JP2002062664A - Tanning developing agent, method for forming relief image, and lithographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a relief image having high oleophilicity and high strength by tanning development. SOLUTION: A hydrazine compound expressed by formula (I): L(-X-NHNH- Ar)n is used as a tanning developing agent. In formula, L is a n-valent organic residue, X is -NH-CO-, -CO-, -NH-SO2- or -O-CO-, Ar is an aromatic group or aromatic heterocyclic group, n is an integer >=2, and n of-X-NHNH-Ar may be different from one another.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a tanning developer, a relief image forming method and a lithographic printing plate.

[0002]

2. Description of the Related Art Tanning development is a phenomenon that has long been known in the art of silver halide photography (for example,
TH James, The Theory of the Photographic Proces
s, 4thedition, pages 326-327). Pyrogallol,
When a silver halide photosensitive material is developed using a phenolic developing agent such as hydroquinone or catechol, the gelatin contained in the silver halide emulsion layer hardens in the exposed areas. This tanning effect occurs because the oxidation product of the phenolic developing agent has a hardening effect on gelatin. Tanning development has the effect of softening the image of a normal silver halide photograph. That is, since the gelatin in the exposed area is hardened, the penetration of the developing solution in the exposed area is suppressed, whereby the progress of development is suppressed.

A method has been proposed in which the hardening of gelatin in an exposed portion is used for forming a relief image. If the uncured gelatin in the unexposed area is eluted, a relief image of the cured gelatin can be formed. The relief image of hardened gelatin can be used as a lithographic printing plate.
If a relief image of hardened gelatin is formed on a hydrophilic support (aluminum plate), the surface of the support exposed by removal functions as a hydrophilic region, and the relief image functions as a lipophilic region. In lithographic printing, an image is printed by dampening water adhering to a hydrophilic area and oil-based ink adhering to a lipophilic area. A method of utilizing a relief image of hardened gelatin as a lithographic printing plate is described in JP-A-53-135.
No. 702, No. 54-49202, No. 54-15250
No. 2, No. 55-12625, JP-A-4-324866
And JP-A-5-289228.

[0004]

The method of using a relief image of hardened gelatin as a lithographic printing plate is that silver halide, which is an optical sensor, has higher sensitivity than other lithographic printing plate making methods, There is an advantage that plate making can be performed with simple processing. When a relief image of hardened gelatin is used as a lithographic printing plate, the exposed surface of the support functions as a hydrophilic region and the relief image functions as a lipophilic region. Hardened gelatin is not strongly lipophilic, even though it is relatively lipophilic compared to the support surface (hardened gelatin is
It is more common to treat them as hydrophilic substances). In lithographic printing using a fountain solution, the hardened gelatin easily absorbs the fountain solution and swells or softens. For the above reasons, when a relief image of hardened gelatin is used as a lithographic printing plate, the hardened gelatin has problems of insufficient lipophilicity (ink receptivity) and low strength (press life).

JP-A-53-135702 and JP-A-54-4
Nos. 9202, 54-152502, 55-126
No. 25, JP-A-4-324866 and 5-28922
The method described in each publication of No. 8 proposes to perform a treatment (heating treatment, light irradiation treatment, chemical treatment) on the hardened gelatin after image formation in order to improve ink receptivity and printing durability. However, when post-processing is performed after image formation, the advantage that plate making can be performed with simple processing is lost. In addition, the heat treatment has a problem that the adhesiveness between the hardened gelatin and the support decreases. In the light irradiation process, a powerful light irradiation device is required. The chemical treatment has a problem that the toxicity of the chemical substance used and the treatment effect are insufficient. The purpose of the present invention is
An object of the present invention is to provide a tanning developer capable of forming a hardened gelatin having high lipophilicity and high strength.

[0006]

The object of the present invention is to provide a tanning developer of the following (1) to (5);
This was achieved by the relief image forming method of (7) and the lithographic printing plate of (8) below. (1) A tanning developer comprising a compound represented by the following formula (I): (I) L (-X-NHNH-Ar) _n [wherein L is an n-valent organic residue; , -NH-
CO -, - CO -, - NH-SO 2 - or -O-CO
Ar is an aromatic group or an aromatic heterocyclic group; n is an integer of 2 or more;
-NHNH-Ar may be different from each other].

(2) In the formula (I), L represents an aliphatic group, an aromatic group, —O—, —CO—, —SO ₂ —, —N
N selected from <, -PO <and a combination thereof.
The tanning developer according to (1), which is a valent organic residue. (3) In the formula (I), L includes the main chain of the polymer, and -X-NHNH-Ar forms a side chain or a terminal of the side chain of the polymer. . (4) The tanning developer according to (1), wherein in the formula (I), X is -NH-CO-. (5) In the formula (I), Ar represents cyano, nitro, carbamoyl, sulfamoyl, a halogen atom, a halogen-substituted alkyl group, an alkoxy group, an aliphatic sulfonyl group,
(1) The aromatic group or aromatic heterocyclic group having an aromatic sulfonyl group, an aliphatic substituted carbamoyl group, an aromatic substituted carbamoyl group, an aliphatic substituted sulfamoyl group, or an aromatic substituted sulfamoyl group as a substituent. Tanning developer.

