JPH03157663A - Original printing plate for electrophotographic process - Google Patents

Abstract

PURPOSE:To obtain an original printing plate having high sensitivity, satisfactory aging stability and leachability and hardly causing printing stain by using a phthalocyanine pigment as a photoconductive pigment in a photoconductive layer and further incorporating a specified compd. into the photoconductive layer. CONSTITUTION:When a photoconductive layer contg. a photoconductive pigment and binding resin is formed on an electrically conductive substrate and the photoconductive layer of the resulting original plate in the non-image area is removed to form a printing plate by electrophotography, a phthalocyanine pigment is used as the photoconductive pigment and a compd. represented by formula I is further incorporated into the photoconductive layer. In the formula I, Z is S or O, each of R<1> and R<2> is H, alkyl, aryl or aralkyl which may have a substituent and A is optionally substd. alkyl, aryl or aralkyl or a monovalent heterocyclic group which may have a substituent. An original printing plate having high sensitivity, satisfactory aging stability and leachability and hardly causing printing stain is obtd.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention has a photoconductive layer containing a phthalocyanine pigment as a photoconductive pigment, and after forming a toner image by electrophotography, the toner image area is This invention relates to a novel printing original plate for electrophotographic platemaking with improved electrophotographic sensitivity, which is made into a printing plate by removing the photoconductive layer in non-image areas (hereinafter referred to as etching). It is something.

(Prior art) Today, lithographic offset printing plates include positive type photosensitive plates mainly composed of diazo compounds and phenolic resins, and PS plates using negative type photosensitizers mainly composed of acrylic monomers and prepolymers. have been put into practical use, but all of these have low sensitivity, so plate making is performed by contact exposure of a film original plate with a rough image recorded on it. On the other hand, due to advances in computer image processing, human device data storage, and data communication technology, in recent years, everything from inputting, correcting, editing, and layout to page strings can now be controlled using a combusheter, and instant remote control is now available via high-speed communication networks and satellite communications. Electronic editing systems that can output to local plotters have been put into practical use. The demand for electronic editing systems is particularly high in the newspaper printing field where immediacy is required, and in fields where originals are stored in the form of original film and printed versions are reproduced as needed based on this. However, with the development of ultra-high capacity recording media such as optical discs, it is thought that originals will be stored as digital data on these recording media.

However, direct printing plates that create printing plates directly from the output of terminal plotters have hardly been put into practical use.
Even in places where electronic file collection systems are in operation, output is performed on silver halide photographic film, and based on this, output is indirectly
In reality, printing plates are created by contact exposure to S plates. This is the light source of the output screener (e.g. He
One of the reasons was that it was difficult to develop a direct printing plate with a sensitivity high enough to make a printing plate within a practical time using a laser (NeL/- laser, diagonal conductor laser, etc.).

Electrophotographic photoreceptors are considered as photoreceptors having high photosensitivity that can be used in direct printing plates. After forming 1.10 images,
There are already many known printing plates for electrophotographic platemaking that allow removal of the photoconductive layer in non-image areas.
No. -7758, No. 41-2426, No. 46-39, 1
No. 05, Japanese Patent Application Publication No. 19509, No. 50-195
No. 10, No. 52-2437, No. 51-145538, No. 54-134632, No. 55-105254,
No. 55-153948, No. 55=161250, No. 56-107246, No. 57-147656, No. 5
No. 7-161863, etc., and printing original plates for electrophotographic platemaking are mentioned.

JP-A-56-107246 describes an electrophotographic method in which an oxazole compound is added as an organic photoconductive compound to a binding resin soluble in an aqueous alkali or alcohol solution, and a photoconductive layer prepared by adding a sensitizing dye is coated on an aluminum plate. A printing original plate for type plate making is disclosed. Also, JP-A-56-1461
No. 45 discloses a printing original plate for electrophotographic platemaking which contains an oxadiazole compound as an organic photoconductive compound, a fused polycyclic non-pigment as a charge generating agent, and an alkali-soluble carboxyl group-containing polymer. has been done. Furthermore, JP-A No. 62-54266 contains a hydrazone compound as an organic photoconductive compound, a pigment or dye such as a phthalocyanine pigment or a quinacridone pigment as a charge generating agent, and a bond soluble in an aqueous or alcoholic solvent. A printing original plate for electrophotographic plate making made of resin is disclosed.

(Problems to be Solved by the Invention) As described above, in order to use an electrophotographic photoreceptor as a printing plate, it is usually necessary to remove the non-image area with an alkaline ethotinda solution to expose the hydrophilic surface. As the binding resin, a binding resin that dissolves in an alkaline solvent or swells and is released is often used. However, compared to polycarbonate resins that are widely used as binding resins for electrophotographic photoreceptors, most of the resins that dissolve or swell in these alkaline solvents, including oxazole, hydrazone, oxadiazole, and birapurin, are generally poor compatibility with organic photoconductive compounds. Therefore, when these organic photoconductive compounds are dissolved and contained in a printing plate, there is a problem that the organic photoconductive compounds separate and precipitate over time. In addition, these organic photoconductive compounds have poor solubility in etching solutions, resulting in insufficient elubility in etching solutions in non-image areas, resulting in background smudges on white background areas when printed.

Further, printing original plates for electrophotographic plate making that do not contain an organic photoconductive compound soluble in a binding resin as shown in the above examples are also known. This is a printing original plate for electrophotographic plate making in which an organic photoconductive pigment such as a phthaloanine pigment is dispersed in a binding resin soluble in an aqueous alkali or alcohol solution to form a photoconductive layer.
No. 54 and JP-A-55-161250 disclose a printing original plate for electrophotographic plate making in which a photoconductive layer in which a phthalocyanine pigment is dispersed in a phenolic resin is provided on an aluminum plate. The problem with printing master plates for plate making was their lack of sensitivity. It is known that an electrophotographic photoreceptor in which a phthalocyanine pigment is dispersed in a binding resin and does not contain an organic photoconductive compound such as a hydrazone compound or an oxazole compound exhibits an induction effect, resulting in a decrease in sensitivity. . (Weigl “Curre
nt Problems in Electrophoto
ography P278″, WalLer deG
It is also known that by adding an electron-withdrawing compound such as tetranitrofluorenone or trinitrofluorenone to the photoreceptor, it is possible to reduce this induction effect and improve sensitivity. There is. (Journal of Electrophotography Society 60, 116, 2
0. (19B2)) However, since these electron-withdrawing compounds are toxic, it is problematic to put them into practical use.

