JPH06130708A - Planographic printing original plate - Google Patents

Abstract

PURPOSE:To provide a planographic printing original plate free from excellent in desensitization and having high resistance to plate wear. CONSTITUTION:A binding resin (A) containing a functional group forming a hydrophilic group by chemical reaction treating and a photo/thermosetting group is contained in the surface layer of the planographic printing original plate as a binding resin and a binding resin (B), which is a graft type copolymer containing a macromonomer (M) made by joining a polymerizable double bond to one terminal of the B block of an AB block copolymer composed of A block containing a specific polar group and a B block containing a specific polymer component, is contained in a photoconductive layer as a binding resin.

Description

Detailed Description of the Invention

[0001]

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

[0002]

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

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

In recent years, a method of preparing a printing plate of a hydrophilic treatment type on the surface of a non-image area by providing a specific resin layer on an ordinary electrophotographic photosensitive member has been proposed.
No. 6 publication. That is, a printing plate is disclosed in which a surface layer comprising a vinyl ether, a maleic anhydride copolymer, and a hydrophobic resin compatible with the vinyl ether is provided on the electrophotographic photosensitive layer. This layer is a layer (hydrophilizable layer) which can be hydrophilized by hydrolyzing the acid anhydride ring portion by treating the non-image portion with an alkali after forming a toner image.

However, the vinyl ether-maleic anhydride copolymer used therein becomes water-soluble when it is ring-opened and hydrophilized, so that it is compatible with other hydrophobic resins. Even if the layer is formed by (1), the water resistance is extremely poor, and the printing durability is limited to 500 to 600 sheets at most.

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

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

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

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

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

[0011]

Such a resin of the type which produces a hydrophilic group by a decomposition reaction is a protective group which is prepared by decomposing a carboxyl group or a hydroxyl group masked with a protective group in advance with a treatment liquid. Therefore, this type of resin is stable and does not hydrolyze under the influence of atmospheric humidity (moisture) during storage, and is rapidly deprotected during hydrophilization treatment. An important characteristic is that the reaction proceeds to form a hydrophilic group and the hydrophilicity of the non-image area can be improved.

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

Further, a more detailed evaluation of the lithographic printing plate precursor using the above-mentioned resin that produces a hydrophilic group will show variations in printing conditions on an offset printing machine (for example, dampening during printing). Depending on the amount of water supply, etc.) or the type of printing machine (Synflow method or Molton method), the number of prints increases from the occurrence of scumming at the time of printing / printing until the production of a scum with no scumming: The problem is that the latitude is narrow to obtain stable and high printing durability at the time of printing, such as a reduction in the number of printed sheets without causing stains.

On the other hand, in the lithographic printing plate precursor using photoconductive zinc oxide, the surface of the lithographic printing plate is made hydrophilic by chemically treating zinc oxide with a desensitizing solution under acidic conditions, as is known.
The treatment liquids exhibiting good desensitizing ability are limited to those containing yellow blood salt as a main ingredient.

Due to these restrictions, it is necessary to limit the waste liquid treatment method of the desensitizing treatment liquid containing yellow blood salt as the main ingredient, and it is necessary to print while maintaining the acidic conditions. , When using neutral paper printing paper, the number of printable sheets decreases sharply (that is, printing durability deteriorates),
Alternatively, since the principle of desensitization is the formation of a hydrophilized product by a chelation reaction, it easily interacts with polyvalent metal ions contained in the color ink during printing, which causes abnormal emulsification of the ink. As a result, in particular, when performing color printing, there are various problems and restrictions such as a reduction in the number of printable sheets.

The present invention improves the above-mentioned problems of the conventional lithographic printing plate precursor. That is,
One of the objects of the present invention is to provide an offset original plate which is stable even when the printing conditions in the printing process are varied and is color printed, and produces not only uniform background stains but also spotwise background stains. It is an object of the present invention to provide a lithographic printing plate precursor that is excellent in desensitizing property and that is not caused.

A second object of the present invention is to provide a lithographic printing plate precursor having a high printing durability and having very little loss of paper at the time of printing to any offset printing machine having a different printing system. . An object 3 of the present invention is to provide a lithographic printing plate precursor having high printing durability, which can use a combination of a desensitizing treatment liquid and a fountain solution with a treatment liquid having no environmental hygiene problem. .

An object 4 of the present invention is to provide a lithographic printing plate precursor capable of high printing durability, even if neutral paper is used as the printing paper, like the acidic paper, without causing any problems in the printing process. That is.

[0019]

The present invention has the above-mentioned object of providing at least one photoconductive layer containing at least a photoconductive compound and a binder resin on a conductive support, and further providing the uppermost layer thereof. In a lithographic printing plate precursor using an electrophotographic photosensitive member having a surface layer provided on, the binder resin of the surface layer,
A lithographic printing plate precursor comprising at least one binder resin [A] below and at least one binder resin [B] below as a binder resin in the photoconductive layer. It As the binder resin [A], a polymer component (a) containing at least one functional group capable of forming a —COOH group by a chemical reaction treatment, —SO ₃ H group, —S by the treatment.
Polymer component (b) containing at least one functional group selected from functional groups forming O ₂ H group and —PO ₃ H ₂ group
And a copolymer containing at least the polymer component (c) containing at least one heat and / or photocurable group. The binder resin [B] has a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , and has —PO ₃ H ₂ groups, —COOH groups,
-SO ₃ H group, a phenolic OH group, -P (= O) (O
H) R ¹ [R ¹ represents a hydrocarbon group or a —OR ² (R ² represents a hydrocarbon group) group] and a cyclic acid anhydride group containing at least one polar group. Terminal of polymer main chain of B block of AB block copolymer composed of A block containing at least one combination component and B block containing at least polymer component represented by the following general formula (I) A graft copolymer containing at least one monofunctional macromonomer (M) having a polymerizable double bond group bonded thereto as a copolymerization component is used.

[0020]

[Chemical 3]

[In the formula (I), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. V ¹ was -COO -, - OCO-, chromatography (CH _{2) a} O
CO-, (is a represents an integer of 1-3.) Over _{(CH 2) a COO-, -} O -, - SO 2 over, over CO-, over CON
(Z ¹ )-, -SON (Z ¹ )-, -CONHCOO
Represents —, —CONHCONH— or —C ₆ H ₄ — (wherein Z ¹ represents a hydrogen atom or a hydrocarbon group). R
³ represents a hydrocarbon group. However, when V ¹ represents —C ₆ H ₄ —, R ³ represents a hydrogen atom or a hydrocarbon group. ]

Preferably, in the copolymer component (a) contained in the binder resin [A], at least one functional group which produces a --COOH group is a polymer chain main chain of the copolymer. Is directly connected to. More preferably, the surface layer of the present invention contains a heat and / or photocurable compound together with the binder resin [A].

In a preferred embodiment of the binder resin [B], the resin [B] is used as a copolymer component which is copolymerized with the macromonomer (M), represented by the following general formula (XIIIa) and the following general formula (XIIIa) It contains at least one of the aryl group-containing methacrylate components of XIII b).

[0024]

[Chemical 4]

[In the formulas (XIII a) and (XIII b), A
¹ and A ² are each independently a hydrogen atom and a carbon number of 1 to 1.
0 hydrocarbon group, chlorine atom, -COZ ² or -COOZ
² (Z ² represents a hydrocarbon group having 1 to 10 carbon atoms), B ¹ and B ² each represent a single bond or a connecting group having 1 to 4 connecting atoms for connecting —COO— and the benzene ring. Represent ]
Further, the photoconductive compound used in the photoconductive layer of the present invention may be any one as long as it is used by being dispersed in the binder resin, but it is particularly low cost and non-polluting, A system using at least a conductive zinc oxide and / or a photoconductive titanium oxide and a spectral sensitizing dye in combination is preferable.

[0026]

The lithographic printing plate precursor of the present invention is different from the conventional system in which zinc oxide is chemically treated to express hydrophilicity and utilizes the desensitizing property for printing ink, and therefore, is oxidized due to hydrophilicity. The binder resin used for the surface layer is designed to be water-insoluble and hydrophilic without using zinc at all. Therefore, as the photoconductor, any one can be used as long as it is used in the resin dispersion type, in consideration of the cost and pollution-free as the lithographic printing plate precursor, as described above, Conductive zinc oxide and / or titanium oxide are preferred.

The conventional lithographic printing plate precursor using zinc oxide has a printing durability of about 10,000 sheets under specific conditions, but the reduction or solution of these specific conditions is described above. This is a difficult problem in principle. Therefore, the present inventors have a performance as an electrophotographic photosensitive member that forms a copied image showing as good reproducibility as possible on a document,
In addition, when it was used as a printing original plate after desensitizing treatment, it was previously disclosed in order to eliminate the above-mentioned various restrictions during printing and to maintain high printing durability of 10,000 sheets or more. Further advanced study including the contents of the applied technology. As a result, since the binder resin [A] and the binder resin [B] of the present invention are arbitrarily adjusted and used, and further, the surface layer has a higher-order structure, the original plate of the present invention is extremely excellent. , Has been found to exhibit excellent performance.

That is, in the photoconductive layer, a good copy image is formed by an electrophotographic method, and in the surface layer, only the binder resin is used to make a printing original plate by desensitizing treatment by a chemical reaction. Is. In order to show the excellent performance of the printing original plate after chemical treatment by using only the binder resin in the surface layer, wetting of the surface layer film (non-image area) after desensitization to water It is extremely important that the property is extremely good (specifically, the contact angle value to distilled water is 0 °), and at the same time, the entire surface layer after the desensitizing treatment has an appropriate water absorption amount. Whether or not this greatly affects or is stable with respect to the difference in the printing method or the change in the dampening water supply amount (that is, the balance between the dampening water and the printing ink on the printing machine) during printing It has become clear that they have control. Furthermore,
It was also clarified that whether or not this state can be maintained as printing continues affects high printing durability.

In order to achieve and maintain such a film structure in the surface layer of the lithographic original plate, as shown in the binder resin [A] of the present invention, the hydrophilic group formed by the desensitizing treatment is used. A carboxyl group and at least one hydrophilic group selected from a sulfo group, a sulfino group and a phosphono group in the same polymer chain, and more preferably, the carboxyl group is a polymer main chain. It is important that the binder resin [A] further contains a photo- and / or thermosetting group, and the surface layer after film formation has a high-order cross-linking structure. In addition, it is important to use a photo- and / or thermosetting compound in combination in order to sufficiently form the higher order crosslinked structure.

That is, the polymer chain (surface layer) expressing a hydrophilic group in the desensitizing treatment of the present invention exhibits sufficient desensitizing property and has a high-order crosslinked structure. The hydrophilized polymer is made water-insoluble to maintain the strength of the membrane, and the membrane absorbs water to maintain a constant water absorption amount. At this time, it is considered that the swelling property of the film is different depending on the degree of cross-linking of the high-order cross-linking structure of the film and affects the water absorption amount of the film.

In the case of a lithographic plate using a conventionally known resin which produces a carboxyl group, swelling of the film is suppressed, and although the film strength is high to some extent, a high-order crosslinked structure is formed so as not to damage the film. The surface wettability and the water absorption of the film were insufficient, and depending on the printing conditions and the like as described above, the printed matter was scummed after printing. This is presumed to be because even if the film strength is good, the film state cannot maintain sufficient wettability and water absorption since the hydrophilicity is insufficient with only the carboxyl group.

On the other hand, when a conventionally known resin which produces a sulfone group or a phosphono group is used, the crosslinking necessary for suppressing the swelling property of the film and sufficiently crosslinking until the high printing durability can be maintained. When the components are introduced, these cross-linking components are lipophilic, and as a result, the surface wettability of the resin is lowered, and scumming occurs from printing. On the other hand, when the introduction of the lipophilic cross-linking component is suppressed by using the resin that produces the sulfone group or the phosphono group, the produced sulfo group or phosphono group has very high hydrophilicity as compared with the carboxyl group, and The high-order structure film was able to retain a sufficient amount of water absorption, and it was possible to obtain a printed matter with no background stain after printing. However, when the printing durability was examined on a large-sized printing machine where the printing pressure during printing was severe, the printing durability was reduced. It is considered that this is because it is difficult to satisfy both the strength of the film, the surface wettability of the film and the water absorption amount of the film.

Therefore, as a means for satisfying both the expansion of latitude during printing and high printing durability, an original plate in which the above-mentioned conventional carboxyl group-forming resin and a sulfo group and / or phosphono group-forming resin are mixed is examined. However, the performance was not improved. However, by using the binder resin [A] of the present invention, that is, the resin [A] containing a carboxy group, a sulfo group / phosphono group and a heat / photocurable group, a film as an original plate as described above is formed. It was confirmed that it was possible to control the state and find a high-performance original plate.

Further, the chemical structure of the polymer component in which at least one of the generated carboxyl groups is directly linked to the main chain of the polymer, the surface wettability is further improved, and the latitude of printing conditions is further expanded. Found. As a premise for effectively utilizing the performance as the printing original plate as described above, it is necessary to improve the reproducibility of the copied image at the same time. This was made possible by containing the binder resin [B] of the present invention in the photoconductive layer and using it in combination with the binder resin [A].

That is, a low molecular weight binder resin [B] containing a specific polar group is used in a photoconductive layer together with photoconductive particles and various sensitizers in the dispersion system. [B] is capable of sufficiently adsorbing to photoconductive particles to uniformly disperse the particles, and suppressing the aggregation between the particles due to the very short polymer chain, and also a spectral sensitizing dye / chemical Do not exclude that the sensitizer molecules such as sensitizers are sufficiently adsorbed on the surface of the particles, and the binder resin [B] is sufficiently adsorbed on the active sites on the surface of the photoconductor to compensate the trap. It is considered that the electrophotographic photosensitive member has good electrostatic characteristics and actual reproduced image reproducibility (imaging property).

Further, in the present invention, as the low molecular weight resin [B], a methacrylate component having a specific substituent containing a benzene ring or a naphthalene ring, which is represented by the above general formula (XIIIa) and general formula (XIIIb). When a resin [B] containing a resin (hereinafter, this low molecular weight compound is particularly referred to as a resin [BB]) is used, electrophotographic characteristics (especially V ₁₀ , D.R.R. , E
_1/10 ) improvement can be achieved.

The reason for this is not clear, but one reason is that due to the effect of the planar benzene ring or naphthalene ring, which is the ester component of the methacrylate, these polymers at the surface of the photoconductor particles in the film. This is probably because the molecular chains are arranged properly. This effect was particularly remarkable with polymethine dyes or phthalocyanine pigments, which are particularly effective as dyes for spectral sensitization from near infrared to infrared light.

The binder resin [A] of the present invention will be described in detail below. The weight average molecular weight of the resin [A] is preferably 5 × 10 ³ to 1 × 10 ⁶ , and more preferably 1 × 1.
It is 0 ^{4 to} 5 × 10 ⁵ , and the glass transition point of the resin [A] is preferably in the range of −10 ° C. to 110 ° C., more preferably −5 ° C. to 100 ° C. When the molecular weight of the resin [A] is smaller than 5 × 10 ³ , the effect of crosslinking the higher-order structure after forming the photoconductive layer is insufficient, and it becomes difficult to maintain the film strength as a printing original plate. On the other hand, when the molecular weight is more than 1 × 10 ⁶ , the uniformity of the coating film is impaired, and the electrostatic properties of the photoreceptor are deteriorated or the film strength is reduced.