(6) a step of imagewise exposing a silver halide light-sensitive material having a support and a silver halide gelatin emulsion layer, a step of tanning the silver halide light-sensitive material to harden gelatin in an exposed portion, and a step of not exposing Forming a relief image of hardened gelatin by dissolving a part of unhardened gelatin in this order, using a tanning developer comprising a compound represented by the following formula (I). (I) L (-X-NHNH-Ar) _{n wherein} L is an n-valent organic residue; and X is -NH −
CO -, - CO -, - NH-SO 2 - or -O-CO
Ar is an aromatic group or an aromatic heterocyclic group; n is an integer of 2 or more;
-NHNH-Ar may be different from each other]. (7) The tanning developer according to (6), wherein the tanning developer comprising the compound represented by the formula (I) is contained in a silver halide gelatin emulsion layer or an optional hydrophilic layer of the silver halide photosensitive material. Relief image forming method. (8) A lithographic printing plate having a relief image of hardened gelatin formed on a hydrophilic support, wherein the hardened gelatin is a gelatin crosslinked with an oxide of a compound represented by the following formula (I). A lithographic printing plate characterized in that:

[0009]

The present inventor has started to improve the tanning developer instead of adding post-processing as proposed in the prior art. As a result of this research, hardened gelatin with high lipophilicity and high strength was obtained using a hydrazine compound, which is completely different from the conventional tanning developers (phenolic compounds such as pyrogallol, hydroquinone, and catechol), as the tanning developer. Successfully formed. The hydrazine compound represented by the formula (I)
In the field of ordinary color silver halide photography, it has been proposed as a color developing agent capable of obtaining a high color density (described in Japanese Patent Application Laid-Open No. H11-125887). However, no tanning development effect of the hydrazine compound represented by the formula (I) has been reported. The improved lipophilicity and strength of hardened gelatin has made it possible to use the relief image of hardened gelatin as a lithographic printing plate. As described above, a lithographic printing plate comprising a relief image of hardened gelatin has a feature that silver halide as an optical sensor has high sensitivity and can be made by simple processing.

[0010]

DETAILED DESCRIPTION OF THE INVENTION [Tanning developer] In the present invention, a hydrazine-based compound represented by the following formula (I) is used as a tanning developer. (I) L (-X-NHNH-Ar) _n

In the formula (I), L is an n-valent organic residue. L is an aliphatic group, an aromatic group, -O-, -CO
_{-, - SO 2 -, -} N <, - PO < and is preferably an n-valent organic residue selected from the combinations thereof. In the formula (I), n is an integer of 2 or more. The aliphatic group may have a cyclic structure or a branched structure. Saturated aliphatic groups are preferred over unsaturated aliphatic groups. The number of carbon atoms of the aliphatic group is preferably 1 to 60, more preferably 1 to 40,
Most preferably, it is 1 to 20. The aliphatic group may have a substituent. Substituent of the aliphatic group is an aromatic group, -O -, - CO -, - SO 2 - or is preferably formed of a combination of -N <. The aromatic group preferably comprises a benzene ring or a naphthalene ring, more preferably a benzene ring. The aromatic group may have a substituent. Substituents of aromatic groups, aliphatic groups, -O -, - CO -, - SO 2 - or is preferably formed of a combination of -N <.

When the hydrazine compound represented by the formula (I) is a compound other than a polymer, n is preferably an integer of 2 to 12, more preferably 2 to 8. It is preferably 2, 3, 4, 5 or 6. The hydrazine-based compound represented by the formula (I) may be a polymer. In the case of a polymer, L comprises the main chain of the polymer, and -X-NHNH-Ar
Preferably forms a side chain or a terminal of the side chain of the polymer. Preferably, the backbone of the polymer is a saturated hydrocarbon chain. The repeating unit containing -X-NHNH-Ar is preferably a repeating unit derived from an ethylenically unsaturated monomer. When the hydrazine compound represented by the formula (I) is a polymer, n is -XN
This corresponds to the number of repeating units containing HNH-Ar. Hereinafter, examples of L will be described. L38 is an example of a repeating unit contained in the polymer.

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In the formula (I), X is -NH-CO
-, - CO -, - NH -SO 2 - or -O-CO-
(Here, the left side is bonded to L, and the right side is bonded to -NHNH-). X is particularly preferably -NH-CO-.

In the formula (I), Ar is an aromatic group or an aromatic heterocyclic group. The aromatic group of Ar includes an aryl group and a substituted aryl group. The aromatic group is
It is preferably phenyl, substituted phenyl group, naphthyl or substituted naphthyl group, more preferably phenyl or substituted phenyl group, and most preferably substituted phenyl group. The aromatic group includes cyano, nitro, carbamoyl, sulfamoyl, a halogen atom, a halogen-substituted alkyl group, an alkoxy group, an aliphatic sulfonyl group, an aromatic sulfonyl group, an aliphatic substituted carbamoyl group, an aromatic substituted carbamoyl group, and an aliphatic substituted sulfamoyl. It is preferable to have a group or an aromatic substituted sulfamoyl group as a substituent.

As the halogen atom, a fluorine atom,
A chlorine atom or a bromine atom is preferred, a fluorine atom or a chlorine atom is more preferred, and a chlorine atom is most preferred.
As the halogen atom of the halogen-substituted alkyl group,
A fluorine atom, a chlorine atom or a bromine atom is preferred, a fluorine atom or a chlorine atom is more preferred, and a fluorine atom is most preferred. The halogen-substituted alkyl group preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, and most preferably has 1 to 3 carbon atoms. The proportion of the hydrogen atom of the alkyl group substituted by the halogen atom is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and most preferably 90 to 100 mol%. .