As can be seen from the above, it has been desired to develop a printing original plate for electrophotographic plate making that is highly sensitive, has good stability over time, and has good elubility in etching solutions.

(Objective of the Invention) The object of the present invention is to improve the above-mentioned conventional drawbacks, provide high sensitivity,
An object of the present invention is to provide a printing original plate for electrophotographic plate making that has good stability over time, good dissolution properties, and little printing stain.

(Means for Solving the Problems) That is, as a result of intensive research, the present inventors have found that a photoconductive layer containing at least a photoconductive pigment and a binding resin is provided on a conductive support, and this is In a printing original plate for electrophotographic platemaking, in which a printing plate is obtained by forming a toner image by a photographic method and then removing a photoconductive layer in a non-image area other than the toner image area, the photoconductive pigment is a phthalocyanine pigment. The above items were achieved by a printing original plate for electrophotographic platemaking, which is characterized in that the photoconductive layer further contains a compound represented by the following general formula (1).

In the general formula (1) -C formula (r), Z represents a sulfur atom or an oxygen atom. R1 and Rz represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have an m group, or an aralkyl group that may have a substituent; may be the same or different groups, and A has a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a substituent. represents an optionally monovalent heterocyclic group.

(Specific structure and effects of the present invention) That is, the first component constituting the photoconductive layer of the printing original plate for electrophotographic platemaking of the present invention is a phthalocyanine pigment which is a photoconductive pigment. There are a wide variety of phthalocyanine pigments, including those with different central metals, those with different crystal forms, and those with substituents on the Hensen ring. Various central metals are known, including metals such as copper, nickel, iron, vanadium, aluminum, gallium, indium, silicon, titanium, magnesium, cobalt, platinum, and germanium, as well as metal-free phthalocyanine. Various different crystal forms of phthalocyanine are known, which are confirmed by X-ray crystal diffraction for each metal phthalocyanine and metal-free phthalocyanine.6 For example, copper phthalocyanine has α-type, β-type, τ-type,
Polymorphisms such as δ-type, ε-type, η-type, α-type, etc. are present in metal-free phthalocyanine, α-type, β-type, χ-type, τ-type, and other polymorphisms; titanyl phthalocyanine has polymorphisms such as α-type, β-type, M-type and other polymorphisms are known. Furthermore, the benzene ring of phthalocyanine can contain halogen atoms such as fluorine, chlorine, and bromine, as well as alkyl groups, carboxyl groups, amide groups,
Substituted phthalocyanines substituted with sulfonyl groups and other substituents are also known. Each of these has a different absorption wavelength and can be used depending on the application, but for electrophotography, phthalocyanine pigments that absorb at wavelengths compatible with semiconductor lasers of 780 nm to 830 nm are being studied. All these known phthalonanine pigments can be used.

Examples of such phthalocyanine pigments include the following. However, the present invention is not limited to the phthalocyanine pigments illustrated below.

(1) Special Publication No. 44-14106, No. 45-304
No. 69, No. 46-42512, No. 48-34189, JP-A-58-182639, No. 6247054,
No. 63-55554, No. 631546138, No. 6
No. 3-180962, No. 60 243089 1.1.
Chem, Phys.

Metal-free phthalocyanine pigments such as X-type, τ-type, α-type and derivatives thereof described in Vol-55, 3178 (1971) etc. (2) JP-A-50-38543, JP-A-51-23738
No. 51109841, No. 55-59648, No. 57-54943, No. 57185044, No. 62-
No. 121459, No. 5646235, No. 62-141
Copper phthalocyanine pigments such as α-type, β-type, and ε-type described in No. 563, etc. and derivatives thereof (3) JP-A-59-49544 and JP-A-59-16695
No. 9, No. 63-116158, No. 63198067, No. 61275272, No. 61-671366, No. 61-217050, No. 59-214034, No. 6
No. 3-364, No. 63-365, No. 63-37163
Various titanyl phthalocyanine pigments and derivatives thereof (4) JP-A-63-18361, JP-A No. 57-14625, etc.
No. 5, No. 57-147641, No. 6128557,
Appl, Phys, Lett.

Vanadyl phthalocyanine pigments and conductors (5) described in Vol-38, 445 (1981) etc., JP-A-59-204839, JP-A-57-211149, JP-A-6
No. 2-163060, No. 62177069, No. 63-
No. 43155, No. 5L-214034, No. 57-90
No. 058, Appl, Phys, Lett, Vo
Aluminum phthalocyanine pigments and derivatives thereof (6) described in JP-A-61-84655, JP-A No. 5-144054, etc.
No. 59-128544, No. 60-59355,
No. 63-261265, No. 59155851, No. 6
Indium phthalocyanine pigments and derivatives thereof described in JP-A Nos. 3-27562 and 6356564, etc. (7) JP-A-54144053 and 5! IJ-133
No. 551, No. 60-59354, No. 60-26005
Gallium phthalocyanine pigments and derivatives thereof described in No. 4, etc. (8) JP-A-62-220958, JP-A-62-2292
Lead phthalocyanine pigments and derivatives thereof (9) Magnesium phthalocyanine pigments and derivatives thereof described in JP-A No. 62-223761 etc. In printing original plates for electrophotographic platemaking, electrophotographic phosphors for copying machines and Since higher charge retention properties are often required compared to photoconductors for optical printers, it is preferable to use phthalocyanine pigments with high charge retention properties (ability to maintain surface potential in the dark).

