JP2001312031A - Tanning developing agent, silver halide photosensitive material, tanning developer, method for producing planographic printing plate and planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form an image comprising an image area having high lipophilic property and a non-image area having high hydrophilic property by tanning development. SOLUTION: A compound having a benzene ring which forms a quinoid structure by oxidation and also having a substituent containing carboxyl, sulfo, phosphono or a salt of one of those and bonding to the benzene ring is used as the objective tanning developing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a tanning developer, a silver halide photosensitive material, a tanning developer, a method of making a lithographic printing plate, 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 the 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 using a relief image of hardened gelatin as a lithographic printing plate is described in JP-A-53-135702 and JP-A-5-135702.
4-49202, 54-152502, 55-
No. 12625, JP-A-4-324866 and 5-28
No. 9228 and British Patent No. 1567844,
It is described in each specification of JP-A-1571155 and JP-A-1590058.

[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 high sensitivity as compared with other lithographic printing plate 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 an oleophilic region. Although hardened gelatin is relatively lipophilic compared to the surface of the support, it is not strongly lipophilic. 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 a problem of insufficient lipophilicity (ink receptivity) and durability (printing durability).

JP-A-53-135702 and JP-A-54-1
No. 52502, No. 55-12625, JP-A-4-32
The methods described in JP-A Nos. 4866 and 5-289228 propose that the hardened gelatin be treated (heat treatment, light irradiation treatment, chemical treatment) after image formation in order to improve ink receptivity. However, there is a problem that when the hardened gelatin is heated, the adhesiveness between the hardened gelatin and the support decreases. Further, in order to irradiate light to the extent that the ink receptivity of the hardened gelatin is improved, a powerful light irradiation device is required. The chemical treatment involves problems of toxicity of the chemical substances used and an insufficient treatment effect. An object of the present invention is to form an image composed of an image portion having high lipophilicity and a non-image portion having high hydrophilicity by tanning development.

[0006]

The object of the present invention is to provide a tanning developer of the following (1) to (4), a silver halide photosensitive material of the following (5), a tanning developer of the following (6), and a tanning developer of the following (7). ), And a lithographic printing plate of the following (8). (1) A tanning developer comprising a compound having a benzene ring which forms a quinoid structure by oxidation, and further having a substituent containing carboxyl, sulfo, phosphono or a salt thereof bonded to the benzene ring. (2) The tanning developer according to (1), wherein the quinoid structure formed is a quinone type, quinone imine type or quinone diimine type. (3) The tanning developer according to (1), wherein the carboxyl, sulfo, phosphono, or a salt thereof and a benzene ring that forms a quinoid structure by oxidation are directly connected by a single bond. (4) carboxyl, sulfo, and a phosphono or a benzene ring forming the quinoid structure by oxidation and any salt thereof -CO -, - O -, - NH -, - SO 2 -,
The tanning developer according to (1), wherein the tanning developer is bound by a divalent linking group selected from alkylene, phenylene, and a combination thereof.

(5) A silver halide photosensitive material having a support and a silver halide gelatin emulsion layer, wherein the silver halide gelatin emulsion layer or an optional hydrophilic layer forms a quinoid structure by oxidation. A silver halide light-sensitive material comprising a tanning developer comprising a compound having a ring and further having a substituent containing a carboxyl, sulfo, phosphono or any salt thereof bonded to the benzene ring. (6) Tanning development comprising an alkaline aqueous solution of a compound having a benzene ring forming a quinoid structure by oxidation and further having a substituent containing carboxyl, sulfo, phosphono or a salt thereof bonded to the benzene ring. liquid.

(7) A step of imagewise exposing a silver halide light-sensitive material having a silver halide gelatin emulsion layer on a hydrophobic support, which has a benzene ring forming a quinoid structure by oxidation, and further has a carboxyl, sulfo, phosphono Or a step of tanning the silver halide light-sensitive material by using a tanning developer comprising a compound having a substituent having a salt bonded to any of the benzene rings to harden the gelatin in the exposed area. A method of making a lithographic printing plate, wherein the step of forming a relief image of hardened gelatin by eluting unhardened gelatin in an exposed portion is performed in this order to make a lithographic printing plate. (8) A lithographic printing plate having a relief image of hardened gelatin on a hydrophobic support, wherein the hardened gelatin has a benzene ring forming a quinoid structure by oxidation, and further has a carboxyl, sulfo, phosphono or any of them. A lithographic printing plate characterized in that the lithographic printing plate is formed by a hardening reaction of gelatin with an oxidized form of a tanning developer comprising a compound having a salt bonded to the benzene ring.

[0009]

The inventor of the present invention, contrary to the prior art,
An attempt was made to use a relief image formed by tanning development not as a lipophilic area but as a hydrophilic area. In the prior art, a relief image of hardened gelatin was used as the lipophilic region, despite the problem of lipophilicity (ink receptivity). One of the reasons is due to the relationship with the aluminum support. In the use of a printing plate, an aluminum plate is used as a very excellent support from the viewpoint of light weight or durability. The surface of the aluminum support can be made to function as a very excellent hydrophilic region by graining. Therefore, in the prior art, it was considered that the relief image remaining on the aluminum support naturally functions as a lipophilic region. However, as a result of research conducted by the present inventors, it has been found that a relief image formed on a hydrophobic support by tanning development can be used as a hydrophilic region. The relief image of the hardened gelatin has insufficient hydrophilicity to be used as it is as a hydrophilic region (fountain solution receiving portion). As a result of the study of the present inventors, a compound having a benzene ring forming a quinoid structure by oxidation and further having a substituent containing a carboxyl, sulfo, phosphono or a salt thereof bonded to the benzene ring is subjected to tanning development. By using it as a medicine, the relief image of the hardened gelatin can be made more hydrophilic than before.

According to the present invention, a relief image of hardened gelatin, which has been used as a lipophilic area (ink receiving area) in the prior art, can be used as a hydrophilic area (fountain solution receiving area). And the surface of the hydrophobic support is
It can function as a good hydrophobic region (ink receiving portion). As a result, it has become possible to form an image (lithographic printing plate) having higher lipophilicity than the conventional technology. In the printing plate, generally, the image area has a smaller area than the non-image area. When a lithographic printing plate is made according to the present invention, a relief image of hardened gelatin functions as a non-image portion, and an area where unhardened gelatin elutes becomes an image portion. Therefore, the elution amount of the present invention which elutes the image part is generally smaller than that of the conventional technique which elutes the non-image part. Therefore, the present invention has reduced the problem of waste liquid treatment of the eluate as compared with the prior art.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION [Tanning developer] In the present invention, a benzene ring which forms a quinoid structure by oxidation is used, and a substituent containing carboxyl, sulfo, phosphono or a salt thereof is substituted with the benzene ring. Is used as a tanning developer. There are two types of quinoid structures, p-quinoids and o-quinoids. Although p-quinoids are generally used, o-quinoids are also effective in tanning development.

[0012]

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[0013] The quinoid structure is classified according to the type of atom bonded to the exocyclic double bond. Quinone, quinone imine and quinone diimine types are preferred.

[0014]

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A benzene ring substituted with two hydroxyl groups in a para (p-) or ortho (o-) positional relationship forms a quinone-type quinoid structure by oxidation.

[0016]

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A benzene ring substituted with a hydroxyl group having a para (p-) or ortho (o-) position and a primary or secondary amino group forms a quinone imine type quinoid structure by oxidation.

[0018]

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A benzene ring substituted with two primary or secondary amino groups in a para (p-) or ortho (o-) positional relationship forms a quinone diimine type quinoid structure by oxidation.

[0020]

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Further, a substituent containing a carboxyl, a sulfo, a phosphono or a salt thereof is bound to a benzene ring. The substituent attached to the benzene ring is preferably carboxyl or sulfo. As the counter ion when the substituent forms a salt, an alkali metal ion or an ammonium ion is preferable. The substituent and the benzene ring may be directly connected by a single bond or may be connected via a divalent linking group. When the benzene ring forming the quinone imine-type or quinone diimine-type quinoid structure has a secondary amino group, the secondary amino group and the substituent are directly connected by a single bond or bonded via a divalent linking group. May be. The divalent linking group is -CO-, -O-, -N
H -, - SO ₂ -, alkylene, it is preferably selected from phenylene and combinations thereof. Above -N
H- includes a secondary amino group for forming a quinoid structure. The alkylene includes a cyclic alkylene (eg, cyclohexylene). Examples of the divalent linking group formed by the combination are shown below. The left side is bonded to the benzene ring, and the right side is bonded to the substituent.

[0022] L1: -CO- alkylene - L2: -SO ₂ - alkylene - L3: -NH-CO- alkylene - L4: -NH-CO- phenylene - L5: -O-CO- alkylene - L6: -O- CO- phenylene - L7: -CO-NH- alkylene - L8: -SO ₂ -NH- alkylene - L9: -CO-O-alkylene - L10: -SO ₂ -O- alkylene -

The benzene ring which forms the quinoid structure upon oxidation may have other substituents (other than carboxyl, sulfo, phosphono or any salt thereof). Further, the secondary amino group also has a substituent bonded to a nitrogen atom (except when bonded to carboxyl, sulfo, phosphono or a salt thereof). Further, the alkylene and phenylene constituting the divalent linking group may have another substituent. Examples of the substituent include a halogen atom, cyano, nitro, an aliphatic group, an aromatic group, a heterocyclic group, -OR, -CO-R, -CO-O-.
R, -O-CO-R, -S-R, -SO 2 -R, -SO
_{2 -O-R, -O-SO} 2 -R, -NH-R, -CO-
NH-R, -NH-CO- R, include -SO ₂ -NH-R and -NH-SO ₂ -R. R is a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, respectively.

The aliphatic group includes an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group and a substituted alkynyl group. The alkyl group preferably has 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 3 to 15 carbon atoms. The alkyl group may have a cyclic structure. The chain alkyl group may have a branch. The alkyl part of the substituted alkyl group is the same as the above-mentioned alkyl group. Examples of the substituent of the substituted alkyl group include a halogen atom, cyano, nitro, an aromatic group, a heterocyclic group, -OR,
-CO-R, -CO-OR, -O-CO-R, -S-
_{R, -SO 2 -R, -SO 2} -O-R, -O-SO 2 -
R, -NH-R, -CO-NH-R, -NH-CO-
R, include -SO ₂ -NH-R and -NH-SO ₂ -R. R is a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, respectively.

The alkenyl group has 2 to 25 carbon atoms.
Is preferably, 2 to 20, more preferably, 2 to 20, and most preferably, 3 to 15. The alkenyl group may have a cyclic structure. The chain alkenyl group may have a branch. The alkenyl part of the substituted alkenyl group is the same as the above alkenyl group.
Examples of the substituent of the substituted alkenyl group are the same as the examples of the substituent of the substituted alkyl group. The alkynyl group preferably has 2 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, and most preferably 3 to 15 carbon atoms. The alkynyl group may have a cyclic structure. The chain alkynyl group may have a branch. The alkynyl part of the substituted alkynyl group is the same as the above alkynyl group. Examples of the substituent of the substituted alkynyl group are the same as those of the substituent of the substituted alkyl group.

The aromatic group includes an aryl group and a substituted aryl group. The aryl group has 6 to 1 carbon atoms.
It is preferably 9, more preferably 6 to 10, and most preferably 6 (phenyl) or 10 (naphthyl). The aryl part of the substituted aryl group is the same as the above-mentioned aryl group. Examples of the substituent of the substituted aryl group include a halogen atom, cyano, nitro, an aliphatic group, an aromatic group, a heterocyclic group, -OR, -CO-R,-
CO-O-R, -O- CO-R, -S-R, -SO 2 -
_{R, -SO 2 -O-R,} -O-SO 2 -R, -NH-
R, -CO-NH-R, -NH-CO-R, -SO 2 -
NH-R and -NH-SO ₂ -R include. R is
Each is a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.

The heterocyclic ring of the heterocyclic group is preferably a 5- or 6-membered ring. As the hetero atom of the hetero ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. Heterocycles may be saturated. A heterocycle, another heterocycle,
An aliphatic ring or an aromatic ring may be condensed. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as those of the substituent of the substituted aryl group.

The tanning developer has the following formula (Ip):
(Io), (IIp), (IIo), (IIIp), (IIIo),
Compounds represented by (IVp), (IVo), (Vp) or (Vo) are preferred.

[0029]

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Wherein L is a single bond or a divalent linking group; Q is carboxyl, sulfo, phosphono or a salt thereof; R ¹ is a halogen atom, cyano, nitro, aliphatic Group, aromatic group, heterocyclic group, -O-
R, -CO-R, -CO-OR, -O-CO-R,-
_{S-R, -SO 2 -R,} -SO 2 -O-R, -O-SO
₂ -R, -NH-R, -CO-NH-R, -NH-CO
-R, a -SO ₂ -NH-R or -NH-SO ₂ -R, R are each a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; and, n is 0 1, 2, or 3. L is a single bond or -CO-,-
O -, - NH -, - SO 2 -, alkylene, it is preferably selected from phenylene and combinations thereof. Q is preferably carboxyl or sulfo. R ¹ is the same as defined above for the substituent on the benzene ring. N is preferably 0, 1, or 2, and more preferably 0 or 1.

[0031]

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In the formula, L is a single bond or a divalent linking group.
Yes; Q is carboxyl, sulfo, phosphono or
Any of these salts; R¹Is a halogen atom,
Ano, nitro, aliphatic group, aromatic group, heterocyclic group, -O-
R, -CO-R, -CO-OR, -O-CO-R,-
SR, -SO_Two-R, -SO_Two-OR, -O-SO
_Two-R, -NH-R, -CO-NH-R, -NH-CO
-R, -SO_Two-NH-R or -NH-SO_TwoAt -R
R represents a hydrogen atom, an aliphatic group, an aromatic group,
R or a heterocyclic group;^TwoIs a hydrogen atom, a halogen
Atom, cyano, nitro, aliphatic group, aromatic group, heterocycle
Group, -OR, -CO-R, -CO-OR, -OC
OR, -SR, -SO_Two-R, -SO_Two-OR,
-O-SO _Two-R, -NH-R, -CO-NH-R,-
NH-CO-R, -SO_Two-NH-R or -NH-S
O_Two-R wherein R is a hydrogen atom, an aliphatic
Group, aromatic group or heterocyclic group; and n is
0, 1, 2 or 3. L is a single bond or
-CO-, -O-, -NH-, -SO_Two-, Alkyre
Selected from phenylene, phenylene and their combinations
Is preferred. Q is a carboxyl or sulfo
It is preferred that R above¹Is the benzene
It is the same as the substituent of the ring. R above^TwoIs the second class
It is the same as the substituent of the amino group. N is 0, 1 or
It is preferably 2 and more preferably 0 or 1.
Preferred.

[0033]

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Wherein L is a single bond or a divalent linking group; Q is carboxyl, sulfo, phosphono or a salt thereof; R ¹ is a halogen atom, cyano, nitro, Group, aromatic group, heterocyclic group, -O-
R, -CO-R, -CO-OR, -O-CO-R,-
_{S-R, -SO 2 -R,} -SO 2 -O-R, -O-SO
₂ -R, -NH-R, -CO-NH-R, -NH-CO
-R, a -SO ₂ -NH-R or -NH-SO ₂ -R, R are each a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; and, n is 0 1,2,
3 or 4. L is a single bond or -CO
-, - O -, - NH -, - SO 2 -, alkylene, it is preferably selected from phenylene and combinations thereof. Q is preferably carboxyl or sulfo. R ¹ is the same as defined above for the substituent on the benzene ring. The above n is preferably 0, 1, 2 or 3, more preferably 0, 1 or 2, and most preferably 0 or 1.

[0035]

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Wherein L is a single bond or a divalent linking group; Q is carboxyl, sulfo, phosphono or a salt thereof; R ¹ is a halogen atom, cyano, nitro, Group, aromatic group, heterocyclic group, -O-
R, -CO-R, -CO-OR, -O-CO-R,-
_{S-R, -SO 2 -R,} -SO 2 -O-R, -O-SO
₂ -R, -NH-R, -CO-NH-R, -NH-CO
—R, —SO ₂ —NH—R or —NH—SO ₂ —R, wherein R is a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; and R ² and R ³ are Each independently represents a hydrogen atom, a halogen atom, cyano, nitro, an aliphatic group, an aromatic group, a heterocyclic group, -OR, -CO-R,
-CO-O-R, -O- CO-R, -S-R, -SO 2
_{-R, -SO 2 -O-R,} -O-SO 2 -R, -NH-
R, -CO-NH-R, -NH-CO-R, -SO 2 -
NH-R or a -NH-SO ₂ -R, R are each a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group; and, n is 0, 1, 2 or 3 is there. L is a single bond or -CO-, -O-, -NH-,
It is preferably selected from —SO ₂ —, alkylene, phenylene and a combination thereof. Q is preferably carboxyl or sulfo. R ¹ above
Is the same as the above-mentioned substituent of the benzene ring. R above
² and R ³ are the same as the above-mentioned substituents for the secondary amino group. N is preferably 0, 1, or 2, and more preferably 0 or 1.

[0037]

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In the formula, L is a single bond or a divalent linking group.
Yes; Q is carboxyl, sulfo, phosphono or
Any of these salts; R¹Is a halogen atom,
Ano, nitro, aliphatic group, aromatic group, heterocyclic group, -O-
R, -CO-R, -CO-OR, -O-CO-R,-
SR, -SO_Two-R, -SO_Two-OR, -O-SO
_Two-R, -NH-R, -CO-NH-R, -NH-CO
-R, -SO_Two-NH-R or -NH-SO_TwoAt -R
R represents a hydrogen atom, an aliphatic group, an aromatic group,
R or a heterocyclic group;^TwoIs a hydrogen atom, a halogen
Atom, cyano, nitro, aliphatic group, aromatic group, heterocycle
Group, -OR, -CO-R, -CO-OR, -OC
OR, -SR, -SO_Two-R, -SO_Two-OR,
-O-SO _Two-R, -NH-R, -CO-NH-R,-
NH-CO-R, -SO_Two-NH-R or -NH-S
O_Two-R wherein R is a hydrogen atom, an aliphatic
Group, aromatic group or heterocyclic group; and n is
0, 1, 2, 3 or 4. L is a single bond
Or -CO-, -O-, -NH-, -SO_Two-, Archi
Selected from len, phenylene and their combinations
Preferably. Q is a carboxyl or sulfo
E is preferred. R above¹Is the previously mentioned Benze
The same applies to the substituents of the ring. R above^TwoIs the second class
It is the same as the substituent of the amino group. The above n is 0, 1, 2
Or 3, preferably 0, 1, or 2.
More preferably, it is most preferably 0 or 1.
Good.

The following is an example of a tanning developer.

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Two or more tanning developers may be used in combination. A compound having a benzene ring forming a quinoid structure by oxidation and further having a substituent containing carboxyl, sulfo, phosphono or a salt thereof bound to the benzene ring, 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-
And indane). When used in combination, a compound having a benzene ring which forms a quinoid structure by oxidation, and further having a substituent containing carboxyl, sulfo, phosphono or a salt thereof bound to the benzene ring, is a tanning developer. Is preferably 50 to 95% by weight, more preferably 60 to 90% by weight, and most preferably 70 to 85% by weight of the total amount.

The tanning developer is used by adding it to a silver halide photosensitive material or a tanning developer. When added to a silver halide light-sensitive material, a coating solution for a silver halide gelatin emulsion layer or a hydrophilic layer optionally provided,
The tanning developer may be dissolved, emulsified or dispersed. The tanning developer can be generally dissolved in a coating solution for a silver halide gelatin emulsion layer or a 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 preferably 10 ^{-5 to} 10 ^-1 mol / l.

[Silver halide gelatin emulsion layer] The silver halide gelatin emulsion layer contains gelatin as a binder. In tanning development, a relief image can be formed by hardening gelatin. In addition to gelatin, tanning development can be performed on a hydrophilic polymer having a primary amino group, an amide bond, and a mercapto group (for example, a protein other than gelatin and 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 coating amount of silver halide is preferably 0.01 to 5 g / m ² , more preferably 0.03 to 1 g / m ² , and more preferably 0.05 to 0.3 g / m ^{2 in} terms of silver. Is most preferred. The thickness of the silver halide emulsion layer is
It is preferably from 0.07 to 13 μm, more preferably from 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.

In the silver halide emulsion layer, hydrophilic fine particles (eg,
(Silica powder) can be added to increase the hydrophilicity of the relief image. The hydrophilic fine particles also have the effect of increasing the mechanical strength of the relief image. The hydrophilic fine particles preferably have an average particle size of 0.01 to 5 μm. There is no particular limitation on the shape of the fine particles.

In order 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 tanning developer may be added to the silver halide emulsion layer. Known surfactants 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.

[Hydrophobic Support] As the support, paper, synthetic paper, synthetic resin (eg, polyethylene, polypropylene,
Polystyrene) laminated paper, plastic (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate) film, metal (eg, aluminum, aluminum alloy, zinc, iron, copper) plate, these metals are laminated or evaporated Paper or plastic film can be used. Aluminum plate, plastic film,
Paper and synthetic paper are preferred. Further, a composite sheet in which an aluminum sheet is laminated on a polyethylene terephthalate film is also preferable. When a hydrophilic material such as an aluminum plate is used, it can be used as a hydrophobic support by providing a hydrophobic undercoat layer described below.
The “hydrophobicity” of the hydrophobic support is preferably such that the contact angle with water is 50 degrees or more. Further, the surface of the hydrophobic support (the surface of the undercoat layer when the following hydrophobic undercoat layer is provided) is preferably made of a substance having a degree of swelling in water of 10% or less.

[Hydrophobic Undercoat Layer] The hydrophobic undercoat layer is formed using a hydrophobic polymer. Hydrophobic polymers include:
Polyacrylic acid ester, polymethacrylic acid ester (eg, polymethyl methacrylate, polybenzyl methacrylate), polyacrylamide, polymethacrylamide, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polymethacrylonitrile, polyethylene, Polystyrene, polyvinyl pyridine, polyvinyl imidazole, polyvinyl butyral,
Polyvinyl formal, polyvinyl pyrrolidone, chlorinated polyethylene, chlorinated polypropylene, polyester,
Polyamide, polyurethane, polycarbonate, cellulose ether (eg, ethyl cellulose) and cellulose ester (eg, cellulose triacetate, cellulose diacetate, cellulose acetate propionate) are included. To improve the affinity between the hydrophobic polymer and gelatin, an acidic group may be introduced into the hydrophobic polymer. Examples of acidic groups include carboxyl, acid anhydride groups,
Includes phenolic hydroxyl groups, sulfo, sulfonamides and sulfonimides. Carboxyl is particularly preferred. An acidic group can be introduced into a polymer by copolymerizing a monomer having an acidic group such as acrylic acid, methacrylic acid, styrene sulfonic acid or maleic anhydride during the synthesis of the polymer. The proportion of the repeating unit having an acidic group in the copolymer is preferably 1 to 60 mol%, more preferably 1 to 50 mol%, and most preferably 1 to 20 mol%. A homopolymer having an acidic group (eg, polyhydroxystyrene) may be used. The molecular weight of the hydrophobic polymer is 10
It is preferable that the number be in the range of 00 to 500,000. Two or more kinds of hydrophobic polymers may be used in combination.

[Adhesive Layer] An adhesive layer for improving adhesiveness may be provided between the hydrophobic support (or hydrophobic undercoat layer) and the silver halide emulsion layer. The adhesive layer is provided to enhance the adhesive strength between the support (hydrophobic) and the silver halide emulsion layer (hydrophilic). As long as the function of the adhesive layer is maintained, a layer other than the adhesive layer may be interposed between the support and the silver halide emulsion layer. A water-insoluble polymer having a glass transition temperature of 0 ° C. or lower can be used for the adhesive layer. The glass transition temperature of 0 ° C. or lower means that the polymer is in a rubbery soft state at a temperature (0 ° C. or higher) under normal handling conditions of the photosensitive material.
The glass transition temperature is preferably −5 ° C. or less,
More preferably, the temperature is -10 ° C or lower. Water-insoluble means that the solubility of the polymer in water at normal temperature (25 ° C.) is 1
Means less than% by weight. The solubility is preferably less than 0.1% by weight, more preferably less than 0.01% by weight, and most preferably less than 0.001% by weight. As a water-insoluble polymer having a glass transition temperature of 0 ° C. or lower, a (synthetic) polymer generally known as a (synthetic) rubber is representative. Examples of polymers include styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polychloroprene, polyvinyl acetate, ethylene-vinyl acetate copolymer and polyurethane.

Fine particles having a hydrophilic portion and a hydrophobic portion on the surface may be added to the adhesive layer. The hydrophilic portion and the hydrophobic portion may be present on the particle surface at the molecular level (as a hydrophilic group and a hydrophobic group). Further, as a region on the particle surface, a hydrophilic region and a hydrophobic region may be mixed. Such fine particles can be easily obtained by performing a hydrophobic treatment on (part of) the surface of the hydrophilic fine particles. It is actually very difficult to completely hydrophobize the surface of the hydrophilic fine particles by ordinary hydrophobic treatment. For this reason, a hydrophilic part and a hydrophobic part can be easily formed on the particle surface only by performing the normal hydrophobic treatment on the hydrophilic fine particles. The hydrophilic fine particles are preferably inorganic fine particles. The inorganic fine particles are generally hydrophilic, and a hydrophobic portion may be formed on a part of the surface. As the hydrophilic inorganic fine particles, silica particles are preferably used.
As fine particles other than silica, alumina, titania, zinc oxide or zircon oxide may be used. In the silica fine particles, the hydroxyl groups of the silica function as hydrophilic groups on the particle surface. In the hydrophobic treatment, it is preferable to use a coupling agent. That is, by reacting a hydroxyl group present on the surface of the silica fine particles with the coupling agent, the surface of the particles can be partially hydrophilized. As the coupling agent, a silane coupling agent, an aluminate coupling agent or a titanate coupling agent is preferably used. Silane coupling agents (eg, organochlorosilane, organoalkoxysilane) are particularly preferred.

The silane coupling agent preferably has a molecular structure in which one to three hydrophobic functional groups are bonded to a silicon atom. As the hydrophobic functional group, an alkyl group, an alkenyl group, an aryl group and an aralkyl group are preferred.
Each group may have a substituent. Examples of the alkyl group and the substituted alkyl group include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, cyclohexyl, chloromethyl, γ-chloropropyl, γ-methacryloyloxypropyl, γ-aminopropyl, γ
Glycidyloxypropyl, 3,4-epoxycyclohexylethyl, γ-mercaptopropyl and 3,
3,3-trifluoropropyl is included. Examples of the alkenyl group include vinyl and allyl. Examples of the aryl group and the substituted aryl group include phenyl and tolyl. One to four hydroxyl groups are bonded to the silicon atom. Two or more coupling agents may be used in combination.

Instead of the surface treatment of the particles, a coupling agent may be condensed to form fine particles having a hydrophilic portion and a hydrophobic portion on the surface. For example, fine particles may be formed by reacting a silane coupling agent such as an organochlorosilane or an organoalkoxysilane in an acidic or alkaline solution. In this method, the hydroxyl group generated by the partial hydrolysis of the silane coupling agent,
Functions as a hydrophilic group on the surface of the fine particles. Some of the hydrophobic groups are left on the surface of the fine particles. In order to form fine particles, the silane coupling agent preferably has at least three hydrolyzable functional groups such as alkoxy groups. That is, a crosslinked structure (three-dimensional structure) is required to form fine particles, and three or more hydrolyzable functional groups are required to form a crosslinked structure. However, even when a silane coupling agent having one or two hydrolyzable functional groups is used, fine particles can be formed by using the silane coupling agent having four hydrolyzable functional groups in combination. Can be. Examples of the silane coupling agent having four hydrolyzable functional groups include tetramethoxysilane, tetra-n-propoxysilane, and tetrachlorosilane. The fine particles added to the adhesive layer preferably have an average particle size of 0.005 to 5 μm, and more preferably have an average particle size of 0.01 to 2 μm.

The adhesive layer preferably contains a hydrophilic polymer as a binder. The hydrophilic polymer is a polymer compound having a hydrophilic group or a hydrophilic bond in a molecular structure. Examples of the hydrophilic group include a carboxyl, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfone, a sulfonamide group, a sulfonimide group, an amide group, and an alkylamino group. Examples of hydrophilic bonds include urethane bonds,
Includes ether and amide bonds. As the hydrophilic polymer, a natural, synthetic or semi-synthetic polymer compound can be used. For the hydrophilic polymer, see Japanese Unexamined Patent Publication No.
No. 2,496,667. The application amount of the adhesive layer
It is preferably 0.01 to 2.5 g / m ² ,
It is more preferably 0.02 to 2.0 g / m ² , and most preferably 0.05 to 1.5 g / m ² . When a hydrophilic polymer is used as a binder, the amount used is preferably 1 to 90% by weight, more preferably 3 to 50% by weight, and more preferably 5 to 30% by weight of the amount of the fine particles. Is most preferred.

[Arbitrary Layer] The layer optionally provided in the silver halide light-sensitive material is preferably a hydrophilic layer containing a hydrophilic polymer as a binder, similarly to the silver halide emulsion layer. It is more preferable that the layer be a binder. 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 photosensitive material and preventing adhesion when the silver halide photosensitive 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 was 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. The hydrophilic layer optionally provided may contain the above-mentioned microcapsules, antifoggant, silver development accelerator for promoting silver development, a stabilizer or a surfactant.

FIG. 1 is a schematic sectional view of a silver halide photosensitive material. As shown in FIG. 1, a silver halide gelatin emulsion layer (2) is provided on a hydrophobic support (1). The silver halide gelatin emulsion layer (2) contains silver halide grains (21) and gelatin (22).

[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.

FIG. 2 is a schematic sectional view of a silver halide photosensitive material in image exposure. As shown in FIG. 2, when the silver halide photosensitive material is irradiated with light (L), a latent image (21a) is formed on the silver halide grains in the exposed portions. In contrast, there is no change in the unexposed portions of the silver halide grains (21).

[Tanning Development Step] The tanning development of the silver halide photosensitive material is performed using a developer. The tanning developer is usually added to the developer. The developer is generally an alkaline solution. The pH of the developer 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 preferably 5 to 40 ° C., and 20 to 35 ° C.
It is more preferable that the temperature is ° C. The development time is preferably from 10 seconds to 10 minutes, and more preferably from 20 seconds to 3 minutes. 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.

A tanning developer is generally added to a developer. In addition to tanning developers, auxiliary developers can also be used. Examples of auxiliary developing agents include amidole, metol and aminophenol. Metol is particularly preferred. The auxiliary developing agent can be added to a tanning developer or a silver halide photosensitive material. The amount of the auxiliary developer is preferably 5 to 200 mol% of the amount of the tanning developer.

FIG. 3 is a schematic sectional view of a silver halide photosensitive material in tanning development. As shown in FIG.
When the silver halide photosensitive material after image exposure is immersed in a tanning developer (D), the silver halide particles in the exposed area are developed to form a silver image (21b). The oxidized product (quinone) of the tanning developer generated during the development crosslinks the gelatin (22a) in the exposed area. In contrast, there is no change in the unexposed portion of the gelatin (22).

[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 area to form a relief image of the cured gelatin. Can be. The temperature of hot water is
The temperature is preferably from 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.

FIG. 4 is a schematic cross-sectional view of a silver halide photosensitive material during elution. As shown in FIG. 4, when the silver halide photosensitive material after the tanning development is treated with the eluate (S), the unexposed portions of the silver halide gelatin emulsion layer are eluted. Silver halide gelatin emulsion layer in exposed area (2a)
Has a crosslinked gelatin (22a) and remains on the hydrophobic support (1) to form a relief image. In this way, a lithographic printing plate can be made.

[0178]

EXAMPLES Example 1 (Formation of Undercoat Layer) A polyethylene terephthalate film having a thickness of 175 μm was used as a support. Gelatin was coated on the support so that the dry film thickness was 0.2 μm, to form an undercoat layer (primer layer).

(Preparation of silver halide emulsion) In a reaction vessel containing gelatin, potassium bromide and water and heated to 55 ° C,
1. The following thioether compound was added to the amount of silver nitrate added.
It was added in an amount equivalent to 0 × 10 ⁻³ mol. PAg of reaction vessel
While maintaining the value at 9.2, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide containing rhodium ammonium chloride at a molar ratio of rhodium to the total amount of potassium iodide and silver nitrate of 4 × 10 ⁻⁸ mol were used. And pAg control by a double jet method to form silver iodobromide grains. Next, at 55 ° C. and pAg = 8.9, a silver nitrate aqueous solution and a molar ratio of iridium to silver of 1 × 10 5 were used.
A core / shell type silver iodobromide emulsion having the following composition was prepared by adding two steps of a potassium bromide solution to which hexachloroiridate (III) was added so as to be ^-7 mol by a double jet method.

[0180]

Embedded image

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

[0183]

Embedded image

(Formation of Silver Halide Gelatin Emulsion Layer) A coating solution having the following composition was prepared, coated on the undercoat layer, and dried to form a silver halide gelatin emulsion layer having a dry coating amount of 1.2 μm. Formed. Thus, a silver halide photosensitive material was produced.

{Coating Solution for Silver Halide Gelatin Emulsion Layer}銀 Silver halide emulsion 5 g 10% by weight aqueous solution of gelatin 25 g Water 20 g ─── ─────────────────────────────────

"Preparation of tanning developer" Tanning developers A and B having the following composition were prepared,
And used.

{Tanning Developer A Solution} ───────────────────────────── Tanning developer (1) 3 g Pyrogallol 1 g Metol 1 g Citric acid 1 g Water 500 g ───── ───────────────────────────────

{Tanning developer B solution}カ リ ウ ム Potassium carbonate 200g Potassium iodide 1g Water 500g ──────────── ────────────────────────

(Image formation) Light of 670 nm was separated by a sharp cut interference filter with a light emission time of 10 ^-4 seconds by a xenon flash using a silver halide photosensitive material, 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 the prepared tanning developer for 30 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 unexposed portions 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) showed good ink repellency without receiving ink. On the other hand, unexposed portions (exposed hydrophobic support) showed good ink receptivity. A lithographic printing plate is converted to an offset printing machine (RY
It was mounted on an OBI3200 CCD (Ryobi Co., Ltd.) and printed to check the printing durability. As a result, it was possible to print 10,000 or more sheets.

[Examples 2 to 8] Instead of the tanning developer (1) added to the tanning developer A, the tanning developers (2), (3), (4), (5), (6), (7)
Example 1 was repeated except that the same amounts of and (8) were used.
As in the above, a lithographic printing plate was made and evaluated. First result
It is shown in the table.

Comparative Example 1 Example 1 was repeated except that the tanning developer (1) was not added to the tanning developer A (only pyrogallol functions as the tanning developer).
In the same manner as in the above, a lithographic printing original plate was prepared and evaluated. The results are shown in Table 1.

[0192]

[Table 1] Table 1 ──────────────────────────────────── Tanning developer Tanning developer Ink Repellency ──────────────────────────────────── Example 1 Pyrogallol + (1) Good Example 2 Pyrogallol + (2) Good Example 3 Pyrogallol + (3) Good Example 4 Pyrogallol + (4) Good Example 5 Pyrogallol + (5) Good Example 6 Pyrogallol + (6) Good Example 7 Pyrogallol + (7) Good Example 8 Pyrogallol + (8) Good Comparative Example 1 Only pyrogallol was insufficient. ──

[Example 9] "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} .

(Formation of Hydrophobic Undercoat Layer) A coating solution having the following composition was prepared and applied on an aluminum support.
Dried. Next, P using a metal halide lamp as a light source
Exposure was performed with ultraviolet light using an S-plate exposure machine to polymerize the coating solution components. Thus, a hydrophobic undercoat layer having a dry film thickness of 1.0 μm was formed.

{Coating Solution for Hydrophobic Undercoat Layer} ─────────────────────────────── pentaerythritol tetraacrylate 2.5 g allyl methacrylate / methacrylic acid copolymer (copolymer molar ratio = 80/20) 20 wt% propylene glycol monomethyl ether solution 37.5 g 20 wt% propylene glycol monomethyl ether solution of polyhydroxystyrene 5.6 g Photopolymerization initiator 0.9 g methyl ethyl ketone 74.0 g ───────────────────────────────

[0196]

Embedded image

(Formation of Silver Halide Gelatin Emulsion Layer) The coating solution for the silver halide gelatin emulsion layer used in Example 1 was coated on a hydrophobic undercoat layer and dried to obtain a dry coating amount of 1.2 μm. Was formed. Thus, a silver halide photosensitive material was produced.

(Image formation) Light of 670 nm was separated by a sharp cut interference filter with a light emission time of 10 ^-4 seconds by a xenon flash using a silver halide photosensitive material, 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 the tanning developer prepared in Example 1 for 30 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 unexposed portions 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)
Showed good ink repellency without accepting ink. On the other hand, unexposed portions (exposed hydrophobic undercoat layer) exhibited good ink receptivity. Lithographic printing plate is offset printed by RYOBI3200 CCD (Ryobi Co., Ltd.)
And printing was performed to check the printing durability. As a result, printing of 10,000 sheets or more was possible.

Comparative Example 2 Example 9 was repeated except that the tanning developer (1) was not added to the tanning developer A (only pyrogallol functions as the tanning developer).
In the same manner as in the above, a lithographic printing original plate was prepared and evaluated. As a result, background dirt occurs in the relief image portion serving as a non-image portion,
Good prints were not obtained.

[Example 10] (Formation of silver halide gelatin emulsion layer) A coating solution having the following composition was prepared, coated on the hydrophobic undercoat layer formed in Example 9, dried, and dried and coated. A silver halide gelatin emulsion layer having an amount of 1.2 μm was formed. Thus, a silver halide photosensitive material was produced.

{Coating Solution for Silver Halide Gelatin Emulsion Layer}銀 Silver halide emulsion 5 g Tanning developer (1) 1.5 g Gelatin 10 25% by weight aqueous solution 20 g water 20 g

"Preparation of tanning developer" A tanning developer A and a solution B having the following composition were prepared,
And used.

{Tanning developer A solution} ───────────────────────────── Pyrogallol 3 g Metol 1 g Citric acid 1 g Water 500 g ──────────── ────────────────────────

{Tanning developer B solution}カ リ ウ ム Potassium carbonate 200g Potassium iodide 1g Water 500g ──────────── ────────────────────────

(Image formation) The 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 seconds 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 the prepared tanning developer for 30 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 unexposed portions 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) showed good ink repellency without receiving ink. On the other hand, unexposed portions (exposed hydrophobic support) showed good ink receptivity. A lithographic printing plate is converted to an offset printing machine (RY
The printer was mounted on an OBI3200CCD, manufactured by Ryobi Co., Ltd.) and printing was performed to check the printing durability. As a result, printing of 10,000 or more sheets was possible.

Comparative Example 3 A tanning developer (1) was not added to the silver halide gelatin emulsion layer coating solution (only pyrogallol contained in the tanning developer A solution functions as a tanning developer). As in Example 10, a lithographic printing original plate was prepared and evaluated. As a result, background stains occurred on the relief image portions serving as non-image portions, and good printed matters could not be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view of a silver halide photosensitive material.

FIG. 2 is a schematic cross-sectional view of a silver halide photosensitive material during image exposure.

FIG. 3 is a schematic cross-sectional view of a silver halide photosensitive material in tanning development.

FIG. 4 is a schematic cross-sectional view of a silver halide photosensitive material during elution.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Hydrophobic support 2 Silver halide emulsion layer 2a Silver halide emulsion layer of exposed part 21 Silver halide grain 21a Latent image of silver halide grain 21b Silver image 22 Gelatin 22a Crosslinked gelatin D Tanning developer L Light S Elution liquid

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H016 AA01 AD04 AE01 AG01 2H023 CD06 2H096 AA07 BA17 EA02 EA04 GA01 GA08 GA15 HA02 HA11

Claims (8)

[Claims] 1. A tanning developer comprising a compound having a benzene ring which forms a quinoid structure by oxidation, and further having a substituent containing carboxyl, sulfo, phosphono or a salt thereof bonded to the benzene ring. . 2. The tanning developer according to claim 1, wherein the quinoid structure formed is of a quinone type, a quinone imine type or a quinone diimine type. 3. The tanning developer according to claim 1, wherein carboxyl, sulfo, phosphono or a salt thereof and a benzene ring which forms a quinoid structure by oxidation are directly connected by a single bond. 4. A carboxyl, sulfo, phosphono or any salt thereof and a benzene ring forming a quinoid structure by oxidation are represented by —CO—, —O—, —NH—, and —S
The compound is bonded by a divalent linking group selected from O _2- , alkylene, phenylene and a combination thereof.
2. The tanning developer according to item 1. 5. A silver halide light-sensitive material having a support and a silver halide gelatin emulsion layer, wherein the silver halide gelatin emulsion layer or an optional hydrophilic layer is provided.
Has a benzene ring that forms a quinoid structure by oxidation,
A silver halide photosensitive material further comprising a tanning developer comprising a compound in which a substituent containing carboxyl, sulfo, phosphono or a salt thereof is bonded to the benzene ring. 6. An alkaline aqueous solution of a compound having a benzene ring forming a quinoid structure by oxidation and further having a substituent containing carboxyl, sulfo, phosphono or a salt thereof bonded to the benzene ring. Tanning developer. 7. A step of imagewise exposing a silver halide photosensitive material having a silver halide gelatin emulsion layer on a hydrophobic support, comprising a benzene ring forming a quinoid structure by oxidation, and further comprising a carboxyl, sulfo, phosphono or A step of tanning the silver halide light-sensitive material by using a tanning developer comprising a compound having a substituent containing a salt bound to any of the benzene rings to harden the gelatin in the exposed area, and A plate making method for a lithographic printing plate, wherein a step of forming a relief image of a hardened gelatin by eluting a part of the unhardened gelatin is performed in this order to make a lithographic printing plate. 8. A lithographic printing plate having a relief image of hardened gelatin on a hydrophobic support, wherein the hardened gelatin comprises:
Has a benzene ring that forms a quinoid structure by oxidation,
Furthermore, a substituent containing carboxyl, sulfo, phosphono or a salt thereof is formed by a hardening reaction of gelatin by an oxidized form of a tanning developer comprising a compound bonded to the benzene ring. Lithographic printing plate.