The number of carbon atoms of the alkoxy group is preferably 1 to 12, more preferably 1 to 6, and most preferably 1 to 3. The aliphatic group contained in the aliphatic sulfonyl group, the aliphatic substituted carbamoyl group and the aliphatic substituted sulfamoyl group may have a cyclic structure or a branched structure. Saturated aliphatic groups are preferred over unsaturated aliphatic groups. The aliphatic group preferably has 1 to 60 carbon atoms, and has 1 to 4 carbon atoms.
It is more preferably 0, and most preferably 1 to 20. The aliphatic group may have a substituent. Examples of the substituent of the aliphatic group include hydroxy and alkoxy groups. The aromatic group contained in the aromatic sulfonyl group, aromatic substituted carbamoyl group and aromatic substituted sulfamoyl group is preferably phenyl, substituted phenyl group, naphthyl, substituted naphthyl group, and may be phenyl or substituted phenyl group. More preferably, it is most preferably phenyl.

The aromatic heterocyclic group for Ar generally includes an unsaturated heterocyclic ring. The heterocyclic ring of the aromatic heterocyclic group preferably contains the largest number of double bonds. The heterocyclic ring of the aromatic heterocyclic group is preferably a 4- to 8-membered ring, more preferably a 5- or 6-membered ring. The hetero atom of the heterocyclic ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom. It is particularly preferred to include a nitrogen atom as a heteroatom. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. Examples of the heterocycle include a pyridine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, an oxazole ring, an oxadiazole ring, a thiazole ring, an isothiazole ring, and a thiadiazole. Ring, thiophene ring, furan ring and pyran ring. Examples of fused rings include a quinazoline ring, a quinoxaline ring,
Quinoline ring, indazole ring, benzimidazole ring,
1,3,3a, 7-tetrazaindene ring, 1,2,3
3a, 7-Pentazaindene ring, benzothiazole ring, benzoxazole ring and benzoisothiazole ring are included.

The aromatic heterocyclic group of Ar is preferably bonded to -NHNH- at a carbon atom (not a hetero atom) constituting the ring. Aromatic heterocyclic groups include cyano, nitro, carbamoyl, sulfamoyl, halogen atoms,
It preferably has a halogen-substituted alkyl group, alkoxy group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic-substituted carbamoyl group, aromatic-substituted carbamoyl group, aliphatic-substituted sulfamoyl group or aromatic-substituted sulfamoyl group as a substituent. The definition and examples of each group are the same as those of the substituent of the aromatic group. The aromatic group or aromatic heterocyclic group of Ar may have a substituent other than those described above (eg, an aliphatic group, an aromatic group).

In the formula (I), a plurality (n) of -X-
NHNH-Ar may be different from each other. When the hydrazine compound represented by the formula (I) is a compound other than a polymer, the total number of carbon atoms is 10 to 12
It is preferably 0, more preferably 12 to 100, and most preferably 14 to 80. When the hydrazine compound represented by the formula (I) is a polymer, its molecular weight is from 1,000 to 100,000.
And more preferably 5,000 to 50,000. Hereinafter, examples of the hydrazine-based compound represented by the formula (I) will be shown.

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The hydrazine compound represented by the formula (I) is obtained by reacting an aromatic substituted hydrazine or an aromatic heterocyclic substituted hydrazine corresponding to NH ₂ —NH—Ar with two or three reactive groups in the molecule. It can be synthesized by reacting with a compound having a functional group (eg, acid halide group, acid anhydride group or isocyanate bond). An example of synthesizing the hydrazine-based compound represented by the formula (I) is described in JP-A No. 11-125887. Two or more hydrazine compounds represented by the formula (I) may be used in combination as a tanning developer. A hydrazine compound represented by the formula (I) and a known tanning developer (eg, hydroquinone, t-butylhydroquinone,
Catechol, phenylcatechol, pyrogallol, nordihydrguaiaretinic acid, 3,3,3'3'-tetramethyl-5,6,5 ', 6'-tetrahydroxyspiro-
Bis-indane). When used in combination, the amount of the hydrazine compound represented by the formula (I) is preferably 50 to 95% by weight, more preferably 60 to 90% by weight, more preferably 70 to 90% by weight of the total amount of the tanning developer. Most preferably, it is 85% by weight.

The tanning developer is used by adding it to a silver halide photosensitive material or a tanning developer. It is preferably added to a silver halide photosensitive material. When added to a silver halide photosensitive material, a tanning developer may be dissolved, emulsified or dispersed in a coating solution for a silver halide gelatin emulsion layer or an optional hydrophilic layer. The amount added to the silver halide photosensitive material is preferably 0.01 to 1 mol / mol Ag, and more preferably 0.03 to 1 mol Ag. When added to the tanning developer, the tanning developer may be dissolved, emulsified or dispersed in the developer. The amount added to the developer is 10
It is preferably from ^{-5 to} 10 ^-1 mol / l.

An auxiliary developer may be used in addition to the tanning developer. The auxiliary developing agent includes a compound that functions as a silver halide developing agent and a compound that has a function of cross-oxidizing a tanning developing agent with an oxidized form of the developing agent generated in silver development. Examples of auxiliary developing agents include pyrazolidones, dihydroxybenzenes, reductones and aminophenols. Pyrazolidones are particularly preferred.

[Support] As the support, paper, synthetic paper,
Paper laminated with synthetic resin (eg, polyethylene, polypropylene, polystyrene), plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate), metal plate (eg, aluminum, aluminum alloy,
Zinc, iron, copper), and paper or plastic film on which these metals are laminated or deposited can be used. When the photosensitive material is used for the production of a lithographic printing plate, a preferred support is an aluminum plate, a plastic film,
Paper and synthetic paper. Further, a composite sheet in which an aluminum sheet is laminated on a polyethylene terephthalate film is also preferable. Aluminum plates and plastic films are more preferred, and aluminum plates are particularly preferred.