The content of the phthalocyanine pigment in the photoconductive layer is 3 to 50% by weight, preferably 5 to 30% by weight based on the solid content in the photoconductive layer.
Weight%.

Next, the second component of the present invention is a binding resin.

The binding resin can be any resin that dissolves or swells in a solvent that does not elute the toner image area but elutes the non-image area (i.e., the photoconductive layer), but preferably alcohol and/or alkaline earth. It is a resin that dissolves or swells in metal. These resins include phenolic resin, styrene/maleic anhydride copolymer, vinyl acetate, crotonic acid copolymer, vinyl acetate/maleic anhydride copolymer,
Examples include alcohol-soluble nylon, or copolymers of two or more elements containing acidic group-containing polymers such as acrylic acid, methacrylic acid, crotonic acid, or itaconic acid and monomers such as methacrylic esters, acrylic esters, or styrene. However, any copolymer containing an acidic group can be used.

Examples of copolymers containing acidic groups include the following compounds, but are not limited thereto.

(1) Benzyl methacrylate-methacrylic acid copolymer (molar ratio 60:40) (2) Benzyl methacrylate-methacrylic acid-hydroxymethyl methacrylate copolymer (molar ratio 60:
20:20) (3) Methyl methacrylate-methacrylic acid-hydroxymethyl methacrylate copolymer (molar ratio 70:10:20) (4) Methyl methacrylate-ethyl meccrylate-acrylic acid copolymer (molar ratio 50:20= 30) (5) Benzyl methacrylate-methyl methacrylate-acrylic acid copolymer (molar ratio 50:20:30) (6) Methyl methacrylate-hydroxyethyl meccrylate-acrylonitrile-acrylic acid (molar ratio
40:20:30:10) (7) Benzyl methacrylate-hydroxyethyl methacrylate-acrylonitrile-methacrylic acid copolymer (molar ratio 20:20:50:10) (8) Vinyl acetate-crotonic acid copolymer (molar ratio 90
:10) (9) Vinyl acetate-vinyl hexanoate-crotonic acid copolymer (molar ratio 85:5:10) (10) Vinyl acetate-maleic anhydride copolymer (molar ratio 80:20) (11) Styrene-maleic anhydride copolymer (molar ratio 50:50) (12) Styrene-hydroxyethyl methacrylate-methacrylic acid copolymer (molar ratio 50:20:30) (13) Styrene-methacrylic acid-methyl methacrylate copolymer Combined (mole ratio 40:30:30) These resins can be used alone or in a mixture of two or more.

The third component constituting the photoconductive layer of the present invention functions as a sensitizer that improves the photoconductivity of the photoconductive layer composed of the phthalocyanine pigment and the binding resin. As described above, when a photoconductive layer that does not contain the third component is used, an inductillin effect occurs that causes a delay in the attenuation of the surface potential immediately after irradiation with light, causing a decrease in sensitivity. The reason for this is not clear, but it is thought that there are carrier traps on the surface of the phthalocyanine particles, and carriers generated by light irradiation are captured by these carrier traps, so that no attenuation of the surface potential is observed during this period. It is being The compounds of the present invention are considered to be sensitizers that reduce this inductigone effect, shorten the time during which the surface potential does not decay (induction period), and improve sensitivity as a result.

The compound of general formula (1) of the present invention will be explained in more detail.

In general formula (I), R1 and R2 represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. Examples of substituents when these groups are substituted include cyano group, hydroxy group, carboxyl group, nitro group, base, halogen atoms such as fluorine and bromine, amino group, alkoxy group, and aryol group. , Ori-ruoxy group, alkoxycarbonyl group, acyloxy group,
Examples of Rt8 include an amino group substituted with an alkyl group, an aryl group, or an aralkyl group, a trifluoroI]methyl group, etc. Specific examples of Rt8 include a methyl group, an ethyl group, an nbutyl group, a -Propyl group, n-butyl group, 5ec-butyl group, n-hexyl group, 2-ethylhexyl group, fluoromethyl group, chloromethyl group, I.lifluoromethyl group, perfluoroalkyl group, methoxymethyl group, cyanomethyl group Straight chain alkyl groups, branched alkyl groups, substituted alkylmethylphenyl groups, 0-)lifluoromethylphenyl groups, p-cyanophenyl groups, 0-cyanophenyl groups, P-
Nitrophenyl 5, o-nitrophenyl group, p-bromophenyl group, 0-bromophenyl group, p-=chlorphenyl group, o-chlorphenyl Bv5, p-fluorophenyl group, o-fluorophenyl L P-carboxylphenyl L pMe[xyphenyl group, 0-methoxyphenyl group, N,N--diethylaminophenyl group, N,N-diphenylaminophenyl L N,N-dihendylaminophenyl group, N N-dimethylaminophenyl group, naphthyl group, methoxynaphthyl group, N, N diethylaminonaphthyl group, benzyl group, P bromohensyl group, p-
Cyanobenzyl group, p-nitrobenzyl group, p)lifluoromethylhensyl group, 0-bromobenzyl 15, o-cyanohensyl group, o-nitrobenzyl group, phenylethyl group, 3-phenylpropyl group, p-chlorobenzyl group , an aryl group such as a naphthylmethyl group, a substituted aryl group, an aralkyl group, and a substituted aralkyl group. R' and Rt may be the same or different groups.

In general formula (1), A represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a monovalent heterocyclic group which may have a substituent. represent.

Among these, when an alkyl group, aryl group, aralkyl group or heterocyclic group is substituted, the substituent is R
The same groups listed as substituents for 1 and Rt can be mentioned.