The abundance ratio of each polymer component of the resin [A] of the present invention is such that the total amount of the functional group-containing components expressing the hydrophilic group [that is, the polymer component (a) and the polymer is 100 parts by weight of the total polymer]. The total amount of component (b)] is 60 to 55% by weight, preferably 60
Is about 90% by weight. Moreover, the ratio of the polymer component (a) and the polymer component (b) is such that the total amount of the component (a) and the component (b) is 1
The amount of component (a) / component (b) is 5 to 90 as 100 parts by weight.
% / 95 to 10% by weight, preferably 10 to 80% by weight / 80 to 20% by weight.

The abundance ratio of the component (c) containing a photo- and / or thermosetting group is 5 to 40% by weight, preferably 1%.
It is 0 to 30% by weight. In addition, the content of other copolymerization components other than these is at most 35% by weight.

If the content of each polymer component is out of the above range, the effect of the present invention as a printing original plate will be reduced. That is, the reduction of the background stain suppression from the printing at the time of printing,
The number of printed sheets may decrease. First, the functional group used in the present invention for decomposing to generate at least one carboxyl group (hereinafter, may be simply referred to as a carboxyl group-forming functional group) will be described in detail.

The carboxyl group-forming functional group of the present invention produces a carboxyl group by decomposition, but the number of carboxyl groups produced from one functional group may be one or two or more. According to one preferred embodiment of the present invention, the carboxyl group-forming functional group-containing resin has the general formula (II) [—COO
-L ₁ ] is a resin containing at least one functional group.

In the general formula (II) [-COO-L ₁ ], L ₁ is

[0044]

[Chemical 5]

Represents However, R ₁ and R _{2, which} may be the same or different, each represents a hydrogen atom or an aliphatic group, X represents an aromatic group, Z is a hydrogen atom, a halogen atom, a trihalomethyl group, an alkyl group, CN, -N
_{O 2, -SO 2 R 1 '} , -COOR 2', -O-R 3 '
Or —CO—R ₄ ′ (provided that R ₁ ′, R ₂ ′, R ₃ ′,
R ₄ ′ each represents a hydrocarbon group), and n, m
Represents 0, 1 or 2.

A ₁ and A ₂ may be the same or different and Ha
It represents an electron-withdrawing group having a positive substituent constant σ value of mmett. R ₃ represents a hydrogen atom or a hydrocarbon group. R _4, R _5, R _6, which may be the same or different from each other, represent a hydrocarbon group or -O-R ₅ '(where, R _5' represents a hydrocarbon group).

Y ₁ represents an oxygen atom or a sulfur atom,
R ₇ , R ₈ and R ₉ may be the same or different and each represents a hydrogen atom or an aliphatic group, and p represents an integer of 5 or 6. Y ₂ represents an organic residue forming a cyclic imide group.
Formula (II) - functional group [COO-L _1], which generates a carboxyl group by decomposition is described hereinafter in more detail.

L ₁ is

[0049]

[Chemical 6]

In the case of representing, R ₁ and R ₂ may be the same or different from each other, preferably a hydrogen atom,
Or a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, trifluoromethyl group, butyl Group, hexyl group, octyl group, decyl group, hydroxyethyl group, 3-
Chloropropyl group), X is preferably a phenyl group or naphthyl group which may be substituted (for example, phenyl group, methylphenyl group, chlorophenyl group, dimethylphenyl group, chloromethylphenyl group, naphthyl group, etc.), Z is preferably a hydrogen atom, a halogen atom (for example, chlorine atom, fluorine atom, etc.), a trihalomethyl group (for example, trichloromethyl group, trifluoromethyl group, etc.), a linear chain having 1 to 12 carbon atoms which may be substituted, or Branched alkyl group (for example, methyl group, chloromethyl group, dichloromethyl group, ethyl group, propyl group, butyl group, hexyl group, tetrafluoroethyl group, octyl group, cyanoethyl group, chloroethyl group, etc.), -CN,- NO ₂ , -SO
₂ R ₁ ′ [R ₁ ′ is an aliphatic group (for example, an optionally substituted alkyl group having 1 to 12 carbon atoms: specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a chloroethyl group, a pentyl group, Aralkyl group having 7 to 12 carbon atoms which may be substituted such as octyl group: specifically, benzyl group, phenethyl group, chlorobenzyl group, methoxybenzyl group, chlorophenethyl group, methylphenethyl group, etc.) or aromatic group ( For example, a phenyl group or naphthyl group which may contain a substituent: specifically, a phenyl group, a chlorophenyl group, a dichlorophenyl group, a methylphenyl group, a methoxyphenyl group, an acetylphenyl group, an acetamidophenyl group, a methoxycarbonylphenyl group, represents a naphthyl group)], -COOR ₂ '(R _2' is the R ₁ 'is synonymous _{with), - O-R 3'} ( ₃ 'the R _1' represents the same meaning as) or _{-CO-R 4 '(R 4} ' has the same meaning as above R ₁ '). n and m represent 0, 1 or 2.

L ₁ is

[0052]

[Chemical 7]

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

L ₁ is

[0055]

[Chemical 8]

In the case of representing, A ₁ and A ₂ may be the same or different from each other, at least one of which is an electron-withdrawing group, and the sum of the Hammett σ _p values of -A ₁ and -A ₂ is the same. It may be 0.45 or more. Examples of the electron-withdrawing group here include, for example, an acyl group, an aroyl group,
Formyl group, alkoxycarbonyl group, phenoxycarbonyl group, alkylsulfonyl group, aroylsulfonyl group, nitro group, cyano group, halogen atom, halogenated alkyl group, carbamoyl group and the like can be mentioned.

The Hammett's σ _p value is usually used as an index for estimating the degree of electron withdrawing / donating of a substituent, and the larger it is on the + side, the stronger the electron withdrawing group. Specific numerical values for each substituent are described in Naoki Inamoto, "Hammett's Rule-Structure and Reactivity," Maruzen (1984) and the like. In addition, Ham in this system
The σ _p value of mett is considered to be additive, and −A
_{Both 1} and -A ₂ need not be electron withdrawing groups. Therefore, for example, when -A ₁ is an electron-withdrawing group, the other substituent of -A ₂ has a sum of σ _p values of -A ₁ and -A ₂ of 0.
Any material may be used as long as it is 45 or more, and there is no particular limitation.

L ₁ is

[0059]

[Chemical 9]

In the case of representing, Y ₁ represents an oxygen atom or a sulfur atom. R ₇ , R ₈ and R ₉ may be the same or different from each other, preferably a hydrogen atom, and an optionally substituted linear or branched alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group,
Octadecyl group, chloroethyl group, methoxyethyl group,
Methoxypropyl group etc.), optionally substituted alicyclic group (eg cyclopentyl group, cyclohexyl group etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg benzyl group, phenethyl group, chlorobenzyl group, Methoxybenzyl group, etc.), optionally substituted aromatic group (eg, phenyl group, naphthyl group, chlorophenyl group, tolyl group, methoxyphenyl group, methoxycarbonylphenyl group, dichlorophenyl group, etc.) or —O—R ₆ ′ ( R ₆ ′
Represents a hydrocarbon group, specifically, the above R ₇ , R ₈ and R
_The same substituents as the hydrocarbon group ₉ are shown).

P represents an integer of 5 or 6. L ₁ is

[0062]

[Chemical 10]

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

[0064]

[Chemical 11]

In the formula (III), R ₁₂ and R ₁₃ may be the same or different and each may be substituted with a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.) or a C 1-18 substituent. Alkyl group [eg methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2
-Chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, 3-chloropropyl group, 2- (methanesulfonyl) ethyl group, 2- (ethoxyoxy) ethyl group, etc.], substituted with 7 to 12 carbon atoms Aralkyl group (eg, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, dimethylbenzyl group, methoxybenzyl group, chlorobenzyl group, bromobenzyl group, etc.), which may be substituted with 3 to 18 carbon atoms Good alkenyl groups (eg allyl group, 3-methyl-2-propenyl group, 2
-Hexenyl group, 4-propyl-2-pentenyl group,
12-octadecenyl group, etc.), —S—R ₇ ′ [R ₇ ′ is a substituent having the same meaning as the alkyl group, aralkyl group, alkenyl group of R ₁₂ or R ₁₃ above, or an aryl group which may be substituted. (For example, phenyl group, tolyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group,
Ethoxyphenyl group, ethoxycarbonylphenyl group, etc.)] or —NHR ₈ ′ (R ₈ ′ has the same meaning as R ₇ ′). Further, R ₁₂ and R ₁₃ may represent a ring-forming residue [eg, a 5- or 6-membered monocyclic ring (eg, cyclopentyl ring, cyclohexyl ring) or a 5- or 6-membered bicyclo ring (eg, bicyclo ring). Heptane ring,
Bicycloheptane ring, bicyclooctane ring, bicyclooctene ring, etc.), and these rings may not be substituted, and the substituents include the same as those described above for R ₁₂ and R ₁₃ .

Q represents an integer of 2 or 3. Formula (IV)
In the above, R ₁₄ and R ₁₅ may be the same or different, and the above R ₁₂ ,
It has the same contents as R ₁₃ . Furthermore, R ₁₄ and R ₁₅
May represent an organic residue that continuously forms an aromatic ring (eg, benzene ring, naphthalene ring, etc.). 6-membered monocyclic ring (for example, cyclopentyl ring, cyclohexyl ring, etc.),
It represents a 5-membered to 12-membered aromatic ring (for example, a benzene ring, a naphthalene ring, a thiophene ring, a pyrrole ring, a pyran ring, a quinoline ring, etc.).

L ₁ is

[0068]

[Chemical 12]

In the case of representing, R ₁₀ and R ₁₁ have the same meanings as R ₆ . Furthermore, another preferable embodiment of the present invention is a resin containing at least one oxazolone ring represented by the following general formula (V).

[0070]

[Chemical 13]

In the general formula (V), R ₁₆ and R _{17, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group, or R ₁₆ and R ₁₇ together form a ring. May be. Preferably, R ₁₆ and R ₁₇ may be the same as or different from each other, and each is a hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 12 carbon atoms (eg, methyl group, ethyl group, propyl group). Group, butyl group, hexyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-
Methoxycarbonylethyl group, 3-hydroxypropyl group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, 4-chlorobenzyl group, 4
-Acetamidobenzyl group, phenethyl group, 4-methoxybenzyl group, etc.), optionally substituted carbon number 2 to 1
2 alkenyl groups (eg ethylene group, allyl group, isopropenyl group, butenyl group, hexenyl group, etc.), optionally substituted 5- to 7-membered alicyclic groups (eg cyclopentyl group, cyclohexyl group, chlorocyclohexyl group) Groups, etc.), optionally substituted aromatic groups (eg phenyl groups,
Chlorophenyl group, methoxyphenyl group, acetamidophenyl group, methylphenyl group, dichlorophenyl group,
Nitrophenyl group, naphthyl group, butylphenyl group, dimethylphenyl group, etc.), or R ₁₆ and R ₁₇ together form a ring (eg, tetramethylene group, pentamethylene group, hexamethylene group, etc.) May be.

The functional group which forms at least one sulfo group by a chemical reaction is, for example, a compound represented by the general formula (VI)
Alternatively, a functional group represented by (VII) may be mentioned. Formula _{(VI) -SO 2 -O-L} 2 Formula _{(VII) -SO 2 -S-L} 2 formula in L ₂ is,

[0073]

[Chemical 14]

Represents Specifically, the general formula (II)-
It has the same meaning as the corresponding protecting group for COO-L ₁ .
In addition, examples of the functional group that forms at least one sulfinic acid group by a chemical reaction include a functional group represented by the general formula (VIII).

[0075]

[Chemical 15]

Further, the functional group which forms a —PO ₃ H ₂ group includes, for example, the general formula (IX).

[0077]

[Chemical 16]

In the formula, L ₃ and L ₄ may be the same or different, and specifically have the same contents as the protecting group L ₁ of the general formula (II) -COO-L ₁ . The general formula (I
Specific examples of the contents of I) to (IX) will be illustrated. However, the content of the present invention is not limited to these. In the following specific examples, each symbol represents the following content.

[0079]

[Chemical 17]

[0080]

[Chemical 18]

[0081]

[Chemical 19]

[0082]

[Chemical 20]

[0083]

[Chemical 21]

Copolymer containing a functional group which is used in the present invention to form a hydrophilic group of --COOH, --SO ₃ H, --SO ₂ H or --PO ₃ H ₂ by the above-mentioned chemical reaction. The components are not particularly limited. Preferred are those represented by the following general formula (X).

[0085]

[Chemical formula 22]

[In the above formula (X), Z'is -COO-,-
OCO -, - O -, - CO -, - CON (r 1) -, -
_{SO 2 N (r 1) -} (r 1 represents a hydrogen atom or a hydrocarbon group), - CONHCOO -, - CONHCONH
_{-, - CH 2 COO -,} - CH 2 OCO-,

[0087]

[Chemical formula 23]

Represents Y 'represents an organic residue bonded to or directly connected to -Z'- and -W _0. further

[0089]

[Chemical formula 24]

[0090]

[Chemical 25]

Alternatively, -W ₀ may be directly bonded. —W ₀ represents a functional group represented by any one of formulas (II) to (IX). b
₁ and b ₂ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aralkyl group or an aryl group. The general formula (X) will be described in more detail.

Preferably Z'is

[0093]

[Chemical formula 26]

Represents However, r ₁ is a hydrogen atom and has 1 carbon atom
To 8 optionally substituted alkyl groups (eg, methyl groups,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxyethyl group,
2-hydroxyethyl group, 3-bromopropyl group, etc.),
An optionally substituted aralkyl group having 7 to 9 carbon atoms (eg, benzyl group, phenethyl group, 3-phenylpropyl group,
Chlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloro-methyl-benzyl group, dibromobenzyl group, etc.), an optionally substituted aryl group (for example, phenyl group, tolyl group, xylyl group, mesityl group, Methoxyphenyl group, chlorophenyl group, bromophenyl group, chloro-methyl-phenyl group, etc.) and the like.

Y'is a direct bond for connecting, or -Z'- and-
Represents an organic residue connecting W ₀ . When Y'represents an organic residue to be linked, this linking group represents a carbon-carbon bond which may be passed through a hetero atom (as the hetero atom, an oxygen atom, a sulfur atom or a nitrogen atom is shown), for example,

[0096]

[Chemical 27]

The binding units such as the above may be used alone or in combination. (However, r ₂ , r ₃ , r ₄ , r ₅ , r
₆ represents the same contents as the above r ₁ ). b ₁ , b
₂ may be the same or different, and is a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom, etc.), a cyano group, a hydrocarbon group (eg methyl group, ethyl group, propyl group, butyl group, methoxycarbonyl group, ethoxycarbonyl). Group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, methoxycarbonylmethyl group,
An optionally substituted alkyl group having 1 to 12 carbon atoms such as an ethoxycarbonylmethyl group and a butoxycarbonylmethyl group, an aralkyl group such as a benzyl group and a phenethyl group, an aryl group such as a phenyl group, a tolyl group, a xylyl group and a chlorophenyl group. Etc.).

Further, in the general formula (X)

[0099]

[Chemical 28]

[0100]

[Chemical 29]

Alternatively, -W ₀ may be directly connected. Specific examples of the polymer component containing a functional group represented by the general formulas (II) to (IX) of the present invention are shown below. However, the scope of the present invention is not limited to these. In addition, an example (b-
During 1) ~ (b-36) , b represents -H or -CH _3. n represents 2-8. m represents 0 or an integer of 1 to 8.

[0102]

[Chemical 30]

[0103]

[Chemical 31]

-COO as described above used in the present invention
The functional groups that express H, —SO ₃ H, —PO ₃ H ₂ and —SO ₂ H in a chemical reaction are functional groups that protect the hydrophilic group, and these protective groups are chemically bonded to the hydrophilicity. The method of introduction according to J. et al. Can be easily performed by a conventionally known method, for example, J. F. W. McOmie "Protectiv
e groups in Organic Chemi
story ”(Plenum Press. 1973), F.I. W. Greene, "Protective
groups Organic Syntheses
is ”(Wiley-linterscience, 19
1981), Chemical Society of Japan, "New Experimental Chemistry Course, No. 14"
Volume, Synthesis and Reaction of Organic Compounds "[Maruzen Co., Ltd., 1978] Yoshio Iwakura, Keisuke Kurita" Reactive Polymer "(Kodansha)
Each unit reaction described in, etc. is used.

As a method for introducing these functional groups to be used in the present invention into the resin [A], --COOH and --SO ₃ H, --PO ₃ H ₂ , --SO, which are important for the present invention, are used.
A method by a so-called polymer reaction in which a polymer each containing at least one hydrophilic group selected from ₂ H is converted into a functional group in which each hydrophilic group is protected by a reaction, or by the above-mentioned general formula By synthesizing one or more monomers containing one or more of the functional groups shown, and then polymerizing with any other monomer copolymerizable therewith to form a polymer. can get.

For the reason that the functional group necessary for the present invention can be arbitrarily adjusted in the polymer or that impurities (catalyst or by-product used in the case of polymer reaction) are not mixed, the latter It is preferably produced by a method (preliminarily obtaining a desired monomer and carrying out a post-polymerization reaction). For example −
In the case of introducing a functional group that produces COOH, specifically, a carboxylic acid containing a polymerizable double bond or an acid halide thereof, for example, a carboxyl group is generally used in accordance with the method described in the above-mentioned publicly known documents. Formula (I) [-C
[OO-L ₁ ] is converted into a functional group, and then a polymerization reaction is carried out for production.

Further, the resin containing an oxazolone ring represented by the general formula (IV) as a functional group which produces a carboxylic acid by a reaction is a resin containing one or more monomers containing the oxazolone ring, or It can be obtained by a method of polymerizing the monomer and another monomer copolymerizable therewith. The oxazolone ring-containing monomer can be produced by a dehydration ring-closing reaction of N-acylloyl-α-amino acids having a polymerizable unsaturated bond. Specifically, it can be produced by the method described in the literature cited in the review article of Yoshio Iwakura: Keisuke Kurita, “Reactive Polymer” Chapter 3 (published by Kodansha).

Next, contained in the resin [A] of the present invention,
The copolymer component containing a heat and / or photocurable group will be described. "Thermal and / or photo-curable functional group" refers to a functional group that cures the resin by at least one of heat and light. Specific examples of the photocurable functional group include Hideo Inui, Mototaro Nagamatsu, "Photosensitive Polymer" (Kodansha, published in 1977), Takahiro Tsunoda, "New Photosensitive Resin" (Publishing Society of Japan, published in 1981), G ． E. Green
and B. P. Strak, J .; Macro. Sc
i. Reas. Macro. Chem. , C21
(2), 187-273 (1981-82), C.I. G.
Rattee, "Photopolymirizati
on of Surface Coatings "
(A. WileyInter Science Pu
b. The functional group used in a conventionally known photosensitive resin or the like is used as the photocurable resin cited in the review article such as 1982).

Further, the "thermosetting functional group" in the present invention
For example, Takeshi Endo, “Refining thermosetting polymer” (CMC Co., Ltd., published in 1986), Yuji Harazaki “Latest Binder Technology Handbook” Chapter II-I (Comprehensive Technical Center). , 1985), Takayuki Otsu "Synthesis and design of acrylic resin and new application development" (Chubu Business Development Center Publishing Department, 1985), Eizo Omori "Functional Acrylic Resin" (Technosystem, 1985), etc. The functional groups cited in the reviews can be used.

For example, --COOH group, --PO ₃ H ₂ group,-
SO ₂ H group, -OH group, -SH group, -NH ₂ group, -NH
R _A group [ _RA represents a hydrocarbon group having, for example, 1 to 1 carbon atoms.
8 alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, 2-chloroethyl group, 2-methoxyethyl group, 2-cyanoethyl group, etc.). ], Cyclic acid anhydride-containing group [The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and as the cyclic acid anhydride to be contained, aliphatic dicarboxylic acid anhydride, aromatic Group dicarboxylic acid anhydrides may be mentioned.

Examples of the aliphatic dicarboxylic acid anhydride include:
Succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-1,2-dicarboxylic acid anhydride ring, cyclohexane-1,2-dicarboxylic acid anhydride ring, cyclohexene-1,2-dicarboxylic acid ring Acid anhydride ring,
2,3-bicyclo [2,2,2] octanedicarboxylic acid anhydride ring and the like can be mentioned, and these rings include, for example, halogen atoms such as chlorine atom and bromine atom, methyl group, ethyl group,
An alkyl group such as a butyl group and a hexyl group may be substituted.

Examples of aromatic dicarboxylic acid anhydrides include phthalic anhydride ring, naphthalene-dicarboxylic acid anhydride ring, pyridine-dicarboxylic acid anhydride ring, and thiophene-ring.
Dicarboxylic acid anhydride ring and the like, these rings, for example, a chlorine atom, a halogen atom such as a bromine atom, a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group,
A hydroxyl group, a cyano group, a nitro group, an alkoxycarbonyl group (as the alkoxy group, for example, a methoxy group, an ethoxy group, etc.) may be substituted. ],-
N = C = O group, blocked isocyanate group [a functional group that is decomposed by heat with an adduct of an isocyanate group and an active hydrogen compound to form an isocyanate group. For example, as the active hydrogen compound, 2,2,2-trifluoroethanol,
2,2,2,2 ', 2', 2'-hexafluoroisopropyl alcohol phenols (phenol, chlorophenol, cyanophenol, cresol, methoxyphenol, etc.), active methylene compounds (acetylacetone,
Acetoacetic esters, malonic acid diesters, malonic dinitrile etc.), cyclic N atom-containing compound (e.g. imidazole, piperazine, morpholine, etc.), etc.], -CONHCH ₂ OR _B [R _B is a hydrogen atom or a carbon atoms It represents an alkyl group of 1 to 8 (specifically the same as the alkyl group of _RA ). ], A silane coupling group containing at least one -OR group [for example, -Si (OR)]
₃ , -Si (OR) ₂ (R), -Si (OR) (R) ₂
And -OR or -R represents a hydrocarbon group, and specifically R ₁ shown in the general formula (II) —COOL ₁ above.
Represents the same content as. ], A titanate coupling group containing at least one -OR group,

[0113]

[Chemical 32]

A heteroatom-containing cyclic functional group having high stericity, such as Cd ₁ ═CH, which facilitates the ring-opening reaction.
d ₂ group (d ₁ and d ₂ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.) or an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group, etc.), etc. be able to. Further, as the polymerizable double bond group,
In particular

[0115]

[Chemical 33]

Examples thereof include: The copolymer component containing heat and / or photocurability as described above can be copolymerized with the monomer corresponding to the above-mentioned copolymer component containing a functional group expressing a hydrophilic group. Any monomer may be used as long as it is a monomer. For example, as a copolymer component, the general formula (X
I) is indicated.

[0117]

[Chemical 34]

W ₁ represents a heat and / or photocurable group described above. Furthermore, the resin [A] of the present invention comprises a functional group-containing polymer component expressing a hydrophilic group as described above, light and / or
Alternatively, a polymer component other than these may be contained together with the polymer component containing a thermosetting group. Any other polymer component may be used as long as it copolymerizes with a monomer corresponding to the above polymer component. For example, “Polymer Data Handbook [Basic Edition]” edited by the Society of Polymer Science, Baifukan (1986).
Annual), J. Brandrup. E. H. Immerg
ut. "Polymer Handbook" (Jo
hn Wileyd Sons, published in 1989) and the like.

Specifically, acrylic acid, α and / or β
Substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form Body, β-chloro form, β-bromo form,
α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg 2-pentenoic acid) , 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-
Hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids In addition to half-ester derivatives of vinyl group or allyl group, methacrylic acid esters, acrylic acid esters, crotonic acid esters, α-olefins, vinyl carboxylates or acrylic acid esters (for example, acetic acid, propionic acid as carboxylic acid) , Butyric acid, valeric acid, benzoic acid,
Naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (eg, dimethyl ester, diethyl ester, etc.),
Acrylamides, methacrylamides, styrenes (eg styrene, vinyltoluene, chlorostyrene,
Hydroxystyrene, N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compound, vinylketone-containing compound, heterocyclic vinyls (eg vinylpyrrolidone, vinylpyridine, vinylimidazole, Vinyl thiophene, vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine, etc.) and the like.

Next, the light and / or thermosetting compound used together with the resin [A] of the present invention will be explained.

The light and / or thermosetting compound may be any of a low molecular weight compound, an oligomer and a polymer containing at least one kind of the curable group. The light and / or thermosetting group refers to a functional group that cures the resin by at least one of heat and light. Specific examples of the “photo-curable functional group” and “thermo-curable functional group” include those having the same content as the functional group of the polymer component (c) contained in the resin [A].

Examples of these curable compounds include compounds usually used as a crosslinking agent. Specifically, the compounds described in "Crosslinking Agent Handbook" edited by Shinzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981), "Polymer Data Handbook Basic Edition", Baifukan (1986), etc. Can be used. For example, an organic silane-based compound (for example, a silane coupling agent such as vinyltrimethoxysilane, vinyltributoxysilane, γ-glycidokichipropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane). Etc.), polyisocyanate compounds (for example, toluylene diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate). Isocyanates, high molecular weight polyisocyanates, etc.), polyblocked isocyanate compounds (blocking agents include those having the same contents as those described for the polymer (c) component), polycarbocarbonate Acid compounds and their carboxylic acid anhydrides (such as phthalic acid, maleic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, benzene 1,2,4,5
Tetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, etc. and their anhydrides, etc.),
Polyol compounds (for example, 1,4-butanediol, polyoxypropylene glycol, polyoxyalkylene glycol, 1,1,1-trimethylolpropane, etc.), polyamine compounds (for example, ethylenediamine, γ-hydroxypropylated ethylenediamine, Phenylenediamine, hexamethylenediamine, N-aminoethylpiperazine, modified aliphatic polyamines, etc.), titanate coupling compounds (eg, tetrabutoxy titanate, tetrapropoxy titanate, isopropyl tristearoyl titanate, etc.), aluminum coupling compounds [ For example, aluminum butyrate,
Aluminum acetyl acetate, aluminum oxide octate, aluminum tris (acetyl acetate), etc.], polyepoxy group-containing compound and epoxy resin (for example, “New Epoxy Resin” by Hiroshi Kakiuchi, Shokoido (19
1985), "Epoxy resin" edited by Kuniyuki Hashimoto, compounds described in Nikkan Kogyo Shimbun (Published in 1969), melamine resin (e.g. edited by Ichiro Miwa, Hideo Matsunaga, "Uria."
"Melamine resin", compounds described in Nikkan Kogyo Shimbun (1969), poly (meth) acrylate compounds (for example, Shin Okawara, Takeo Saegusa, Toshinobu Higashimura "Oligomer" Kodansha (1976), Omori The compounds described in Eizo “Functional Acrylic Resin” Techno System (published in 1985) and the like can be mentioned. Specifically, styrene derivatives such as divinylbenzene and trivinylbenzene: polyhydric alcohol (for example, ethylene glycol , Diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.), or Methacrylic acid, esters of acrylic acid or crotonic acid, vinyl ethers or allyl ethers of rehydroxyphenols (eg hydroquinone, resorcin, catechol and their derivatives): dibasic acids (eg malonic acid, succinic acid, glutaric acid, Adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.) vinyl esters, allyl esters, vinyl amides or allyl amides: polyamines (eg ethylenediamine, 1,3-propylenediamine, 1,4-
Butylenediamine, etc.) with a vinyl group-containing carboxylic acid (eg, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.), vinyl group-containing carboxylic acid (eg, methacrylic acid, acrylic acid, methacryloyl acetic acid) , Acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl acetic acid,
Itaconiloylpropionic acid, carboxylic acid anhydride, etc.) and alcohol or amine reactants (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid,
Ester derivatives or amide derivatives containing vinyl groups such as 2-allyloxycarbonylbenzoic acid and allylaminocarbonylpropionic acid (eg vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, itacone) Allyl acid, vinyl methacryloyl acetate, vinyl methacryloyl propionate, allyl methacryloyl propionate, vinyl oxycarbonyl methyl ester methacrylate, vinyloxy carbonyl methyl oxycarbonyl ethylene acrylate, N-allyl acrylamide, N-allyl methacrylamide, N-allyl Itaconic acid amide, methacryloylpropionic acid allylamide, etc.) or amino alcohols (eg aminoethanol, 1-aminopropanol, 1-amido) Butanol, 1-amino hexanol, 2-amino butanol) and the like condensates of carboxylic acids containing vinyl groups.

Further, a polymer containing the same photo- and / or thermosetting group-containing polymer component as that contained in the resin [A] can be mentioned. The weight average molecular weight of these light and / or thermosetting resins is 1 × 10 ³ to 1 × 10 ⁶ , preferably 3 × 1.
It is in the range of 0 ³ to 1 × 10 ⁵ . As described above, the binder resin of the surface layer of the present invention is preferably used in a crosslinking reaction in the coexistence of a curable compound in a combination in which a chemical bond between polymer chains easily proceeds. For example, as a polymer reaction by a combination of functional groups, a well-known method is usually mentioned, and a combination of a functional group of group A and a functional group of group B as shown in Table A below is exemplified. However, it is not limited to these.

[0124]

[Table 1]

[0125] In Table A, represents a R ₁ ^0, R ₂ ⁰ alkyl group. It represents R ₃ ⁰ ~R ₅ ⁰ alkyl group or an alkoxy group, and at least one of the substituents represents an alkoxy group. In the present invention, in order to promote the crosslinking reaction in the surface layer film, a reaction accelerator may be added to the resin as the main component, if necessary. When the crosslinking reaction is a reaction mode in which a chemical bond between functional groups is formed, for example, organic acids (acetic acid, propionic acid, butyric acid, benzenesulfonic acid, p-toluenesulfonic acid, etc.), phenols (phenol, chlorophenol, Nitrophenol, cyanophenol, bromophenol, naphthol, dichlorophenol, etc.), organometallic compounds (acetylacetonate zirconium salt, acetylacetone zirconium salt, acetylacetocobalt salt, etc., dibutoxytin dilaurate, etc.), dithiocarbamic acid compound (diethyldithiocarbamate) Etc.), thiuram disulfide compounds (tetramethyl thiuram disulfide, etc.), carboxylic acid anhydrides (phthalic anhydride, maleic anhydride, succinic anhydride, butyl succinic anhydride, etc.,
3,3 ′, 4,4′-tetracarboxylic acid benzophenone dianhydride, trimellitic acid anhydride, etc.) and the like.

When the crosslinking reaction is in a polymerizable reaction mode, a polymerization initiator (such as a peroxide and an azobis compound) can be used. The resin which is the main component of the surface layer of the present invention is light and / or heat cured after applying the surface layer forming material. In order to carry out heat curing, for example, the drying conditions are set to be more severe than the conventional drying conditions for producing a photoreceptor.
For example, the drying conditions are high temperature and / or long time. Alternatively, it is preferable to further heat-treat the coating solvent after drying. For example, the treatment is performed at 60 ° C to 150 ° C for 5 to 120 ° C. When the above reaction accelerator is used in combination, the treatment can be performed under milder conditions.

As a method of curing the specific functional group in the resin which is the main component of the surface layer of the present invention by irradiation with light, a step of irradiation with "chemically active light" may be included. As the “chemically actinic ray” used in the present invention,
Visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, γ-ray, α
Any of lines and the like may be used, but ultraviolet rays are preferable. More preferably, a wavelength of 310 nm to a wavelength of 500 n
It can emit light rays in the range of m, and generally, a low-pressure, high-pressure or ultra-high-pressure mercury lamp, a halogen lamp or the like is used. Light treatment is usually 5 cm to 50 c
Irradiation from a distance of m for 10 seconds to 10 minutes can be sufficiently performed.

As the resin used in the surface layer of the present invention, another binder resin may be used in combination. Examples of the resins that can be used include conventionally known binder resins for electrophotographic photosensitive layers. For example, Ryuji Shibata and Jiro Ishiwatari, Kogaku, Vol. 17, p. 278 (1968) Harumi Miyamoto. , Hidehiko Takei, Imaging, 1973 (No.8), Koichi Nakamura, "Practical Technology of Binder for Recording Material", Chapter 10, C.I.
H. C. Published (1985) edited by The Electrophotographic Society of Japan, "Presentation Symposium on Organic Photoreceptors for Electrophotography" (1985)
), Hiroshi Komon, “Recent Development of Photoconductive Materials and Photoconductors.
Practical application ”, Japan Science Information Co., Ltd. (1986), edited by The Institute of Electrophotography,“ Basics and Applications of Electrophotographic Technology ”Chapter 5, Corona Publishing Co., Ltd. (1988), D.I. Tatt, S.M. C. Hei
decker, Tappi, 49 (No. 10), 43
9 (1966), E.I. S. Baltazzi, R .; G.
Blanclotte et al, Photo. Sc
i. Eng. 16 (No. 5), 354 (1972),
Nguyen Chang Kae, Isamu Shimizu, Eiichi Inoue, Electrophotographic Society Journal 18 (No. 2), 22 (1980) and the like.

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

These other binder resins which may be contained are
After the desensitizing treatment with the light-sensitive material of the present invention, it is used within a range that does not impair the function of expressing water retention. Specifically, the content is at most 30% by weight, preferably 20% by weight or less, in 100 parts by weight of the total binder resin. In order to improve the strength of the hydrophilizable surface layer itself, the adhesiveness with the electrophotographic photosensitive layer, the electrophotographic characteristics, etc., a resin other than the resin of the present invention described above is added, or a crosslinking agent or a plasticizer is added. You may add.

As the crosslinking agent, a commonly used organic peroxide, metal soap, organic silane, a crosslinking agent such as polyurethane, a curing agent such as an epoxy resin and the like can be used. Specifically, it is described in "Crosslinking Agent Handbook" edited by Fuzo Yamashita and Tosuke Kaneko, published by Taiseisha (1981). Further, the surface layer which can be hydrophilized has developing characteristics during toner development,
The surface of the toner image may be mechanically matted or a layer may contain a matting agent for the purpose of improving the adhesiveness of the toner image or the water retention after the hydrophilic treatment. Examples of the matting agent include fillers such as silicon dioxide, zinc oxide, titanium oxide, zirconium oxide, glass particles, alumina and clay, polymethylmethacrylate and polystyrene,
Examples thereof include polymer particles such as phenol resin.

What is important in constructing the surface layer is that the non-image area becomes sufficiently hydrophilic after the desensitizing treatment, as described above. That is, this hydrophilicity can be confirmed by, for example, measuring the contact angle with water. The contact angle of water on the surface of the surface layer (hydrophilizable layer) before the desensitizing treatment is about 60 ° to 120 °, but it decreases to about 0 ° to 5 ° after the desensitizing treatment. And then get very wet with water. Therefore, the printing plate has an image portion made of lipophilic toner and a highly hydrophilic non-image portion formed on its surface. Therefore,
The surface layer after desensitizing treatment may have a contact angle with water of 5 degrees or less.

The present invention is particularly excellent in that it is more hydrophilic than the conventional ones. Next, the binder resin [B] contained in the photoconductive layer of the present invention will be described in detail. The weight average molecular weight of the resin [B] is 1 × 10 ³ to
It is 2 × 10 ⁴ , preferably 3 × 10 ³ to 1 × 10 ⁴ , and the glass transition point of the resin [B] is preferably −40 ° C. or higher.
110 degreeC, More preferably, it is -20 degreeC-90 degreeC.

When the molecular weight of the resin [B] is less than 1 × 10 ³ , the film forming ability is deteriorated and the sufficient film strength cannot be maintained.
On the other hand, when the molecular weight is more than 2 × 10 ⁴ , even in the case of the resin of the present invention, particularly in a photoreceptor using a near infrared to infrared spectral sensitizing dye, high temperature / high humidity, low temperature / low humidity under severe conditions. The fluctuation of the electrophotographic characteristics (particularly the initial potential, the dark decay retention rate and the photosensitivity) in the above-mentioned method becomes a little large, and the effect of the present invention that a stable copy image can be obtained is weakened.

In the resin [B] of the graft copolymer of the present invention, the abundance ratio of the macromonomer (M) and the other monomer (for example, the monomer of the formula (XIII) described later) is 1 to 60 /.
99-40 (weight ratio), preferably 5-40 / 9
It is 5 to 60 (weight ratio).

When the content of the macromonomer in the binder resin [B] is less than 1.0% by weight, the electrophotographic characteristics (especially dark decay rate and photosensitivity) are deteriorated, and the electrophotographic characteristics vary under environmental conditions. In particular, it becomes large when combined with a near infrared to infrared spectral sensitizing dye. It is considered that this is because the macromonomer that becomes the graft portion becomes fine, resulting in almost the same composition as the conventional homopolymer or random copolymer. On the other hand, when the content of the macromonomer exceeds 60% by weight, the copolymerizability of the monomer corresponding to the other copolymerization component and the macromonomer according to the present invention becomes insufficient, and the macromonomer is sufficiently used as the binder resin. The electrophotographic characteristics cannot be obtained.

The amount of the polar group-containing component contained in the macromonomer (M) in the resin [B] of the present invention is
The amount is preferably 1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the resin [B]. That is, the abundance ratio of the polar group in the resin [B] depends on the composition ratio of the A block in the macromonomer (M) and the copolymerization ratio of the macromonomer (M) in the resin [B].
It can be adjusted to a preferable ratio.

When the content of the polar group in the resin [B] is less than 1% by weight, the initial potential is low and a sufficient image density cannot be obtained. On the other hand, the polar group content is 20% by weight
If the amount is larger than the above value, dispersibility of the low molecular weight compound is lowered, and scumming is increased when it is used as an offset master.

The use ratio of the binder resin [A] and the resin [B] is 95 to 40 parts by weight to 5 to 60 parts by weight, preferably 90 to 50 parts by weight to 10 to 50 parts by weight. The monofunctional macromonomer (M) used in the graft copolymer of the present invention will be described more specifically.

The copolymer component in the macromonomer (M) in the resin [B] of the present invention is composed of the A block and the B block as described above.
The existence ratio of the B block is preferably 1 to 70/99.
30 (weight ratio), and more preferably 3 to 50/97.
˜50 (weight ratio).

The polar group contained in the component constituting the A block of the macromonomer (M) includes —PO ₃ H ₂
Group, -COOH group, -SO ₃ H group, a phenolic OH
Group, -P (= O) (OH) R ¹ {R ¹ is a hydrocarbon group or-
OR ² (R ² represents a hydrocarbon group) group} and / or a cyclic acid anhydride-containing group, and preferably —COOH
Group, -SO ₃ H group, a phenolic OH group or -P (=
O) (OH) R ¹ group.

Here, -P (= O) (OH) R ¹ represents a group represented by the following formula 35, and R ¹ is a hydrocarbon group or-
OR ² (R ² represents a hydrocarbon group) and R ¹
And R ² is preferably an aliphatic group having 1 to 22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 2-chloroethyl group, 2 -Methoxyethyl group, 3
-Ethoxypropyl group, allyl group, crotonyl group, butenyl group, cyclohexyl group, benzyl group, phenethyl group, 3-phenylpropyl group, methylbenzyl group, chlorobenzyl group, fluorobenzyl group, methoxybenzyl group, etc.) or substituted Good aryl group (for example, phenyl group, tolyl group, ethylphenyl group, propylphenyl group, chlorophenyl group, fluorophenyl group, bromophenyl group, chloro-methyl-phenyl group, dichlorophenyl group, methoxyphenyl group, cyanophenyl group, Acetamidophenyl group, acetylphenyl group, butoxyphenyl group, etc.) and the like.

[0143]

[Chemical 35]

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and the cyclic acid anhydride to be contained is an aliphatic dicarboxylic acid anhydride or an aromatic dicarboxylic acid anhydride. Things can be mentioned. Examples of the aliphatic dicarboxylic acid anhydride include succinic anhydride ring, glutaconic anhydride ring, maleic anhydride ring, cyclopentane-
1,2-dicarboxylic acid anhydride ring, cyclohexane-1,
2-dicarboxylic acid anhydride ring, cyclohexene-1,2-
Dicarboxylic acid anhydride ring, 2,3-bicyclo [2.2.
2] Octanedicarboxylic acid anhydride ring and the like, and these rings are substituted with, for example, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group or a hexyl group. May be.

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

The "polymer component containing a specific polar group" as described above is, for example, a polymer component constituting another block component of the macromonomer (M) of the present invention, that is, represented by the general formula (I). Any vinyl compound containing the polar group, which is copolymerized with a corresponding vinyl compound such as a methacrylate component, can be used.

For example, it is described in “Polymer Data Handbook [Basic Edition]” edited by The Society of Polymer Science, Ltd., Baifukan (1986). Specifically, acrylic acid, α and / or β
Substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-bromo form, α-fluoro form, α-tributylsilyl form, α-cyano form Body, β-chloro form, β-bromo form,
α-chloro-β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides, crotonic acid, 2-alkenylcarboxylic acids (eg 2-pentenoic acid) , 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-
Hexenoic acid, 4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acids Examples thereof include a compound having a vinyl group or an allyl group half ester derivative, and a carboxylic acid or sulfonic acid ester derivative or amide derivative containing the polar group in the substituent.

The following can be mentioned as specific examples of these compounds. However, in each of the following examples, p
¹ is _{-H, -CH 3, -Cl, -Br} , -CN, -CH
₂ COOCH ₃ or —CH ₂ COOH, p ² is —
H or indicates -CH _3, b represents an integer of 2 to 18, c
Represents an integer of 1 to 12, and d represents an integer of 1 to 4.

[0149]

[Chemical 36]

[0150]

[Chemical 37]

[0151]

[Chemical 38]

[0152]

[Chemical Formula 39]

[0153]

[Chemical 40]

[0154]

[Chemical 41]

[0155]

[Chemical 42]

[0156]

[Chemical 43]

[0157]

[Chemical 44]

[0158]

[Chemical formula 45]

Two or more kinds of the polar group-containing components as described above may be contained in the A block, and these two or more kinds of polar group-containing components are contained in the A block by either random copolymerization or block copolymerization. It may have been done. Further, together with the polar group-containing component, a component that does not contain a polar group {for example, a component represented by the formula (I) described below} may be contained in the A block, but the polar group-containing component is 30 to 30% in the A block. It is preferably present at 100% by weight.

Next, in the above-mentioned macromonomer, the component constituting the B block, that is, the repeating unit represented by the general formula (I) will be described. In the general formula (I), V ¹
Is -COO -, - OCO -, - (CH 2) a OCO-,
_{- (CH 2) a COO- (} a is an integer of 1~3), - O -, - SO 2 -, - CO -, - CON
^{(Z 1) -, - SO} 2 N (Z 1) -, - CONHCOO
-, - CONHCONH or -C ₆ H ₄ - represents a. Here, Z ¹ is not only a hydrogen atom but also a preferable hydrocarbon group is an alkyl group having 1 to 18 carbon atoms which may be substituted (
For example, methyl group, ethyl group, propyl group, butyl group,
Heptyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group,
2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, and the like, alkenyl group having 4 to 18 carbon atoms which may be substituted (eg, 2-methyl-1-propenyl group, 2-butenyl group) , 2-pentenyl group, 3-
A methyl-2-pentenyl group, a 1-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 4-methyl-2-hexenyl group, etc.) and an optionally substituted aralkyl group having 7 to 12 carbon atoms (for example, benzyl. Group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group,
A dimethylbenzyl group, a dimethoxybenzyl group, etc.), an alicyclic group having 5 to 8 carbon atoms which may be substituted (for example, a cyclohexyl group, a 2-cyclohexylethyl group, a 2-cyclopentylethyl group, etc.) or a C6-12 An optionally substituted aromatic group (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group). Group, decyloxyphenyl group, chlorophenyl group,
Dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.) To be

R ³ represents a hydrocarbon group, and is preferably the same as those listed as the preferable hydrocarbon group for Z ¹ . When V ¹ represents —C ₆ H ₄ —, R ³ represents a hydrogen atom in addition to the above hydrocarbon, and the benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group, Ethoxy group, propioxy group, butoxy group, etc.) and the like.

A ¹ and a ² may be the same or different from each other, preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group, a carbon number of 1 to 4
An alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), —COOZ ³ or COOZ ³ (Z ³ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, Represents an aralkyl group, an alicyclic group or an aryl group, which may be substituted,
Specifically, it represents the same contents as those described for Z ¹ ). COOZ via the above hydrocarbons
Examples of the hydrocarbon in the ^three groups include a methylene group, an ethylene group, a propylene group and the like.

More preferably, in the general formula (I),
V ¹ is -COO-, -OCO-, -CH ₂ OCO-,-.
_{CH 2 COO -, - O -} , - CONH -, - SO 2 NH
- or -C ₆ H ₄ - represents, a ¹ and a ^2, which may be the same or different, a hydrogen atom, a methyl group, -COO
Z ³ or —CH ₂ COOZ ³ {Z ³ is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.)
Represents}. Even more preferably, a ¹ and a
^{In 2} , one of them represents a hydrogen atom.

Further, the B block may contain a polymer component other than the monomer of the formula (I), and another repeating unit copolymerizable with the polymer component of the formula (I). Examples of the monomer corresponding to acrylonitrile, methacrylonitrile, heterocyclic vinyls (for example, vinyl pyridine, vinyl imidazole, vinyl pyrrolidone, vinyl thiophene, vinyl pyrazole, vinyl dioxane, vinyl oxazine, etc.) and the like. These other monomers are used within a range not exceeding 20 parts by weight based on 100 parts by weight of the total polymer component of the B block. Also, in the B block,
It is preferable not to include a polymer component containing a polar group, which is a component of the A block. 2 in block B
When two or more copolymerization components are present, these two or more copolymerization components may be contained in the B block by either random copolymerization or block copolymerization.
It is preferable that they are contained at random for the convenience of synthesis.

Next, in the macromonomer (M) of the present invention, the A block consisting of the above-mentioned component containing a polar group and the B block consisting of containing the polymer component represented by the general formula (I) are taken as AB. The polymerizable dipolymerizable group which is linked by a mold and is linked to the other end of the B block which is linked to the A block will be described.

Specifically, a polymerizable double bond group represented by the following general formula (XII) is exemplified.

[0167]

[Chemical formula 46]

[In the formula (XII), V ² is V ¹ in the formula (I).
Represents the same content as. c ¹ and c ² may be the same as or different from each other and have the same meaning as a ¹ and a ² in the formula (I). That is, as the polymerizable double bond group represented by the general formula (XII), more specifically, CH ₂ ═CH—C
_{OO-, CH 2 = C (CH} 3) OCOO-, CH (CH
_{3) = CHCOO-, CH 2 =} C (CH 2 COOC
_{H 3) COO-, CH 2 =} C (CH 2 COOH) COO
_{-, CH 2 = CHCONH-, CH} 2 = C (CH 3) C
_{ONH-, CH (CH 3) =} CHCONH-, CH 2 =
_{CHOCO-, CH 2 = CHCH 2 OCO-} , CH 2 =
_{CH-O-, CH 2 = C} (COOH) CH 2 COO-,
_{CH 2 = C (COOCH 3)} CH 2 COO-, CH 2 =
_{CH-C 6 H 4 -,} CH 2 = CH (CH 2) 2 COO
_{-, CH 2 = CH-CO-} , CH 2 = CH (CH 2) 2
OCO- and the like can be mentioned.

The macromonomer (M) used in the present invention has a polymerizable double bond group represented by the general formula (XII) directly bonded to one end of the B block as described above, or optionally. It has a chemical structure bonded by the linking group of. The linking group includes a carbon-carbon bond (single bond or double bond), a carbon-hetero atom bond (as a hetero atom, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.), a hetero atom-hetero atom. It is composed of any combination of bonding atomic groups. That is, specifically, a mere bond or -C (Z ⁴ ) (Z ⁴ )-
[Z ⁴ may be the same or different, and are a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.),
A cyano group, a hydroxyl group, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.) and the like],-(CH =
_{CH) -, - C 6 H} 10 -, - C 6 H 4 -, -O -, -
S -, - CO -, - N (Z 5) -, - COO -, - C
(= S) -, - SO 2 -, - CON (Z 5) -, - SO
₂ N (Z ⁵ )-, -NHCOO-, -NHCONH
-, -C (Z ⁵ ) (Z ⁵ )-[Z ⁵ represents a hydrogen atom, a hydrocarbon group or the like having the same content as R ³ in the above formula (I)] and the like. It represents a single linking group or a linking group composed of any combination.

When the weight average molecular weight of the macromonomer (M) exceeds 2 × 10 ⁴ , the copolymerizability with other monomers (for example, the monomer corresponding to the formula (XIII) described later) decreases, which is not preferable. On the other hand, if the weight average molecular weight is too small, the effect of improving the electrophotographic characteristics of the photosensitive layer becomes small, so that it is preferably 1 × 10 ³ or more.

The macromonomer (M) of the present invention can be produced by a conventionally known synthetic method. For example,
In the monomer corresponding to the polymer component containing the specific polar group, the polar group is preliminarily protected as a functional group, and an organometallic compound (eg, alkyllithium, lithium diisopuramide, alkylmagnesium halide, etc.) )
Alternatively, after synthesizing an AB block copolymer by a known so-called living polymerization reaction such as a photopolymerization reaction using a porphyrin metal complex as a catalyst by an ionic polymerization reaction using hydrogen iodide or iodine, etc. Various reagents are reacted with the ends of the living polymer to introduce a polymerizable double bond group. After this, a deprotection reaction is performed by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, or a photolysis reaction of the functional group with the polar group protected,
The method of forming a polar group is mentioned. One example thereof is shown in the following reaction scheme (1).

[0172]

[Chemical 47]

For example, P. Lutz, P. Masson et al, Polym. B
ull., 12 , 79 (1984) BCAnderson, GDAndrews eta
l, Macromolecules, 14 , 1601 (1981) K. Hatada, K. Ut
e.etal, Polym. J. 17 , 977 (1985), 18 , 1037 (1986), Koichi right hand, Koichi Hatada, Polymer processing, 36 , 366 (1987) Toshinobu Higashimura, Mitsuo Sawamoto, Polymers, 46 , 189 (1989) M. Kuro
ki, T. Aida, T. Am. Chem. Soc. 109 , 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43 , 300 (1985) DYSog
ah, WRHertler et al, Macromolecules, 20 , 1473 (198
The living polymer can be easily synthesized according to the synthetic method described in 7) and the like. Further, as a method for introducing a polymerizable double bond group to the terminal of the living polymer, the macromonomer of the present invention can be easily obtained according to a conventionally known synthesis method of a macromonomer method.

Specifically, P. Dreyfuss & RPQuirk, En
cycl, Polym.Sci.Eng., 7 , 51 (1987), PFRempp, E.
Franta, Adu., Polym.Sci. 58 , 1 (1984), V.Per-cec, Ap
pl., Polym. Sci., 285, 95 (1984), R. Asami, M. TakaR
i, Makvamol.Chem.Suppl. 12 , 163 (1985), P.Rempp.eta
l, Makvamol.Chem.Suppl. 8 , 3 (1984) Yusuke Kawakami, Chemical Industry, 38 , 56 (1987), Yuya Yamashita, Polymer, 31 , 988 (198)
2), Kobayashi Shiro, Kogaku, 30 , 625 (1981), Toshinobu Higashimura,
Journal of the Adhesion Society of Japan, 18, 536 (1982), Koichi Ito, polymer processing, 35, 262 (1986), AzumaTakashi Shiro, Takashi Tsuda, functional materials, 19
It can be synthesized according to the methods described in 87 Nos. 10 and 5, etc. and the references and patents cited therein.

The protecting group for protecting the specific polar group of the present invention and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing the conventionally known knowledge. For example, various references are given in the above-mentioned references, and further, Yoshio Iwakura, Keisuke Kurita, "Reactive Polymer" published by Kodansha Co., Ltd. (1977), TW Greene "Protective Groups in
Organic Synthesis ", John Wiley & Sous (1981),
JFWMcOmie, `` Protective Groups in Organic Che
mistry "Plenum Press, (1973) and the like, which are described in detail in the review, can be appropriately selected and performed.
As another method for synthesizing an AB type block copolymer, it can be synthesized by a photoiniferter polymerization method using a diciocarbamate compound as an initiator. For example, Takayuki Otsu, Polymer, 37 , 248 (1988), Shunichi Hinomori, Ryuichi Otsu, Po
lym. Rep. Jap. 37 , 3508 (1988), JP-A-64-111, JP-A-64-26619 and the like.
The macromonomer of the present invention can be obtained by utilizing the above-described macromonomer synthesis method.

Specific examples of the macromonomer (M) of the present invention can include the following compounds. However, the scope of the present invention is not limited to these. However, in the following compound examples, p ³ , p ⁴ and p ⁵
Each, -H, -CH ₃ or -CH ₂ COOCH ₃
, P ⁶ represents —H or —CH ₃ , and R ¹¹ represents —C _p
H _{2p +} 1 (p is 1 to 18 _{integer), - (CH 2) q} C 6 H
₅ (q is an integer of 1 to _{3), - C 6 H 4 -Y} 1 (Y 1 is -
_{H, -Cl, -B r, -CH} 3, -OCH 3 or -CO
CH ₃ shows a) or _{- (CH 2) r -C 10} H 7 (r 0
Or an integer of 1 to 3) indicates, R ¹² is -C _s H _{2s +} 1 _(s is an integer of 1 to 8) or - (CH ₂₎ shows the _q C ₆ H _5, Y
² _{-OH, -COOH, -SO 3 H,} -OP (= O)
(OH) ₂ or -OP (= O) (OH) OCH ₃ ,
Y ³ is _{-COOH, -SO 3 H, -OP (} = O) (OH)
₂ or -OP (= O) (OH) OCH ₃ and t = 2
12 represents an integer, and u represents an integer of 2 to 6.

[0177]

[Chemical 48]

[0178]

[Chemical 49]

[0179]

[Chemical 50]

[0180]

[Chemical 51]

Further, in this resin [B], as a component to be copolymerized with the macromonomer (M), the following general formula (XII
The monomers represented by I) are preferred.

[0182]

[Chemical 52]

In the formula (XIII), b ¹ and b ² are each a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom), a cyano group or an alkyl group having 1 to 4 carbon atoms (eg methyl group, ethyl group, propyl group). Group, butyl group, etc.) and the like.

R ⁴ represents a hydrocarbon group, specifically an alkyl group, an aralkyl group or an aromatic group, preferably an aralkyl group or an aromatic group which is a hydrocarbon group containing a benzene ring or a naphthalene ring. is there.

Further, R ^Four Preferably having 1 to 18 carbon atoms
It represents a hydrocarbon group which may be substituted. Polymer backbone
Inside is -PO ₃ H ₂ Group, -SO ₃ H group, -COOH
Group, -OH group, -SH group and -PO ₃ R ¹ H group polar group
Those containing no copolymerization component containing
Thus, as the substituent, the polar group in the resin [B] is used.
Substituent other than the polar group contained in the contained polymer component
The halogen atom (for example, fluorine atom
Fluorine atom, chlorine atom, bromine atom, etc.), -OZ ⁶ , -CO
OZ ⁶ , -OCOZ ⁶ (Z ⁶ Is an alky having 1 to 22 carbon atoms
Group, for example, methyl group, ethyl group, propyl group
Group, butyl group, hexyl group, octyl group, decyl group, dodecyl group
Decyl group, hexadecyl group, octadecyl group, etc.)
And the like. As a preferred hydrocarbon group
Is an optionally substituted alkyl group having 1 to 18 carbon atoms (eg,
For example, methyl group, ethyl group, propyl group, butyl group,
Butyl, hexyl, octyl, decyl, dodecyl
Group, hexadecyl group, octadecyl group, 2-chloroene group
Cyl group, 2-bromoethyl group, 2-cyanoethyl group, 2
-Methoxycarbonylethyl group, 2-methoxyethyl
Group, 3-bromopropyl group, etc.), substituted with 4 to 18 carbon atoms
Optionally alkenyl groups (eg 2-methyl-1-
Propenyl group, 2-butenyl group, 2-pentenyl group, 3
-Methyl-2-pentenyl group, 1-pentenyl group, 1-
Hexenyl group, 2-hexenyl group, 4-methyl-2-he
Xenyl group, etc.), an alkyl group having 7 to 12 carbon atoms which may be substituted.
Aralkyl group (eg, benzyl group, phenethyl group, 3-
Phenylpropyl group, naphthylmethyl group, 2-naphthyl
Ethyl group, chlorobenzyl group, bromobenzyl group, methyl
Rubenzyl group, ethylbenzyl group, methoxybenzyl group
Group, dimethylbenzyl group, dimethoxybenzyl group, etc.),
An alicyclic group having 5 to 8 carbon atoms which may be substituted (for example,
Chlorohexyl group, 2-cyclohexylethyl group, 2-cyclohexyl group
(Clopentylethyl group, etc.) or substituted with 6 to 12 carbon atoms
Optionally aromatic groups (eg phenyl, naphthyl)
Group, tolyl group, xylyl group, propylphenyl group, buty
Ruphenyl group, octylphenyl group, dodecylphenyl
Group, methoxyphenyl group, ethoxyphenyl group, butoki
Cyphenyl group, decyloxyphenyl group, chlorophenyl
Group, dichlorophenyl group, bromophenyl group, cyano
Phenyl group, acetylphenyl group, methoxycarbonyl
Phenyl group, ethoxycarbonylphenyl group, butoxy
Carbonylphenyl group, acetamidophenyl group, pro
Pioamidophenyl group, dodecyloylamidophenyl group
Etc.) and the like.

In the repeating unit of the general formula (XIII) which is a component having such a substituent R ⁴ , more preferably the above general formula (XIII a) and / or the general formula (XIII a)
A methacrylate component having a specific substituent, which is represented by b) and contains a benzene ring or an unsubstituted naphthalene ring having a specific substituent at the 2-position and / or at the 2-position and the 6-position, is preferable. (Hereinafter, this low molecular weight substance is particularly referred to as resin [BB]).

[0187]

[Chemical 53]

[In the formulas (XIII a) and (XIII b), A
¹ and A ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, -COZ.
² or -COOZ ² (Z ² represents 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, which bonds —COO— and the benzene ring. When the above-mentioned specific resin [BB] is used, the electrophotographic characteristics (particularly V ₁₀ , DRR, E _1/10 ) can be further improved as compared with the case of the resin [B].

The reason for this is unknown, but one reason is that the effect of the planar benzene ring or naphthalene ring having a substituent at the ortho position, which is the ester component of methacrylate, causes the zinc oxide interface in the film. It is considered that the arrangement of these polymer molecular chains in 1 is appropriately performed.

In formula (XIII a), preferred A ¹ and A ² are, independently of each other, a hydrogen atom, a chlorine atom and a bromine atom, respectively, and a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 carbon atom. To 4 alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group, carbon number 7 to 9)
Aralkyl groups (eg, benzyl group, phenethyl group, 3
-Phenylpropyl group, chlorobenzyl group, dichlorobenzyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, chloromethylbenzyl group) and aryl groups (eg phenyl group, tolyl group, xylyl group, bromophenyl group, methoxyphenyl) Group, chlorophenyl group, dichlorophenyl group), and -COOZ ² and-
COOZ ² (Preferred Z ² has 1 to 1 carbon atoms as described above.
0 may be mentioned as preferable hydrocarbon groups of 0).

In formulas (XIIIa) and (XIIIb), B ¹ and B ² are each a single bond connecting —COO— and a benzene ring or — (CH ₂ ) _e — (e is an integer of 1 to 3). _{represented), - CH 2 OCO -,} - CH 2 CH 2 OCO-,
_{- (CH 2) f - (} f is an integer of 1 or 2), - C
It is a linking group having 1 to 4 connecting atoms such as H ₂ CH ₂ O-, and more preferably a single bond or a connecting group having 1 to 2 connecting atoms.

Formula (XII used in the resin [B] of the present invention
Specific examples of the repeating unit represented by Ia) or (XIIIb) are shown below. However, the scope of the present invention is not limited to this.

[0194]

[Chemical 54]

[0195]

[Chemical 55]

[0196]

[Chemical 56]

[0197]

[Chemical 57]

[0198]

[Chemical 58]

[0199]

[Chemical 59]

[0200]

[Chemical 60]

[0201]

[Chemical formula 61]

Furthermore, in the graft copolymer of the present invention, the component copolymerizable with the macromonomer (M) is represented by the general formula (XIII), (XIIIa) or (XIIIb).
It may be a monomer other than, for example, the general formula (XIII)
In addition to methacrylic acid esters, acrylic acid esters, and crotonic acid esters containing a substituent other than those described above, α-olefins, vinyl carboxylates or allyl acid esters (for example, acetic acid and propionic acid as carboxylic acids). , Butyric acid, valeric acid, benzoic acid, naphthalenecarboxylic acid, etc.), acrylonitrile, methacrylonitrile, vinyl ethers, itaconic acid esters (eg, dimethyl ester, diethyl ester, etc.), acrylamides,
Methacrylamides, styrenes (eg styrene, vinyltoluene, chlorostyrene, hydroxystyrene,
N, N-dimethylaminomethylstyrene, methoxycarbonylstyrene, methanesulfonyloxystyrene, vinylnaphthalene, etc.), vinylsulfone-containing compound, vinylketone-containing compound, heterocyclic vinyls (eg vinylpyrrolidone, vinylpyridine, vinylimidazole, vinylthiophene, Vinyl imidazoline, vinyl pyrazole, vinyl dioxane, vinyl quinoline, vinyl tetrazole, vinyl oxazine and the like). Preferred examples include vinyl alkanoates or allyl esters having 1 to 3 carbon atoms, acrylonitrile, methacrylonitrile, styrene and styrene derivatives (for example, vinyltoluene, butylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, ethoxy). Styrene etc.) and the like.

For the binder resin of the present invention, at least one compound selected from the macromonomer (M) and other monomers (for example, the monomer represented by the general formula (XIII)) is desired. It can be produced by copolymerizing at a ratio of. As the polymerization method, solution polymerization, suspension polymerization,
It can be produced by using a known method such as precipitation polymerization or emulsion polymerization. For example, benzene in solution polymerization,
It is possible to obtain a copolymer solution obtained by adding a monomer at a predetermined ratio to a solvent such as toluene and polymerizing it with an azobis compound, a peroxide compound and a radical polymerization initiator. The desired copolymer can be obtained by drying or adding it to a negative solvent. In suspension polymerization, a monomer can be suspended in the presence of a dispersant such as polyvinyl alcohol or polyvinylpyrrolidone and copolymerized in the presence of a radical polymerization initiator to obtain a copolymer.

The photoconductive layer containing the resin [B] of the present invention may have a higher order structure like the surface layer. The higher order structure in the photoconductive layer can be formed by the same crosslinking agent and crosslinking method as those for the surface layer. The lithographic printing plate precursor having a surface layer of the present invention is one in which the surface layer is applied after coating the photoconductive layer, and therefore, when the photoconductive layer is crosslinked, the resistance of the photoconductive layer to the coating solvent of the surface layer is improved. Solvent properties are fully exhibited.

Resin for use in the photoconductive layer of the present invention [B]
The ratio of the resin [B] used in combination is preferably 5 to 40 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the total binder resin used in the photoconductive layer. Parts by weight. If the proportion of the resin [B] is 5 parts by weight or less, the effect of improving the electrostatic characteristics will be weakened, and if it exceeds 40 parts by weight, the film strength of the photoreceptor will be reduced.

As the binder which can be combined with the binder resin [B], all conventionally known binders can be used. Typical examples are vinyl chloride-vinyl acetate copolymer, styrene-
Examples thereof include butadiene copolymer, styrene-butyl methacrylate copolymer, polymethacrylate, polyacrylate, polyvinyl acetate, polyvinyl butyral, alkyd resin, silicone resin, epoxy resin, epoxy ester resin, polyester resin and the like. It is also possible to combine with an aqueous acrylic emulsion or acrylic ester emulsion.

For examples of specific polymeric materials useful as binders, see Research Disclosure (Research
Disclosure), 109, pages 61-67, under the title "Electrophotographic Elements, Materials and Methods". Generally, the amount of binder present in the photoconductive composition used in the present invention can be varied. Typically, a useful amount of binder is based on the total amount of mixture of photoconductive material and binder.
It is in the range of about 10 to about 90% by weight.

For the electrophotographic photosensitive layer (photoconductive layer) used in the present invention, any photoconductive substance can be used regardless of whether it is an inorganic photoconductive compound or an organic photoconductive compound. As the inorganic photoconductive substance, for example, zinc oxide, titanium oxide, zinc sulfide, selenium, selenium alloy, cadmium sulfide,
Examples thereof include cadmium selenide and silicon, and these may form a photoconductive layer together with a binder resin, or may be independently formed by vapor deposition or sputtering. As the organic photoconductive substance, for example, in the case of polymer, the following (1) to (5) can be mentioned. (1) Polyvinylcarbazole and its derivatives described in JP-B-34-10966, (2) Polyvinylpyrene, polyvinylanthracene, and poly-2-vinyl- described in JP-B-43-18674 and JP-B-43-19192 4- (4 '
-Dimethylaminophenyl) -5-phenyl-oxazole, vinyl polymers such as poly-3-vinyl-N-ethylcarbazole, (3) Polyacenaphthylene, polyindene, acenaphthylene and styrene described in JP-B-43-19193. (4) Condensation resins such as pyrene-formaldehyde resin, bromopyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin described in JP-B-56-13940.
(5) Various triphenylmethane polymers described in JP-A-56-90833 and JP-A-56-161550.

For low molecular weight compounds, for example, the following (6)
(18) can be mentioned. (6) Triazole derivatives described in US Pat. No. 3,112,197, etc. (7) US Pat. No. 3,189,447
Oxadiazole derivatives described in JP-B No. 3615402, (8) Imidazole derivatives described in JP-B-37-16096, and (9) US Pat. No. 3615402.
No. 3820989, No. 3542544, Japanese Patent Publication No. 45-555,
JP-B-51-10983, JP-A-51-93224, JP-A-55-17105
JP-A-56-4148, JP-A-55-108667, JP-A-55-
No. 156953, JP-A-56-36656, and the like, polyarylalkane derivatives described in (10) US Pat. No. 31.
80729, 4278746, JP-A-55-88064, JP-A
55-88065, JP-A-49-105537, JP-A-55-51086,
JP-A-56-80051, JP-A-56-88141, JP-A-57-45545
Nos. 54-112637, 55-74546, and the like, and pyrazoline derivatives and pyrazolone derivatives described in the gazette, (11) U.S. Pat. No. 3,615,404, Japanese Patent Publication No. 51-10105. , JP-A-54-83435, JP-A-54-110836
Japanese Patent Publication No. 54-119925, Japanese Patent Publication No. 46-3712, Japanese Patent Publication No. 47
-28336, the phenylenediamine derivatives described in gazettes, (12) U.S. Pat. No. 3567450, Japanese Patent Publication No. 49-35702, West German Patent (DAS) 1110518, U.S. Pat. No. 3180703, U.S. Pat. No. 3240597, U.S. Patent No.
3658520, U.S. Pat.No. 4,232,103, U.S. Patent No. 4175
961, U.S. Pat.No. 4012376, JP-A-55-144250,
JP-A-56-119132, JP-B-39-27577, JP-A-56-224
Nos. 37, 37, and the like, (13) amino-substituted chalcone derivatives described in US Pat. No. 3,526,501, and (14) US Pat. No. 354254.
N, N-bicarbazyl derivatives described in No. 6, etc.,
(15) Oxazole derivatives described in US Pat. No. 3,257,203 and the like, (16) Styrylanthracene derivatives described in JP-A-56-46234, and (17) JP-A-54.
Fluorenone derivatives described in JP-A-110837, (18) US Pat. No. 3717462, JP-A-54-59143
No. 55, JP-A-55-52063, JP-A-55-52064, JP-A-55-4
6760, JP-A-55-85495, JP-A-57-11350, JP-A-SHO
No. 57-148749 Hydrazone derivatives disclosed in their respective specifications and publications.

Two or more kinds of these photoconductive substances may be used in combination depending on the case. Among these photoconductive materials are poly-N-vinylcarbazole; triarylamines such as tri-p-tolylamine and triphenylamine; 4,4'-bis (diethylamine) -2,2'-
Polyarylmethanes such as dimethyltriphenylmethane; and 3- (4-dimethylaminophenyl) -1,
Unsaturated heterocycle-containing compounds represented by pyrazoline derivatives such as 5-diphenyl-2-pyrazoline are preferably used.

Further, a conventionally known compound can be added as a spectral sensitizer. For example, xanthene dye,
Examples thereof include triphenylmethane-based dyes, azine-based dyes, phthalocyanine-based dyes (metal-containing), and polymethine-based dyes. Specifically, Harumi Miyamoto, Hidehiko Takei, “Imaging” 1973 (No. 8), 2 ; CJYou-ng, RCA Review 1
5, 469 (1954); Kohei Kiyota, Transactions of the Institute of Electrical Communication J63
-C (No. 2), 97 (1980); Yuji Harasaki et al., Journal of Industrial Chemistry, 6
6, 78 and 188 (1963); Tadaaki Tani, Journal of the Photographic Society of Japan, 35, 208.
(1972); Rese-arch Disclosure, 1982 216, 117-118
The publicly known materials and the like, which are referred to in general reviews, such as the collection of comprehensive technical data “Recent development and practical application of photoconductive materials and photoconductors” published by Nippon Kagaku Information Co., Ltd. (1986), are listed.

The photoconductive layer may be formed of one layer, or may be formed of two or more layers. In the case of a multi-layer, for example, the inorganic photoconductor or a phthalocyanine pigment, a charge generating layer composed of an organic pigment such as an azo pigment and a binder resin optionally added, and the above-mentioned polymer compound or low-molecular compound A so-called function-separated type photoconductive layer in which a charge transport layer made of a binder resin is laminated is considered.

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

Specifically, as an example of the conductive substrate or the conductive material, Yukio Sakamoto, “Electrophotography” 14, (No. 1),
2-11 (1975); Hiroyuki Moriga "Introduction to Special Paper Chemistry" Polymer Publishing (1975); MF Hoover, J. Mac-romol. Sci. Ch
Those described in em., A-4 (6), pages 1327 to 1417 (1970) and the like can be used. The coating thickness of the photoconductive composition on a suitable support can vary widely.
Generally, it can be applied in the range of about 10 microns to about 300 microns, but before drying. It has been found that the preferred range of coating thickness before drying is in the range of about 50 microns to about 150 microns. However, even if it deviates from this range, a beneficial result can be obtained. The dried thickness of this coating may be in the range of about 1 micron to about 50 microns.

The thickness of the hydrophilizable surface layer of the present invention is 10 μm.
m or less, especially 0.1 for Carlson process
It is preferably ˜5 μm. If it is thicker than 5 μm, there may occur inconveniences such as a decrease in sensitivity of the lithographic printing original plate as an electrophotographic photoreceptor and an increase in residual potential. In order to actually make the lithographic printing plate precursor of the present invention, generally, an electrophotographic photosensitive layer (photoconductive layer) is first formed on a conductive support according to a conventional method. Next, on this layer, the resin of the present invention and, if necessary, the above-mentioned additives and the like have a boiling point of 200 ° C.
It can be produced by dissolving or dispersing in the following volatile hydrocarbon solvent, coating and drying it. As the organic solvent used, specifically, a halogenated hydrocarbon having 1 to 3 carbon atoms such as dichloromethane, chloroform, 1,2-dichloroethane, tetrachloroethane, dichloropropane or trichloroethane is particularly preferable. Other aromatic hydrocarbons such as chlorobenzene, toluene, xylene or benzene, acetone or 2
It is also possible to use various solvents used in the coating composition and mixtures of the above solvents, such as ketones such as butanone, ethers such as tetrahydrofuran and methylene chloride.

A toner image is formed on the original plate obtained as described above according to a usual electrophotographic method. A printing plate can be obtained by treating this with a desensitizing treatment liquid (for example, an acidic or alkaline aqueous solution or an aqueous solution in which a reducing agent is dissolved) to change the non-image area to hydrophilic. As described above, by using the hydrophilizable layer in the invention, any conventionally known electrophotographic photoreceptor can be used as a high quality lithographic printing original plate. The hydrophilizable layer is a film that has both high hydrophilicity and water resistance after hydrophilic treatment, and also has very good adhesion to a toner image,
Therefore, the obtained lithographic printing plate precursor has extremely suppressed generation of background stain and has high printing durability.

Further, since the printing plate of the present invention can maintain the original sensitivity of the electrophotographic photosensitive layer almost as it is, it is possible to obtain a printing plate plate having a remarkably high sensitivity as compared with the conventional printing plate for electrophotographic plate making. . Further, conventionally, only one material such as zinc oxide can be used because it has to have the property that photoconductivity and hydrophilicity can be obtained in one layer, but in the printing original plate of the present invention, a photoconductive layer and Since the functions are separated in the hydrophilizable layer, the range of selection of the photoconductive layer is widened. Therefore, if a material having high sensitivity in the long-wavelength light region is selected, for example, a He-Ne laser which has been impossible in the past can be obtained. It becomes possible to write with a semiconductor laser.

In the present invention, various dyes can be used together as a spectral sensitizer depending on the kind of light source such as visible light exposure or semiconductor laser light exposure. For example, Harumi Miyamoto, Hidehiko Takei: Imaging 1973 (N
o. 8) Page 12, C.I. J. Young et al .: RCA R
view 15, pp. 469 (1954), Kouhei Kiyota et al .: Transactions of the Institute of Electrical Communication, J63-C (No. 2), 9
7 pages (1980), Yuji Harazaki et al., Journal of Industrial Chemistry, 6
6,78 and 188 (1963), Tadaaki Tani, Journal of the Photographic Society of Japan, 35, 208 (1972), and other general references, carbonium dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, phthalein dyes. , Polymethine dyes (for example, oxonol dyes, merocyanine dyes, cyanine dyes, rhodacyanine dyes, styryl dyes, etc.), phthalocyanine dyes (which may contain a metal), and the like.

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

Examples of polymethine dyes such as oxonol dyes, merocyanine dyes, cyanine dyes and rhodacyanine dyes include F.I. M. Harmmer "The Cyanin
eDyes and Related Compound
The dyes described in "ds" and the like can be used, and more specifically, U.S. Pat. Nos. 3,047,384 and 3,110,591,
3121008, 3125447 and 312817
9, No. 3132942, No. 3622317,
British Patent Nos. 1226892, 1309274 and 14
No. 05898, Japanese Patent Publications Nos. 48-7814, 55
The dyes described in each publication of 18892 are mentioned.

Furthermore, near-infrared light with a long wavelength of 700 nm or more
As polymethine dyes for spectrally sensitizing infrared light, JP-A-47-840, JP-A-47-44180 and JP-B-51-41 are known.
061, ibid 49-5034, ibid 49-45122, ibid 5
7-46245, 56-351141, 57-157.
No. 254, No. 61-26044, No. 61-27551, U.S. Pat. Nos. 3,619,154 and 4,175,956, and "Research Disclosure".
e ”, 1982, 216, pp. 117-118.

The photoconductor of the present invention is also excellent in that its performance does not easily change depending on the sensitizing dye even when various sensitizing dyes are used in combination. Furthermore, if necessary, various conventionally known additives for electrophotographic photoreceptors can be used in combination. These additives include chemical sensitizers for improving electrophotographic sensitivity, various plasticizers for improving film properties, surfactants and the like.

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

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

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

With respect to the lithographic printing original plate having the toner image thus formed, the non-image area is then desensitized to produce a printing plate. In the desensitizing treatment used in the present invention, the above-mentioned protected hydrophilic group chemically reacts with the treatment liquid to express the hydrophilic group. Specifically, a basic treatment liquid is used, preferably pH 8
Any of the water-soluble treatment liquids Nos. 14 to 14 may be used.

The compound that makes the treatment liquid basic may be any of conventionally known inorganic compounds and organic compounds, for example, carbonates, sodium hydroxide, potassium hydroxide, potassium silicate, sodium silicate, organic amine compounds. Etc., and any of these may be used alone or in combination. Furthermore, as a compound used in combination to accelerate the hydrophilization reaction, the nucleophilic constant n [R. G. Pearson, H .; Sobel, J .;
Songstad, J.M. Amer. Chem. So
c. , 90, 319 (1968)] contains a substituent having a value of 5.5 or more, and in 100 parts by weight of distilled water,
A hydrophilic compound that dissolves in an amount of 1 part by weight or more can be used.

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

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

The amount of the nucleophilic compound present in these treatment solutions is 0.05 mol / liter to 10 mol / liter, preferably 0.1 mol / liter to 5 mol / liter. Further, the pH of the treatment liquid is preferably 4 or more. The treatment conditions are preferably a temperature of 15 ° C. to 60 ° C. and an immersion time of 10 seconds to 5 minutes. The treatment liquid contains the above-mentioned nucleophilic compound and p
Other compounds may be contained in addition to the H regulator. For example, a water-soluble organic solvent is added in an amount of 1 to 50 parts by weight in 100 parts by weight of water.
You may contain a weight part. Examples of such water-soluble organic solvents include alcohols (methanol, ethanol, propanol, propanol alcohol, benzyl alcohol, phenethyl alcohol, etc.), ketones (acetone, methyl ethyl ketone, acetophenone, etc.), ethers (dioxane, Trioxane, tetrahydrofuran, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, tetrahydropyran, etc.) amides (dimethylformamide, dimethylacetamide, etc.), esters (methyl acetate, ethyl acetate, ethyl formate, etc.) These may be used alone or in admixture of two or more.

Further, the surfactant may be contained in 100 parts by weight of water in an amount of 0.1 to 20 parts by weight. Examples of the surfactant include conventionally known anionic, cationic or nonionic surfactants. For example, compounds described in Hiroshi Horiguchi "New Surfactants" Sankyo Publishing Co., Ltd. (published in 1975), Ryohei Oda, Kazuhiro Teramura "Synthesis of Surfactants and Their Applications" Maki Shoten (published in 1980), etc. Can be used.

The treatment conditions are preferably a temperature of 15 ° C. to 60 ° C. and an immersion time of 10 seconds to 5 minutes. Further, the hydrophilic treatment containing the nucleophilic compound can obtain the same effect even when the immersing water at the time of printing is used by containing the nucleophilic compound.

[0233]

[Synthesis of macromonomer]

Synthesis Example 1 of Macromonomer (M) 1: (M-1) A mixed solution of 30 g of triphenylmethyl methacrylate and 100 g of toluene was thoroughly degassed under a nitrogen stream-20
Cooled to ° C. 1,1-diphenylbutyllithium 1.
0 g was added and reacted for 10 hours.

Further, a mixed solution of 70 g of ethyl methacrylate and 100 g of toluene was thoroughly degassed in a nitrogen stream, and then added to this mixed solution, and the mixture was further reacted for 10 hours.
After this mixture was brought to 0 ° C., carbon dioxide gas was bubbled at a flow rate of 60 ml / min for 30 minutes to stop the polymerization reaction.

The temperature of the resulting reaction solution was raised to 25 ° C. with stirring, 6 g of 2-hydroxyethyl methacrylate was added,
Furthermore, dicyclohexylcarbodiimide 12 g, 4-
A mixed solution of 1.0 g of N, N-dimethylaminopyridine and 20 g of methylene chloride was added dropwise over 30 minutes, and 3 as it was.
Stir for hours.

After separating the precipitated insoluble matter by filtration, 10 ml of 30% hydrogen chloride ethanol solution was added to this mixed solution, and the mixture was stirred for 1 hour. Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation in 1 liter of petroleum ether. The polymer obtained by collecting the precipitate and drying under reduced pressure has a weight average molecular weight (Mw) of 6.5 × 10 ³ and a yield of 56.
It was g.

[0237]

[Chemical formula 62]

Synthesis Example 2 of Macromonomer (M): (M-
2) A mixed solution of 5 g of benzyl methacrylate, 0.1 g of (tetraphenylporphinato) aluminum methyl and 60 g of methylene chloride was heated to 30 ° C. under a nitrogen stream.
This was irradiated with light of 300 W-xenon lamp through a glass filter from a distance of 25 cm and reacted for 12 hours. 45 g of butyl methacrylate was further added to this mixture, and the mixture was similarly irradiated with light for 8 hours.
10 g of bromomethylstyrene was added, and the reaction was stopped by stirring for 30 minutes. Next, Pd-C was added to this reaction mixture, and catalytic reduction reaction was performed at a temperature of 25 ° C. for 1 hour.

After filtering off the insoluble matter, petroleum ether 500 m
The precipitate was collected and dried. The yield of the obtained polymer was 33 g, and the Mw was 7 × 10 ³ .

[0240]

[Chemical formula 63]

Synthesis Example 3 of Macromonomer (M): (M-
3) A mixed solution of 20 g of 4-vinylphenyloxytrimethylsilane and 100 g of toluene was thoroughly degassed under a nitrogen stream and cooled to 0 ° C. 2 g of 1,1-diphenyl-3-methylpentyllithium was added and stirred for 6 hours. Further, a mixed solution of 80 g of 2-chloro-6-methylphenylmethacrylate and 100 g of toluene was thoroughly degassed in a nitrogen stream, added to this mixture, and reacted for 8 hours. Ethylene oxide was bubbled through the reaction mixture at a flow rate of 30 ml / min for 30 minutes with sufficient stirring, and the temperature was 15 ° C.
After cooling, 12 g of methacrylic acid chloride was added dropwise over 30 minutes, and the mixture was further stirred for 3 hours.

Next, 10 g of 30% hydrogen chloride ethanol solution was added to the reaction mixture, and the mixture was stirred at 25 ° C. for 1 hour,
The precipitate was reprecipitated in 1 liter of petroleum ether, and the collected precipitate was washed twice with 300 ml of diethyl ether and dried. The yield of the obtained polymer was 55 g, and the Mw was 7.8 × 10 ³ .

[0243]

[Chemical 64]

Synthesis Example 4 of Macromonomer (M): (M-
4) A mixed solution of 40 g of triphenylmethyl methacrylate and 100 g of toluene was thoroughly deaerated under a nitrogen stream,
Cooled to 0 ° C.

2 g of sec-butyllithium was added and reacted for 10 hours. Next, to this mixed solution, a mixed solution of 60 g of styrene and 100 g of toluene was thoroughly degassed under a nitrogen stream and added, and the mixture was reacted for 12 hours. After this mixture was heated to 0 ° C., 11 g of benzyl bromide was added and reacted for 1 hour and further reacted at a temperature of 25 ° C. for 2 hours. 3 in this reaction mixture
10 g of an ethanol solution containing 0% hydrogen chloride was added, and the mixture was stirred for 2 hours. The insoluble matter was separated by filtration and then reprecipitated in 1 liter of n-hexane, and the precipitate was collected and dried under reduced pressure. The yield of the obtained polymer was 58 g, and the Mw was 4.5 × 10 ³ .

[0246]

[Chemical 65]

Synthesis Example 5 of Macromonomer (M): (M-
5) Phenylmethacrylate 70 g, benzyl-N-hydroxylethyl-N-ethyldithiocarbamate 4.8 g
The mixture of (1) was sealed in a container under a nitrogen stream and heated to a temperature of 60 ° C. This was irradiated with light from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 10 hours to perform photopolymerization. After 30 g of acrylic acid and 180 g of methyl ethyl ketone were added thereto, the atmosphere was replaced with nitrogen, and light was again irradiated for 10 hours. 12 g of 2-isocyanatoethyl methacrylate was added dropwise to the obtained reaction mixture at a temperature of 30 ° C. for 1 hour, and the mixture was further stirred for 2 hours.

The resulting reaction product was reprecipitated in 1.5 l of hexane, collected, and dried. The polymer obtained had a Mw of 68 g.
It was 6.0 × 10 ³ .

[0249]

[Chemical formula 66]

[Synthesis of Resin [B]] Synthesis Example 1 of Resin [B] 1: [B-1] 80 g of ethyl methacrylate, macromonomer (M-
1) A mixed solution of 120 g and 150 g of toluene was heated to a temperature of 95 ° C. under a nitrogen stream. Add 6 g of 2,2'-azobis (isobutyronitrile) (AIBN) and add 3
Reacts for an hour, and after every 2 hours A. I. B. N. 2 g was added and reacted.

The Mw of the obtained copolymer was 9 × 10 ³ .

[0252]

[Chemical formula 67]

Synthesis Example 2 of Resin [B]: [B-2] 70 g of 2-chlorophenyl methacrylate, 30 g of macromonomer (M-2), 2 g of n-dodecyl mercaptan.
And a mixed solution of 100 g of toluene under a nitrogen stream at a temperature of 8
Warmed to 0 ° C. 3,2 g of 2,2′-azobis (isovaleronitrile) (AIVN) was added and reacted for 3 hours,
Furthermore, A. I. V. N. 1 g was added and reacted for 2 hours. Then A. I. V. N. 1 g was added and the mixture was heated to a temperature of 90 ° C. and reacted for 3 hours. The Mw of the obtained copolymer was 7.6 × 10 ^3.
Met.

[0254]

[Chemical 68]

Synthesis Examples 3 to 18 of Resin [B]: [B-3]
~ [B-18] Under the same polymerization conditions as in Synthesis Example 1 of Resin [B], ethyl methacrylate was replaced with another monomer to synthesize the copolymers shown in Table B below. The Mw of each polymer obtained was 5 × 10 ^{3 to} 9
It was × 10 ³ .

[0256]

[Table 2]

[0257]

[Table 3]

[0258]

[Table 4]

Synthesis Examples 19 to 35 of Resin [B]: [B-1
9] to [B-35] In Synthesis Example 2 of Resin [B], the macromonomer (M-
Copolymers shown in Table C below were synthesized under the same polymerization conditions as in Synthesis Example 2 except that another macromonomer (M) was used instead of 2). The Mw of each polymer obtained was 2 × 10 ³ to 1
It was × 10 ⁴ .

[0260]

[Table 5]

[0261]

[Table 6]

[0262]

[Table 7]

[0263]

[Table 8]

Example 1 and Comparative Examples A to D Example 1 33.6 g of a binder resin [PB-1] having the following structure, 8.4 g of a binder resin [B-8], 200 g of photoconductive zinc oxide, and uranine A mixture of 0.02 g, rose bengal 0.04 g, bromphenol blue 0.03 g, salicylic acid 0.15 g and toluene 300 g was placed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 1 × 10 ⁴ r.p. p. m. Was dispersed for 10 minutes at the rotation speed of. To this, 0.1 g of phthalic anhydride, o
-Add 0.02 g of chlorophenol and rotate at 1 x 1
0 ³ r. p. m. Dispersed for 1 minute. The photosensitive layer-forming dispersion was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 25 g / m ² , dried at 100 ° C. for 30 seconds, and further heated at 140 ° C. for 1 hour.

[0265]

[Chemical 69]

A solution having the following content was applied on the surface of the photoreceptor by a wire bar, dried by touch with a finger, and further heated at a temperature of 140 ° C. for 1 hour to form a surface layer having a thickness of 2.3 μm. Then, the mixture was left in the dark at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material. Resin [A-1] having the following structure 8 g Resin [P-1] having the following structure 2 g Phthalic anhydride 0.1 g O-chlorophenol 0.02 g Tetrahydrofuran 90 g

[0267]

[Chemical 70]

Comparative Example A An electrophotographic photosensitive material was prepared in the same manner as in Example 1, except that 8 g of resin [R-1] having the following structure was used instead of 8 g of resin [A-1]. Was produced.

[0269]

[Chemical 71]

Comparative Example B An electrophotographic photosensitive material was prepared in the same manner as in Example 1 except that 8 g of the resin [R-2] having the following structure was used instead of 8 g of the resin [A-1] in Example 1. It was made.

[0271]

[Chemical 72]

Comparative Example C Instead of 8 g of the resin [A-1] in Example 1, 5.9 g of the resin [R-1] and 2.1 g of the resin [R-2] (resin [R-1] / resin [R-1] / R-2] = 73/27 (weight ratio)]
An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that was used. Comparative Example D In Example 1, the binder resin [PB-1] 3 for the photoconductive layer was used.
An electrophotographic photosensitive material was produced in the same manner as in Example 1 except that only 42 g of the binder resin [PB-1] was used instead of 3.6 g and [B-8] 8.4 g.

The imaging properties and printability of these light-sensitive materials were examined. As for printability, a fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.) is used with a developer to perform an exposure / development process to form an image, and a desensitizing solution E-
It was examined by using a lithographic printing plate obtained by desensitizing treatment using No. 1. The printability was evaluated using each of the Synflow system and Molton system printers in order to investigate the influence of the difference between the dampening water and the printing ink supply system of the printer. Furthermore, by using a large-sized printing machine that prints a Kikuzen size (1003 × 800 mm), the durability of the printing plate when the printing pressure on the offset printing machine becomes strong is determined by how many clear prints can be obtained. The printing durability was evaluated.

[0274]

[Table 9]

Embodiments of the evaluation items shown in Table-D are as follows. Note 1) Imaging: Each photosensitive material and fully automatic plate-making machine ELP4
04V (manufactured by Fuji Photo Film Co., Ltd.) is left at room temperature and normal humidity (20 ° C, 65%) for one day and then plate-made to form a copy image, and the obtained copy original image (fog, image Visually observe the image quality). Note 2) Water retention after printing: Each light-sensitive material itself was dipped for 3 minutes in E-1 (desensitizing treatment solution of the following formulation) having a temperature of 40 ° C. (original plate not made into a plate: abbreviated as raw plate). These plates were printed using F-1 below as dampening water, and the presence or absence of background stains on the 50th printed sheet after printing was visually evaluated. Desensitizing treatment liquid: E-1 Monoethanolamine 60 g Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) 8 g Benzyl alcohol 100 g was diluted with distilled water to a total volume of 1.0 liter, and then adjusted to pH 13.5 with potassium hydroxide. It was adjusted.

Damping water: F-1 Damping water for PS plate Alky A (manufactured by Toyo Ink Co., Ltd.) was diluted 200 times with distilled water (pH 9.5) Imprint water retention I: Molton A Ryobi 3200CD type (manufactured by Ryobi Co., Ltd.) was used as a type printing machine. Imprinted water retention II: Ryobi 3200MCD type was used as a synflow type printing machine. Note 3) Printing durability After sensitizing each photosensitive material in the same manner as in Note 3) above, immersing it in the processing solution of E-1 used in Note 4) for 3 minutes, ) And the neutralizing paper as the printing paper, and as the printing machine, Oliver 94
Using a mold (Sakurai Mfg. Co., Ltd.), the number of prints of a printed matter on which a clear image free of background stain was obtained was examined. The surface smoothness of each photographic material was good. The electrostatic characteristics of the materials of the present invention and Comparative Examples A to C were good, and the actual image pickup properties and the copied images were all good. However, in Comparative Example D, fine lines and missing characters were observed in the copied image, and ground fog also occurred in the non-image portion.

Next, each of these photoconductors is subjected to a desensitizing treatment to determine the degree of presence / absence of ink adhesion (water retention) in the non-image area on the actual printing machine at the 50th sheet of printed matter after printing. The degree of scumming was visually evaluated. Each of the original plates of the present invention and Comparative Example D showed extremely good water retention without any ink adhesion, regardless of the printing machine.

On the other hand, Comparative Example A, which is a plate producing a carboxyl group, caused a large difference in the occurrence of background stains on the printed matter due to the difference in the fountain solution and the ink supply system. That is, when the printing was started, the supply of dampening water was insufficient as compared with the Molton system, and in the insufficient synflow system, ink adhered to the non-image portion of the printed matter and became scumming. This means that in the original plate of Comparative Example A, the surface of the hydrophilized photoconductive layer has sufficiently good wettability with water, but the amount of water held by the entire photoconductive layer (particularly the film If the balance of the supply of dampening water is lost due to insufficient water retention), an extremely thin water layer (Vienna reversal layer: WBL) is formed on the plate surface at the start of printing. It is presumed that it cannot be retained.

Also, Comparative Example B, which is a version producing a sulfo group
In comparison with Comparative Example A, the ink adhesion was improved even in the case of the synflow system. However, since the water retention capacity of the membrane increases in this case, W. B. L. It is presumed that the formation of spores will be insufficient. Further, Comparative Example C, which was used by blending both resins used in Comparative Examples A and B, could not fill the defects of both, and as a result, the same result as Comparative Example A was obtained.

Next, when the printing durability was examined using a large-sized printing machine, the image quality of the printed matter of the present invention was clear even after printing 5,000 sheets. On the other hand, Comparative Examples A, B and C are 5
It became about 600 or 1,000. The reason why the printing durability of Comparative Example A was deteriorated was that, when a large number of sheets were imprinted, the water retention amount of the film caused the W.I. B. L.
It is also considered that the amount of water retention is no longer sufficient. In the case of Comparative Examples B and C, it is presumed that the resin having a sulfo group-containing crosslinked structure has a large water retention amount, so that the strength of the film is insufficient and the printing durability is deteriorated due to the breakage of the film. It was In the case of Comparative Example D, the image pick-up property was poor (fine lines / missing characters), which occurred as it was after being printed on the printed matter.

From these facts, it was only the material of the present invention that it was possible to print a large number of excellent printed matter even when the printing conditions varied. Example 2 and Comparative Examples E to H Binder resin [PB-2] 28 g and binder resin [B
-20] 9 g, the resin [P-1] 8 g, photoconductive zinc oxide 200 g, uranine 0.02 g, dye [I] 0.015 g having the following structure, dye [II] 0.01 having the following structure:
A mixture of 2 g, 0.18 g of N-hydroxyphthalimide and 300 g of toluene was placed in a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 7 × 10 ³ r. p. m. At 8 rpm
Dispersed for minutes. To this, 0.1 g of phthalic anhydride and 0.002 g of acetylacetone zirconium salt were added, and the rotation speed was 1 × 10 ³ r. p. m. Dispersed for 1 minute. This photosensitive layer-forming dispersion has a dry adhesion amount of 25 g /
Apply with a wire bar to make m ²
It was dried for 0 seconds and further heated at 140 ° C. for 1 hour.

[0282]

[Chemical formula 73]

[0283]

[Chemical 74]

A coating solution having the following content was coated on the photosensitive layer with a wire bar, dried by touch with a finger, and then heated at a temperature of 140 ° C. for 1 hour to form a surface layer having a thickness of 2.5 μm. Then, the mixture was left in the dark at 20 ° C. and 65% RH for 24 hours to prepare an electrophotographic photosensitive material. Resin [A-2] having the following structure 8.5 g Resin [P-2] having the following structure 1.5 g Phthalic anhydride 0.05 g Acetylacetone zirconium salt 0.001 g O-chlorophenol 0.001 g Toluene 90 g

[0285]

[Chemical 75]

Comparative Example E An electronic device was prepared in the same manner as in Example 2 except that 8.5 g of the resin [R-3] having the following structure was used instead of 8.5 g of the resin [A-2] in Example 2. A photographic light-sensitive material was produced.

[0287]

[Chemical 76]

Comparative Example F In Example 2, except that 8.5 g of the resin [R-3] having the following structure was used in place of 8.5 g of the resin [A-2],
An electrophotographic photosensitive material was prepared in the same manner as in Example 2.

[0289]

[Chemical 77]

Comparative Example G Instead of 8.5 g of the resin [A-2] in Example 2, 5.0 g of the resin [R-3] and 3.5 of the resin [R-4] were used.
g (Resin [R-3] / Resin [R-4] = 58.8 / 4
1.2 (weight ratio)] was used and an electrophotographic photosensitive material was produced in the same manner as in Example 2. Comparative Example H In Example 2, the binder resin [PB-2] 3 for the photoconductive layer was used.
0 g and [B-30] 15 g instead of the binder resin [PB
-2] was operated in the same manner as in Example 2 except that only 45 g was used to prepare an electrophotographic photosensitive material.

The image pick-up property and the water retention after printing of each light-sensitive material were examined in the same manner as in Example 1. In addition, the fountain solution used in printing has a different pH (that is, pH 4.5, pH
7.0, pH 9.5) was used to examine the degree of influence on the printed matter. The above results are shown in Table-E.

[0292]

[Table 10]

Note 6) Dependence on fountain solution Printing was carried out in the same manner as in Note 5) above. However, as the dampening water used for printing, three kinds of the following contents were used. I: Damping water for pS plate EU-3 (manufactured by Fuji Photo Film Co., Ltd.) diluted 100 times with distilled water (pH 4.5) II: Damping water for pS plate SG-23 (Tokyo Ink Co., Ltd.
Made by diluting 130 times with distilled water (pH)
7.0) III: Fountain solution Alky A for pS plate (Toyo Ink Co., Ltd.)
Made by diluting 200 times with distilled water (pH)
9.5) In both Example 2 and Comparative Examples E to G, the image pickup property was good. However, in Comparative Example H, thin lines and missing characters were generated, and scumming was observed in the non-image area.

Next, when the water retention after printing was examined, it was found that those of the present invention and Comparative Example H were good, but Comparative Examples EG
Had reduced water retention on a Symflow printing press. In addition,
For Comparative Example E, in Shinfuro manner, why it does not reach the good water retention, the resin [R-4], the -PO ₃ H ₂ group expressed in the desensitizing, water capacity of the membrane is sufficient However, since the hydrophilic group is bonded to the polymer main chain through a hydrophobic linking group, the wettability with water on the surface of the film appears as insufficient during printing. It is estimated to be.

Further, evaluation of printing durability was carried out by changing the kind of dampening water. With the present invention, 5,000 good prints were obtained regardless of the type of dampening water. On the other hand, Comparative Examples E to G are good only in the case of the fountain solution (III),
With other dampening waters, the background stains caused by ink adhered more or less to the extent of printing, and did not improve even after further printing. Further, in Comparative Example H, the image pick-up property was poor, and therefore fine lines and missing characters occurred in the printed matter after printing.

These are greatly influenced by the pH of the dampening water,
It is considered to be related to the dissociation constant of the hydrophilized hydrophilic group. That is, since the influence is dominant in Comparative Example E, the —COOH group of the resin [R-3] is
Although it exists in a state of being dissociated to the —COOH ⁻ group, the affinity with water is remarkably improved. It is considered that when the pH becomes low, the amount of dissociated groups decreases, and the affinity with water decreases.

That is, the dissociation constant (: p
It was found that unless the water having a small Ka) is used in combination, the water retention greatly varies depending on the type of dampening water. As described above, since the material of the present invention can be printed even with the dampening water of the PS plate printed by a large-sized printing press, it can be easily printed on another printing original plate without cleaning and inspecting the printing press. It became possible to use it in common with. Examples 3 to 13 Each electrophotographic photosensitive material was operated in the same manner as in Example 1 except that each resin [A] shown in Table F below was used in place of the resin [A-1]. Was produced.

[0298]

[Table 11]

[0299]

[Table 12]

[0300]

[Table 13]

Various properties of each light-sensitive material were evaluated in the same manner as in Example 1. All showed the same electrostatic characteristics and image pick-up property as the light-sensitive material of Example 1. As for the performance as a printing plate, good water retention was exhibited from the start of printing on both the Molton type and the Synflow type printing machines, and the printing durability was more than 5,000 sheets. Examples 14 to 25 In Example 1, instead of the resin [A-1], the resin [P-1] and the crosslinking compound [phthalic anhydride and o-chlorophenol], the compounds shown in Table G below were used. Others were operated in the same manner as in Example 1 to prepare each light-sensitive material.

[0302]

[Table 14]

[0303]

[Table 15]

[0304]

[Table 16]

[0305]

[Table 17]

[0306]

[Table 18]

Various performances of each light-sensitive material were evaluated in the same manner as in Example 1. All showed the same electrostatic characteristics and image pick-up property as the light-sensitive material of Example 1. As for the performance as a printing plate, good water retention was exhibited from the start of printing on both the Molton type and the Synflow type printing machines, and the printing durability was more than 5,000 sheets. Example 26 X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) 1
g, resin [PB-3] having the following structure 10 g, resin [B-3
5] 2 g, 0.3 g of resin [P-1] and 80 g of tetrahydrofuran were put together with glass beads in a 500 ml glass container, dispersed with a paint shaker (manufactured by Toyo Seiki Seisakusho) for 60 minutes, and further ethylene glycol diglycidyl ether 0. After adding 3 g and dispersing for 2 minutes, the glass beads were filtered to obtain a photosensitive layer dispersion liquid.

[0308] Then, this dispersion was applied on a 0.2 mm thick base paper for a master for a printing plate with a wire bar and dried by touch with a finger, and then in a 110 ° C circulating oven, It was dried for 20 seconds. 1 at 140 ° C
Heated for hours. The film thickness of the obtained photosensitive layer was 8 μm.

[0309]

[Chemical 78]

A coating solution having the following contents was applied onto this photosensitive member.
Apply with a wire bar, dry to the touch, and 1 at 140 ° C.
It was heated for an hour to form a surface layer having a film thickness of 2.0 μm. Resin [A-25] having the following structure 8.0 g Resin [P-1] 2 g Phthalic anhydride 0.1 g o-Cresol 0.02 g Toluene 90 g

[0311]

[Chemical 79]

This light-sensitive material was allowed to stand for one day under the conditions of (20 ° C., 65% RH), and then the light-sensitive material was charged with −6 kV, and a 2.8 mW output gallium-aluminum-arsenic semiconductor laser was used as a light source. Oscillation wavelength of 780 nm) and a dose of 64 erg / cm ² on the surface of the photosensitive material at a pitch of 25 μm and a scanning speed of 300 m / s.
ELP-T as a liquid developer after speed exposure of ec
A copy image (fog, image quality) obtained by developing with (Fuji Photo Film Co., Ltd.), washing with a rinse solution of isoparaffin Isopar G (Esso Chemical Co., Ltd.) solvent, and fixing. When it was visually evaluated, a clear image free of background fog was given.

Next, the plate prepared by the above method was desensitized and printed under the same conditions as in Example 1. As a result, both the water retention after printing (I) and (II) were good. When the printing durability was examined, more than 5,000 clear prints were obtained. Example 27 In Example 26, 8 g of resin [A-25], resin [P
-1] 2 g and Example 26 except that only 10 g of the resin [A-26] having the following structure was used in place of the crosslinking compound.
A light-sensitive material was produced in the same manner as in. However, cross-linking of the film was performed by irradiating with light for 3 minutes at a distance of 80 cm using a lamp having a high pressure mercury lamp as a light source, instead of heating (140 ° C., 1 hour).

[0314]

[Chemical 80]

When the electrostatic characteristics and printing characteristics of the light-sensitive material of the present invention were evaluated by the same methods as in Example 26, all showed good results as in the case of the light-sensitive material of Example 26. Examples 28 to 30 Each photosensitive material was prepared in the same manner as in Example 1 except that 8 g of each resin [A] shown in Table H below was used instead of 8 g of the resin [A-1]. It was made.

[0316]

[Table 19]

When each of the light-sensitive materials was evaluated for electrostatic properties and printability in the same manner as in Example 1, all showed good results equivalent to those of the light-sensitive material in Example 1. Examples 31 to 44 In Example 1, the photoconductive layer resin [B-8] 8.4 g
Each electrophotographic photosensitive material was prepared in the same manner as in Example 1 except that 8.4 g of each resin [B] shown in the following Table-I was used instead of.

[0318]

[Table 20]

When each light-sensitive material was subjected to printing evaluation as a printing original plate in the same manner as in Example 1, the same good performance as in Example 1 was shown. Examples 45 to 56 Using each of the light-sensitive materials prepared in Examples 1 to 44, desensitizing treatment was operated as follows to prepare an offset printing original plate.

Distilled water was added to 0.2 mol of the nucleophilic compound shown in Table J below, 100 g of an organic solvent and 2 g of Newcol B4SN [manufactured by Nippon Emulsifier Co., Ltd.] to make 1 liter, and then
The pH of each mixture was adjusted to 13.5. Each photosensitive material,
It was immersed in the treatment liquid at a temperature of 35 ° C. for 3 minutes to perform a desensitizing treatment. The obtained plate was printed under the same printing conditions as in Example 1. Each of the light-sensitive materials exhibited good performance equivalent to that of Example 1.

[0321]

[Table 21]

[0322]

According to the present invention, it is possible to provide a lithographic printing plate precursor that is free of background stain, is excellent in desensitization and has high printing durability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03G 5/09 101 9221-2H 13/28

Claims (5)

[Claims] 1. An electrophotographic photosensitive member comprising a conductive support, at least one photoconductive layer containing at least a photoconductive layer compound and a binder resin, and a surface layer on the uppermost layer. In the lithographic printing plate precursor using, the binder resin of the surface layer contains at least one of the following binder resins [A]:
A lithographic printing plate precursor containing a seed and containing at least one of the following binder resins [B] as a binder resin in the photoconductive layer. Binder resin [A]: a polymer component (a) containing at least one functional group that produces a —COOH group by a chemical reaction treatment,
The polymer component (b) containing at least one functional group selected from the functional groups that generate —SO ₃ H group, —SO ₂ H group, and —PO ₃ H ₂ group in the treatment, and heat and / or light. A copolymer containing at least a polymer component (c) containing at least one curable group. Binder resin [B]: having a weight average molecular weight of 1 × 10 ³ to 2 × 10 ⁴ , a —PO ₃ H ₂ group, a —COOH group, and a —SO ₃ group.
H group, phenolic OH group, -P (= O) (OH) R
¹ [R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group) group] group and a polymer component containing at least one polar group selected from cyclic acid anhydride groups. The AB block copolymer composed of at least one A block and a B block containing at least a polymer component represented by the following general formula (I) is polymerizable at the end of the polymer main chain of the B block. A graft copolymer containing at least one monofunctional macromonomer (M) having a double bond group bonded as a copolymerization component. [Chemical 1] [In the formula (I), a ¹ and a ² each represent a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group. V ¹ is-
COO -, - OCO-, chromatography (CH _{2) a} OCO-, chromatography _{(CH 2) a COO-, (} a is an integer of 1-3.)
-O -, - SO ₂ over, over CO-, chromatography CON (Z ¹⁾ -,
Over SON (Z ¹⁾ -, over CONHCOO-, over CONH
CONH- or chromatography C ₆ H ₄ - represents a (wherein Z ¹ represents a hydrogen atom or a hydrocarbon group). R ³ represents a hydrocarbon group. However, when V ¹ represents —C ₆ H ₄ —, R ³ represents a hydrogen atom or a hydrocarbon group. ] 2. In the binder resin [A], in the copolymer component (a), at least one functional group that produces a —COOH group is directly bonded to the main chain of the polymer chain of the copolymer. The lithographic printing plate precursor according to claim 1, wherein 3. Along with the binder resin [A], heat and / or
Alternatively, it contains a photocurable compound.
Or the lithographic printing plate precursor as described in 2. 4. The resin [B] as a copolymer component copolymerized with the macromonomer (M) is represented by the following general formula (X
III a) and at least one of the aryl group-containing methacrylate components represented by the following general formula (XIII b) are contained.
The lithographic printing plate precursor as described in the item. [Chemical 2] [In formulas (XIII a) and (XIII b), A ¹ and A ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a chlorine atom, —COZ ² or —COOZ ² (Z ² is Represents a hydrocarbon group having 1 to 10 carbon atoms), B ¹ and B
Each of ^2's represents a single bond or a linking group having 1 to 4 connecting atoms for connecting -COO- to the benzene ring. ] 5. The photoconductive layer comprises photoconductive zinc oxide and / or
Alternatively, the lithographic printing plate precursor as claimed in any one of claims 1 to 4, which contains at least a photoconductive compound made of photoconductive titanium oxide and a spectral sensitizing dye.