The case where an aluminum plate is used as a support will be further described. The aluminum support is subjected to a surface treatment such as a surface roughening treatment (graining treatment) or a surface hydrophilic treatment as necessary. The surface roughening treatment may be performed by an electrochemical sanding method (for example, a method of sanding an aluminum plate by passing an electric current in a hydrochloric acid or nitric acid electrolyte) and / or a mechanical sanding method. (For example, a wire brush grain method in which the aluminum surface is scratched with a metal wire, a ball grain method in which the aluminum surface is sanded with a polishing ball and an abrasive, a brush grain in which the surface is sanded with a nylon brush and an abrasive) Method). Next, the grained aluminum plate is chemically etched with acid or alkali. An industrially advantageous method is etching using an alkali. Examples of the alkaline agent include sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of the alkaline solution is preferably in the range of 1 to 50% by weight. The temperature of the alkali treatment is preferably in the range of 20 to 100 ° C. Further, it is preferable to adjust the processing conditions so that the amount of aluminum dissolved is 5 to 20 g / m ² .

Usually, after the alkali etching, the aluminum plate is washed with an acid to remove dirt (smut) remaining on the surface. Preferred acids are nitric acid, sulfuric acid,
Phosphoric acid, chromic acid, hydrofluoric acid and borofluoric acid. The smut removal treatment after the electrochemical graining treatment can be performed by a known method such as a method of contacting with sulfuric acid at a concentration of 15 to 65% by weight at 50 to 90 ° C. The aluminum plate subjected to the surface roughening treatment as described above can be subjected to an anodic oxidation treatment or a chemical conversion treatment, if necessary. The anodic oxidation treatment can be performed by a known method. Specifically, an anodic oxide film is formed on the aluminum surface by passing a direct current or an alternating current through an aluminum plate in an acid solution. Examples of acids include sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid and benzenesulfonic acid. Anodizing conditions vary depending on the electrolyte used. Generally, the concentration of the electrolyte is 1 to 80% by weight, the temperature of the electrolyte is 5 to 70 ° C., and the current density is 0.5%.
To 60 amps / dm ^2, a voltage of ^from 1 to 100v, and electrolysis time is preferably in the range of 10 to 100 seconds. Particularly preferred anodic oxidation methods are a method of performing anodization at a high current density in sulfuric acid and a method of performing anodization using phosphoric acid as an electrolytic bath. After the anodizing treatment, the aluminum plate may be subjected to an alkali metal silicate treatment (for example, a treatment of immersing the aluminum plate in an aqueous solution of sodium silicate). In order to improve the adhesion between the aluminum support and the curable layer and the printing characteristics, an undercoat layer may be provided on the support surface.

[Undercoat Layer] The undercoat layer is provided as a hydrophilic layer on a support (eg, a polymer film) whose surface is not sufficiently hydrophilic, in addition to the above aluminum support. As a component constituting the undercoat layer, a polymer (eg,
Gelatin, casein, polyvinyl alcohol, ethyl cellulose, phenolic resin, styrene-maleic anhydride resin, polyacrylic acid); amines (eg, monoethanolamine, diethanolamine, triethanolamine,
Tripropanolamine) and their hydrochlorides, oxalates or phosphates; monoaminomonocarboxylic acids (eg, aminoacetic acid, alanine); oxyamino acids (eg,
Serine, threonine, dihydroxyethylglycine);
Sulfur-containing amino acids (eg, cysteine, cystine); monoaminodicarboxylic acids (eg, aspartic acid, glutamic acid); diaminomonocarboxylic acids (eg, lysine); amino acids having an aromatic nucleus (eg, p-hydroxyphenylglycine, phenylalanine) Aliphatic aminosulfonic acid (eg, sulfamic acid, cyclohexylsulfamic acid); and (poly) aminopolyacetic acid (eg, ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediamine) Acetic acid, ethylenediaminediacetic acid, cycloethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid). A compound in which some or all of the acid groups of the above compounds have become salts (eg, sodium salt, potassium salt, ammonium salt) can also be used. The above components can be used in combination of two or more.

When a plastic film is used as the support, it is preferable to add hydrophilic fine particles (eg, silica powder) to the hydrophilic undercoat layer instead of sanding the aluminum support.

[Silver halide emulsion layer] The silver halide emulsion layer generally contains gelatin as a binder. In tanning development, a relief image can be formed by hardening gelatin. Besides gelatin,
Tanning development can be performed on a hydrophilic polymer having an amide bond or a primary amino group (eg, a protein other than gelatin, polyacrylamide). However, tanning development is usually performed on gelatin. Gelatin may be used in combination with another hydrophilic polymer (eg, polyvinylpyrrolidone, starch, albumin, polyvinyl alcohol, gum arabic, hydroxyethyl cellulose). The amount of silver halide applied is
It is preferably 0.01 to 5 g / m ² , more preferably 0.03 to 1 g / m ² , and most preferably 0.05 to 0.3 g / m ² in terms of silver. The thickness of the silver halide emulsion layer is from 0.07 to 13
μm, more preferably 0.2 to 5 μm.