When A is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or fi-substituted aralkyl group, specific examples include a hydrogen atom, a methyl group, an ethyl group, and an n-propyl group. , iso-propyl group, n
-butyl group, sec-butyl group, +1-hexyl group, 2
-ethylhexyl group, fluoromethyl group, chloromethyl group, trifluoromethyl group, perfluoroalkyl group,
rL chain alkyl groups, branched alkyl groups, substituted alkyl groups such as methoxymethyl group, cyanomethyl group, phenyllli, p-)rifluoromethylphenyl group, 0
-Trifluoromethylphenyl L p-cyanophenyl group, 0-cyanophenyl group, p-nitrophenyl J5,
o-nitrophenyl group, P-bromophenyl 5, o-bromophenyl lls, p-chlorophenyl L O-chlorophenyl L p-fluorophenyl group, o-fluorophenyl L p-carboxylphenyl group, p-methoxyphenyl group , 0-methoxyphenyl L N,N-
diethylaminophenyl group, N,N-diphenylaminophenyl group, N,N-dihendylaminophenyl group, N.

N-dimethylaminophenyl group, naphthyl group, methoxynaphthyl group, cyanonaphthyl group, di-10 naphthyl group, chloronaphthyl group, bromonaphthyl group, fluoronaphthyl group, trifluoromethylnaphthyl L N,N-diethylaminonaphthyl group, hensyl group , phenylethyl group, 3
-Phenylpropyl group, p-chlorobenzyl group, P-bromohensyl L p-cyanobenzyl L p-nitrobenzyl group, p-trifluoromethylbenzyl group, 0-bromobenzyl group, 0-cyanobenzyl group, 0-nitrohensyl group, naphthyl Examples include aryl groups such as methyl groups, substituted aryl groups, aralkyl groups, and substituted aralkyl groups.

When A is a monovalent heterocyclic group which may have a substituent, examples of the heterocyclic group include furan, virol, thiophene, indole, benzofuran, benzothiofuran,
Oxazole, imidazole, thiazole, isoxazole, pyridine, quinoline, isoquinoline, pyridazine, pyrimidine, pyrazine, phthalazine and derivatives thereof, such as 2-thio-4-thiazolidinone, 3
Examples include -pyrazolidinone, 5-isoxaduron, 2-oxazolidone, 2,4-thiazolidinedione, 2-thiophenone, 2-furanone, and 4-pyrimidone.

These groups may be substituted with substituents. When these groups are substituted, the substituents include:
The same groups listed as substituents for R1 and Rt can be mentioned.

Next, specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited to these compounds.

Exemplary compound (])] 1.3-diethyl 5-methyl, 2-
Thiobarbylic acid (2) (3) (4) (5) (6) (7) (8) (9) 0ω 1.3-dimethyl, 5-n propyl, 2-thiobarbylic acid 1.3-diethyl, 5- Phenyl, 1,3-diphenyl 2-thiobarbylate, 5-methyl, 13-diethyl 2-thiobarbylate, 5-benzyl, 1,3-diphenyl 2-thiobarbylate, 5-p-methylbenzyl, 2-thioparpylic acid 1 -P-chlorophenyl, 3-phenyl, 5-ethyl, 1-ethyl 2-thiobarbiturate, 3-phenyl, 5-isobutyl, 13-dibenzyl 2-thioparpyrate, 5-n-pebutyl, 2- 1,3-Diethyl 5-(2-furyl)methyl thiobarbylate, 2-thioparpylate 001-phenyl, 5-phenethyl, 2-thiobarpyrate 0211-3 di-n-propyl, 5-p chlorobenzyl, 2- Thioparbylic acid 0■ 1,3-dimethyl, 5-P-nitrobenzyl, 2
-Thioparpylic acid 041-phenyl, 3-methyl, 5-cyanomethyl, 2-thioparpylic acid 1,3.5-)limethylbarbituric acid 0ω l, 3-diethyl, 5-benzylbarbituric acid 0 force 1-ethyl, 3-methyl, 5-P-fluorophenylbarbic acid 08) 1-methyl, 3-P-fluorophenyl, 5-
Isopropyl barbituric acid 0! ill, 3-diphenyl, 5-(3phenyl, 2-
Methyl)propylbarbic acid C! I) 1.3-diethyl, 5-(3-pyridyl)methylbarbylic acid These compounds can be prepared by reacting (A) monoalkylmalonic acid with urea or thiourea in the presence of acetyl chloride or acetic anhydride. . Alternatively, (B) a monoalkyl malonic acid ester and urea or thiourea are reacted in alcohol in the presence of sodium methoxide. (C) Barbylic acid or thiobarbylic acid is 5-alkylated with an alkyl halide or the like. (D) Catalytic hydrogen reduction of 5-benzylidenethiobarbylic acid in the presence of baladurum. It can be synthesized using methods such as

These synthetic methods are described in Ber, 65, 123 (
1932), J, Am, Chem, Soc, + Lee-Q-
, 993 (193B), J. Am. Chem.

Soc, +6. ,． 3.356 (1941
), etc. There is no limit to the amount of the compound (General 2ml), which is the second component of the present invention, added;
The preferred range is 1-100% by weight. More preferably, the amount is in the range of 72 to 40% by weight based on the phthalosoanine pigment.

The photoconductive layer of the printing original plate for electrophotographic platemaking of the present invention can contain, in addition to the compound of the present invention, various known additives conventionally used in electrophotographic photoreceptors. These additives include chemical enhancers for improving the true sensitivity, charge transport agents, various plasticizers for improving film properties, surfactants, etc. Chemical sensitizers Examples include p-benzoquinone, chloranil, fluorenone, bromanil, dinitrobenzene, anthraquinone, 25-dichlorobenzoquinone, nitrophenol, tetrachlorophthalic anhydride, 2.3tsuk L111-5
6-Diciazhenzoquinone, dinitrofluorenone, trinitrofluor! Electron-withdrawing compounds such as /non, tetracyanoethylene, JP-A-58-65439, JP-A-58-65439, JP-A-58-65439
No. 102239, No. 58-129439, No. 627
Examples include compounds described in No. 1965 and the like.

