α).

Next, the dispersion resin α7.5 g (as solid content), 2-
A mixed solution of 50 g of hydroxyethyl methacrylate and 200 g of n-heptane was heated to 65 ° C. while stirring under a nitrogen stream. To this was added 0.7 g of 2,2-azobis (isovaleronitrile) (abbreviated as AIVN) and reacted for 6 hours.

Twenty minutes after the addition of the initiator (AIVN), the homogeneous solution began to become cloudy and the reaction temperature rose to 90 ° C. After cooling, a white dispersion was obtained through a 200-mesh nylon cloth. Average particle size 0.
It was a 19 μm latex.

Production Example 2 of hydrophilic resin particles: L-2 2-phosphonoethyl methacrylate 50 g, dispersion resin α8
g (as solid content), ethyl acetate 150 g, n-hexane 1
50 g of the mixed solution was heated to 55 ° C. while stirring under a nitrogen stream. 0.5 g of AIVN was added and reacted for 4 hours to obtain a white dispersion. After cooling through a 200 mesh nylon cloth,
The resulting dispersion was a latex having an average particle size of 0.45 μm.

Production Example 3 of hydrophilic resin particles: Reaction was carried out in the same manner as in Production Example 1, except that a mixed solution of 50 g of L-3 N-vinylpyrrolidone, 10 g of dispersion resin α (as solid content), and 200 g of toluene was reacted. 0.30 μm white latex was obtained.

Production Example 4 of hydrophilic resin particles: L-4 A mixture of 31.5 g of ethylene glycol, 51.8 g of phthalic anhydride, 6.0 g of methacrylic acid, 10 g of trichloroethylene and 0.7 g of p-toluenesulfonic acid was heated and reacted for 6 hours. The reaction temperature was started at 107 ° C. and increased to 150 ° C. in 6 hours (water produced as a by-product of the reaction was removed by the Dean-Stark method).

Next, a mixed solution of 6 g of methacrylic acid, 76 g of chloroform, 11.6 g of ethanol, and β5.8 g (as a solid content) of the dispersion obtained in the above reaction was refluxed under a nitrogen stream.
0.8 g of AIBN was added thereto and reacted for 3 hours to obtain a white dispersion. It was a latex having an average particle size of 0.40 μm.

Preparation Example 5 of Hydrophilic Resin Particles: A mixed solution of 50 g of L-5 N, N-dimethylaminoethyl methacrylate, 15 g of poly (dodecyl methacrylate) and 300 g of toluene was prepared. Thus, a white dispersion having an average particle diameter of 0.28 μm was obtained.

Production Example 6 of hydrophilic resin particles: L-6 (2-hydroxyethyl acrylate / methyl methacrylate) copolymer (weight composition ratio 1/1) powder 10 g, (dodecyl methacrylate / acrylic acid) copolymer (weight composition ratio) 95/5) A mixture of 2 g and 100 g of toluene was mixed with a ball mill for 48 hours.
After a time treatment, a dispersion was obtained. The latex had an average particle size of 0.38 μm.

Production Example 7 of Hydrophilic Resin Particles: L-7 (vinyl alcohol / methacrylic acid) copolymer (weight composition ratio: 7/3) 10 g, (decyl methacrylate / N, N-dimethylaminoethyl acrylate) copolymer (weight 95/5)
A mixture of 1.8 g and 100 g of toluene was treated with a ball mill for 56 hours to obtain a dispersion. The latex had an average particle size of 0.32 μm.

Production Example 8 of hydrophilic resin particles: L-8 In Production Example 1 of hydrophilic resin particles, 2 was added to the dispersion resin α.
Except for adding 1 g of ethylene glycol dimethacrylate in addition to -hydroxyethyl methacrylate and n-heptane, the same operation as in Production Example 1 of hydrophilic resin particles was carried out to obtain latex particles having an average particle diameter of 0.25 µm.

Production Example 9 of Hydrophilic Resin Particles: L-9 In Production Example 2 of hydrophilic resin particles, 2 was added to the dispersion resin α.
-Except for adding 1.2 g of divinylbenzene in addition to phosphonoethyl methacrylate, ethyl acetate and n-hexane, the same operation as in Production Example 1 of hydrophilic resin particles was performed to obtain latex particles having an average particle diameter of 0.40 µm. Was.

Production Example 10 of hydrophilic resin particles: L-10 In Production Example 3 of hydrophilic resin particles, N was added to the dispersion resin α.
-Except for adding 1.5 g of ethylene diglycol methacrylate in addition to vinylpyrrolidone and toluene, the same operation as in Production Example 3 of hydrophilic resin particles was performed, except that the average particle diameter was the same as that in Production Example 3 of hydrophilic resin particles. Latex particles were obtained.

Production Example 11 of hydrophilic resin particles: L-11 In Production Example 4 of hydrophilic resin particles, in addition to methacrylic acid, chloroform, and ethanol, 1,6-
Except that 0.05 g of hexanediol diacrylate was added, the same operation as in Production Example 4 of hydrophilic resin particles was performed to obtain latex particles having an average particle diameter of 0.45 μm.

Production Example 12 of Hydrophilic Resin Particles: L-12 Except for adding 0.8 g of triethylene glycol dimethacrylate in Production Example 5 of hydrophilic resin particles, the same operation as in Production Example 5 of Hydrophilic Resin Particles was carried out. Particle size
0.43 μm latex particles were obtained.

Production Example 13 of hydrophilic resin particles: L-13 50 g of the following monomer (a), 30 g of methyl methacrylate, 2
A mixed solution of 17 g of hydroxyethyl methacrylate, 3 g of allyl methacrylate and 300 g of tetrahydrofuran was heated to 80 ° C. under a nitrogen stream. After adding 1.5 g of AIBN and reacting for 6 hours, the precipitate was reprecipitated in n-hexane, and the solid was collected by filtration. After drying, 84 g of a powder was obtained.

Production Example 14 of Hydrophilic Resin Particles: A mixture of 50 g of L-14 (2-hydroxypropyl methacrylate / ethyl methacrylate) copolymer (weight composition ratio 7/3) and 200 g of methylcellosolve was heated to 40 ° C. and dissolved. . 1,
1.0 g of 6-hexamethylene diisocyanate was added and stirred for 4 hours. After cooling, the mixture was reprecipitated with water, and the solid was collected by filtration.

 After drying, 35 g of a powder was obtained.

Production Example 15 of Hydrophilic Resin Particles: A mixture of 5 g of L-15 2-methyl-2-oxazoline 5 g, 1,4-tetramethylene-2,2′-bisoxazoline 1.0 g, methyl triflate 0.1 g and acetonitrile 20 g was mixed with 100. Sealing polymerization was performed at 7 ° C. for 7 hours. The obtained reaction product was reprecipitated in methanol, and the solid was collected by filtration. After drying, powder 4.1g
I got

The resin (hydrogel) obtained in this Production Example has the following structure.

Production Example 16 of hydrophilic resin particles: L-16 A mixed solution of 50 g of 2-methanesulfonylethyl methacrylate, 0.8 g of divinylsuccinic acid and 200 g of dimethylformamide was heated to 70 ° C. under a nitrogen stream, and 1.5 g of AIBN was added thereto for 8 hours. Reacted. The obtained reaction product was reprecipitated in hexane, and the solid was collected by filtration. After drying, 38 g of a powder was obtained.

Production Example 17 of Hydrophilic Resin Particles: L-17 A mixed solution of 20 g of acrylic acid, 4 g of monofunctional macromonomer AB-6 (manufactured by Toagosei Co., Ltd.), and 109 g of methyl ethyl ketone was added to a temperature of 65 ° C. under a nitrogen stream. Warmed. AIVN 0.2
g, and react for 2 hours.
Reacted for hours. After cooling, a white dispersion was obtained through a 200-mesh nylon cloth. The latex had an average particle size of 0.23 μm.

Production Examples 18 to 23 of hydrophilic resin particles: L-18 to L-23 Production Example 17 was the same as in Production Example 17, except that acrylic acid 20 g and AB-64 g were replaced with the respective compounds shown in Table A below. Each latex was produced in the same manner.

Synthesis Example 1 of Resin [A] of the Present Invention 1: [A-1] A mixed solution of 98 g of benzyl methacrylate, 2 g of acrylic acid, 3 g of thiosalicylic acid and 200 g of toluene was heated to 70 ° C. in a nitrogen stream.

2,2'-azobisisobutyronitrile (abbreviation AIBN)
1.0 g was added and reacted for 4 hours. Further, 0.4 g of AIBN was added for 2 hours; after that, 0.2 g of AIBN was further added and stirred for 3 hours. Weight average molecular weight (abbreviation w) of the obtained copolymer
Was 6.5 × 10 ³ .

Synthesis Examples 2 to 16 of Resin [A] of the Present Invention: [A-2] to [A
-16] In Synthesis Example 1 of Resin [A], each resin [A] was synthesized in the same manner as in Synthesis Example 1 except that 98 g of benzyl methacrylate and 2 g of acrylic acid were used instead of the monomers shown in Table 1 below. did. The weight average molecular weight of each resin is 6.0 × 10 ³ to 8 × 10 ³
Met.

Synthesis Examples 17 to 27 of Resin [A] of the Present Invention: [A-17] to [A
-27] In Synthesis Example 1 of Resin [A], methacrylate and mercapto compound shown in Table 2 below were used instead of 98 g of benzyl methacrylate and 3 g of thiosalicylic acid, and 150 g of toluene and 50 g of isopropanol were used instead of 200 g of toluene. Reacts in the same manner as in Synthesis Example 1,
Each resin [A] was synthesized.

Synthesis Example 28 of resin (A) of the present invention: (A-28) 1-naphthyl methacrylate 97 g, methacrylic acid 3 g,
A mixed solution of 150 g of toluene and 50 g of isopropanol,
The mixture was heated to a temperature of 80 ° C. under a nitrogen stream.

4,4'-azobis (4-cyanovaleric acid) (abbreviation AC
V.) 5.0 g was added and stirred for 5 hours. Further, 1 g of ACV was added, followed by 2 hours, and then 1 g of ACV was further added, followed by stirring for 3 hours.
The weight average molecular weight of the obtained copolymer was 7.5 × 10 ³ .

Synthesis Example 29 of Resin (A) of the Present Invention: (A-29) A mixed solution of 97 g of benzyl methacrylate, 3 g of vinylbenzenecarboxylic acid, 1.5 g of thiosalicylic acid and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. .

After adding 3.0 g of ACV and reacting for 6 hours, AIBN 0.
4 g was added and reacted for 3 hours. W of the obtained copolymer is 5.
It was 8 × 10 ³ .

Synthesis Example 1 of Resin [B] of the Invention 1: [B-1] A mixed solution of 100 g of ethyl methacrylate, 150 g of toluene and 50 g of methyl alcohol was heated to a temperature of 75 ° C. under a nitrogen stream.

0.8 g of ACV was added and reacted for 5 hours, and 0.2 g of ACV was further added and reacted for 4 hours. W of the obtained polymer is 8 × 10 ⁴
Met.

Synthesis Example 2: Resin (B) of the present invention: (B-2) methyl methacrylate 85 g, ethyl acrylate 15 g,
A mixed solution of 0.8 g of thioglycolic acid and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. (1,1'-azobis (cyclohexane-1-carbonitrile) (abbreviation ABC
C.) 0.8 g was added and reacted for 5 hours, and ABCC 0.2 g was further added and reacted for 4 hours. The w of the obtained polymer was 7.5 × 10 ⁴ .

Synthesis Example 3 of resin [B] of the present invention: [B-3] 3.5 g of methyl methacrylate, 15 g of ethyl acrylate
g, 10 g of styrene, 1.5 g of acrylic acid, and 200 g of toluene were heated to a temperature of 75 ° C. under a nitrogen stream. 1.0 g of 2,2'-azobis (isobutyronitrile) (abbreviation: AIBN)
Was added and reacted for 4 hours, and 0.6 g of AIBN was further added and reacted for 4 hours. W of the obtained polymer was 5.0 × 10 ⁴ .

Synthesis Examples 4 to 20 of resin [B] of the present invention: [B-4] to [B
-20] According to the synthesis method as shown in Synthesis Examples 1 to 3 of resin [B], polymers were synthesized from the following structures as shown in Table-3. W of each polymer was 4 × 10 ⁴ to 10 × 10 ⁴ .

Examples 1 and 2 and Comparative Examples A to C Resin [A-2] 6 g (as solid content), resin [B-
1] 34 g (as solid content), 200 g of photoconductive zinc oxide,
A mixture of 0.03 g of uranine, 0.06 g of rose bengal, 0.02 g of tetrabromophenol blue, 0.20 g of maleic anhydride and 300 g of toluene was mixed with a homogenizer (Nippon Seiki Co., Ltd.).
After dispersion at 1 × 10 ⁴ rpm for 10 minutes, 2 g of resin particles L-17 were added thereto, and the mixture was further dispersed for 1 minute. ^{To be 2} ,
It was applied with a wire bar, dried at 110 ° C. for 30 seconds, and then left in a dark place at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

Comparative Example A: An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 2 g of the dispersed resin particles L-17 were not added.

Comparative Example B: Resin used as binder resin in Example 1 [A-
2] An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 6 g of the resin [R-1] having the following structure was used instead of 6 g.

Comparative Example C: Resin used as binder resin in Example 1 [A-
An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 6 g of the resin [R-2] having the following structure was used instead of 2).

These photosensitive materials were examined for film properties (surface smoothness), charging properties (whether or not charging unevenness occurred), and pre-exposure fatigue properties. Further, the printability (ground stain, printing durability) when these photosensitive materials were used as an offset master plate was examined.

 The following results are summarized in Table-4.

The embodiments of the evaluation items shown in Table 4 are as follows.

Note 1) Smoothness of photoconductive layer: The obtained photosensitive material was measured for its smoothness (sec / cc) using a Beck smoothness tester (manufactured by Kumagaya Riko Co., Ltd.) under the condition of an air capacity of 1 cc. It was measured.

Note 2) Chargeability Each photosensitive material was left under the conditions of 20 ° C. and 65% RH for 24 hours. Next, a fully automatic plate making machine ELP-404V (manufactured by Fuji Photo Film Co., Ltd.) was used with a charging voltage of -4.5 kV and a charging speed of 20 cm / sec.
After remodeling under the forced conditions, a solid black image was used as a copy original, and a solid image (whether or not there was unevenness during charging, density of a solid portion) obtained by making a plate using ELP-T as a toner was visually evaluated.

Note 3) pre-exposure fatigue resistance V ₁₀ Recovery rate: temperature 20 ° C., in the dark of RH 65%, at -6kV with the photosensitive material in a paper analyzer (Kawaguchi Denki Co., Ltd. Paper Analyzer SP-428 type) After a corona discharge for 20 seconds, the device was allowed to stand for 10 seconds, and a surface potential V ₁₀ ^{A was} measured at this time. On the other hand, place each photosensitive material 2m below the fluorescent light source (50
0 1ux) for 20 seconds, leave it in the dark for 10 seconds,
Surface potential V ₁₀ ^B was measured in the same manner as for ₁₀ ^A. V ₁₀
The recovery rate was determined by (V ₁₀ ^B / V ₁₀ ^A ) × 100 (%).

Image sensitivity after pre-exposure Each photosensitive material was allowed to stand in a dark room at a temperature of 20 ° C. and 65% RH for 24 hours. Next, after operating under the pre-exposure conditions described in Note 3, a copy image obtained by plate-making the photosensitive material with ELP-404V using ELP-T as a toner was visually evaluated.

Note 4) Printability Background stain of raw material: Desensitizing solution EPL-E for each photosensitive material
X (manufactured by Fuji Photo Film Co., Ltd.) Using a solution diluted twice with distilled water, pass once through an etching processor to desensitize the surface of the photoconductive layer. (Oliver 52, manufactured by Sakurai Seisakusho Co., Ltd.), and visually evaluate the degree to which background stains occur on printed matter.

Printing durability after plate making: Plates were prepared for each photosensitive material under the same conditions as those described in the pre-exposure fatigue imaging property. Next, each of these original plates was passed through an etching processor twice using a desensitizing solution EPL-EX to desensitize the surface of the photoconductive layer. Using this as an offset master, the number of sheets that can be printed on an offset printing machine (identical to the above-mentioned use) without causing background stains on the non-image portion of the printed matter and the image quality of the image portion does not occur. Good performance).

As shown in Table 4, each photosensitive material of the present invention forms a photoconductive layer having good smoothness. In addition, uniform chargeability was obtained without charging unevenness during charging, and even under the condition of a photosensitive material pre-exposed before plate making, the recovery was remarkably good, almost the same as the characteristics under unexposed. Was. The actual copied image had no ground fog, and the copied image quality was clear. This is presumed to be due to the fact that the photoconductor, the spectral image sensitizing agent, and the binder resin are each adsorbed in an optimum state, and that the state is stably maintained.

In addition, the unprepared photographic material itself is desensitized with a desensitizing solution, and the contact angle with water on the surface after the treatment is as small as 10 ° C. or less, and it is sufficiently hydrophilic. I understand. Even when the printed matter was actually printed and the background stain was observed, no background stain was observed.

Furthermore, even when the plate is used as an offset master plate, the chargeability, pre-exposure fatigue property are good, and there is no background fog, and it is a clear copied image. Progress was made, and the printed matter actually printed had clear image quality without background smear even after 10,000 sheets.

In Comparative Example A in which the resin particles L did not coexist, the electrostatic properties and the image-capturability were satisfactory, but the printability was insufficient.

On the other hand, in Comparative Examples A and B using the known low-molecular-weight products, uneven charging occurred under severe conditions. Also, the pre-exposure fatigue property is large, affecting the actual imaging performance, and the copied image is deteriorated (the occurrence of ground fog, scattering of fine lines and characters, a decrease in density, etc.). Also, when the desensitization by the desensitizing treatment solution was examined, the photosensitive material at the time of the unmade plate did not have background stain on the printed matter,
It was confirmed that they were sufficiently hydrophilized. However, when the original plate that was actually made was desensitized and printed as an offset master and printed, the printed matter had noticeable background stains in the non-image area and the image quality of the image area had deteriorated since printing (thin lines and characters). Omission, decrease in concentration, etc.). This indicates that the deterioration of the image quality of the original plate obtained by plate making is not compensated by the desensitizing treatment, is reflected as it is on the printed matter, and is not practical.

From the above, only the photosensitive material of the present invention was favorable in all aspects of the smoothness, electrostatic properties and printability of the photoconductive layer.

Examples 2 to 17 In Example 1, the resin [A-2] and the resin [B-
In the same manner as in Example 1 except that 6 g of the resin [A] in Table 5 below and 34 g of each resin [B] were used instead of 1),
Each electrophotographic photosensitive material was produced.

The photosensitive material of the present invention has a chargeability, a dark charge retention rate,
Excellent light sensitivity and the actual copy image is high temperature and high humidity (30 ℃,
Even under severe conditions (80% RH) or pre-exposure fatigue conditions, clear images without fog were obtained.

Further, when this was used as an offset master master, at least 7,000 or more prints of clear image quality without background fog could be printed.

Example 18 Resin [A-30] 6.5 g having the following structure, resin [B-19]
33.5 g, zinc oxide 200 g, uranine 0.03 g, methine dye (III) 0.040 g having the following structure, methine dye (IV) 0.0 having the following structure
A mixture of 35 g, 0.01 g of 4-hydroxybenzoic acid and 240 g of toluene was dispersed in a homogenizer at 1 × 10 ⁴ rpm for 10 minutes. To this dispersion, 0.5 g of glutanic anhydride was added, and further dispersed in a homogenizer at 5 × 10 ³ rpm for 1 minute.

This was applied to a conductive treated paper with a wire bar so as to have a dry adhesion amount of 22 g / cm ^2, and heated at 110 ° C. for 15 seconds.
Next, after further heating at 140 ° C. for 2 hours, the mixture was allowed to stand at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

The characteristics of each photosensitive material were examined in the same manner as in Example 1. As a result, each photosensitive material is excellent in chargeability and pre-exposure fatigue, and the actual copied image is clear even under such severe conditions without occurrence of background fogging and fine line skipping. Gave the picture. Further, when printed as an offset master original, at least 10,000 or more prints of a clear image having no background fogging in the non-image area could be printed in any case.

Examples 19 to 22 Instead of 6.5 g of the resin [A-30] and 0.5 g of glutanic anhydride as a cross-linking agent in Example 18, each of the compounds shown in Table 12 below was used instead of the resin [B-19]. And resin [B-
20] Except for using 33 g, the same procedures as in Example 36 were carried out to prepare respective photosensitive materials.

The characteristics of each photosensitive material were examined in the same manner as in Example 18. As a result, each photosensitive material is excellent in chargeability and pre-exposure fatigue, and the actual copied image is clear even under such severe conditions without occurrence of background fogging and fine line skipping. Gave the picture. Further, when printed as an offset master plate, more than 8,000 sheets of printed matter having clear images without background fog in the non-image area could be printed in any case.

Examples 23 to 32 In Example 1, except that 2 g (as solid content) of each of the resin particles in Table 7 below was used instead of 2 g of the binder resin particles,
Each photosensitive material was produced in the same manner as in Example 1.

The electrostatic properties and printing properties were evaluated by operating in the same manner as in Example 2.

In each photosensitive material, both the electrostatic characteristics and the imaging properties were the same as those in Example 1.
It showed almost the same characteristics as.

In addition, when the performance of the offset lithographic original plate was evaluated by desensitization treatment, the water retention of the raw plate was good, and the printing result after the actual plate making was able to print 6,000 or more sheets.

Example 33 and Comparative Examples DF Resin [A-1] 6 g, resin [B-2] 34 g, resin particles [L-19] 2 g, zinc oxide 200 g, heptamethylenediamine dye 0.02 represented by the following structural formula g and 300 g of toluene were dispersed in a homogenizer at a rotation speed of 1 × 10 ⁴ rpm for 10 minutes.

With this in conductive treated papers, coated at a dry coating weight 20 g / m ² and made as a wire bar, after heating for 15 seconds at 100 ° C., 1
Heat at 20 ° C. for 2 hours. Then, it was left standing in a dark place at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material.

Comparative Example D An electrophotographic photosensitive material was produced in the same manner as in Example 33 except that the resin particles L-2 g were removed.

Comparative Example E An electrophotographic photosensitive material was prepared in the same manner as in Example 33, except that 6 g of the resin [A-1] was used instead of 6 g of the resin [A-1].

Comparative Example F An electrophotographic photosensitive material was produced in the same manner as in Example 33, except that 6 g of the resin [A-1] was used instead of 6 g of the resin [A-1].

Various characteristics of these light-sensitive materials were examined in the same manner as in Example 1. The results are summarized in Table-8.

In the evaluation items of Table-8, the imaging method and the printing durability after plate making were performed by the following methods, and the other items were performed by the same method as each item of Example 1.

Note 5) Image-capability after pre-exposure: Each photosensitive material was left in a dark room at a temperature of 20 ° C. and a humidity of 65% RH for 24 hours, and then operated under the pre-exposure conditions described in Note 3). Is charged at −6 kV, and a 2.8 mW gallium-aluminum-arsenic semiconductor laser (oscillation wavelength
780 nm) on a photosensitive material surface at an irradiation dose of 64 erg / cm ² at a pitch of 25 μm and a scanning speed of 300 m / sec, and ELP-T (Fuji Photo Film Co., Ltd.) as a liquid developer Was developed and fixed, and the copied image (fog, image quality) obtained by fixing was visually evaluated.

Note 6) Printing durability after plate making Each plate of the photosensitive material was made under the same conditions as described in Note 5). The desensitizing treatment and printing operation are described below in Note 4).
And the printed matter was evaluated.

In the photosensitive material of the present invention, the photoconductive layer has sufficient smoothness, no unevenness during charging, and even if there is pre-exposure, the recovery is remarkably quick, and the actual copied image is stable and good. ,
A clear image without fog was obtained. Even when used as an offset master, the non-image area is sufficiently hydrophilic and no background stains are seen, and a clear image of 8000 prints is obtained.
It was obtained even after printing.

However, Comparative Example D, which does not coexist with the resin particles of the present invention,
The printability deteriorated remarkably.

On the other hand, in Comparative Examples E and F using the known low-molecular-weight compounds, the chargeability and the pre-exposure fatigue property were reduced. Worsened. In addition, when used as an offset master, a fugitive print cannot be obtained due to fogging of printed matter and deterioration of image quality.

As described above, an electrophotographic photosensitive member that satisfies electrostatic characteristics and printability only when the resin of the present invention is used is obtained.

Examples 34 to 41 In Example 33, instead of the resin [A] 6.5 g and resin [B] 33.5 g shown in Table 9 below as a binder resin, and instead of the cyanine dye [I] 0.02 g, a dye having the following structure [ II) 0.018g
An electrophotographic light-sensitive material was produced under the same conditions as in Example 33 except that the above was used.

Each photosensitive material of the present invention is excellent in chargeability and pre-exposure fatigue property, and an actual copied image can produce a clear image without occurrence of ground fog or fine line jump even under such severe conditions. Gave. Further, when printed as an offset master original, 8,000 or more printed materials with clear images without background fog in the non-image area could be printed.

Examples 42 to 49 In Example 33, 6 g of each of the resin [A] and 2 g of each of the resin particles L were used.
Were replaced with the compounds shown in Table 10 below, and heptamethine cyanine dye [III] was replaced with 0.02 g of heptamethine cyanine dye [V] having the following structure. Produced.

The characteristics of each of these photosensitive materials were measured in the same manner as in Example 33. The results are summarized in Table-10.

Each photosensitive material of the present invention was excellent in charging unevenness and pre-exposure fatigue, and an actual copy image obtained a clear image without occurrence of background fogging and fine line skipping. Further, in the case of a resin containing a specific methacrylate component, better imaging properties were exhibited.

When each photosensitive material is used as an offset master plate, the desensitizing treatment with the desensitizing solution proceeds sufficiently, and the contact angle with water of the non-image portion of each master plate is as small as 10 degrees or less, It was sufficiently hydrophilic.
At the actual printing, 8000 sheets of clear prints without fog were printed.

(Effect of the Invention) According to the present invention, it is possible to obtain an electrophotographic photosensitive member having improved charging characteristics and pre-exposure fatigue. In addition, a lithographic printing original plate capable of obtaining a printed matter having a clear print quality can be obtained as an electrophotographic lithographic printing original plate.

Further, as a copolymer component of the resin [A], the above-mentioned formula (IIa)
Alternatively, when a specific methacrylate component represented by (IIb) is contained, better imaging properties can be obtained.

Claims (2)

(57) [Claims] 1. An electrophotographic lithographic printing plate precursor comprising a conductive support plate and a photoconductive layer containing at least one layer of photoconductive zinc oxide and a binder resin. Contains hydrophilic resin particles having an average particle diameter equal to or smaller than the maximum particle diameter of the photoconductive zinc oxide particles, and the binder resin is at least one of the following resins [A]
A lithographic printing plate precursor comprising at least one of a seed and a resin [B]. Resin [A]: having a weight average molecular weight of 1 × 10 ³ to 1 × 10 ⁴ , containing 30% by weight or more of a polymerization component represented by the following general formula (I), and -PO ₃ H
₂ group, -SO ₃ H group, -COOH group, R represents a hydrocarbon group or an -OR 'group (R' represents a hydrocarbon group) and a polymerization component containing at least one acidic group selected from cyclic acid anhydride-containing groups. A resin containing at least one acidic group selected from the same acidic groups as described above at one end of the polymer main chain. General formula (I) [In the formula (I), a ₁ and a ₂ each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. R ₁ represents a hydrocarbon group. Resin [B]: A resin having a weight average molecular weight of 3 × 10 ⁴ to 1 × 10 ⁶ and containing at least 30% by weight of a polymerization component represented by the following general formula (III). General formula (III) [X in the formula (III) is CH _{2 n} COO−, CH _{2 m} OCO−, −
O- or (Where n and m each represent 0 or an integer of 1 to 3). b ₁ , b ₂ and R ₂ represent the same contents as a ₁ , a ₂ and R ₁ in the formula (I). ] 2. The lithographic printing plate precursor according to claim 1, wherein at least one of the resin [A] and the resin [B] contains a heat and / or photocurable functional group.