As silver halide, silver chloride, silver bromide,
Any grain of silver iodide, or silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide can be used. The shape of the silver halide grains is preferably cubic or tetradecahedral, but is not limited to those having a regular crystal form, and may be those having an irregular crystal form or a complex form thereof. Potato-shaped,
Spherical, plate-like and plate-like crystal forms are included. In the case of tabular grains, the grain size is generally at least five times the grain thickness.
There is no particular limitation on the grain size of the silver halide.
Fine particles of 0.01 μm or less can also be used. Meanwhile, 1
Large particles of about 0 μm can also be used. With respect to grain size distribution, monodisperse grains are preferred over polydisperse emulsions.
Monodispersed emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748. The crystal structure of silver halide grains is
It may be uniform or the inside and the outside may have different halogen compositions. It may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining. Further, it may be bonded to a compound other than silver halide. Examples of compounds other than silver halide include silver rhodan and lead oxide.

The silver halide grains may contain salts of other elements. Examples of other elements include copper, thallium, lead, bismuth, cadmium, zinc, chalcogens (eg, sulfur, selenium, tellurium), gold and VI.
Group II noble metals (eg, rhodium, iridium, iron, platinum, palladium) can be mentioned. Salts of these elements can be added during or after the formation of silver halide grains and included in the grains. Specific methods are described in U.S. Patent Nos. 1195432 and 1951933,
No. 2448060, No. 2628167, No. 2950
No. 972, No. 3488709, No. 3737313,
Nos. 3772031 and 4269927, and Research Disclosure (RD), No. 13,
No. 4, No. 13452 (June 1975). By adding an aqueous solution of an iridium compound to the emulsion during the preparation of the silver halide emulsion, iridium ions can be introduced into the silver halide grains. Examples of water-soluble iridium compounds include hexachloroiridium (II
I) acid salts and hexachloroiridium (IV) salts. Similarly, rhodium ions may be introduced into silver halide grains by adding an aqueous solution of a rhodium compound to the emulsion. Examples of the water-soluble rhodium compound include rhodium ammonium chloride, rhodium trichloride and rhodium chloride.

The iridium compound or the rhodium compound may be used by dissolving it in an aqueous solution of a halide for forming silver halide grains. Further, the aqueous solution of the iridium compound or the rhodium compound may be added before the particles are formed, or may be added during the formation of the particles. Further, it may be added during the period from grain formation to chemical sensitization treatment. It is particularly preferred to add while the particles are being formed. The iridium ion or the rhodium ion is preferably used in an amount of 10 ^{-8 to} 10 ^-3 mol, more preferably 10 ^{-7 to} 10 ^-5 mol, per 1 mol of silver halide. Two or more silver halide grains having different halogen compositions, crystal habits and grain sizes can be used in combination. Silver halide is preferably used as an emulsion. Silver halide emulsions are described in Research Disclosure (RD) Magazine, No. 17643 (December 1978), pp. 22-23, "I. Emulsion Production (Emulsion p.
reparation and types) "and No. 18716
(November 1979), page 648.

The silver halide emulsion is usually subjected to chemical sensitization after physical ripening. It is preferable to use silver halide grains having a relatively low fog value. Additives used in such a process are described in Research Disclosure Magazine, No. 1
No. 7643 and the same No. 18716. Regarding chemical sensitizers, 17643 (p. 23) and
No. 18716 (page 648, right column). Known additives other than those described above are also described in the above two Research Disclosures. For example, as for the sensitivity enhancer, 18716 (648
In the right column of the page), for the antifoggant and the stabilizer, N
o. No. 17643 (pages 24 to 25) and no. 18716
(From page 649, right column).

The silver halide emulsion is usually used after spectral sensitization. As the sensitizing dye used in the light-sensitive material, a silver halide sensitizing dye known in the photographic art can be used. Examples of sensitizing dyes include cyanine dyes,
Examples include merocyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Spectral sensitizing dyes are used to adjust the spectral sensitivity of photosensitive materials to different light source wavelengths such as various lasers (eg, semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser, YAG laser) and light emitting diodes. Can also be used. For example, applying a plurality of spectral sensitizing dyes having different spectral wavelengths to silver halide in the same or different photosensitive layers to enable writing on the same photosensitive material using light sources having different wavelengths. Can also. In addition to the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization (supersensitizer) can be added to the emulsion. Good. Spectral sensitizing dyes are described in Research Disclosure Magazine, No. 17643 (197
December, 8), pp. 23-24, for supersensitizers
No. 18716 (November 1979), p. 649,
Each is listed.

Fine particles of a lipophilic resin can be added to the silver halide emulsion layer to enhance the lipophilicity of the relief image. The fine particles of the lipophilic resin also have the effect of increasing the mechanical strength of the relief image. Examples of lipophilic resins include polyester, polyamide, phenol-aldehyde resin, polyvinyl chloride, polyurethane, epoxy resin, silicon resin, alkylphenol resin, ketone resin, alkyd resin, polyamine, polystyrene, polyacrylate, and rosin-modified maleic resin. , Rosin-modified fumaric acid resin, polyvinyl acetate, hydroxypropyl methylcellulose,
Rosin modified phenolic resin and hexahydrophthalate are included. Polystyrene, polyacrylate, polyvinyl acetate, polyurethane, hydroxypropyl methylcellulose and hexahydrophthalate are preferred.
Further, a photosensitive resin (a photopolymerizable polymer or a photocrosslinkable polymer) may be used as the lipophilic resin. Two or more types of lipophilic resins may be used in combination. The fine particles of the lipophilic resin preferably have an average particle size of 0.01 to 5 μm. There is no particular limitation on the shape of the fine particles.