Examples of the electric Gj transport agent include (a) triazole derivatives described in U.S. Pat. No. 3,112,197, and (b) U.S. Pat.
, 189゜447, (C) imidazole derivatives described in Japanese Patent Publication No. 37-16,096, etc., (d) U.S. Patent No. 3,615,402. No. 3820.
No. 989, No. 3,542,544, Special Publication No. 45-55
No. 5, No. 51-10,983, JP-A-51-93.2
No. 24, No. 55-108667, No. 55-15695
Polyallylalkane derivatives described in U.S. Pat. No. 3, No. 56-36.656, publications, etc., (e) U.S. Pat.
．． No. 746, JP-A-55-88,064, JP-A No. 55-8
No. 8.065, No. 49-105,537, No. 55-5
No. 1.086, No. 56-80゜051, No. 56-88
．． No. 141, No. 57-45.545, No. 54-112
．． Pyrazoline derivatives and pyrazolone derivatives described in No. 637, No. 55-74.546, publications, etc., Cf) U.S. Patent No. 3,615.404, Japanese Patent Publication No. 5
m-10,105, m-46-3,712, m-4'1
-28.336, JP-A-54-83,435, 5
1110.836, U.S. Pat. No. 54-119.925, publications, etc., (g) U.S. Pat. No. 3.567.450, U.S. Pat. No. 3.180
．． No. 703, No. 3,240.597, No. 3.658,
No. 520, No. 4,232.103, No. 4,175.9
No. 61, No. 4,012,376, West German Patent (DAS
)! , No. 110.518, Japanese Patent Publication No. 49-35.702, No. 39-27.577, Japanese Patent Publication No. 144.25-1983
No. 0, No. 56119.132, No. 56-22.437
(h) Amino-substituted chalcone derivatives described in US Pat. No. 3,526.501; (1) US Pat. No. 3,542.546; N,N-bicalbasil derivatives described in et al., (j) U.S. Pat.
, 257,203, etc.; (k) styryl anthracene derivatives described in JP-A-56-46.234, etc.; (1) oxazole derivatives described in JP-A-51110.837, etc.; (m) U.S. Patent No. 3,717,462, JP-A-1988-
-59,143 (corresponding to U.S. Patent No. 4.150987), U.S. Patent No. 55-52,063, U.S. Patent No. 55-52,064
No. 55-46,760, No. 55-85.495, No. 57-11,350, No. 5'l-148,749
(n) U.S. Pat. No. 4,047,948, U.S. Pat.
．． No. 949, No. 4,265,990, No. 4.273,
No. 846, No. 4,299,897, No. 4,306,0
Hengejin derivatives described in the specification of No. 08, etc., (0) JP-A-58-190,953, JP-A No. 5995.5
No. 40, No. 59-97,148, No. 59-195,6
58, stilbene derivatives described in 62-36,674, etc., (p) Japanese Patent Publication No. 34-10, 96
Polyvinylcarbazole and derivatives thereof described in Publication No. 6, (q) Japanese Patent Publication Nos. 43-18,674 and 43-19.
Polyvinylpyrene, polyvinylanthracene, poly-2-vinyl-4(4'-dimethylaminophenyl)-5-phenyloxazole, poly-3-
Vinyl polymers such as vinyl-N-ethylcarbazole; (r) Polymers such as polyacenaphthylene, polyindene, and copolymers of acenaphthylene and styrene described in Japanese Patent Publication No. 43-19.193; (s) Polymers such as copolymers of acenaphthylene and styrene; Condensation resins such as pyrene-formaldehyde resin, brompyrene-formaldehyde resin, and ethylcarbazole formaldehyde resin described in JP-A-56-13,940, (1) JP-A-56-90,883, JP-A-56-1 (IL)
, and various triphenylmethane polymers described in Japanese Patent No. 550.

In the present invention, the charge transport agent is not limited to the compounds listed in (a) to (L), and all known charge transport agents can be used.

Two or more types of these organic photoconductive compounds can be used in combination depending on the case.

Examples of plasticizers include dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, diisobutyl adipate, dimethyl sebacate, dibdel sebacate, butyl laurate, methyl phthalyl ethyl glycolate, dimethyl glycol phthalate, etc. Can be added to improve the flexibility of the layer.

These plasticizers can be contained within a range that does not deteriorate the electrostatic properties and etching properties of the photoconductive layer.

Furthermore, if the thickness of the photoconductive layer of the present invention is too thin, it will not be possible to charge the surface potential necessary for development, and conversely, if the photoconductive layer is too thick, it will be difficult to remove the photoconductive layer in the planar direction called side etching. The thickness of the photoconductive layer, which causes etching and makes it impossible to obtain a good printing plate, is 0.1 to 30 .mu.m, preferably 0.5 to 10 .mu.m.

Electrically conductive supports used in the invention include plastic sheets with an electrically conductive surface or papers made especially solvent-impermeable and electrically conductive, aluminum plates, zinc plates, or copper-aluminum plates, copper-stainless steel plates, chromium - A conductive support with a hydrophilic surface such as a bimetallic plate such as a copper plate, or a trimetallic plate such as a chromium-copper-aluminum body, a chromium-lead iron plate, a chromium-copper-stainless steel plate, etc. is used, and its thickness is , 0.1-3■ is preferable, especially 0.
Among these supports, aluminum plates are preferably used.

The aluminum plate used in the present invention is a plate-like material such as pure aluminium whose main component is aluminum or an aluminum alloy containing a small amount of foreign atoms, and its composition is not specified. It can be used as appropriate.

