JPS61217295A - Planographic plate blank - Google Patents

Abstract

PURPOSE:To further enhance adhesion of a surface layer and enable high-speed processing with high sensitivity and high durability in printing, by a method wherein a photoconductive layer comprising a photoconductive substance and a resin selected from phenoxy resins and the like as main constituents and a surface layer are sequentially provided on a conductive base. CONSTITUTION:The photoconductive layer 2 comprising a photoconductive substance and a resin selected from phenoxy resins, polybutyral resins, polyallylate resins and linear saturated polyester resins as main constituents and the surface layer 3 comprising a reaction product of a crosslinking agent with a resin having an annular acid anhydride structure as main constituents are sequentially laminated to the conductive base 1. The reaction product, per se, is hydrophobic and has sufficient resistance for holding an electrostatic latent image, but when it is treated with an alkaline liquid, the surface thereof becomes hydrophilic. In this case, the surface becomes hydrophilic but not water- soluble and has sufficient water resistance, so that high durability in printing can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a lithographic printing original plate made by electrophotography, and more specifically, a layer (having specific properties) on a photoconductive layer (
A layer whose surface changes from hydrophobic to hydrophilic is provided. This invention relates to a lithographic printing original plate made as described above.

Prior art lithographic printing original plates include those provided with layers of various photosensitive resins, layers of silver halide photosensitive materials, or layers of photoconductive materials on a substrate (or conductive substrate). etc. are used.

Among these, printing original plates made by the playback photography method using photoconductivity are widely used mainly in the field of light printing because they can be easily made directly from an original (direct plate making). This printing original plate has a photoconductive layer of a zinc oxide-resin dispersion system on a conductive support, and after forming a toner image by electrophotography, it is treated with an aqueous solution containing, for example, ferrocyanate. Either the surface of the non-image area is made hydrophilic to form a printing plate, or the strength of the photoconductive layer is insufficient, resulting in a problem that the printing durability is only about 5,000 to 10,000 sheets.

On the other hand, the special public service No. 37-17162, the special public service No. 38-7758
, JP 46-39405, JP 52-2437, JP 56-10724-6, JP 55-105254
, JP-A-55-153948, JP-A-56-1612
5, JP-A-57-147656, JP-A-56-1461
45, JP-A No. 57-161863, etc., disclose, for example, a layer consisting of an organic photoconductive compound and an alkali-soluble resin on a hydrophilic conductive support such as a grained aluminum plate, or A printing original plate for electrophotographic engraving that has a layer in which a charge-generating pigment such as a phthalocyanine pigment is dispersed in an alkali-soluble resin, or a layer sensitized by adding an electron-withdrawing substance or an electron-donating substance to this dispersed layer. It is shown. This type of printing original plate is made by forming a toner image on the photosensitive layer using an electrophotographic method, and then eluting and removing the photosensitive layer in the non-image area with an alkaline solution.It is a printing plate with high printing durability using direct platemaking. However, as a photoreceptor for electrophotography, it has low sensitivity and requires a high-output light source, and also has the disadvantage that the plate-making speed is slow because the elution process takes time.

Sumita, Japanese Patent Publication No. 1983-5606 discloses a method of creating a printing original plate with surface treatment for non-image areas that is easy to make by providing a specific resin layer (surface layer) on an electrophotographic X photoreceptor. ing. This surface layer is composed of a vinyl ether-maleic anhydride copolymer and a hydrophobic resin compatible with this. When the toner is treated with an alkali after image formation, the top part of the acid anhydride in the non-image area becomes hydrophilic due to hydrolysis and ring opening. A printed version is available. However, the vinyl ether-maleic anhydride copolymer used here becomes water-soluble when the acid anhydride top part is ring-opened and becomes hydrophilic, so high printing durability cannot be obtained. There wasn't.

The present inventors previously discovered a hydrophilic surface layer (hereinafter referred to as a hydrophilic layer) consisting of a reaction product of a resin having a cyclic acid anhydride structure and a crosslinking agent on an electrophotographic photosensitive layer (photoconductive layer). ) 8 original printing plates were proposed. This surface layer can be easily made hydrophilic, but unlike the surface layer made of the vinyl ether-maleic anhydride copolymer and hydrophobic resin described above, it is cross-linked and therefore does not remain water resistant even after being made hydrophilic. It has high mechanical strength and high printing durability. however,
This printing original plate was not necessarily fully satisfactory in terms of adhesion to the surface layer in all cases, and it was observed that there were cases in which the strength of the surface layer itself could not be fully demonstrated.

Purpose The purpose of the present invention is to further improve the adhesion of the surface layer in the printing original plate having a surface layer that can be made hydrophilic on the electrophotographic photosensitive layer, thereby achieving high sensitivity, cylinder resistance, and high speed processing. The objective is to provide a lithographic printing original plate that is capable of

Structure The lithographic printing original plate of the present invention has a photoconductive layer on a conductive support, the main components of which are a photoconductive substance and a resin selected from phenoxy resins, polyvinyl butyral resins, polyarylate resins, and edge-shaped saturated polyester resins. This is a lithographic printing original plate in which a surface layer containing a reaction product of a resin having a cyclic acid anhydride structure and a crosslinking agent as a main component is sequentially laminated.

A typical example of the resin having a cyclic acid anhydride structure is a maleic anhydride copolymer, and a typical example of the crosslinking agent is a polyisocyanate compound.

Hereinafter, the present invention will be explained in more detail based on the accompanying drawings. FIG. 1 is a cross-sectional view showing the structure 8 of the basic lithographic printing plate according to the present invention, in which 1 is a conductive support, 2 is a photoconductive layer, and 3 is a surface layer that can be made hydrophilic (hydrophilizable layer). ) is shown.

In the image forming process in electrophotography, a silent X latent image is formed by positive or negative charging and subsequent image exposure.

At this time, the surface layer 4 that holds the electrostatic latent image needs to be highly resistive and hydrophobic to the extent that charge diffusion in the surface direction does not occur (if it is hydrophilic, the resistance will be low due to moisture adsorption). , it is not possible to retain the silence as a latent image). The electrostatic latent image is then developed with toner charged to the opposite polarity to the surface charge.
A toner image is formed on the surface layer 4 by being fixed.

Since printing is performed based on the difference between the lipophilicity (inkphilicity) of this toner image and the hydrophilicity of the non-image area, the surface of the surface layer 40 needs to be hydrophilic during printing.

In this way, the surface layer 4 is hydrophobic when forming an electrostatic latent image.
The ability to change to hydrophilic properties during printing is required. In the present invention, the reaction product of a resin having a cyclic acid anhydride structure and a crosslinking agent used for the surface) C@4 (hydrophilizable layer) is originally hydrophobic and has a sufficient amount of water to maintain an electrostatic latent image. Although it has resistance, the surface becomes hydrophilic when treated with alkaline liquid. Moreover, it is hydrophilic or water-soluble.
Due to sufficient water resistance, high one-printing properties can be obtained.

The photoconductive layer 2 is mainly composed of a photoconductive substance and a resin selected from phenoxy resin, polyvinyl butyral resin, polyarylate resin, and linear saturated polyester resin, or the photoconductive substance used here. as,
For example, zinc oxide, titanium oxide, selenium, selenium alloys,
Inorganic photoconductive materials such as cadmium sulfide and silicon;
Alternatively, there are organic photoconductive substances such as those shown in (1) to (to) below.

(1) Triphenylmethane dyes such as malachite green and crystalline iolet, thiazine dyes such as methylene blue and methylene green, anthracene dyes such as Astrazone Orange R1, Astrazone Yellow 3GL, and Anthracene Red 6B, Eisen Astrafuroxine F' Cyanine dyes such as F, rhodamine B
xanthine dyes such as 2,6-diphenyl-4-(N
, N-dimethylaminophenyl) thiapyrylium verchlorate, benzopyrylium salts, and other biryllium dyes.

(2) Perylene pigments such as perylene anhydride and perylene imide.

(3) Indigo thread pigment.

(4) Quinacridone pigment.

(5) Polycyclic quinones such as anthraquinones, pyrenequinones, anthoanthros, and flavanthrones.

(6) Bisbenzimidazole pigment.

(7) Square methine pigment.

(8) Indathlon thread pigment.

(9) Phthalocyanine pigments such as metal phthalocyanines such as copper phthalocyanine and metal-free phthalocyanines.

(a) A charge transfer type complex consisting of an electron-donating substance such as poly-N-vinylcarnozole and an electron-accepting substance such as 2,4,7-trinitrofluorenone.

01) A eutectic lead body formed from a biryllium ring dye and a precarbonate resin.

(2) Noronurubitric acid derivative or thiobarbic acid derivative.

(To) Azo pigments such as monoazo pigments, disazo pigments and trisazo pigments. Examples of monoazo pigments include monoazo pigments having a central skeleton such as anthraquinone and N-phenylcarnozole, and examples of disazo pigments include benzidine pigments such as Diane Blue and Chlordiane Blue, or N-ethylcarnosol. , stilbene, disinalbenzene, naphthalene, fluorenone, fluorene, anthraquinone, 2,5-diphenyl-1,3,4-oxadiazole, dipenzothiophene, dibenzothiophene dioxite, acridone, phenanthrenequinone, etc. Examples of the disazo pigment include trisazo pigments having a central skeleton of triphenylamine or N-phenylcarnozole.

Q41&1I-N-vinylcal 2? Sole, halogenated poly-N-vinylcal 2? Sole, polyvinylpyrene,
Polymeric photoconductive compounds such as polyvinylanthracene.

(a) 2,5-bis(4-diethylaminophenyl)
1,3.4-oxadiazole, 2,5-bis[4-
(4-diethylaminostyryl)phenyl) -1,3
,4-oxadiazole, 2-(9-ethylcarnozolyl-3-)-5-(,4-diethylaminophenyl)
-Oxadiazole compounds such as 1,3,4-txadiazole, 2-vinyl-4-(2-chlorophenyl)
-5-(4-diethylamino)oxazole, 2-(4
Oxazole compounds such as -4-phenyloxazole, 1-phenyl-3-(
4-diethylaminostyryl)-5-(4-diethylaminophenyl)pyrazoline, 1-phenyl-3-(4-
Pyrazoline compounds such as dimethylaminostyryl)-5-(4-diethylaminophenyl)pyrazoline, 2,
Diphenylmethane compounds such as 2'-dimethyl-4゜4'-bis(diethylamino)triphenylmethane, 1,1-bis(4-dibenzylaminophenyl)pronozone, tris(4-diethylaminophenyl)methane, 9-
(4-dimethylaminostylidene)fluorene, 3-(
Fluorene compounds such as -9-ethylcarnozole, styryl anthracene compounds such as 9-(4-diethylaminostyryl) anthracene, 9-bromo-10-(4-diethylaminostyryl) anthracene, 1゜2-bis Distyrylbenzene compounds such as (4-diethylaminostyryl)benzene and 1,2-bis(2,4-dimethoxystyryl)benzene, 9
-ethylcarbasol-3-aldehyde 1-methyl-1
-Phenylhydrazone, 9-ethylcarbazole-3-
Aldehyde 1-benzyl-1-phenylhydrazone, 4
-diethylaminobenzaldehyde 1,1-diphenylhydrazone, 2,4-dimethoxybenzaldehyde 1-
Hydrazone compounds such as benzyl-1-phenylhydrazone, 4-diphenylaminobenzaldehyde 1-methyl-1-phenylhydrazone, stilbene compounds such as 4-diphenylaminostilbene, 4-dibenzylaminostilbene, and 4-ditolylaminostilbene, 1 −(
4-diphenylaminostyryl) naphthalene, 1-(4
Styrylnaphthalene compounds such as -diethylaminostyryl) naphthalene, α-phenylstylin compounds such as 4'-diphenylamino-α-phenylstilbene, 4'-methylphenylamino-α-phenylstilbene, 3-styryl-9-ethyl carno, etc. sol, 3-(4
styrylcarbazole compounds such as -diethylamino)styryl-9-ethylcarbazole, chloranil, bromoanil, tetracyanoethylene, tetracyanoquinone dimethane, 2,4.7-)linitro 9-fluorenone, 2,4,5,7-tetranitro -9-fluorenone, 2,4,5.7-ketranitroxanthone, 2.4
．． 8-) linitrothioxanthone, 2,6.8-trinitro-4H-indeno(1,2-b)thiophene-
Compounds such as 4-one, 1,3.7-trinitrodipenzothiophene-5,5-dioxide.

At least one resin selected from phenoxy resin, polyvinyl alcohol resin, polyarylate resin, and linear saturated polyester resin is used as the binder resin for the light guide'-1 layer.

Phenoxy resin is generally obtained by condensation polymerization of bisphenol A and epichlorohydrin, and is represented by the following structural formula. For example, phenoxy resin manufactured by Union Carnoids (PKHO, PKHH, P
KHJ) and other resins that are easily available.

Polyvinyl alcohol resin is generally obtained by converting polyvinyl alcohol to butyraldehyde and has good adhesion to many resins such as polystyrene resins, acrylic resins, polycarbonate resins, polyester resins, and epoxy resins. Show your gender.

Polyarylate resins generally contain aromatic radicals such as terephthalic acid, isophthalic acid, and phthalic acid.
It is an aromatic ester resin obtained by polycondensation of dihydric phenol such as phosphoric acid and bisphenol A, and is easily available as U-polymer manufactured by Unitika, for example.

The linear saturated polyester resin is generally a resin obtained by polycondensation of an acid component such as terephthalic acid or isophthalic acid and a glycol component such as ethylene glycol, propylene glycol or butylene glycol. The acid component here preferably contains not only terephthalic acid but also isophthalic acid from the viewpoint of bath agent solubility and coating properties.

A surface layer containing a resin having a cyclic acid anhydride structure is formed on the photoconductive layer, but when the above-mentioned specific resin is used as the binder resin of f in Photoconductive 11, this surface layer is not good. Shows good adhesion. Furthermore, among V4☆1 resins, the blush layer on the photoconductive layer using polyarylate resin or linear knotted polyester resin is completely the same as the surface layer alone.
Extremely easy to hydrate 8 The photoconductive layer contains phenoxy resin, polyvinylzotyral resin, polyarylate resin and linear saturation 7! It is also possible to add resins other than resins selected from seriester resins, such as polycarbonate resins, polyester resins, polystyrene resins, etc., but in this case as well, the proportion of the binder resin in the resin component is 50% or more. It is preferable from the viewpoint of adhesiveness.

The photoconductive layer 2 may be formed of a single layer as shown in FIG. 1, or may be formed of a multilayer of two or more layers as shown in FIG. (a) A layer in which an inorganic photoconductive substance such as zinc oxide or cadmium sulfide or an organic pigment such as a phthalocyanine pigment or an azo pigment is dispersed; Cb) A compound as shown in (g) above or a layer as shown in q4 A layer containing a polymer compound such as (c
) A layer containing a compound as shown in 4 above or a polymer compound shown in α◆ and a dye (as shown in 11) dissolved therein; A possible example is a layer formed by

In the case of a multi-layer structure, for example, a layer containing the above-mentioned inorganic photoconductive substance or an organic pigment such as a phthalocyanine pigment or an azo pigment, and a polymeric compound as shown in a→ above or an OQ-based layer may be used. Compounds such as (charge transport substances)
It is conceivable to consider a structure in which heavy conveyances containing . In this case, the configuration of the original printing plate will be as shown in Figure 2,
In the figure, 2' represents one photoconductive layer, 4 represents a charge generation layer, and 5 represents a charge transport layer.

When the photoconductive layer is formed of multiple layers in this way, at least the layer in contact with the surface layer, for example in the structure shown in FIG. 2, the binder resin of the charge transport layer 5 may include polyvinyl butyral resin, phenoxy resin, polyarylate resin,
A resin selected from linear saturated polyester resins is used.

As mentioned above, the resin having a cyclic acid anhydride structure used in the surface layer 3 (hydrophilizable layer) is a copolymer containing maleic anhydride as one copolymerization component (hereinafter referred to as maleic anhydride copolymer). ) are preferred; more specifically, for example, methyl vinyl ether, ethyl vinyl ether, 2-chlorovinylethyl ether, propyl vinyl ether, isophthyl vinyl ether, 2-,
i') *Copolymers of lower alkyl vinyl ethers such as diethyl vinyl ether and maleic anhydride, copolymers of styrene and maleic anhydride, copolymers of ethylene and maleic anhydride, copolymers of vinyl acetate and maleic anhydride. and so on. Furthermore, these maleic anhydride copolymers in which some of the acid anhydride rings are open can also be used.

Further, the surface layer 3 (hydrophilicizable layer) is preferably crosslinked using a crosslinking agent in order to improve water resistance and strength after hydrophilization. As the crosslinking agent, it is preferable to use an f-isocyanate compound, and specific examples thereof include toluene-2,4-diisocyanate, toluene-2,4-diisocyanate, and toluene-2,4-diisocyanate.
2,6-diisocyanate, diphenylmethane-4,4
'-diisocyanate, naphthylene-], 5-diisocyanate, 3,3'-dimethylpiphenyl-4,4'-
Diisocyanate, triphenylmethane-4,4',4
-Aromatic polyisocyanates such as triisocyanate, tris(p-incyanatophenyl)thiophosphite, polymethylene polyphenyl isocyanate, and xylylene diisocyanate, or aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and isophorone diisocyanate. Examples of the conductive support 1 include polyisocyanate or a trimer thereof, a plastic film having a 4'' hard surface such as an aluminum vapor-deposited film, water-resistant and conductive treated paper, Metal plates such as aluminum plates, copper plates, zinc plates, and stainless steel plates are used.

To produce the lithographic printing original plate of the present invention, first, a coating containing a photoconductive substance and a resin selected from phenoxy resins, polyvinyl butyral resins, polyarylate resins, and linear saturated polyester resins is applied onto a conductive support. The solution is applied by a conventional method and dried to form a photoconductive layer. Subsequently, a solution containing a resin having a cyclic acid anhydride structure and a crosslinking agent is applied thereon. The organic solvent used at this time is a solvent that does not react with the crosslinking agent, such as N, N-
Examples include dimethylformamide, dioxane, and tetrahydrofuran. After coating, drying and heat treatment are performed to cause a crosslinking reaction to form a surface layer (hydrophilic layer). The temperature and time of this heat treatment vary depending on the type of resin and crosslinking agent, but are generally 80 to 200°C for several minutes to
You can choose within a few hours.

In addition, in order to promote this crosslinking reaction, for example, dibutyltin dilaurate, dibutyltin diacetate, 2
- Appropriate amounts of organometallic compounds such as lead ethylhexanoate and amines such as triethylamine can be added.

The surface layer (hydrophilicizable layer) is mainly made of a reaction product of a resin having a cyclic acid anhydride structure and a crosslinking agent, but in order to improve the strength of the layer, other resins such as polyester resin and polyamide resin may be used to improve the strength of the layer. , polycarbonate resin, acrylic resin, polystyrene resin, vinyl acetal resin or vinyl acetate resin. However, in this case, the proportion of these resins contained in the entire layer is 50 parts (
It is desirable that the amount is J-% or less; if it is more than this, the rate of residual water will be slow and the hydrophilicity will be insufficient in the water treatment on the surface of the non-image area after image formation, and background stains will occur on the printed matter.

In addition, the thickness of the surface layer is 0.05 to 5 μm, preferably 0.
．． It is 1 to 2 μm. Above this range, the sensitivity decreases in the electrophotographic process, the residual potential increases, and background staining occurs, and below this range, printing durability decreases. The proportion of sexual substances is
10 to 95% by weight, preferably 30 to 90% by weight. ] If it is less than 0 weight ratio, the sensitivity as an electrophotographic photoreceptor is insufficient, and if it is 295 weight ratio or more, the mechanical strength of the film is so poor that it cannot be put to practical use.

The plate making of the original printing plate for electrophotographic platemaking of the present invention is performed by first uniformly charging it in a dark place using a corona charger or the like, using a tungsten lamp, halogen lamp, etc., according to the usual electrophotographic method.
Electrostatic latent images are created by reflective image exposure using a light source such as a xenon lamp or fluorescent lamp, contact image exposure through a transparent positive film, or scanning exposure with laser light such as a He-Ne laser, argon laser, or semiconductor laser. This electrostatic latent image is developed with toner and fixed by heating to obtain a toner image on the electrophotographic photosensitive layer (FIG. 4).

Next, when the printing plate on which this toner image has been formed is immersed in an alkaline hydrophilic treatment liquid, the surface of the non-image area that is not masked by the toner image is made hydrophilic, and a good printing plate is obtained (Figure 5). The hydrophilic treatment liquid used here is, for example, an alkaline aqueous solution of inorganic salts such as sodium silicate, sodium phosphate, sodium hydroxide, and sodium carbonate, or an alkaline aqueous solution containing organic amines such as triethanolamine and ethylenecyamine, or these. ethanol, benzyl alcohol, ethylene glycol,
A solution of glycerin sodium chloride in an organic solvent or a surfactant added thereto is used.

The time required for hydrophilization varies depending on the formulation of the surface layer (hydrophilizable layer) 4 and the concentration of the hydrophilic treatment liquid, but it can be carried out in about 1 to 60 seconds by selecting appropriate conditions. After the hydrophilic treatment, water washing and drying are performed as necessary to obtain a lithographic printing plate.

The hydrophilicity of the surface of the non-image area can be measured, for example, by measuring the contact angle with respect to water. In other words, the contact angle on the surface of the surface layer (hydrophilizable layer) 4 before the hydrophilic treatment 2 is 60
The angle is ~80°, but after the hydrophilic treatment, the angle decreases to approximately 10-15°, resulting in a surface that wets well with water.

Since the printing original plate of the present invention hydrophilizes only the non-image area, it is preferable that the toner component used for development contains a resin component that has resistivity to the hydrophilic treatment liquid. For example, acrylic resin using methacrylic acid, methacrylic acid ester, etc., vinyl acetate resin, copolymer of vinyl acetate and ethylene or vinyl chloride, vinyl chloride resin, etc. Vinylidene chloride resin, vinyl acetal resin such as polyvinyl butyral, polystyrene, copolymer of nutylene and sitadiene, methacrylic acid ester, etc., polyethylene, polyethylene and its chloride, polycarbonate, polyester resin 1. f! Examples include lyamide resin, phenolic resin, xylene resin, alkyd resin, wax, polyolefin, and wax.

After completing five or more plate-making processes, the original printing plate of the present invention becomes a printing plate having an image area coated with lipophilic toner and a highly hydrophilic non-image area surface.

In normal planographic printing, oil-based ink adheres only to the image area, resulting in good printed matter without background stains. The surface layer (hydrophilizable layer) after hydrophilic treatment is a highly aqueous coating and also has good adhesion to the photoconductive layer, so the resulting printing plate has a high durability of tens of thousands of copies or more. Furthermore, since the printing original plate of the present invention can maintain almost the same sensitivity of the photoconductive layer (electrophotographic photosensitive layer) itself, higher sensitivity can be obtained compared to conventional printing original plates. In addition, since the photoconductivity and the property of changing from hydrophobic to hydrophilic are shared in separate layers, the range of choices for the photoconductive layer is expanded, allowing for example the selection of materials with high sensitivity in the long wavelength light region. For example, it becomes possible to write with a He-Ne laser or a semiconductor laser, which has been difficult to do in the past.Next, the lithographic printing original plate of the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, in the following examples and comparative examples, all "parts" represent parts by weight.

(Left below) 25-Example 1 1 part of a disazo pigment having a fluorenone central skeleton represented by the above structural formula (I), 19 parts of tetrahydrofuran, and a polyvinyl butyral resin (Denkazotyral+4
000-1: A mixture consisting of 6 parts of a 5 weight solution of Tetrahydrofuran (manufactured by Ashigin Kagaku Kogyo Co., Ltd.) was sufficiently pulverized using an I-lumil. Next, this mixture was taken out and diluted by adding 304 parts of tetrahydrofuran while stirring slowly. This liquid was deposited with aluminum to a thickness of 100 mm.
It was coated on a μ-sized polyester film (conductive support) and dried at 80° C. for 5 minutes to form a charge generation layer with a thickness of about 0.5 μm.

A solution consisting of 112 parts of a hydrazone compound represented by the following structural formula (]]), 12 parts of phenoxy resin (Union Carnoide 21#: pKE+n) and 76 parts of tetrahydrofuran was applied to this charge generation layer soil, and the solution was heated at 80°C for 2 hours. Sow for 5 minutes and dry at 105℃ for 5 minutes to a thickness of approximately 16 μm.
'l'l'i: A load carrying layer was formed.

This charge generation layer and the load carrier! 1 part of methyl vinyl ether-maleic anhydride copolymer (manufactured by Aldrich Chemical Company: polymerization molar ratio: ]), 2 parts of toluene, 011 parts of 4-diisocyanate and N, N-
Apply a solution consisting of 32 parts of dimethylformamide,
After drying at 10° C. for 5 minutes, heat treatment was performed at 50° C. for 30 minutes to cause a crosslinking reaction, thereby forming a surface layer (hydrophilicizable layer) with a thickness of about 0.3 μm.

In order to examine the adhesion of the surface layer of the lithographic printing original plate 1 obtained as described above, a peel test was conducted using cellophane tape. The results are shown in Table 3a.

Examples 2 to 4 Example 1 except that those shown in Table 1a below were used as the resin and charge transport material of the charge transport layer in Example 1.
In the same manner as above, lithographic printing plates 2 to 4 each consisting of a photoconductive layer (charge generation layer, charge transport layer) and a surface layer were prepared. The adhesion of the surface layer was similarly evaluated for these, and the results are shown in Table 38.

Comparative Examples 1 to 4 Example 1 except that the resin shown in Table 2a was used instead of the phenoxy resin as the resin for the charge transport layer in Example 1.
In the same manner as above, comparative printing original plates Curated-1 to Ratio-4 were created. The adhesion of the surface layer was evaluated in the same manner as in Examples 1 to 4, and the results are shown in Table 38.・・・
・Good adhesion and no peeling at all △: Adhesion is somewhat poor and some peeling occurs. .

×: Adhesiveness is poor and the entire surface peels off easily.

Example 5 A solution consisting of 8 parts of a hydrazone compound represented by the structural formula (Il'1), 8 parts of polyvinyl butyral resin (manufactured by Union Carido Co., Ltd.: XYHL'') and 84 parts of tetrahydrofuran was used as a charge transport layer forming solution. The exact same procedure as in Example 1 was repeated except for the following.The results obtained are shown in Table 3b below.

Examples 6 to 8 Example 5 except that those shown in Table 1b below were used as the charge transport layer resin and heavy transport material in Example 5.
In the same manner as above, lithographic printing original plates 6 to 8 each consisting of a photoconductive layer (charge generation layer, charge transport layer) and a surface layer were prepared. The adhesion of the surface layer was similarly evaluated for these, and the results are shown in Table 3b.

Table-]b Table-3b Surface adhesion (from cellophane tape peel test)○...
・Good adhesion and does not peel off at all.

△: Adhesiveness is slightly poor, and some parts peel off.

×: Adhesiveness is poor and the entire surface peels off easily.

From the above examples, it can be seen that the printing original plate of the present invention using polyvinyl butyral resin in the photoconductive layer has superior adhesiveness of the surface layer compared to the comparative printing original plate.

Example 9 1 part of a disazo pigment having a central skeleton of fluorenone represented by the above structural formula (I), 19 parts of tetrahydrofuran, and a polyvinyl butyral resin (Denka Butyral + 4
000-1: A mixture consisting of 6 parts of a 5% by weight tetrahydrofuran solution (manufactured by Kikagaku Kogyo Co., Ltd.) was sufficiently ground in a ball mill.

Next, this mixture was taken out and diluted by adding 104 parts of tetrahydrofuran while stirring slowly. This liquid was applied onto a polyester film (conductive support) having a thickness of 1,100 p on which aluminum was vapor-deposited and dried at 80° C. for 5 minutes to form a charge generation layer having a thickness of about 0.5 μm.

A solution consisting of 12 parts of a hydrazone compound represented by the following structural formula (II)C, 12 parts of polyarylate resin (manufactured by Unitika: U-1060) and 76 parts of tetrahydrofuran was coated on this charge generation layer, and heated at 80°C.
Approximately 16μ
A charge transport layer of m was formed.

On this photoconductive layer (electrophotographic photosensitive layer) consisting of two layers, a charge generation layer and a charge transport layer, 1 part of methyl vinyl ether-maleic anhydride copolymer (Aldrich Chemical Company MEM combined molar ratio 1:1) was applied. , toluene-2,4
- A solution consisting of 0.11 parts of diisocyanate and 32 parts of N,N-dumenalformamide was applied, dried at 110°C for 5 minutes, and then heat-treated at 150°C for 30 minutes to cause a crosslinking reaction, resulting in a thickness of approximately 0.3 μm. surface layer (hydrophilic layer)
was formed.

In order to examine the adhesion of the surface layer of the lithographic printing original plate 9 obtained as described above, a peel test was conducted using cellophane tape. In addition, in order to control the speed of hydrophilization, treatment was performed with a 3% by weight sodium metasilicate aqueous solution, and the treatment time required to reduce the contact angle to water to 10° was determined. Here, the contact angle was measured by a liquid part method using a sample that had been subjected to hydrophilic treatment, washed with water, and dried.

These results are shown in Table 3c.

Examples 1O to 12 Example 9 except that in Example 9, those shown in Table 10 below were used as the charge transport layer resin and charge transport substance.
In the same manner as above, lithographic printing original layers 10 to 12 consisting of a photoconductive layer (charge generation layer, charge transport layer) and a surface layer were prepared. The adhesion and hydrophilicity of the surface layer were evaluated in the same manner, and the results are shown in Table 30.

Table-IC Comparative Examples 5 to 7 A printing original plate layer for comparison was prepared in the same manner as in Example 9, except that the resin shown in Table 2b was used instead of the polyarylate resin as the resin for the jet load transport layer in Example 9. Ratio-5 to Ratio-7 were created. The adhesion and hydrophilicity of the surface layer were evaluated in the same manner as in Examples 9 to 12, and the results are shown in Table 30.

Table 2b Table 3c Surface adhesion (from 1-tape peel test) ○...
・Good adhesion and does not peel off at all.

Δ: Adhesiveness is slightly poor, and some parts peel off.

×: Poor adhesion and easily peels off completely.

The time required for hydrophilization The time required for the contact angle (to water) to decrease to 10° The hydrophilic treatment liquid is 3% by weight metasilicate. It can be seen that the printing original plate of the present invention using a resin is superior to the comparative printing original plate in terms of speed of hydrophilization and adhesiveness of the surface layer.

Example 13 In Example 9, instead of polyarylate resin, linear saturated polyester resin (manufactured by Toyobo Co., Ltd.:) Iron 200 was used.
The exact same operating procedure as in Example 9 was repeated, except that % ) was used. The results obtained are shown in Table 3d below.

Examples 14 to 16 In the same manner as in Example 13, except that the charge transport substances shown in Table 1d below were used, the photoconductive layer (charge generation layer, cellar transport layer) and surface layer were prepared. Planographic printing original plates 14 to 16 were prepared. The adhesion of the surface layer and the speed of hydrophilicization were similarly evaluated for these, and the results are shown in Table 3d.

-39= Table-1d (hereinafter blank) Table-3d As is clear from the above Examples 13 to 16 and Comparative Examples 5 to 7, the printing original plate of the present invention using a linear saturated polyester resin for the photoconductive layer is It can be seen that this printing plate is superior in terms of speed of hydrophilicization and adhesiveness of the surface layer compared to the comparative printing original plate.

(Leaving space below) 41-Example 17 The original printing plate prepared in Example 1 was subjected to corona discharge of 16 KV for 20 seconds using a Seiyozen Shashi Testing Device (newly manufactured by Kawaguchi Denki Seisakusho: 5P-428). After charging the shield, it was irradiated in a dark place for 20 seconds, then the surface potential Vpn (yg volts) was set, and then the surface was irradiated with light using a tungsten lamp so that the illuminance was 4.5 lux. Then, the time required for the surface potential to become 1/2 of Vpo was calculated, and the half-reduced exposure amount E1/2 was calculated.The results were as follows: Vpo = -1210 (volts), E'/
2; 1.3 (lux seconds).

This printing original plate is charged to approximately -800 zert, and then imagewise exposed using a halogen lamp through a lens system to form an electrostatic latent image, which is then developed with positively charged copier toner and heated. It was fixed to form a toner image.

Next, in order to make the surface of the non-image area hydrophilic,
1 part of image source DP-4 (manufactured by Fuji Photo Film Co., Ltd.) and 8 parts of water
The sample was immersed in an alkaline solution consisting of 300ml for 1 minute.

When the printing plate obtained by plate making in this way was printed using a Ricoh offset printing machine AP-13104r+ according to the usual method, two clear prints with no background stains were obtained.
I was able to print more than 10,000 copies.

Example 18 Regarding the printing original plate S2 created in Example 2, VpO and E]/! in the same manner as in Example 17. When measured, Vpo =
-1240 (Nk), E'/=1.3 (lux fist seconds).

In addition, a toner image was formed on this printing original plate in the same manner as in Example 17, and then the surface of the non-image area was made hydrophilic by hydrophilic treatment. We were able to print over 20,000 clear, clean prints.

1 part of trisazo pigment whose central skeleton is triphenylamine represented by the above structural formula (lO), polyvinyl butyral resin (manufactured by Denki Kagaku Kogyo Co., Ltd.: Dencaptyral-+4)
After thoroughly grinding a mixture consisting of 0.33 parts of 000-1) and 12 parts of cyclohexanone in a Zeel mill, 31 parts of cyclohexanone was added with stirring to dilute the mixture. This solution was applied onto a polyester film coated with aluminum vapor and dried at 120℃ for 5 minutes to a thickness of approximately 0.5μ.
A charge generation layer of m was formed. On this charge generation layer, the structural formula (12 parts of the old hydrazone compound, phenoxy resin (
A solution consisting of 12 parts of Union Car (manufactured by Guido: PKHJ) and 76 parts of tetrahydrofuran was applied and heated to 80°C.
for 2 minutes, then dried at 105℃ for 5 minutes to a thickness of approx.
A charge transport layer of .mu.m was formed.

Next, a surface layer was formed on this cargo transport layer in the same manner as in Example 1. This surface layer showed good adhesion.

When Vpo and E1/2 of the printing original plate thus prepared were measured, it was found that Vpo=-870 (approx.) and E'/=0.8 (lux seconds).

In addition, a toner image was formed on this printing original plate in the same manner as in Example 5, and then hydrophilic treatment was performed to make the surface of the non-image area hydrophilic. When the resulting printing plate was printed on a printing machine, it was found that there was no background stain. More than 20,000 prints were obtained.

Example 20 Example 1 regarding the printing original plate/I65 created in Example 5
The same operating procedure as in 7 was followed. The results obtained are shown below.

Vpo = −] 1 ] 07+? Root B/=1
．． 4 lux-second printing durability: 20,000 sheets or more, clear printing with no background stains 8 Example 21 The same operating procedure as in Example 17 was performed on the printing master plate 6 prepared in Example 6. The results obtained are shown below.

Vpo = -1190 Zelt E/, = 1.4 lux φ seconds Printing durability = 220,000 or more, clear printing without background stains, Example 22 Hydrazone compound 8 of the above structural formula (n) as charge transport layer forming solution The same procedure as in Example 19 was repeated, except that a solution consisting of 1 part, 8 parts of polyvinyl butyral resin (manufactured by Union Carnoids Co., Ltd.: XYHL), and 84 parts of tetrahydrofuran was used. The results obtained are shown below.

Vpo = -810 Zelt B/, = 1.0 lux e seconds Printing durability = 220,000 or more, printing without background stains.

Example 23 The same operating procedure as in Example 17 was performed on the original printing plate plate 9 prepared in Example 9.

However, it was immersed in the hydrophilic treatment solution for only 10 seconds instead of 1 minute.

The results obtained are shown below.

Vpo = -1250 volts E]/2=1.3 lux・sec Printing durability = 220,000 or more, clear printing with no background stains.

Example 24 About the original printing plate created in Example 10 Example 2
The same cleaning procedure as in 3 was performed.

The results obtained are shown below.

Vpo=-1300 volts B/2=t, 4 lux-second printing durability=220,000 or more, clear printing without background stains, Example 25 Polyarylate resin (Unitika H; U-100) was used instead of phenoxy resin. Example 9 except that ) was used.
I repeated the exact same operation.

The results obtained are shown below.

Vpo = -900 Zelt B’/=0.8 lux e seconds Printing durability: Over 20,000 prints without surface stains.

Example 26 Example 2 about the printing plate shop 13 created in Example 13
The same procedure as in 3 was followed.

The results obtained are shown below, Vpo=-1120 volts B/=1. (Looks φ second printing durability ===20,000 or more sheets, clear printing with no background stains,
Example 27 Example] Example 2 about the printing plate shop 14 created in 4
The same procedure as in 3 was followed.

The results obtained are shown below.

Vpo ==-1,160N E/=1.3 lux seconds Printing durability: Over 20,000 sheets, clear printing with no background stains.

Example 28 Linear saturated polyester resin (
The same procedure as in Example 9 was repeated except that Ninoseiron 200 manufactured by Toyobo Co., Ltd. was used. The results obtained are shown below.

Vpo = -800 volts E/=0.8 lux-sec Printing durability = 220,000 or more, printing without background stains.

Effects As described above, according to the present invention, the adhesiveness of the surface layer is significantly improved, and a lithographic printing original plate having high sensitivity and high printing durability can be obtained.

[Brief explanation of drawings]

1 and 2 are enlarged cross-sectional views of typical lithographic printing original plates according to the present invention, and FIGS. 3 and 4 are diagrams illustrating the plate-making process of the lithographic printing original plate of the present invention. , 3rd
The figure shows the state after toner image formation, and FIG. 4 shows the state after hydrophilic treatment. 1... Conductive support 2.2'... Photoconductive layer (electron photosensitive layer) 3...
Surface layer (hydrophilicizable layer) 4... 'Burden generation layer 5...' Charge transport layer 6... Toner image 7... Hydrophilic portion of surface layer Patent applicant Rico Co., Ltd. Kazutsu 1 Zuzuzu 2zonozou 3gaku

Claims (1)

[Claims] 1. A photoconductive layer and a cyclic acid anhydride structure containing a photoconductive substance and a resin selected from phenoxy resin, polyvinyl butyral resin, polyarylate resin, and linear saturated polyester resin as main components are formed on a conductive support. A lithographic printing original plate in which surface layers containing a reaction product of a resin and a crosslinking agent as main components are successively laminated.