To improve photographic characteristics, additives such as an antifogging agent, a silver development accelerator for accelerating silver development, and a stabilizer may be added to the silver halide emulsion layer. Examples thereof include mercapto compounds (JP-A-59-111636).
Azoles and azaindenes (Research Disclosure No. 17643, 24-25)
Page (1978)), carboxylic acids and phosphoric acids containing nitrogen (described in JP-A-59-168442),
Cyclic amide (described in JP-A-61-151841),
Thioethers (described in JP-A-62-151842), polyethylene glycol derivatives (JP-A-62-1)
No. 51843), thiols (JP-A-62-15)
No. 1844), acetylene compounds (Japanese Unexamined Patent Publication No. Sho 62)
-87957) and sulfonamide (described in JP-A-62-178232). As a silver development accelerator or an antifoggant, an aromatic ring (carbon ring or heterocyclic) mercapto compound (Japanese Patent Laid-Open No.
-313967) is particularly preferred. Aromatic heterocyclic mercapto compounds, particularly mercaptotriazole derivatives, are more preferred. The mercapto compound may be added to the light-sensitive material as a mercapto silver compound (silver salt).
The amount of these compounds used is 1 to 1 mole of silver halide.
It is in the range of ^0-7 mol to 1 mol.

A known surfactant may be added to the silver halide emulsion layer. Any of a nonionic activator, an anionic activator, a cationic activator and a fluorine activator can be used. The surfactant is described in JP-A-2-195356. Sorbitans, polyoxyethylenes and fluorinated surfactants are particularly preferred.

[Arbitrarily Provided Layer] The layer optionally provided in the silver halide light-sensitive material is preferably a layer containing a hydrophilic polymer as a binder similarly to the silver halide emulsion layer, and gelatin is used as a binder. It is further preferable that the layer is a layer that is formed. A tanning developer can be added to the optional hydrophilic layer.

A back layer containing a matting agent or an overcoat layer containing a matting agent for the purpose of reducing the tackiness of the front or back surface of the silver halide light-sensitive material and preventing adhesion when the silver halide light-sensitive materials are stacked. Can be provided on the silver halide photosensitive material. As the matting agent, inorganic or organic solid particles that can be dispersed in a water-soluble polymer are used. Examples of materials for the matting agent include oxides (eg, silicon dioxide), alkaline earth metal salts, natural polymers (eg, starch, cellulose) and synthetic polymers. The particle size of the matting agent is preferably in the range of 0.5 to 50 μm. The application amount of the matting agent is 0.
It is preferably in the range of 1 to 1 g / m ² .

A protective layer is provided on the silver halide emulsion layer,
The lipophilic resin fine particles described above may be added to the protective layer.
The protective layer containing the lipophilic resin fine particles is 0.01 to 5 μm
Preferably, it has a thickness of 0.2 to 2 μm. The protective layer preferably has voids between the lipophilic resin particles to such an extent that the developer can penetrate. To the optional layer, the above-mentioned antifoggant, silver development accelerator for accelerating silver development, stabilizer and surfactant may be added.

[Exposure Step] The image exposure is performed with light having a wavelength corresponding to the spectral sensitivity of silver halide. The wavelength is visible light,
Near-ultraviolet light and near-infrared light are generally used, but X-rays and electron beams may be used. Examples of light sources include lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, carbon arc lamps, and various lasers (eg, semiconductor lasers, helium neon lasers, argon ion lasers, helium cadmium lasers, YAG laser), light emitting diode, cathode ray tube and the like. Exposure doses generally range from 0.001 to 1000 μJ / cm ² , preferably from 0.01 to 100 μJ / cm ² . When the support is transparent, exposure can be performed through the support from the back side of the support.

[Tanning Development Step] The tanning development of the silver halide photosensitive material is performed using a developer. A tanning developer can be added to the developer. The developer is generally an alkaline solution. The pH of the developer is
It is preferably 9 or more. Examples of the alkaline substance used for adjusting the pH include sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, lithium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, and ammonia. As a solvent for the developer, water is preferable. If necessary, an organic solvent may be added to water. The temperature of the developer is
The temperature is preferably from 5 to 40 ° C, more preferably from 20 to 35 ° C. Development time is 10 seconds to 1
The time is preferably 0 minutes, more preferably 20 seconds to 3 minutes. The actual processing time in the developing machine is determined by the advance speed and the capacity of the processing bath. Linear velocity is 500
It is preferably from about 4000 mm / min to about 4000 mm / min. In the case of a small-sized developing machine, the linearity is particularly preferably from 500 to 2500 mm / min. After the development processing, the lipophilicity of the image area may be enhanced by processing with a liquid containing a mercapto compound (described in JP-A-4-324866). Further, an acidic treatment or a fixing treatment may be performed. After the tanning development, a desilvering treatment may be performed. The time required for all processing steps from tanning development (start of immersion of the photosensitive material in the developer) to drying (the developer comes out of the drying section of the processor) is preferably 360 seconds or less, and is 120 seconds or less. More preferably, it is most preferably 30 to 90 seconds.

[Elution Step] The silver halide photosensitive material after the tanning development is immersed in hot water and rubbed on the surface to elute the uncured gelatin in the unexposed areas to form a relief image of the cured gelatin. Can be. The temperature of the hot water is preferably 40 to 70 ° C. The surface of the photosensitive material may be rubbed with a sponge or a brush. The formed relief image can be used as a lithographic printing plate by drying. As the post-treatment, heat treatment, light irradiation treatment, or chemical treatment may be performed.