This aluminum plate can be used after being grained and anodized using a conventionally known method. Prior to the graining treatment, in order to remove rolling fat from the surface of the aluminum plate, degreasing treatment with a surfactant or an alkaline aqueous solution is performed, if desired, and then the graining treatment is performed. Graining treatment methods include a method of mechanically roughening the surface, a method of electrochemically dissolving the surface, and a method of selectively dissolving the surface chemically. As a method of mechanically roughening the surface,
A known method called a ball polishing method, a brush polishing method, a blast polishing method, a puff polishing method, etc. can be used.

Further, as an electrochemical surface roughening method, there is a method in which alternating current or direct current is used in a hydrochloric acid or nitric acid electrolyte. Furthermore, a method combining both methods can also be used, as disclosed in Japanese Patent Application Laid-Open No. 54-63902.

The aluminum plate thus roughened is subjected to E7 alkali enoting treatment and neutralization treatment as necessary.

How treated aluminum plate is anodized. As the electrolyte used in the anodizing treatment, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used, and the electrolyte and its concentration are determined as appropriate depending on the type of electrolyte. The conditions for anodic oxidation vary depending on the electrolyte used, so it is difficult to specify, but - for boat fishing, the concentration of electrolyte is 1 to 80% by weight? 8 liquid, liquid temperature is 5
-70'C, current density 5~60A/dbo, voltage 1~1
oov, and the electrolysis time is preferably in the range of 10 seconds to 50 minutes. The positive oxidation film area is preferably in the range of 0.1 to 10 (/nf, but more preferably in the range of 1 to 6 g/nf.
There is e.

Further, as described in Japanese Patent Publication No. 47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is also preferably used. In addition, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. The treatment with polyvinylsulfonic acid described in West German Published Patent Application No. 1621478 is also suitable. In addition, in the present invention, it is necessary to improve the adhesion between the conductive support and the photoconductive layer and to improve the printing original plate for electrophotographic plate making. If necessary, an alkali-soluble intermediate layer made of casein, polyvinyl alcohol, ethyl cellulose, phenol resin, styrene-maleic anhydride copolymer, polyacrylic acid, etc. can be provided for purposes such as improving the electrostatic properties of .

In addition, in the present invention, electrostatic properties, development properties during toner development, or image properties,
For the purpose of improving printing characteristics and the like, an overcoat layer that can be removed at the same time as the light guiding KN can be provided. This overcoat layer may be mechanically matted or a resin layer containing a matting agent. In this case, the matting agent may include silicon dioxide, glass particles, alumina, starch, titanium oxide, etc. , particles of polymers such as zinc oxide, polymethyl methacrylate, polystyrene, phenolic resins, and U.S. Pat.
The matting agents described in Japanese Patent No. 01245 and No. 2992101 are included.

Two or more of these can be used in combination. The resin used for the overcoat layer is appropriately selected depending on the combination with the etching solution for removing the photoelectric layer. Specific examples include gum arabic, glue, cellulose, starch, polyvinyl alcohol, polyethylene oxide, polyacrylic acid, polyacrylamide, polyvinyl methyl ether, epoxy resin, phenol resin, polyamide, and polyvinyl butyral. Two or more of these can be used in combination.

The toner used in the present invention has a process of removing non-image areas.
Any type of developer used as a toner for electrophotography, such as a dry developer or a liquid developer, can be used as long as it has resistance to the etching solution and has the function of preventing the elution of the leading tH in the toner image area from the etching solution. Although it is possible to use liquid developers, it is preferred to use liquid developers to obtain high-resolution images.9 Additionally, those that provide hydrophobic, ink-receptive toner images are desirable. For example, toner particle components include polystyrene resins, polyvinyltoluene resins, polyester resins, acrylic ester homopolymers and copolymers, methacrylic ester homopolymers and copolymers, ethylene copolymers, cyclized rubber, Polymeric materials such as vinyl acetate homopolymers and copolymers, vinyl chloride, etc. are used. In addition, colorants such as carbon black, nigrosine pigments,
Pigments and dyes such as Phthalocyanine Blue, Phthalocyanine Green, Benzidine Yellow, Alkalipur, Carmine 6B, etc. may also be included. moreover,
It may contain various charge control agents and other additives.

As the etching solution for removing the photoconductive insulating layer in the I/toner non-image area after toner image formation, any solvent can be used as long as it can remove the photoconductive insulating layer, and there are no particular limitations. However, preferably alkaline solvents are used. The alkaline solvent referred to here is an aqueous solution containing an alkaline compound, an organic solvent containing an alkaline compound, or a mixture of an aqueous solution containing an alkaline compound and an organic solvent. Alkaline compounds include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, potassium silicate, sodium metasilicate, potassium mekusilicate, sodium phosphate, potassium phosphate, ammonia, and monoethanolamine and jetanolamine. , amino alcohols such as triethanolamine, and any organic and inorganic alkaline compounds.

As mentioned above, water or many organic solvents can be used as the solvent for the etching solution, but from the viewpoint of odor and pollution, an etching solution mainly composed of water is preferably used. If necessary, various organic solvents can be added to the etching solution mainly composed of water. Preferred organic solvents include lower alcohols and aromatic alcohols such as methanol, ethanol, propatool, butanol, benzyl alcohol, and phenethyl alcohol, as well as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cellosolves, and monoethanolamine and glycol. Amino alcohols such as tanolamine and triethanolamine can be mentioned. Further, the etching solution used contains a surfactant, an antifoaming agent, and various other additives as necessary.

Next, a method for producing a printing plate from the printing original plate for electrophotographic platemaking of the present invention will be explained. An image is formed on the printing original plate for electrophotographic platemaking of the present invention by a conventionally known electrophotographic process. That is, it is charged substantially uniformly in a dark place, and an electrostatic latent image is formed by imagewise exposure. Exposure methods include reflective image exposure using a xenon lamp, tungsten lamp, fluorescent lamp, or the like as a light source, contact exposure through a transparent positive film, and scanning exposure using a laser beam, light emitting diode, or the like. When performing scanning exposure, use a helium-neon laser, helium-cadmium laser, argon ion laser, or krypton ion laser-1Y.
AG laser, ruby laser, nitrogen laser, dye laser, excimer laser, GaAs/GaAfA
s, scanning exposure using a laser light source such as a semiconductor laser such as InGaAsP, alexandrite laser, copper vapor laser, or erbium laser, or scanning exposure using a light emitting diode or liquid crystal shutter (line using a light emitting diode array, liquid crystal shutter array, etc.) (including printer-type light sources).

Next, as a developing method for developing the electrostatic latent image with toner, either a dry developing method (cascade development, magnetic brush development, powder cloud development) or a liquid developing method can be used. Among these, the liquid development method can form fine images and is suitable for creating printing plates. Furthermore, positive-positive development by normal development and negative-positive development by reversal development by applying an appropriate bias voltage are also possible. The formed toner image is fixed by a known fixing method, e.g.
Fixing can be done by heat fixing, pressure fixing, solvent fixing, etc. A print can be created by allowing the toner image thus formed to act as a resist and removing the photoconductive layer in non-image areas with an etching solution.

Synthesis Example Synthesis of Exemplified Compound (1) 10.0 g (0,085 mol) of methylmalonic acid and 11.2 (0,085 mol) of diethylthiourea were dissolved in chloroform food, and 1 mol of acetyl chloride was dissolved in the chloroform food.
After adding 4.97 at room temperature, 30
Heat while stirring for an hour.

After distilling off the solvent under reduced pressure, a solution of 30 g of sodium carbonate dissolved in 400 m of water is added and stirred.

Taking this into consideration, an acidic solution prepared by diluting 51 d of hydrochloric acid with 400 d of water was gradually added to the oral solution to bring the pH to about 1 to 2, and solids precipitated. The obtained solid was taken, dried, and recrystallized with 400 d of n-hexyne to obtain 5 g of Exemplary Compound (1).

Elemental analysis - Ca1c (%) Found (%) H6,5
96,67 C50,4550,16 N 13.07 13.04S
14.96 15.00 Melting point: 6
7.9 to 69.9°C MASS: M” 214 [Example] The present invention will be explained in more detail with reference to Examples, but the present invention is limited to the following Examples unless the gist thereof is exceeded. In addition, all parts in the examples indicate parts by weight.

Example 1 ε9 pot phthalocyanine (Lio photonERP
C2 Toyo Ink ■) 3.0 parts exemplified compound (
1) ・・・・・・・・・・・・・・・・・・・・・
0.3 parts Hensyl methacrylate-methacrylic acid copolymer (monomer composition ratio 60:40 (mole ratio))...
・・・・・・・・・・・・・・・・・・ 15.0 parts Tetrahydrofuran ・・・・・・・・・・・・・・・・・・
100 parts cyclohexanone ・・・・・・・・・・・・
・・・・・・・・・・・・Put 20 parts into a 500d glass container with glass peas, and use a paint shaker (
After dispersing for 120 minutes at Toyo Seiki Seisakusho (@), the glass beads were filtered to obtain a photoconductive layer dispersion.

Next, this photoconductive layer dispersion was grained to a thickness of 0.
．． Coated on a 25M aluminum plate and dried to form a dry film 1!
75. A printing original plate for electrophotographic plate making having a 0μ photoconductive layer was prepared.

Next, the electrophotographic sensitivity of the created printing original plate for electrophotographic platemaking was measured.
Using an electrostatic copying paper tester ffEPA-8100 (manufactured by Kawaguchi Electric), it was statically charged with a corona at +8.0 kV and exposed to monochromatic light of 780 parts m at a light intensity of 10 mW/I to determine the electrophotographic characteristics. Mother beta.

Surface potential immediately after charging (■); Surface potential 30 seconds after charging (■). The charge retention rate (DD, .) is the ratio to
In addition, as for sensitivity, the surface potential before exposure is attenuated by light to 1/2.
Exposure to become! (ES.) and the exposure amount (Es-
) were found to be: Vo: +420V IESII: 5.2 μJ/d E: 6.8 μJ/c DD 3°: 92%.

Next, this sample was charged to a surface potential of +400 V in a dark place, and then exposed to 780 parts of light using a semiconductor laser so that the exposure amount on the printing plate was 5.0 μJ/cd. 5g of polymethyl methacrylate particles (particle size 0.3μ) in IN (manufactured by Esso Standard)
is dispersed as toner particles and 0.01 g of soybean oil lecithin is added as a charge control side. By using a liquid developer prepared by applying a bias voltage of 40 V to the counter electrode, a clear positive toner image can be created. I was able to get

Furthermore, the toner image was fixed by heating at 120° C. for 30 seconds. The non-image area of this printing original plate for electrophotographic plate making was removed with an etching solution prepared by diluting 40 parts of potassium silicate, 10 parts of potassium hydroxide, and 100 parts of ethanol in 800 parts of water, thoroughly washed with water, and then gummed. I was able to create an offset printing plate.

The printing plate produced in this way was
When printing was carried out using a D-offset printing machine in a conventional manner, 50,000 sheets of very clear prints with no stains in the non-image areas could be printed.

Further, when the above printing original plate was stored in an environment of 35°C and 80% for 3 months, it could be used without any particular problem.

Comparative Example 1 For comparison, a printing original plate for electrophotographic plate making was prepared in exactly the same manner as in Example 1 except that the exemplified compound (1) was not contained, and the electrophotographic properties were measured in the same manner.

Vo: +445V Esm: 8.8μJ/cd E,. : 10.6 μJ/c DD,. = 93%, the specific vane induction effect was greater than in Example 1, and the sensitivity was poor.

Comparative Example 2 A printing original plate for electrophotographic platemaking was prepared in exactly the same manner as in Example 1 except that 5 parts of the following hydrazone compound as an organic photoconductor was added instead of Exemplified Compound (1). The electrophotographic properties were measured.

Hydrazone compound Va: +380V E,: 3.5 μJ/cjE,. :
12.6pJ/cj D Ds. : 75%, the charging property was poor compared to Example 1, and the charge retention property was also poor. Further, although no induction effect was exhibited, the attenuation of the surface potential became gradual and the tone reproducibility became soft. Therefore, the sensitivity (E, .), which is a measure of practical sensitivity, was worse than that of the printing original plate for electrophotographic platemaking of Example 1.

Next, this sample was charged to a surface potential of +390 cm in a dark place, and then exposed to light of 780 nm using a semiconductor laser so that the exposure amount on the printing plate was 1O10 μJ/c-.

Thereafter, development, etching and printing were carried out in the same manner as in Example 1, and a printed matter was obtained which was stained in some places.

Further, when it was stored for 3 months in an environment of 35°C and 80%, it was observed that a hydrazone compound, which is an organic photoconductive compound, was deposited on the surface of the printing original plate for electrophotographic plate making.

The electrophotographic properties of the printing original plates for electrophotographic platemaking of Example 1, Comparative Examples 1 and 2 are measured and shown in FIG. (The measurement was performed by the method described in Example 1 above.

) In the figure, (A) is the printing original plate for electrophotographic platemaking of Example 1,
(B) is the printing original plate for electrophotographic platemaking of Comparative Example 1, (C)
is the surface potential decay curve of the printing original plate for electrophotographic platemaking of Comparative Example 2.

Figure 1 - Dark decay from 30 seconds to 0 seconds, 0 seconds to 3 seconds
The surface potential decay curve of light decay up to 0 seconds is shown.

The printing original plate for electrophotographic plate making of Example 1 has less induction effect than the printing original plate for electrophotographic plate making of Comparative Example 1 (the period during which the surface potential is difficult to decay at the initial stage of decay is short).
It can be seen that the addition of Exemplary Compound (1) caused no deterioration in chargeability or charge retention, and also did not impair high-contrast characteristics.

In the printing original plate for electrophotographic plate making of Comparative Example 2, although no induction effect is observed, the light attenuation becomes conventional and the practical sensitivity is lower than that of the printing original plate for electrophotographic plate making of Example 1. Furthermore, it can be seen that charging properties and charge retention properties are also deteriorated.

Examples 2 to 9 Printing original plates for electrophotographic platemaking were prepared in exactly the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of Exemplified Compound (1). Electrophotographic properties were measured in a similar manner. The results are summarized in Table 1.

Example 10 A printing original plate for electrophotographic platemaking was prepared in exactly the same manner as in Example 1, except that instead of using ζε type copper phthalocyanine as the phthalocyanine pigment, X type metal-free phthalonanine was used. As a result of measuring electrophotographic characteristics using a method, Vg: +439V IEso: 1.2 μJ/cd 11:Ill: 1. 5 μJ/dDD. :
It was 92%.

Next, this sample was charged to a surface potential of +450 V in a dark place, and then exposed to 780 nm light using a semiconductor laser so that the exposure amount on the printing plate was 2.0 μJ/cd, and developed in the same manner as in Example 1. When I performed etching printing, I was able to print five very clear prints with no stains in the non-image areas.

Furthermore, when it was stored for 3 months in an environment of 35°C and 80%, it could be used without any particular problems.

Example 11 In Example 1, instead of using ε-type copper phthalocyanine as the phthalocyanine pigment, summer-type metal-free phthalocyanine was used, and instead of using methacrylic acid hensyl ester-methacrylic acid copolymer as the binding resin, vinyl henshade was used. - A printing original plate for electrophotographic platemaking was prepared in exactly the same manner as in Example 1, except that a crotonic acid copolymer (-1:Zummer composition ratio 60:40 (mole ratio)) was used. As a result of measuring the electrophotographic characteristics, ■. : →-428V Eso: 1. 2.17 J/dE-o:
1.4aJ/c4 D+). : 93%.

Next, this sample was charged to a surface potential of +450 V in a dark place, and then exposed to 780 nm light using a semiconductor laser so that the exposure amount on the printing plate was 3.0 μJ/c-, and the same procedure as in Example 1 was carried out. After development and etching printing, it was possible to print 50,000 very clear prints with no 1η deviation in the non-image area.

Also, when it was stored for 3 months in a 35"C 80% environment, there were no particular problems (it was still usable).

(Effects of the Invention) The present invention provides an electrophotographic plate making device that is highly sensitive, has excellent chargeability, has good charge retention in the dark, and has good tone reproduction characteristics, and is excellent as a photoreceptor for printing plates. We were able to obtain the original printing plate. In addition, the elution property with Encinda liquid was also good, and a printing original plate for electrophotographic plate making with excellent stability over time could be obtained.

[Brief explanation of the drawing]

FIG. 1 shows a surface potential decay curve of a printing original plate for electrophotographic platemaking. In FIG. 1, (A) is for Example 1, (B) is for Comparative Example 1, (
C) shows the surface potential decay curve of the original plate of Comparative Example 2.

Claims (1)

[Scope of Claims] A photoconductive layer containing at least a photoconductive pigment and a binding resin is provided on a conductive support, and after a toner image is formed on this layer by electrophotography, a photoconductive layer is formed on the conductive support in areas other than the toner image area. In the printing original plate for electrophotographic plate making, which is made into a printing plate by removing the photoconductive layer in the non-image area, the photoconductive pigment is a phthalocyanine pigment, and the photoconductive layer further contains a compound represented by the following general formula [I]. 1. A printing original plate for electrophotographic platemaking, characterized in that it contains a compound. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [I], Z represents a sulfur atom or an oxygen atom. R^1 and R^2 represent a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent, R^1 and R^2 may be the same or different groups. A represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a monovalent heterocyclic group which may have a substituent.