[0112]

[Example 1] "Preparation of aluminum support" JI having a thickness of 0.24 mm
The surface of the aluminum plate according to SA-1050 was grained with a nylon brush and an aqueous suspension of pamistone (400 mesh), and then thoroughly washed with water. Next, the film was immersed in a 10% by weight aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds for etching, and then washed with running water. 20% by weight
And then washed with water. The obtained aluminum plate was subjected to a square wave alternating current (condition:
The voltage at the time of the anode is 12.7 V, the ratio of the amount of electricity at the cathode to the amount of electricity at the anode is 0.9, and the amount of electricity at the anode is 160 coulomb / dm.
^{Using 2} ), electrolytic surface roughening treatment was performed in a 1% by weight nitric acid aqueous solution containing 0.5% by weight of aluminum nitrate. The surface roughness of the obtained plate was 0.6 μm (Ra indication). Subsequent to this treatment, the substrate was immersed in a 1% by weight aqueous sodium hydroxide solution at 40 ° C. for 30 seconds and then treated in a 30% by weight aqueous sulfuric acid solution at 55 ° C. for 1 minute. Next, when the thickness is 2.
Anodizing treatment was carried out in a 20% by weight aqueous sulfuric acid solution using a direct current at a current density of 2 A / dm ^{2 so} as to obtain 5 g / dm ² . This was washed with water and dried to prepare a support. The prepared support was used as a No. 3 sodium silicate (SI
O _2: 28 to 30 wt%, Na ₂ O: 9 to 10 wt%,
Fe: 0.02% by weight or less 2.5% by weight aqueous solution (p
H: 11.2) at 70 ° C. for 13 seconds and washed with water.
The amount of silicate measured by X-ray fluorescence analysis was 10 mg / m
^{Was 2} .

"Preparation of silver halide emulsion" In a vessel containing gelatin, potassium bromide and water and heated to 55 ° C, the following thioether compound was further added in an amount of 2.0 × 10 ^-3 mol based on the added amount of silver nitrate. A considerable amount was added. Reaction vessel p
While maintaining the Ag value at 9.2, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide containing rhodium ammonium chloride in a molar ratio of rhodium to the total amount of potassium iodide and silver nitrate of 4 × 10 ⁻⁸ mol were used. With pAg
Silver iodobromide grains were formed by the control double jet method. Subsequently, 55 ° C., pAg = 8.
In step 9, a double-stage double jet method was used to add a silver nitrate aqueous solution and a potassium bromide solution to which hexachloroiridate (III) was added in a molar ratio of iridium to silver of 1.0 × 10 ⁻⁷ mol. Thus, a core / shell type silver iodobromide emulsion having the following composition was prepared.

[0114]

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Core: silver iodobromide (silver iodide content: 7.5 mol%) Shell: pure silver bromide Core / shell: 3/7 (silver molar ratio) Average silver iodide content: 2.3 Mol% average particle size: 0.28 μm

The obtained emulsion grains were monodispersed and contained 98% of the total number of grains within ± 40% of the average grain size. Then, after desalting the emulsion, a methanol solution of a spectral sensitizing dye A below (5 × 10 ^- 3M / l) and a spectral sensitizing dye B in methanol in the following (5 × 10
^- The 3M / l), with respect to emulsion per mole of silver nitrate equivalent, respectively 100ml added, 6.2 pH, pAg
Was adjusted to 8.7. Further, gold / sulfur sensitization was performed using sodium thiosulfate and chloroauric acid to prepare an aqueous silver halide emulsion. Solid concentration of emulsion: 29.6% by weight Gelatin concentration of emulsion: 3.5% by weight

[0117]

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[0118]

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"Preparation of Tanning Developer Dispersion" 30 g of compound (I-7), modified polyvinyl alcohol (MP-
203, manufactured by Kuraray Co., Ltd.) and sodium triisopropylnaphthalenesulfonate (Leopol BX,
198 g of water was added to 0.6 g of Takemoto Oil & Fat Co., Ltd. and mixed well to form a slurry. The slurry was placed in a container together with 960 g of dispersed beads (zirconia silicate particles having an average particle size of 0.5 mm), and a disperser sand mill (1
/ 4G sand grinder mill, manufactured by Imex Co., Ltd.) for 5 hours to prepare a tanning developer dispersion having an average particle size of 0.4 μm.

"Formation of silver halide gelatin emulsion layer" The following coating solution was prepared, and coated on an aluminum support.
After drying, a silver halide gelatin emulsion layer having a dry film thickness of 1.5 μm was provided. Thus, a silver halide photosensitive material was produced.

{Coating Solution for Silver Halide Gelatin Emulsion Layer} ───────────────────────────────── The above silver halide emulsion 5 g 10% by weight aqueous solution of gelatin 24 g Tanning developer Dispersion 10 g 1 wt% aqueous solution of the following additive A 0.4 g 0.5 wt% methanol solution of the following additive B 1 g water 34 g ──────────────────

[0122]

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[0123]

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"Preparation of tanning developer" A tanning developer having the following composition was prepared.

{Tanning developer} ──────────────────────────── Water 800ml Potassium phosphate 44g Disodium N, N-bis (sulfonatoethyl) hydroxylamine 10g Potassium chloride 5 g 30% by weight aqueous solution of hydroxyethylidene-1,1-disulfonic acid 4 ml 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1 g Water was added 1000 ml pH (adjusted at 25 ° C., potassium hydroxide) ) 12.0 ────────────────────────────────────

(Image formation) A light of 670 nm was separated from the silver halide photosensitive material by a sharp cut interference filter with a light emission time of 10 ^-4 sec by xenon flash, and the energy on the photosensitive material surface was 2 μJ / cm ² . Control wedge (Fuji Photo Film Co., Ltd.)
Was brought into close contact with each other to perform image exposure. The image-exposed silver halide photosensitive material was immersed in a tanning developer at 25 ° C. for 60 seconds. Then, it was washed with running water at 45 ° C. for 15 seconds. The surface of the silver halide light-sensitive material was lightly rubbed with a sponge to remove an unexposed portion of the silver halide emulsion layer and dried, whereby a relief image having a uniform film surface on the support was obtained. This was used as a lithographic printing plate. The lithographic printing plate was wetted with water and rubbed with a PI ink (manufactured by Fuji Photo Film Co., Ltd.) to examine the ink receptivity. As a result, the image area (relief image) received the ink well. The lithographic printing plate was mounted on an offset printing machine (RYOBI3200CCD, manufactured by Ryobi Co., Ltd.) and printing was performed to check the printing durability. As a result, 15,000 or more sheets could be printed.

[Examples 2 to 5] Instead of the tanning developer (I-7) added to the silver halide gelatin emulsion layer,
Tanning developers (I-12), (I-18), (I-
38) and (I-41) were prepared and evaluated in the same manner as in Example 1 except that the same amounts of (I) and (I-41) were used. The results are shown in Table 1.

[0128]

[Table 1] Table 1 銀 Silver halide photosensitive material Tanning development Chemicals Ink acceptability Printing durability ──────────────────────────────────── Example 1 (I-7 Good 15,000 sheets or more Example 2 (I-12) Good 15,000 sheets or more Example 3 (I-18) Good 15,000 sheets or more Example 4 (I-38) Good 15 1,000 sheets or more Example 5 (I-41) Good 15,000 sheets or more ────

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 24, 2000 (2008.2.
4)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 8

[Correction method] Change

[Correction contents]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

(6) a step of imagewise exposing a silver halide light-sensitive material having a support and a silver halide gelatin emulsion layer, a step of tanning the silver halide light-sensitive material to harden gelatin in an exposed portion, and a step of not exposing Forming a relief image of hardened gelatin by dissolving a part of unhardened gelatin in this order, using a tanning developer comprising a compound represented by the following formula (I). (I) L (-X-NHNH-Ar) _{n wherein} L is an n-valent organic residue; and X is -NH −
CO -, - CO -, - NH-SO 2 - or -O-CO
Ar is an aromatic group or an aromatic heterocyclic group; n is an integer of 2 or more;
-NHNH-Ar may be different from each other]. (7) The tanning developer according to (6), wherein the tanning developer comprising the compound represented by the formula (I) is contained in a silver halide gelatin emulsion layer or an optional hydrophilic layer of the silver halide photosensitive material. Relief image forming method. (8) onto a hydrophilic support, a lithographic printing plate relief image is formed of hardened gelatin, hardened gelatin is gelatin crosslinked by oxidation of the compound represented by the above above formula (I) A lithographic printing plate characterized by the following.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazunori Kato 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film F-term (reference) 2H016 AA01 AD04 AG01 2H096 AA06 BA01 BA17 GA08 GA60

Claims (8)

[Claims] 1. A tanning developer comprising a compound represented by the following formula (I): (I) L (-X-NHNH-Ar) _{n wherein} L is an n-valent organic residue; X is -NH-
CO -, - CO -, - NH-SO 2 - or -O-CO
Ar is an aromatic group or an aromatic heterocyclic group; n is an integer of 2 or more;
-NHNH-Ar may be different from each other]. 2. In the formula (I), L represents an aliphatic group, an aromatic group, —O—, —CO—, —SO ₂ —, —N <, —P
The tanning developer according to claim 1, which is an n-valent organic residue selected from O <and a combination thereof. 3. The tanning according to claim 1, wherein in the formula (I), L includes a main chain of the polymer, and —X—NHNH—Ar forms a side chain or a terminal of the side chain of the polymer. Developer. 4. In the formula (I), X represents —NH—CO
The tanning developer according to claim 1, which is-. 5. In the formula (I), Ar represents cyano, nitro, carbamoyl, sulfamoyl, a halogen atom,
An aromatic group having a halogen-substituted alkyl group, an alkoxy group, an aliphatic sulfonyl group, an aromatic sulfonyl group, an aliphatic substituted carbamoyl group, an aromatic substituted carbamoyl group, an aliphatic substituted sulfamoyl group or an aromatic substituted sulfamoyl group as a substituent or The tanning developer according to claim 1, which is an aromatic heterocyclic group. 6. Image-exposing a silver halide light-sensitive material having a support and a silver halide gelatin emulsion layer,
A step of tanning the silver halide photosensitive material to harden the gelatin in the exposed areas, and a step of eluting the unhardened gelatin in the unexposed areas to form a relief image of the hardened gelatin, in this order. A relief image forming method, wherein tanning development is performed using a tanning developer comprising a compound represented by the following formula (I): (I) L (-X-NHNH-Ar) _{n wherein} L is an n-valent organic residue; X is -NH-
CO -, - CO -, - NH-SO 2 - or -O-CO
Ar is an aromatic group or an aromatic heterocyclic group; n is an integer of 2 or more;
-NHNH-Ar may be different from each other]. 7. The method according to claim 6, wherein the tanning developer comprising the compound represented by the formula (I) is contained in a silver halide gelatin emulsion layer or an optional hydrophilic layer of the silver halide photosensitive material. The relief image forming method as described in the above. 8. A lithographic printing plate having a relief image of hardened gelatin formed on a hydrophilic support, wherein the hardened gelatin is crosslinked with an oxide of a compound represented by the following formula (I). A lithographic printing plate, characterized in that: