JPH06208227A - Plano graphic printing material - Google Patents

Abstract

PURPOSE:To provide the printing material which enables coping with a high illuminant light source such as He-Ne and a semiconductor laser and which has high sensitivity and which is high in resolution and excellent in printing durability and ink adhesion by forming a silver halide emulsion layer with an internal latent image type emulsion layer and incorporating the sensitizing pigment expressed by a specified formula. CONSTITUTION:The material is incorporated with a halation preventive layer on a supporting body and has one layer of an undercoat layer, the silver halide emulsion layer and a physical developing nucleus layer, and employs a silver salt diffusion-transfer process. The silver halide emulsion layer is the internal latent image type emulsion layer, and contains at least one kind of sensitizing pigment expressed by formula I and II. In formula I and II, Z, Z1 and Z11, Z12 is the atom group necessary to form five or six member nitrogen containing heterocyclic nucleus respectively, R1, R2 and R11, R12 is alkyl, aryl, etc., Q1 and Q2 is the nonmetal group necessary to form 4-thiazolidinone, etc., respectively, L, L1-L2 and L11-L15 is methine group, etc., respectively, X1 is an anion, m1 is 0 or 1, (p) and (q) is 0-2 respectively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver salt lithographic printing material, and more particularly to a lithographic printing material for obtaining a negative transfer silver image. More specifically, there are those relating to a silver salt lithographic printing material for silver salt diffusion transfer which has excellent photographic characteristics, less generation of background stains, and improved ink inking property and printing durability. The present invention relates to a lithographic printing material for laser exposure.

[0002]

2. Description of the Related Art Conventionally, many lithographic printing materials utilizing a silver salt transfer method have been known. As a typical printing material, a printing material in which a photographic element having photosensitivity and a physical development nucleus layer which is a printing image element are integrally configured is described in, for example, JP-B-46-42453 and 48-48. It is described in gazettes such as 30562. However, these use an ordinary negative emulsion, and the transferred silver image becomes a positive image. On the other hand, a method of obtaining a negative image as a transferred silver image is disclosed in Japanese Patent Publication No. 61-
13587, Japanese Patent Publication 57-6108, Japanese Patent Publication 56-
26019, JP 61-13587 A, JP 57
-6108, JP-B-56-26019, JP-A-61
No. 173247 and the like. However, with this method, the sensitivity is not sufficient, the transfer silver amount is insufficient, and the performance as a printing plate such as ink receptivity, printing durability and background stain is not sufficient, It hasn't been realized.

As a method of obtaining a negative transfer silver image, there is a method of using a direct reversal emulsion as the emulsion. The direct reversal emulsion includes a precoat type emulsion and an internal latent image type emulsion. Among them, the pre-coating type emulsion has a low sensitivity, is difficult to be made red and infrared sensitive, and when a developing agent is incorporated, a reversal image cannot be obtained and the developing agent is substantially contained. There are some drawbacks such as not being able to be processed by an activator. On the other hand, the internal latent image type emulsion is described in US Pat.
No. 0, No. 2466957, No. 2497875, No. 2
No. 588898, No. 3317322, No. 376126
No. 6, No. 3761276, No. 3796577, No. 4
No. 309499 is described in each specification. This product has high sensitivity, but has the drawback that it is difficult to reverse with a developer containing a silver halide solvent, and is not intended for lithographic printing materials.

On the other hand, in the negative type diffusion transfer method using an internal latent image type emulsion, since the processing is carried out in the presence of a silver halide solvent, rapid fogging development is required.
If the silver halide is dissolved before the fogging development is completed, a good reversal image cannot be obtained and a negative transferred silver image cannot be obtained. Therefore, it is important to devise a time difference between the fogging development and the dissolution of silver halide. Therefore, a fogging agent having strong nucleation activity is required, and a good nucleation accelerator that promotes nucleation is also desired. A method for performing such rapid development is particularly desired.

Further, in EP481562A1, in order to prevent deterioration of reversal developability due to a silver halide solvent in a developing solution, a surface developing solution containing no silver halide solvent and a developing solution containing a silver halide solvent are described. A method is described in which two types of developing solutions are used, development is first performed with the former surface developing solution, and then diffusion transfer is performed with a developing solution containing the latter solvent. Therefore, development of a lithographic printing material applicable to this method is also desired.

[0006] In recent years, with the development of computer technology, a technique of direct printing has been attracting attention, in which a final image is directly exposed by a laser beam or a light emitting diode light source through an image setter or the like. In the case of scanning exposure with a laser or the like, as a lithographic printing material, a negative transfer silver image needs to expose only the image portion such as characters, halftone dots, and lines, and the exposed portion is small, so that there is no background stain. There are few concerns. Further, normally, the negative output can be considered to have an advantage that it is easier to correspond to an output machine such as an image setter which is a main force. However, a negative type lithographic printing material has not been put to practical use, and as described above, a material satisfying the sensitivity and printing characteristics has not been obtained so far.

The laser has a ruby as an oscillation medium.
Helium-neon, argon, krypton, helium-
Some use cadmium, carbon dioxide, and semiconductors. Among these, helium-neon and semiconductors are used because they are inexpensive and can provide stable output. Such a laser usually has an oscillation wavelength of 630 nm or more, and when a negative type direct printing plate is produced using an internal latent image type emulsion, printing characteristics such as sensitivity, resolution, ink receptivity and printing durability are required. A satisfying method was highly desired.

In any case, it is desired to develop a lithographic printing material which has a high sensitivity, is stable in processing, can obtain a negative transfer silver image having excellent printing characteristics, and can be processed rapidly. In particular, it is considered that the reason why a method for obtaining a negative image has not been practically used in the past is that a good inverted image cannot be obtained.
It is necessary to consider how to deal with the above lasers.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a lithographic printing material for obtaining a negative transfer silver image by utilizing a silver salt diffusion transfer method, and in particular, He-Ne, a semiconductor laser, etc. It is possible to deal with the high illuminance light source, high sensitivity, high resolution, and excellent printing durability and ink receptivity. Furthermore, it is to be able to deal with various processing systems.

[0010]

The above object is achieved by the constitution (1) below. (1) A lithographic printing material utilizing a silver salt diffusion transfer method, which comprises, on a support, at least one undercoat layer containing an antihalation layer, a silver halide emulsion layer and a physical development nucleus layer, wherein The silver halide emulsion layer is an internal latent image type emulsion layer and contains at least one of the sensitizing dyes represented by the following chemical formulas 3 and 4 to obtain a negative transfer silver image lithographic printing material.

[0011]

[Chemical 3]

[0012]

[Chemical 4]

[In Chemical Formula 3, Z and Z ₁ each represent an atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₁ and R ₂ each represent an alkyl group or an aryl group. Q ₁ and Q ₂ together represent the non-metallic atomic group necessary to complete the 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone nucleus.
L, L ₁ and L ₂ each represent a methine group. n ₁ and n ₂ each represent 0 or 1. X ₁ represents an anion. m ₁ represents 0 or 1, and when forming an intramolecular salt, m ₁ is 0. In Chemical formula 4, R ₁₁ and R ₁₂
May be the same or different, and each is an alkyl group,
It represents an aralkyl group, an alkenyl group or an aryl group, and R ₁₃ represents a heterocyclic group. Z ₁₁ and Z ₁₂ may be the same or different and each represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. X ₁₁ is a counter ion, L _{11 to} L ₁₅ each represent a methine group, and p and q each represent 0, 1 or 2. ]

[0014]

Specific Structure The specific structure of the present invention will be described in detail below.

In the lithographic printing material of the present invention, the silver halide emulsion layer is an internal latent image type emulsion layer and at least one of the sensitizing dyes represented by Chemical formulas 3 and 4 is contained in the silver halide emulsion layer. It is included.

The sensitizing dyes of Chemical formulas 3 and 4 are 600 to 760.
It has maximum sensitization in the wavelength range of nm, and is excellent in sensitization efficiency, residual color after processing, stability and the like. Therefore, the above silver halide emulsion is sensitized so as to have the maximum sensitization in the wavelength range of 610 to 750 nm. Therefore, in particular, He-N
e, it is possible to deal with light sources for high illuminance such as semiconductor lasers, and direct printing plates can be made with these light sources.

The chemical formulas 3 and 4 will be described.

In Chemical Formula 3, Z and Z ₁ each represent an atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₁ and R ₂ each represent an alkyl group, a substituted alkyl group or an aryl group. Q ₁ and Q ₂ together represent the non-metallic atomic group necessary to complete the 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone nucleus. L, L ₁ and L ₂ each represent a methine group or a substituted methine group. n ₁ and n ₂ each represent 0 or 1. X ₁ represents an anion. m ₁ represents 0 or 1, and m ₁ = 0 when forming an intramolecular salt.

In the sensitizing dye of Chemical formula 3 in the present invention,
As the nitrogen-containing heterocyclic nucleus completed by Z or Z ₁ , the following can be used.

Thiazole nucleus {eg thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-di-phenylthiazole etc.), benzothiazole nucleus {eg benzothiazole,
5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 6-
Iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-carboxybenzothiazole, 5
-Fluorobenzothiazole, 5-dimethylaminobenzothiazole, 5-acetylaminobenzothiazole,
5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5-ethoxy-6-methylbenzothiazole, tetrahydrobenzothiazole, etc.}, naphthothiazole nucleus {for example, naphtho [2 , 1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3]
-D] thiazole, 5-methoxynaphtho [1,2-d]
Thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole,
5-methoxynaphtho [2,3-d] thiazole, etc.},
Selenazole nucleus {eg 4-methylselenazole, 4-
Phenylselenazole, etc., benzoselenazole nucleus {eg benzoselenazole, 5-chlorobenzoselenazole, 5-phenylbenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole , Etc., naphthoselenazole nucleus {eg naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole etc.}, oxazole nucleus {eg oxazole, 4-methyloxazole, 5-methyloxazole, 4,5 -Dimethyloxazole, etc.}, benzoxazole nucleus {eg, benzoxazole, 5-fluorobenzoxazole, 5-
Chlorobenzoxazole, 5-bromobenzoxazole, 5-trifluoromethylbenzoxazole, 5
-Methylbenzoxazole, 5-methyl-6-phenylbenzoxazole, 5,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5,6-dimethoxybenzoxazole, 5-phenylbenzoxazole, 5-carboxybenzoxazole, 5 -Methoxycarbonylbenzoxazole, 5-acetylbenzoxazole, 5-hydroxybenzoxazole, etc.}, naphthoxazole nucleus {eg naphtho [2,1
-D] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, etc.}, 2-quinoline nucleus, imidazole nucleus, benzimidazole nucleus,
A 3,3′-dialkylindolenine nucleus, a 2-pyridine nucleus, a thiazoline nucleus, or the like can be used. Particularly preferably, at least one of Z and Z ₁ is a thiazole nucleus, a thiazoline nucleus, an oxazole nucleus or a benzoxazole nucleus.

As the alkyl group represented by R ₁ or R ₂ in Chemical formula 3, an alkyl group having 5 or less carbon atoms (eg, methyl group, ethyl group, n-propyl group, n-butyl group, etc.), substituted alkyl As the group, a substituted alkyl group having an alkyl radical having 5 or less carbon atoms (for example, a hydroxyalkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, etc.),
Carboxyalkyl group (eg, carboxymethyl group, 2
-Carboxyethyl group, 3-carboxypropyl group, 4
-Carboxybutyl group, 2- (2-carboxyethoxy) ethyl group, etc.), sulfoalkyl group (for example, 2-
Sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-hydroxy-3-sulfopropyl group, 2- (3-sulfopropoxy) ethyl group, 2-acetoxy-3-sulfopropyl group , 3-methoxy-2- (3-sulfopropoxy) propyl group, 2
-[(3-sulfopropoxy) ethoxy] ethyl group, 2
-Hydroxy-3- (3'-sulfopropoxy) propyl group, etc.), aralkyl group (alkyl radical preferably has 1 to 5 carbon atoms, aryl group is preferably phenyl group, for example, benzyl group, phenethyl group, phenylpropoxy group) Group, phenylbutyl group, p-tolylpropyl group, p-methoxyphenethyl group, p-chlorophenethyl group, p-carboxybenzyl group, p-sulfophenethyl group, p-sulfobenzyl group, etc.), aryloxyalkyl group ( The alkyl radical preferably has 1 to 5 carbon atoms,
The aryl group of the aryloxy group is preferably a phenyl group, for example, a phenoxyethyl group, a phenoxypropyl group, a phenoxybutyl group, a p-methylphenoxyethyl group, a p-methoxyphenoxypropyl group, etc.), a vinylmethyl group, etc.}, The aryl group is a phenyl group or the like. L, L ₁ and L ₂ represent a methine group or a substituted methine group = C (R ′)-. R'is an alkyl group (for example, a methyl group, an ethyl group, etc.), a substituted alkyl group (for example, an alkoxyalkyl group (for example, 2-ethoxyethyl group, etc.), a carboxyalkyl group (for example, 2-carboxyethyl group, etc.), an alkoxycarbonylalkyl group. (Eg 2-methoxycarbonylethyl group), aralkyl group (eg benzyl group, phenethyl group etc.), etc., aryl group (eg phenyl group, p-methoxyphenyl group, p-chlorophenyl group, o-carboxyphenyl group) Etc.) etc. Also, L and R ₁ , L ₂ and R ₂
May combine with each other with methines to form a nitrogen-containing heterocycle. Examples of the substituent attached to the nitrogen atom at the 3-position of the thiazolinone nucleus or imidazolinone nucleus formed by Q ₁ and Q ₂ include, for example, an alkyl group (preferably having a carbon number of 1 to 8, for example, a methyl group, an ethyl group, Propyl group), allyl group, aralkyl group (alkyl group radical preferably has 1 to 5 carbon atoms, for example, benzyl group, p-carboxyphenylmethyl group, etc.), aryl group (total carbon number of 6 to 9 is preferable, For example, phenyl group, p-carboxyphenyl group, etc., hydroxyalkyl group (alkyl radical preferably has 1 to 5 carbon atoms, for example, 2-
Hydroxyethyl group, etc.), carboxyalkyl group (alkyl radical preferably has 1 to 5 carbon atoms, eg carboxymethyl group), alkoxycarbonylalkyl group (alkoxy moiety alkyl radical has 1 to 5 carbon atoms).
3 is preferable, and the carbon number of the alkyl portion is preferably 1 to 5, and examples thereof include a methoxycarbonylethyl group and the like.

Examples of the anion represented by X ₁ are halogen ion (iodine ion, bromine ion, chlorine ion, etc.), perchlorate ion, thiocyanate ion, benzenesulfonate ion, p-toluenesulfonate ion, methyl. Examples thereof include sulfate ion and ethyl sulfate ion.

Among the sensitizing dyes represented by Chemical formula 3, the dye represented by Chemical formula 5 is particularly preferable.

[0024]

[Chemical 5]

In formula 5, Z ₂ and Z _{3, which} may be the same or different, each represents a nonmetallic atomic group necessary for completing a thiazole nucleus, a benzothiazole nucleus or a benzoxazole nucleus. R ₀ is an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), allyl group or aralkyl group (alkyl radical preferably has 1 to 5 carbon atoms, for example, benzyl group, p-carboxyphenyl). Represents a methyl group). R ₁ , R ₂ , L, L
₁ , L ₂ , X ₁ and m ₁ have the same meanings as in Chemical formula 3.

Specific examples of the sensitizing dye used in the present invention are shown below. However, the sensitizing dye used in the present invention is not limited to this.

[0027]

[Chemical 6]

[0028]

[Chemical 7]

[0029]

[Chemical 8]

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

[0036]

[Chemical 15]

[0037]

[Chemical 16]

[0038]

[Chemical 17]

[0039]

[Chemical 18]

The sensitizing dye represented by the above chemical formula 3 is a known compound and is described in "Cyanine dyes" by FM Hamer.
and Related Compounds '' Lnterscience Publisbers (196
It can be easily synthesized by referring to 4).

In the chemical formula 4, R ₁₁ and R ₁₂ may be the same or different and each represents an alkyl group, an aralkyl group, an alkenyl group or an aryl group, and R ₁₃ represents a heterocyclic group. Z
₁₁ , ₁₂ may be the same or different and each represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. X ₁₁
Is a counter ion, L _{11 to} L ₁₅ each represent a methine group, and p and q represent 0, 1, and 2, respectively.

In the chemical formula 4, specifically, R ₁₁ and R ₁₂ are each an alkyl group (eg, lower alkyl group such as methyl, ethyl, propyl, butyl, etc., hydroxyalkyl group such as β-hydroxyethyl, γ-hydroxypropyl, etc.). , Β-methoxyethyl, γ-methoxypropyl and other alkoxyalkyl groups, β-acetoxyethyl, γ-acetoxypropyl, β-benzoyloxyethyl and other acyloxyalkyl groups, carboxymethyl, β-carboxyethyl and other carboxyalkyl groups, Alkoxycarbonylalkyl groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl, β-ethoxycarbonylethyl,
β-sulfoethyl, γ-sulfopropyl, δ-sulfobutyl and other sulfoalkyl groups), aralkyl groups (eg, benzyl, phenethyl, sulfobenzyl, etc.), alkenyl groups (eg, allyl), aryl groups (eg,
Phenyl, tolyl, methoxyphenyl, chlorophenyl, carboxyphenyl, sulfophenyl, naphthyl, etc., and R ₁₃ is a heterocyclic group (eg, 3-pyridyl, 4-tetrahydropyranyl, 3-tetrahydrofuryl, 4-tetrahydrothiopyranyl). Etc.).

Z ₁₁ and Z ₁₂ each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. Z ₁₁ , Z ₁₂
Specific examples of, for example, oxazoline ring, oxazole ring, benzoxazole ring, benzisoxazole ring, naphthoxazole ring, thiazoline ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazoline ring, selenazole ring, naphthoselenazole ring,
There are tetrazole ring, benzotetrazole ring, naphthotetrazole ring, pyridine ring, quinoline ring, benzoquinoline ring, indolenine ring, benzoindolenine ring, benzimidazole ring, pyrroline ring, etc., and these heterocyclic rings and condensed benzene ring and naphthalene ring. The ring includes an alkyl group, an aryl group, an alkoxy group (eg, methoxy, ethoxy, propoxy, etc.), a hydroxy group, a carboxy group, an alkoxycarbonyl group (eg, methoxycarbonyl,
It may have a substituent such as ethoxycarbonyl) and a halogen atom (eg, fluorine, chlorine, bromine, iodine). X ₁₁ represents a counter ion, and R ₁₁ , R ₁₂ and Z ₁₁ , Z
_{If 12} does not have an acid substituent, an acid anion (for example,
Alkyl sulfate ion such as methylsulfate and ethylsulfate, thiocyanate ion, toluenesulfonate ion (T _S O
^- ), Halogen such as chlorine, bromine and iodine, and perchlorate ion), and when one acid substituent is present, X ₁₁ does not exist because it forms an intramolecular salt and two or more exist. When it is present, it represents a cation such as an alkali metal atom (eg sodium, potassium etc.), an organic ammonium (eg triethylammonium, tributylammonium, pyridinium etc.). L _{11 to} L ₁₅ are each a methine group (this methine group may be substituted with an alkoxy group in addition to the above-mentioned alkyl group, aryl group. Further, they are linked to each other to form a 5- or 6-membered ring. , And p and q represent 0, 1, and 2.

Next, typical examples of the compounds represented by formula 4 of the present invention will be shown, but the scope of the present invention is not limited to these.

[0045]

[Chemical 19]

[0046]

[Chemical 20]

[0047]

[Chemical 21]

[0048]

[Chemical formula 22]

[0049]

[Chemical formula 23]

[0050]

[Chemical formula 24]

[0051]

[Chemical 25]

[0052]

[Chemical formula 26]

The above-mentioned sensitizing dye of Chemical formula 4 is a known compound, and can be synthesized in the same manner as the sensitizing dye of Chemical formula 3.

The sensitizing dye used in the present invention can be directly dispersed in the emulsion. In addition, these are first a suitable solvent,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. Ultrasonic waves can also be used for dissolution. Further, as a method for adding a sensitizing dye, US-346 is used.
As disclosed in Japanese Patent Application No. 9987, a method of dissolving a dye in a volatile organic solvent, dispersing this solution in a hydrophilic colloid, and adding this dispersion to an emulsion, JP-B-46-
No. 24185, etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to an emulsion; as described in US Pat. No. 3,822,135; A method in which a dye is dissolved in an agent and this solution is added to the emulsion; in addition, the method described in U.S. Pat. Nos. 2,912,343, 3,342,605, 2,996,287 and 3,429,835 can be added to the emulsion. Is also used. Further, the above sensitizing dye may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but it may be dispersed at any stage of preparation of the silver halide emulsion. . However, it is generally preferable to carry out the dispersion after the completion of the chemical ripening.

The addition amount thereof is in the range of 1 × 10 ^-5 to 1 × 10 ^-2 mol per mol of silver halide. The optimum addition amount is the conditions of the silver halide emulsion, for example, the halogen composition,
It varies depending on the average grain size of silver halide grains, crystal habit, and the like.

In the present invention, the compound represented by the following formula (1) can be used in combination with the sensitizing dyes of Chemical formulas 3 and 4 in the silver halide emulsion layer. By using this compound, the supersensitization effect can be enhanced, the stability of the lithographic printing material can be improved, and the resolution and printing durability of the lithographic printing material can be improved.

Formula (1) D ₁ -A ₀ -D ₂

In the formula (1), D ₁ and D ₂ each represent a condensed polycyclic aromatic heterocyclic residue or an aromatic heterocyclic-substituted amino group. These may contain SO ₃ M groups. M
Represents a hydrogen atom or a cation. -A ₀ - represents a divalent aromatic residue, which may contain a -SO ₃ M group. When D ₁ and D ₂ do not include a —SO ₃ M group, —A ₀ — includes a SO ₃ M group.

Examples of the condensed polycyclic aromatic heterocyclic residue represented by D ₁ or D ₂ in the formula (1) include 2-benzotriazole group and 2-naphthotriazolyl group. In addition, as an example of an aromatic heterocycle-substituted amino group, 1,
3,5-triazin-2-ylamino group, 1,3-diazin-2-ylamino group, and the like. These D ₁ and D ₂ may contain a —SO ₃ M group. Examples of the cation represented by M include sodium and potassium. -A ₀ - represents a divalent aromatic residue, these -
It may contain a SO ₃ M group (M has the same meaning as defined above). The D _1, D -SO ₃ M ₂ (M is the same meaning as defined above) -A ₀ when no contain groups - shall contain the -SO ₃ M groups. −A ₀ − is the following Chemical formula 27, Chemical formula 28
The compounds selected from -A _1-of Chemical formula 29 or -A _2-of Chemical formula 29 are useful.

[0060]

[Chemical 27]

[0061]

[Chemical 28]

[0062]

[Chemical 29]

However, in the case of -A ₂ -of Chemical formula 29, D ₁ ,
At least one of D ₂ has a substituent containing SO ₃ M.

Among the compounds represented by the formula (1), particularly useful are the compounds represented by the following chemical formulas 30 and 31.

[0065]

[Chemical 30]

[0066]

[Chemical 31]

First, the chemical formula 30 will be described.

In Chemical formula 30, -A ₀ -has the same meaning as in formula (1). -Y ₁ is _{= CH -, = CB 8 -} , = N
Represents-. Here, B ₈ represents lower alkyl, halogen or the like. B ₄ , B ₅ , B ₆ , and B ₇ are hydrogen atoms,
Hydroxy group, alkoxy group (eg, methoxy group, ethoxy group), lower alkyl group (eg, methyl group, ethyl group, etc.), aryloxy group (eg, phenoxy group, o-
Tolyloxy group, p-sulfophenoxy group), halogen atom (eg chlorine atom, bromine atom), heterocyclic nucleus (eg morpholinyl group, piperidyl group), alkylthio group (eg methylthio group, ethylthio group), heterocyclylthio group ( For example, benzothiazolylthio group), arylthio group (eg phenylthio group, tolylthio group), amino group, alkylamino group or substituted alkylamino group (eg methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group) , Dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di- (β-hydroxyethyl) amino group, β-sulfoethylamino group), arylamino group or substituted arylamino group (for example, anilino group, o- Sulfoanilino group, m- Ruphoanilino group, p-sulfoanilino group, o-anisylamino group, m-anisylamino group, p-anisylamino group, o-toluidino group, m-toluidino group, p-toluidino group, o-carboxyanilino group, m-carboxyanilino group. Group, p-carboxyanilino group, hydroxyanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group),
It represents a heterocyclylamino group (eg, 2-benzothiazolylamino group, 2-pyridyl-amino group), an aryl group (eg, phenyl group), or a mercapto group. B ₄ , B
₅ , B ₆ and B ₇ may be the same as or different from each other. -A ₀ - when has no sulfo group, B _4,
At least one of B ₅ , B ₆ and B ₇ needs to have at least one sulfo group (which may be a free acid group or may form a salt).

In the compounds represented by Chemical formula 30, Y ₁ is
The effect of the present invention is particularly remarkable when the compound is CH =.

Next, referring to Chemical Formula 31, A ₀ has the same meaning as in the case of the formula (1). W ₁ and W ₂ each represent a carbon atom group forming a benzene ring or a naphthalene ring. The benzene ring or naphthalene ring may be substituted with a sulfo group, and at least one of the substituents contains a sulfo group.

Typical examples of the compound represented by the formula (1) used in the present invention are shown below. However, the present invention is not limited to this.

[0072]

[Chemical 32]

[0073]

[Chemical 33]

[0074]

[Chemical 34]

[0075]

[Chemical 35]

[0076]

[Chemical 36]

[0077]

[Chemical 37]

[0078]

[Chemical 38]

[0079]

[Chemical Formula 39]

[0080]

[Chemical 40]

[0081]

[Chemical 41]

The compound represented by the formula (1) is described in JP-B-45.
Compounds already known in JP-A-32741 and the like, and compounds not described therein can be easily synthesized by referring to the synthesis examples described in JP-B-45-32741.

The compound represented by the formula (1) is used in an amount of 1 × 10 ^-5 to 1 × 10 ^-2 mol per mol of silver halide in the emulsion.

The ratio (molar ratio) of the sensitizing dyes of Chemical Formulas 3 and 4 to the compound represented by the formula (1) is [sensitizing dyes of Chemical Formulas 3 and 4 / the compound represented by the formula (1)]. ] = 1/100 ~
It is preferable that the range is 100/1.

The compound represented by the formula (1) can be directly dispersed in the emulsion, and a suitable solvent (water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or these solvents can be used. It is also possible to dissolve in a plurality of mixed solvents and add it to the emulsion.

Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition. Moreover, you may use only 1 type or may use 2 or more types together.

The compound represented by the formula (1) may be added to the emulsion before or after the addition of the chemical sensitizing dyes of chemical formulas 3 and 4 described above. Further, the compound of the formula (1) and the sensitizing dye may be separately dissolved, and these may be separately added to the emulsion at the same time, or may be mixed and then added to the emulsion.

The compound of Chemical formula 23 and the compound of Chemical formula 27 may be used in combination.

In the present invention, the nucleating agent used in combination with the internal latent image type emulsion is preferably at least one selected from the chemical formulas 42 and 43.

By using such a nucleating agent,
The time difference between the fogging development and the dissolution of silver halide can be adjusted to an appropriate level to obtain a good reversal image.

The "nucleating agent" in the present invention is a substance which acts upon surface development processing of an internal latent image type halogenated emulsion which has not been fogged in advance to directly form a positive image.

[0092]

[Chemical 42]

[0093]

[Chemical 43]

In the chemical formula 42, Z ¹ represents a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle. An aromatic ring or a heterocycle may be further condensed with this heterocycle. R ¹ is an aliphatic group, and X is a group represented by Chemical formula 44 or Chemical formula 45. Q represents a 4- to 12-membered non-aromatic hydrocarbon ring or a non-metal atom group necessary for forming a non-aromatic heterocycle. However, at least one of the substituents of R ¹ and Z ^{1 and} the substituent of Q includes an alkynyl group. Further, at least one of R ¹ , Z ¹ and Q may have an adsorption promoting group for silver halide. Y is a counter ion for charge balance, and n is the number required for charge balance.

[0095]

[Chemical 44]

[0096]

[Chemical formula 45]

In Chemical Formula 43, R ²¹ represents an aliphatic group, an aromatic group, or a heterocyclic group. R ²² represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group. G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an iminomethylene group represented by Chemical formula 46, and R ²³ and R
²⁴ is both a hydrogen atom, or one is a hydrogen atom and the other is any one of an alkylsulfonyl group, an arylsulfonyl group and an acyl group. However, G, R ²³ , R
The hydrazone structure of Formula 47 may be formed to include ²⁴ and the hydrazine nitrogen. Further, the above-mentioned groups may be substituted with a substituent, if possible.

[0098]

[Chemical formula 46]

[0099]

[Chemical 47]

The nucleating agent represented by the chemical formula 42 will be described in more detail. Examples of the heterocyclic ring completed by Z ¹ include quinolinium, benzimidazolium, pyridium, thiazolium, selenazolium, imidazolium, tetrazolium, indolenium, pyrrolinium, Examples include phenanthridinium, isoquinolinium, or naphthopyridium nuclei. Z ¹ may be substituted with a substituent, and as the substituent, an alkyl group, an alkenyl group,
Aralkyl group, aryl group, alkynyl group, hydroxy group, alkoxy group, aryloxy group, halogen atom,
Amino group, alkylthio group, arylthio group, acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, Examples thereof include a carbonic acid ester group, a hydrazine group, a hydrazone group, and an imino group. As the substituent of Z ¹ , for example, at least one is selected from the above-mentioned substituents, but when there are two or more, they may be the same or different. Further, the above substituents may be further substituted with these substituents.

[0102] As further substituents of Z ^1, may have a heterocyclic quaternary ammonium group completed by Z ¹ via a suitable linking group L ¹ (described later). In this case, a so-called dimer structure is adopted.

The heterocyclic nucleus completed with Z ¹ is preferably a quinolinium, benzimidazolium, pyridinium, acridinium, phenanthridinium, naphthopyridinium or isoquinolinium nucleus. More preferably, quinolinium, naphthopyridinium,
It is a benzimidazolium nucleus, most preferably a quinolinium nucleus.

The aliphatic group for R ¹ preferably has 1 to 10 carbon atoms.
It is an unsubstituted alkyl group having 18 carbon atoms and a substituted alkyl group having 1 to 18 carbon atoms in the alkyl moiety. Examples of the substituent include those described as the substituent for Z ¹ .

R ¹ is preferably an alkynyl group, and most preferably a propargyl group.

Q is a group of atoms necessary for forming a 4- to 12-membered non-aromatic hydrocarbon ring or non-aromatic heterocycle. These rings may be further substituted with the groups described for the Z ¹ substituent.

As the non-aromatic hydrocarbon ring, when X is a carbon atom, examples thereof include rings such as cyclopentane, cyclohexane, cyclohexene, cycloheptane, indane and tetralin.

The non-aromatic heterocycle includes nitrogen, oxygen, sulfur, selenium and the like as a hetero atom,
For example, when X is a carbon atom, examples thereof include rings such as tetrahydrofuran, tetrahydropyran, butyrolactone, pyrrolidone, and tetrahydrothiophene. When X is a nitrogen atom, examples thereof include rings such as pyrrolidine, piperidine, pyridone, piperazine, perhydrothiazine, tetrahydroquinoline and indoline.

Preferred as the ring nucleus formed by Q is
When X is a carbon atom, it is, in particular, cyclopentane, cyclohexane, cycloheptane, cyclohexeneindane, tetrahydropyran, tetrahydrothiophene and the like.

As the alkynyl group to which at least one of the substituents of R ¹ , Z ^{1 and} the substituent of Q corresponds, some of the alkynyl groups have already been described, but when explained in more detail, it is preferably carbon. The number is from 2 to 18, and examples thereof include an ethynyl group, a propargyl group, a 2-butynyl group, a 1-methylpropargyl group, a 1,1-dimethylpropargyl group, a 3-butynyl group, and a 4-pentynyl group.

Further, these may be substituted with the groups described as the substituent for Z ¹ . The alkynyl group is preferably a propargyl group, and most preferably R ¹ is a propargyl group.

Examples of the adsorption promoting group to silver halide which the substituents of R ¹ , Q and Z ¹ may have are X ^1- (L ¹ ) _m1
Those represented by − are preferable.

X ¹ is an adsorption promoting group on silver halide, and L ¹ is a divalent linking group. m ₁ is 0 or 1
Is. Preferred examples of the adsorption accelerating group for silver halide represented by X ¹ include a thioamide group, a mercapto group and a 5- or 6-membered nitrogen-containing heterocyclic group.

These may be substituted with the substituents described for Z ¹ . The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thioureido group, etc.).

The mercapto group for X ¹ is especially a heterocyclic mercapto group (eg 5-mercaptotetrazole, 3
-Mercapto-1,2,4-triazole), 2-mercapto-1,3,4-thiadiazole, 2-mercapto-1,3,4-oxadiazole and the like) are preferable.

The 5- or 6-membered nitrogen-containing heterocycle represented by X ¹ is a combination of nitrogen, oxygen, sulfur and carbon, and preferably forms iminosilver, such as benzotriazole or aminothiazole. Can be mentioned.

The divalent linking group represented by L ¹ is
An atom or an atomic group containing at least one of C, N, S, and O. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-,
-S -, - NH -, - N =, - CO -, - SO 2 - ( may have these groups the substituents), is made of a single or a combination thereof and the like. As an example of the combination, those shown in Chemical formula 48 are preferable.

[0117]

[Chemical 48]

Examples of the counter ion Y for charge balance include bromine ion, chlorine ion, iodine ion, p
-Toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyan ion, BF ₄ ⁻ , PF ₆ ^{− and the} like can be mentioned.

Of the compounds represented by Chemical formula 42, those having an adsorption promoting group for silver halide are preferable.
In particular, the adsorption promoting group X ¹ is more preferably a thioamide group, an azole group or a heterocyclic mercapto group. Examples of these compounds and their synthesis methods are described in, for example, JP-A-63-301942 and the patents or literatures cited therein.

Specific examples of the compound represented by Chemical formula 42 are shown below, but the invention is not limited thereto.

[0121]

[Chemical 49]

[0122]

[Chemical 50]

[0123]

[Chemical 51]

[0124]

[Chemical 52]

[0125]

[Chemical 53]

[0126]

[Chemical 54]

The compounds described above can be used, for example, in Research Disclosure No. 22.
534 (published January 1983, pp. 50-54), and methods described in US Pat. No. 4,471,044 and the like and similar methods.

The chemical formula 43 will be described in detail.

In the chemical formula 43, the aliphatic group represented by R ²¹ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by R ²¹ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.

The heterocycle of R ²¹ is N, O, or S
It is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of the atoms, which may be a monocycle or may form a condensed ring with another aromatic ring or heterocycle. Good. The heterocycle (also referred to as a heterocycle) is preferably a 5- or 6-membered aromatic heterocyclic group, and examples thereof include a pyridyl group, a quinolinyl group, an imidazolyl group, and a benzimidazolyl group.

R ²¹ may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted.

For example, alkyl group, aralkyl group, alkoxy group, alkyl or aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio group. Group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group and carboxyl group.

When possible, these groups may be linked to each other to form a ring.

R ²¹ is preferably an aromatic group, an aromatic heterocycle or an aryl-substituted methyl group, and more preferably an aryl group.

Preferred among the groups represented by R ²² are:
When G is a carbonyl group, a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, etc.), aralkyl group (eg, o-hydroxybenzyl group, etc.) ), An aryl group (for example, a phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferable.

When G is a sulfonyl group, R ²² is an alkyl group (eg methyl group), an aralkyl group (eg o-hydroxyphenylmethyl group), an aryl group (eg phenyl group) or a substituted amino group. (For example, a dimethylamino group etc.) and the like are preferable.

As the substituent for R ^22, the substituents listed for R ²¹ can be applied, and for example, an acyl group, an acyloxy group, an alkyl or aryloxycarbonyl group, an alkenyl group, an alkynyl group or a nitro group can also be applied.

These substituents may be further substituted with these substituents. If possible, these groups may be linked to each other to form a ring.

R ²¹ or R ²² , and especially R ²¹ preferably contains a non-diffusion group such as a coupler, a so-called ballast group. This ballast group has 8 or more carbon atoms, and is an alkyl group, phenyl group, ether group, amide group, ureido group,
It is composed of one or more combinations of urethane group, sulfonamide group, thioether group and the like.

R ²¹ or R ²² may have a group X ² — (L ² ) _m ² — which promotes adsorption of the compound represented by Chemical formula 43 onto the surface of silver halide grains. X ² here
Has the same meaning as X ¹ in Chemical formula 42, and is preferably a thioamide group (excluding thiosemicarbazide and its substituted product), a mercapto group, or a 5- to 6-membered nitrogen-containing heterocyclic group. L ² represents a divalent linking group and has the same meaning as L ¹ in Chemical formula 42. m ₂ is 0 or 1.

More preferred X ² is a cyclic thioamide group (that is, a mercapto-substituted nitrogen-containing heterocycle, for example, 2-mercaptothiadiazole group, 3-mercapto-group).
1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.) or nitrogen-containing heterocyclic group (for example, benzotriazole) Group, benzimidazole group, indazole group, etc.).

Most preferably, R ²³ and R ²⁴ are hydrogen atoms.

As G in Chemical Formula 43, a carbonyl group is most preferable.

Further, as Chemical Formula 43, those having an adsorption group to silver halide are more preferable. Particularly preferred adsorbing groups for silver halide are the mercapto group, the cyclic thioamide group and the nitrogen-containing heterocyclic group described in the above chemical formula 42.

Specific examples of the compound represented by Chemical formula 43 are shown below. However, the present invention is not limited to the following compounds.

[0147]

[Chemical 55]

[0148]

[Chemical 56]

[0149]

[Chemical 57]

[0150]

[Chemical 58]

[0151]

[Chemical 59]

[0152]

[Chemical 60]

The method of synthesizing the compound represented by the formula 43 used in the present invention is described in, for example, Research Disclosure magazine No. 15162 (November 1976, pp. 76-77), the same publication 22534 (January 1983). 50-54), and the same magazine, 23510 (198).
3rd November, pp. 346-352) and U.S. Pat. Nos. 4,080,207 and 4,269,924.
No. 4,276,364 and the like.

In the present invention, any of the compounds represented by Chemical formulas 42 and 43 may be contained in the photographic light-sensitive material, but any layer may be contained, but it is preferably contained in the silver halide emulsion layer. There is no particular limit to the amount used,
A useful range is from about 1.times.10.sup.- ⁸ mol to about 1.times.10.sup.- ² mol per mol of silver in the silver halide emulsion layer, preferably 1 mol of silver.
It is 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol per mol.

These compounds may be used alone or in combination of two or more, and the total amount of the compounds used in combination may be within the above range.

In the present invention, it is preferable to use the nucleating agent represented by Chemical Formula 42, and the following (1) to
It is particularly preferable to take the modes shown in the order of (8),
The case of (8) is most preferable.

(1) In the case of having an adsorption promoting group for silver halide represented by X ¹ as a substituent.

(2) In the above (1), the adsorption promoting group represented by X ¹ on the silver halide is a thioamide group, a heterocyclic mercapto group, or a nitrogen-containing heterocycle which produces iminosilver.

(3) In the above (2), the heterocycle completed by Z is quinolinium, isoquinolinium, naphthopyridinium or benzothiazolium.

(4) In the above (2), the heterocycle completed by Z is quinolinium.

(5) In the above (2), R ¹ or has an alkynyl group as a substituent of Z.

(6) In the above (5), R ¹ is a propargyl group.

(7) In the above (2), the thioamide group of X ¹ is thiourethane group, and the heterocyclic mercapto group of X ¹ is mercaptotetrazole.

(8) In the case (6), R ¹ is bonded to the heterocycle completed by Z to form a ring.

When the nucleating agent represented by Chemical Formula 43 is used, it is particularly preferable to take the modes shown in the order of (1) to (6) below, and the case shown in (6) is most preferable.

(1) In the case of having an adsorption promoting group for silver halide represented by X ² as a substituent.

(2) In the above (1), the adsorption promoting group for silver halide represented by X ² is a heterocyclic mercapto group or a nitrogen-containing heterocyclic ring forming imino silver.

(3) In the above (2), the group represented by GR ²² is a formyl group.

(4) In the above (3), R ²³ and R
^{When 24} is a hydrogen atom.

(5) In the above (3), R ²¹ is an aromatic group.

(6) In the above (2), the heterocyclic mercapto group represented by X ² is 5-mercaptotetrazole or 5-mercapto-1,2,4-triazole.

In the present invention, the compound of Chemical formula 42 and the compound of Chemical formula 43 can be used in combination.

As the nucleating agent, all compounds conventionally developed for the purpose of nucleating an inner latent type silver halide are applicable. Two or more nucleating agents may be used in combination as described above. More specifically, as the nucleating agent,
For example, “Research Date Closure” (Resarch Di
sclosure) No. 22534 (January 50, 1983)
Page 54), and these are roughly classified into three types: hydrazine compounds, quaternary heterocyclic compounds, and other compounds.

The nucleating agent of Chemical formula 42 can be classified into a quaternary heterocyclic compound, and the nucleating agent of Chemical formula 43 includes a hydrazine compound.

Examples of the hydrazine compound include, for example, Research Disclosure N.
15162 (November 1976, pp. 76-77) and the same magazine 23510 (November 1983, 346-).
Those described on page 352). More specific examples include those described in the following patent specifications. First, examples of the hydrazine-based nucleating agent having a silver halide adsorptive group include, for example, US Pat. No. 40309.
No. 25, No. 4080207, No. 4031127.
Nos. 3,718,470, 4,269,929, 4,276,364, 4,287,748, and 43.
No. 85108, No. 4459347, and British Patent No. 20.
11391B, JP-A-54-74729, and JP-A-55-
163533, 55-74536 and 60-
179734 etc. are mentioned. Examples of other hydrazine-based nucleating agents include, for example, JP-A-57 / 57
-86829, U.S. Pat. Nos. 4,560,638 and 4,
No. 478, and further No. 2563785 and No. 2
The compound described in 588,982 may be mentioned.

Examples of the quaternary heterocyclic compound include Research Disclosure (Resarch Disclosur) described above.
e) Magazine No. 22534, JP-B-49-38164, JP-A-52-19452, JP-A-52-47326, JP-A-5-52
2-69613, 52-3426, 55-13
8742, 60-11837, U.S. Pat. No. 430
No. 6016 and "Research Disclosure"
Magazine No. 23213 (issued in August 1983, 267-27)
Those described on page 0).

In the present invention, the nucleating agents represented by Chemical formulas 42 and 43 may be used in combination with the other nucleating agents described therein. In the present invention, it is particularly preferable to use the nucleating agent of Chemical formula 42.

In the present invention, it is preferable to use a nucleation accelerator together with the nucleating agent. The "nucleating accelerator" in the present invention does not substantially function as the nucleating agent, but it promotes the action of the nucleating agent to directly increase the maximum density of a positive image and / or has a certain level. It is a substance that acts to accelerate the development time required to directly obtain a positive image density.

The nucleation accelerator useful in the present invention is represented by Chemical formula 61.

[0180]

[Chemical formula 61]

In Chemical Formula 61, A represents a group adsorbing to silver halide. Examples of the group adsorbed on the silver halide include a compound having a mercapto group bonded to a heterocycle, a heterocyclic compound capable of forming imino silver, or a hydrocarbon compound having a mercapto group.

Examples of the mercapto compound bonded to the heterocycle include, for example, substituted or unsubstituted mercaptoazoles (for example, 5-mercaptotetrazole, 3-mercapto-1,2,4-triazoles, 2-mercaptoimidazoles). , 2-mercapto-1,3,4-thiadiazoles, 5-mercapto-1,2,4-thiadiazoles, 2-mercapto-1,3,4-oxadiazoles, 2-mercapto-1,3, 4-selenadiazoles, 2-mercaptooxazoles, 2-mercaptothiazoles, 2-mercaptobenzoxazoles, 2
-Mercaptobenzimidazoles, 2-mercaptobenzthiazoles, etc.) substituted or unsubstituted mercaptopyrimidines (e.g., 2-mercaptopyrimidines,
Etc.) and the like.

Examples of the heterocyclic compound capable of forming imino silver include substituted or unsubstituted indazoles, benzimidazoles, benzotriazoles, benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, Triazoles, tetrazoles, azaindenes, pyrazoles,
Examples include indoles.

Examples of the hydrocarbon compound having a mercapto group include alkyl mercaptoptans, aryl mercaptans, alkenyl mercaptans and aralkyl mercaptans.

Y ¹ represents a divalent linking group consisting of an atom or an atom group selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom. Examples of the divalent linking group include those shown in Chemical formula 62.

[0186]

[Chemical formula 62]

These linking groups are linear or branched alkylene groups between A and the heterocyclic ring described later (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group, etc.). Alternatively, it may be bonded via a substituted or unsubstituted arylene group (phenylene group, naphthylene group, etc.).

R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R
³⁷ , R ³⁸ , R ³⁹ and R ⁴⁰ are each a hydrogen atom, a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, etc.), a substituted or unsubstituted aryl group ( For example, phenyl group, 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.),
Alternatively, it represents a substituted or unsubstituted alkyl group (eg, benzyl group, phenethyl group, etc.).

R represents an organic group containing at least one thioether group, amino group (including salt form), ammonium group, ether group or heterocyclic group (including salt form).
Examples of such an organic group include a group in which a group selected from a substituted or unsubstituted alkyl group, an alkenyl group, an aralkyl group or an aryl group and the above group are combined, and a combination of these groups Good. For example, dimethylaminoethyl group, aminoethyl group, diethylaminoethyl group, dibutylaminoethyl group, dimethylaminopropyl group hydrochloride, dimethylaminoethylthioethyl group, 4-dimethylaminophenyl group, 4-dimethylaminobenzyl group, methylthioethyl group. Group, ethylthiopropyl group, 4-methylthio-3-cyanophenyl group, methylthiomethyl group, trimethylammonioethyl group, methoxyethyl group, methoxyethoxyethoxyethyl group, methoxyethylthioethyl group, 3,4-dimethoxyphenyl group , 3-chloro-4-methoxyphenyl group, morpholinoethyl group, 1-imidazolylethyl group, morpholinoethylthioethyl group, pyrrolidinoethyl group, piperidinopropyl group, 2-pyridylmethyl group, 2- (1-imidazolyl ) Echi Thioethyl group, pyrazolylethyl group, triazolyl an ethyl group, and a methoxyethoxy ethoxyethoxycarbonyl aminoethyl group. s represents 0 or 1, and t represents 1 or 2.

Among the compounds represented by Chemical formula 61, preferred compounds are represented by Chemical formulas 63 to 68.

[0191]

[Chemical formula 63]

[0192]

[Chemical 64]

[0193]

[Chemical 65]

[0194]

[Chemical formula 66]

[0195]

[Chemical formula 67]

[0196]

[Chemical 68]

In the formula 63, Q ¹ is preferably an atom necessary for forming a 5- or 6-membered heterocycle composed of at least one atom selected from carbon atom, nitrogen atom, oxygen atom, sulfur atom and selenium atom. Represents a group. The heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring.

As the heterocycle, for example, tetrazoles,
Triazoles, imidazoles, thiadiazoles,
Examples thereof include oxadiazoles, selenadiazoles, oxazoles, thiazoles, benzoxazoles, benzthiazoles, benzimidazoles and pyrimidines.

M ¹ is a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), an ammonium group (eg, trimethylammonium group, dimethylbenzylammonium group, etc.), M ¹ = H or an alkali metal under alkaline conditions. Groups that can be atoms (eg acetyl, cyanoethyl, methanesulfonylethyl, etc.)
Represents

These heterocycles include nitro group, halogen atom (eg chlorine atom, bromine atom), mercapto group, cyano group, and substituted or unsubstituted alkyl group (eg methyl group, ethyl group, propyl group). , T-butyl group, cyanoethyl group, etc.), aryl group (for example, phenyl group, 4-methanesulfonamidophenyl group, 4-
Methylphenyl group, 3,4-dichlorophenyl group, naphthyl group, etc.), alkenyl group (eg, allyl group, etc.),
Aralkyl group (eg, benzyl group, 4-methylbenzyl group, phenethyl group, etc.), sulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, methyl) Carbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), carbonamide group (eg, acetamide group, benzamide group, etc.), sulfonamide Group (for example, methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), acyloxy group (for example, acetyloxy group, benzoyloxy group,
Etc.), sulfonyloxy group (eg methanesulfonyloxy group, etc.), ureido group (eg unsubstituted ureido group, methylureido group, ethylureido group, phenylureido group, etc.), thioureido group (eg unsubstituted thioureido group, etc.) , Methylthioureido group, etc.), acyl group (eg acetyl group, benzoyl group, etc.), oxycarbonyl group (eg methoxycarbonyl group, phenoxycarbonyl group, etc.), oxycarbonylamino group (eg methoxycarbonylamino group, phenoxycarbonyl) Amino group, 2-ethylhexyloxylcarbonylamino group, etc.), carboxylic acid or a salt thereof, sulfonic acid or a salt thereof, which may be substituted with a hydroxyl group, a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, Substitute with hydroxyl group It is preferable in terms of nucleation accelerating effect that is not.

Preferred heterocycles represented by Q ¹ include tetrazoles, triazoles, imidazoles, thiadiazoles and oxadiazoles.

Y ¹ , R, t, and s have the same meanings as those of chemical formula 61, respectively.

In Chemical Formula 64, Y ¹ , R, t, s, and M have the same meanings as those of Chemical Formula 61 and Chemical Formula 63, and Q ² forms a 5- or 6-membered heterocycle capable of forming with iminosilver. Represents the atomic group necessary for. Preferably, it represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring selected from carbon, nitrogen, oxygen, sulfur and selenium. Also, this heterocycle may be fused as a carbon aromatic or heteroaromatic ring. Q ²
The heterocycle formed by, for example, indazoles, benzimidazoles, benzotriazoles,
Examples thereof include benzoxazoles, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, tetraazaindenes, triazaindenes, diazaindenes, pyrazoles and indoles.

In Chemical formula 65, M ¹ , R, Y ¹ and s have the same meanings as those in Chemical formula 63. X ⁵ represents an oxygen atom, a sulfur atom or a selenium atom, preferably a sulfur atom.

In Chemical Formula 66, R ¹⁰ is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a nitro group, a mercapto group, an unsubstituted amino group, a substituted or unsubstituted alkyl group (eg, methyl group). , Ethyl group,
Etc.), alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.), aryl group (eg, phenyl group, 2-methylphenyl group, etc.), Or- (Y ¹ ) _s
Represents -R. R ²⁰ is a hydrogen atom, an unsubstituted amino group or - (Y ¹⁾ represents _s -R, R ¹⁰ and R ²⁰ is - (Y ¹⁾ _s
When representing -R, they may be the same or different from each other. However, at least one of R ¹⁰ and R ²⁰ is-
(Y ¹ ) _s- R. M ¹ , R, Y ¹ and s have the same meanings as those of the chemical formula 63, respectively.

In the chemical formula 67, R ³⁰ is-(Y ¹ ) _s -R
Represents However, M ¹ , R, Y ¹ , and s are each
Synonymous with each of the three.

In Chemical Formula 68, R ¹¹ and R ¹² are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom,
Etc.), a substituted or unsubstituted amino group (for example, an unsubstituted amino group, a methylamino group, etc.), a nitro group, a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, etc.), an alkenyl group ( For example, a propenyl group,
1-methylvinyl group, etc.), aralkyl group (eg, benzyl group, phenethyl group, etc.) or aryl group (eg, phenyl group, 2-methylphenyl group, etc.).
M ¹ and R ³⁰ have the same meanings as those of Chemical Formula 67, respectively.

Specific compounds represented by the formula (61) of the present invention are shown below, but the compounds of the present invention are not limited thereto.

[0209]

[Chemical 69]

[0210]

[Chemical 70]

[0211]

[Chemical 71]

[0212]

[Chemical 72]

[0213]

[Chemical formula 73]

[0214]

[Chemical 74]

[0215]

[Chemical 75]

[0216]

[Chemical 76]

[0217]

[Chemical 77]

[0218]

[Chemical 78]

The nucleation promoter used in the present invention is Berichte der Deutschen Chemischen Gesellschaf.
t) 28 , 77 (1895), JP-A-50-37436.
No. 51-3231, U.S. Pat. No. 3,295,976.
U.S. Pat. No. 3,376,310, Berichte der Germany Chien Hemitschien Gezershyaft.
der Deutschen Chemischen Gesellschaft) 22 , 56
8 (1889), ibid. 29 , 2483 (1896), Journal of Chemical Society (J. Chem. So
c.) 1932 , 1806, Journal of the American Chemical Society (J. Am. Chem. So
c.) 71 , 4000 (1949), US Pat. No. 258.
5388, 2541924, Advances in Heterocyclic Chemistry (Advances in
Heterocyclic Chemistry) 9 , 165 (1968), Organic Synthesis IV, 5
69 (1963), Journal of the American Chemical Society (J. Am. Chem. Soc.) 4
5, 2390 (1923), Chemie Berichte (Chem
ische Berichte) 9, 465 (1876), Japanese Patent Publication Sho 40
-28496, JP-A-50-89034, U.S. Pat. Nos. 3,106,467, 3,420,670 and 22,71.
No. 229, No. 3137578, No. 3148066,
No. 3511663, No. 3060028, No. 3271
No. 154, No. 3251691, No. 3598599,
No. 3,148,066, Japanese Patent Publication No. 43-4135, U.S. Pat. Nos. 3,615,616, 3,420,664 and 307.
No. 1465, No. 2444605, No. 2444606
No. 2444607, No. 2935404, Japanese Patent Application No. 62-145932, and the like.

The nucleation accelerator can be contained in the lithographic printing material or the processing liquid, but in the light-sensitive material, especially the internal latent image type silver halide emulsion layer and other hydrophilic colloid layers (intermediate layer). Layer or protective layer). Particularly preferred is in a silver halide emulsion or its adjacent layer.

The addition amount of the nucleation accelerator is preferably 10 ^-6 to 10 ^-2 mol, and more preferably 10 ^-5 to 10 ^-2 mol, per mol of silver halide.

A nucleation accelerator is used as a processing solution, that is, development.
1 liter when added to liquid or its pre-bath
Per 10^-8-10^-3Mol is preferred, and more preferably
10 ^-7-10^-FourIt is a mole.

In order to further enhance the effect of the nucleation accelerator of the present invention, it is preferable to use the following compounds in combination.

Hydroquinones (eg US Pat. No. 32
Compounds described in 27552 and 4279987; chromans (for example, US Pat. No. 4,268,621, JP-A-5).
4-103031, Research Disclosure 18
No. 264 (1979); quinones (for example, Research Disclosure 21206 (1)
981); aminos (for example, compounds described in U.S. Pat. No. 4,150,993 and JP-A-58-174757); oxidizing agents (for example, compounds described in Research Disclosure 16936 (1978)); catechol. (For example, JP-A-55-21013 and 55
-65944); compounds that release nucleating agents during development (e.g., compounds described in JP-A-60-107029); thioureas (e.g., JP-A-60-95533).
Compounds described in JP-A No. 55-65944);

The non-pre-fogged internal latent image type silver halide emulsion used in the present invention does not have the pre-fogged surface of silver halide grains and contains silver halide which mainly forms a latent image inside the grains. Although it is an emulsion, more specifically, a certain amount of a silver halide emulsion is coated on a transparent support, and this is exposed to light for a fixed time of 0.01 to 10 seconds. 20% in developer)
The maximum density measured by the usual photographic density measuring method when developed at 6 ° C. for 6 minutes was 18 times in the following developing solution B (surface type developing solution) in the following developing solution B (surface type developing solution). Those having a density of at least 5 times higher than the maximum density obtained when developed at 5 ° C. for 5 minutes are preferable, and those having a density of at least 10 times higher are preferable.

Surface developer B Metol 2.5 g L-ascorbic acid 10 g NaBO ₂ .4H ₂ O 35 g KBr 1 g Water added 1 liter

Internal developer A Metol 2 g Sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water was added to 1 liter

Specific examples of the internal latent image type emulsion include, for example, British Patent No. 1011062 and US Patent No. 259225.
Examples thereof include conversion type silver halide emulsions and core / shell type silver halide emulsions described in JP-A No. 0 and 2456943. -32813,
47-32814, 52-134721, 5
2-156614, 53-60222, 53-
66218, 53-66727, 55-127.
No. 549, No. 57-136641, No. 58-7022.
1, No. 59-208540, No. 59-216136.
No. 60-107641, No. 60-247237
No. 61-2148, No. 61-3137, No. 56-18939, No. 58-1412, and No. 58-1.
No. 415, No. 58-6935, No. 58-108528.
No. 61/36424, U.S. Pat. No. 32063.
No. 13, No. 3,317,322, No. 3,761,266, No. 3,761,276, No. 3,850,637, and No. 39235.
No. 13, No. 4035185, No. 4395478, No. 4504570, European Patent No. 0017148,
Research Disclosure Magazine RD16345 (19
Emulsion described in (November 1977) and the like.

As the composition of silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver chloroiodobromide and silver iodobromide are typical. The silver halide preferably used in the present invention does not contain silver iodide or contains 3% mol or less of silver (iodo) bromide, (iodo) silver chloride,
It is silver (iodo) bromide or silver (iodo) bromide containing 20 mol% or more of bromine. Of these, silver chlorobromide or chloro (iodo) bromide having 20 mol% or more of bromine, or silver bromide or (iodo) bromide is particularly preferable.

The average grain size of the silver halide grains (the grain diameter in the case of spherical grains or grains close to spheres, and the peak length in the case of cubic grains is represented by the average based on the projected area) is 2 μ or less. 0.1 μ or more is preferable, but 1 μ or less and 0.15 μ or more is particularly preferable. The particle size distribution may be narrow or wide, but within the range of ± 40% of the average particle size in terms of the number of particles or the weight (more preferably, in order to improve graininess and sharpness).
A so-called "monodisperse" silver halide emulsion having a narrow grain size distribution such that 90% or more, particularly 95% or more of all grains fall within ± 30%, most preferably within ± 20% is used in the present invention. Is preferred. In order to satisfy the target gradation of a lithographic printing material as a light-sensitive material, two or more kinds of monodispersed silver halide emulsions having the same grain size or the same size, or emulsions having substantially the same color sensitivity are used. It is possible to mix a plurality of particles having different sensitivities in the same layer or to coat multiple layers in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention may have a regular crystal such as a cube, octahedron, dodecahedron and tetradecahedron, and may have a spherical shape. It may have an irregular crystal form, or may have a composite form of these crystal forms. Further, tabular grains may be used, and particularly, an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more occupy 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms.

The silver halide emulsion used in the present invention is
It can be prepared in the presence of a silver halide solvent. As the silver halide solvent, there are U.S. Pat. No. 3,271,157.
No. 3,531,289, No. 3,574,628, JP-A Nos. 54-1019, 54-158917 and the like, JP-A No. 53-82408.
Nos. 55-77737 and 55-2982. The emulsion of the present invention can be doped with metals such as Ir, Rh, Ru, Pd, Pt, Pb and Fe during grain formation. The silver halide emulsion used in the present invention can be chemically sensitized inside or on the surface of the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization or the like alone or in combination.

The emulsion layer of the present invention or the other hydrophilic colloid layer may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation. As the filter dye, a dye for further lowering the photographic sensitivity or a dye having substantial light absorption mainly in the range of 330 nm to 800 nm for improving the safety against safelight light is used.

These dyes may be added to the emulsion layer depending on the purpose, or a mordant may be added to the upper portion of the silver halide emulsion layer, that is, the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support. It is preferable to add and fix and use.

[0235] different depending molar extinction coefficient of the dye, but is added in an amount of usually ^{10 -2 g / m 2 ~1g /} m 2. Preferably 5
It is ^{0mg / m 2 ~500mg / m 2} . Specific examples of dyes are described in detail in JP-A-63-64039.

In the present invention, various compounds may be incorporated for the purpose of preventing fog during the production process of the lithographic printing material, during storage or during processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles. Etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindenes) ), Pentaazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. It can be added.

The emulsion layer of the lithographic printing material of the present invention contains, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, for the purpose of increasing sensitivity, increasing contrast, or promoting development. A developing agent such as a quaternary ammonium salt compound, a urethane derivative, a urea derivative, an imidazole derivative, dihydroxybenzenes or 3-pyrazolidones may be contained. Among them, dihydroxybenzenes (hydroquinone, 2-methylhydroquinone, catechol, etc.) and 3-pyrazolidones (1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc.) are preferable. , Usually used at 5 g / m ² or less. In the case of dihydroxybenzenes, 0.
More preferably 01~2.5g / m ^2, in the case of 3-pyrazolidones, 0.01 to 0.5 g / m ² is more preferable.

The silver salt offset printing material which is the lithographic printing material of the present invention (hereinafter simply referred to as the printing material of the present invention) is
An anti-halation layer, which is an undercoat layer, is provided on a support, a photosensitive silver halide emulsion layer is further provided thereon, and a physical development nucleus layer is further provided thereon. An intermediate layer can also be provided.

The printing material of the present invention preferably has a constitution in which a physical development nucleus layer is directly provided on the photosensitive silver halide emulsion layer in the above layer constitution.

In the present invention, the antihalation layer provided closest to the support side is, for example, a hydrophilic colloid layer in which carbon black dye or pigment is dispersed.
Further, in order to impart a printing plate suitability to the antihalation layer or the emulsion layer, a fine powder of 1 to 10 μm such as silica can be added.

The hydrophilic binder which can be advantageously used in the silver halide emulsion according to the present invention is gelatin, and a part or all of gelatin is a synthetic high molecular polymer such as polyvinyl alcohol or poly-N-vinylpyrrolidone. It is possible to use a polyacrylic acid copolymer, a copolymer of methyl vinyl ether and maleic anhydride, or a compound substituted with a cellulose derivative, a gelatin derivative or the like. Further, various compounds can be added to the above emulsion for the purpose of stabilizing the emulsion during the production process or storage or preventing fogging during development.

Further, in addition to the above compounds, various additives such as hardeners and surfactants can be appropriately used. Specific examples of the compounds can be found in "Product Licensing Index" Vol. 92, No. . 9232, 1
07-110, I-XIII, XVI-XVII, XXIII (19
December 71).

By coating the emulsion thus prepared on the above antihalation layer as a layer by a known method, the photosensitive silver halide emulsion layer according to the present invention can be formed.

Next, the development nuclei of the physical development nuclei layer according to the present invention will be described. For example, water-soluble noble metal salts such as gold, silver, platinum, palladium or zinc, lead, cadmium, nickel, cobalt, iron, chromium, Metal colloids obtained by reducing heavy metals such as tin, antimony and bismuth, or their water-soluble metal salts such as nitrates, acetates, borates, chlorides, hydroxides, etc. It is possible to use development nuclei or the like obtained by mixing with a substance such as sodium sulfide.

As the kind of the hydrophilic binder used in the physical development nucleus layer according to the present invention, the same hydrophilic polymer substances as those used in the above-mentioned photosensitive silver halide emulsion layer are applied. Polyvinyl alcohol or a copolymer of methyl vinyl ether and maleic anhydride is preferable, and these may be used in combination. The amount of these hydrophilic binders is not necessarily uniform depending on the type of noble metal or binder, but is in the range of 30% to 100% by weight relative to the physical development nuclei.

The physical development nucleus layer is preferably coated directly on the above-mentioned photosensitive silver halide emulsion layer.

Examples of the support of the offset printing material according to the present invention include a nitrate film, a cellulose acetate film, a cellulose acetate butyrate film, a polystyrene film, a polyethylene phthalate film, a polycarbonate film or a laminate thereof, paper and the like. . Further, baryta or α-olefin polymer, particularly polyethylene, polypropylene, ethylene butylene copolymer, etc., having 2 to 10 carbon atoms.
Paper coated with or laminated with an α-olefin polymer, a method for enhancing adhesiveness with other polymer substances by roughening the surface as described in JP-B-47-19068, or JP-B-56-56 A support according to the roughening method described in No. 135840 can be used.

Further, in order to reduce the plate elongation, a metal foil,
For example, a support obtained by laminating aluminum foil on paper can be used.

Further, colloidal silica can be used in the coating film applied on the surface of the polyolefin for the purpose of improving the adhesiveness to the surface coated with the polyolefin or for improving the printability.

In this regard, US Pat. No. 3,161,151
The method described in the specification No. 9 may be followed.

In order to strengthen the adhesive force between the support and the coating layer,
The surface of the support may be subjected to a pretreatment such as corona discharge, irradiation with ultraviolet rays, and flame treatment. For corona discharge, the method described in US Pat. No. 2012189 is representative.

Hardening treatment of the silver halide emulsion and / or other constituent layers can be carried out by a conventional method. Examples of curing agents are aldehyde compounds such as formaldehyde and glutaraldehyde, diacetyl, ketone compounds such as cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1, Three
5-triazine and others US Pat. No. 3,288,775
No. 2,732,303, British Patent No. 974723.
No. 1167207, compounds having a reactive halogen as shown in each specification, divinyl sulfone,
5-acetyl-1,3-diacryloylhexahydro-
1,3,5-triazine and other US Pat. No. 36357
No. 18, No. 3232763, No. 3490911
Nos. 3,642,486, British Patent No. 994869, and the like, compounds having a reactive olefin, N-hydroxymethylphthalimide,
Other US Pat. Nos. 2,732,316 and 2,586,16
No. 8, N-methylol compounds as shown in each specification, isocyanates as shown in US Pat. No. 3,103,437, US Pat. No. 3,017,280.
No. 2,983,611 and the like, aziridine compounds as shown in each specification, US Pat. No. 2,725,294.
No. 2,725,295 and the like, acid derivatives as shown in the respective specifications, US Pat. No. 3,100,704 and the like as carbodiimide compounds, US Pat. No. 3,091,537 and the like. Epoxy compounds as shown, U.S. Pat. No. 3,321,313,
No. 3543292, isoxazole compounds as shown in the respective specifications, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, or chromium as an inorganic hardener. There are vans and zirconium sulfate. Instead of the above compounds, precursors may be used, for example, alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic nitroalcohols and the like.

Known surfactants may be added to the constituent layers of the offset printing material of the present invention, if necessary, alone or as a mixture. These may be used as coating aids, but in some cases, for other purposes such as emulsion dispersion, acceleration of development, improvement of other photographic characteristics, or adjustment of charge sequence,
It is also applied to prevent static electricity.

These surface active agents include natural products such as saponins, anion or nonionic surface active agents such as the above-mentioned alkylene oxide type, glycerin type and glycidol type, higher alkyl amines, quaternary ammonium salts,
Heterocycles such as pyridine, cationic surfactants such as phosphonium or sulfonium, anionic surfactants having an acidic group such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester, phosphoric acid ester, amino acids, aminosulfonic acids , Amphoteric activators such as sulfuric acid or phosphoric acid esters of amino alcohols.

Some examples of these surfactant compounds that can be used are described in US Pat. Nos. 2,271,623 and 22,
No. 40472, No. 2288226, No. 27398
No. 91, No. 3068101, No. 3158484
No. 3201253, No. 3210191, No. 3294540, No. 3415649, No. 34.
No. 41413, No. 3442654, No. 34757.
No. 74, No. 3545574, British Patent No. 10773.
17 and 11198450, Ryohei Oda et al., "Synthesis of Surfactants and Their Applications" (Maki Shoten, 1964) and A. W. Berry, "Surface Active Agent" (InterScience Publications Incorporated, 1958), J.
P. It is described in "Encyclopedia of Active Agents Vol. 2" (Chemical Publish Company, 1964) by Sisley.

The offset printing material of the present invention may contain a filter dye or an anti-irradiation dye as described above. Examples of such dyes include US Pat. Nos. 2,274,782, 2,527,583 and 29.
No. 56879, No. 3177078, No. 32529
No. 21, and the compounds described in JP-B-39-22069. These dyes may be mordanted by the method described in US Pat. No. 3,282,699, if necessary. Further, as the antihalation layer, a colored layer such as a pigment (for example, lamp black, carbon black, fest black, ultramarine, malachite green, crystal violet) can be used.

As a method of coating the constituent layers of the offset printing material according to the present invention on the above-mentioned support, a coating method well known in the art can be used. For example, there are a dip method, an air knife method, an extrusion doctor method and the like, and particularly preferable is US Pat. No. 27.
It is the bead coating method described in 61791 specification.

A silver halide developing agent may be incorporated in the constituent layers of the offset printing material according to the present invention. In this case, the development after the exposure can be activated by using an alkaline aqueous solution.

The developing agent can be contained in the silver halide emulsion layer, the antihalation layer, or a layer adjacent thereto (undercoat layer, intermediate layer), etc., but it is most preferably contained in the antihalation layer. The alkaline aqueous solution used for development may also contain a developer.

Specific examples of the developer include polyhydroxybenzenes such as hydroquinone, catechol, chlorohydroquinone, pyrogallol, bromohydroquinone, isopropylhydroquinone, tolhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone and 2,5. -Dimethylhydroquinone, 2,3-dibromohydroquinone, 1,4-dihydroxy-2-acetophenone, 4-phenylcatechol, 4-t-butylcatechol, 4-n-butylpyrogallol, 4,5-dipromocatechol, 2, 5-diethylhydroquinone, 2,5-
Benzoylaminohydroquinone, 4-benzyloxycatechol, 4-n-butoxycatechol and the like are included.

Of these, hydroquinone and methylhydroquinone are particularly preferably used.

Other developing agents include 3-pyrazolidone compounds such as 1-phenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone and 1-phenyl-3-pyrazolidone. Phenyl-
4,4-Dimethyl-3-pyrazolidone, 1-p-chlorophenyl-3-pyrazolidone, 1-p-methoxyphenyl-3-pyrazolidone, 1-phenyl-2-acetyl-
3-pyrazolidone, 1-phenyl-5,5-dimethyl-
3-pyrazolidone, 1-o-chlorophenyl-4-methyl-4-ethyl-3-pyrazolidone, 1-m-acetamidophenyl-4,4-diethyl-3-pyrazolidone,
1,5-diphenyl-3-pyrazolidone, 1- (m-tolyl) -5-phenyl-3-pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone,
4,4-dihydroxymethyl-1-tolyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-
Methyl-1- (p-chlorophenyl) -3-pyrazolidone and the like are included.

As aminophenols, for example,
p- (methylamino) phenol, p-aminophenol, 2,4-diaminophenol, p- (benzylamino) phenol, 2-methyl-4-aminophenol,
2-hydroxymethyl-4-aminophenol etc. can be mentioned.

The above developing agents can be used alone or in combination. Particularly, a combination of a polyhydroxybenzene compound and a 3-pyrazolidone compound is preferable. Although the amount of the developing agent used in the constituent layers is not uniform,
It may be in the range of 0.001 g to 1 g per 1 m ^{2, and in} the case of a silver halide emulsion layer 0.01 g to 3 g / g of silver halide.
Used in the range of.

Further, in the constituent layers, a compound capable of easily forming a soluble silver complex salt with an unexposed portion of a silver halide, which is referred to as a complexing agent, may be contained in the constituent layer, if desired, to accelerate the physical development advantageously.

As the complexing agent, for example, thiosulfates, thiocyanates, amine thiosulfates as described in US Pat. No. 3,169,962, or cyclic imides described in US Pat. No. 2,857,276,
A mercapto compound described in JP-B-46-11957 may be contained.

The developing agents may be added to the coating solution after being dissolved in water or a hydrophilic solvent such as methanol, or may be dissolved in a high boiling organic solvent or a low boiling organic solvent and added. . The high boiling point organic solvent generally has a boiling point of about 180 ° C. or higher, and examples thereof include allyl esters of phthalic acid such as ethyl phthalate and n-butyl phthalate, and phosphoric acid esters such as tricresyl phosphate. The low-boiling organic solvent generally has a boiling point of about 30 ° C. to 150 ° C., and examples thereof include lower alkyl acetates such as ethyl acetate and butyl acetate.

These high and low boiling point solvents may be used in combination, and the dissolved developing agent may be dispersed in the hydrophilic colloid by any known method.

When it is added to the constituent layers of the offset printing material according to the present invention, it may be added directly to any layer or dissolved in gelatin or a synthetic polymer compound such as polyvinyl alcohol or polyvinyl pyrrolidone. , U.S. Pat. No. 3,488,708, alkyl acrylates, sulfoalkyl acrylates, acrylic acid copolymers, and the like.

When the offset printing material of the present invention is processed after exposure, various processing liquids can be used.

The main examples are alkaline agents (eg, alkali metal or ammonium hydroxides, carbonates, phosphates), pH adjusters or buffers (eg, weak acids or weak bases such as acetic acid or sulfuric acid, and the like). Salt), a development accelerator (for example, various pyridinium compounds and cationic compounds described in US Pat. Nos. 2,648,604 and 3,671,247), potassium nitrate and sodium nitrate,
U.S. Pat. Nos. 2,533,990 and 2,577,127,
Nonionics such as polyethylene glycol condensates and derivatives thereof described in JP-B-2950970 and polythioethers represented by compounds described in British Patent Nos. 1020033 and 1020032. Compounds, polymer compounds having sulfite ester as represented by the compounds described in US Pat. No. 30,680,97, other organic amines such as pyridine, ethanolamine, cyclic amine, benzyl alcohol, hydrazines, etc.), Antifoggants (for example, alkali chloride, alkali bromide, alkali iodide and nitrobenzimidazoles described in U.S. Pat. Nos. 2,496,940 and 2,656,271, mercaptobenzimidazole, 5-methylbenzotriazole,
1-phenyl-5-mercaptotetrazole, U.S. Pat. Nos. 3,113,864, 3,342,596 and 32.
No. 95976, No. 3615522, No. 35971
Compounds for rapid processing solutions described in Japanese Patent No. 99, etc., thiosulfonyl compounds described in British Patent No. 972211, or phenazine-N-oxide as described in Japanese Patent Publication No. 46-41675. And other fog inhibitors described in "Science Photographic Handbook", Vol. 29, page 47 to page 47), and others, U.S. Pat. No. 31,615.
No. 13, No. 3161514, British Patent No. 10304
No. 42, No. 1144441, No. 1251558, and stain or anti-sludge agents, and preservatives (for example, sulfite, acidic sulfite, hydroxylamine hydrochloride, form sulfite, alkanolamine sulfite adduct). and so on. Further, a sequestering agent such as sodium hexametaphosphate and ethylenediaminetetraacetic acid, a wetting agent such as saponin and ethylene glycol, and the like can be used.

Further, in the developing solution, as a silver halide solvent, sodium thiosulfate, sodium thiocyanate,
Potassium thiocyanate, alkanolamine described in JP-B-61-57631, cyclic imine, alkyl-substituted amino alcohol, thiourea, mesoion described in Japanese Patent Application No. 4-62234, thiosalicylic acid described in JP-B-61-57631. It may contain thiosalicylic acid in an alkaline solution, for example 5-methylcarbamoylthiosalicylic acid.

When it is necessary to stop development of the offset printing material according to the present invention after development, a neutralizing solution can be used. This neutralization solution can be used in a normal acidic stop bath,
May be adjusted to about 3.0 to 8.0. The neutralizing solution may contain a water softening agent, a pH adjusting agent, a buffering agent, a hardening agent, etc. For the purpose of eliminating ink stains on the printing plate to be treated, colloidal silica, polyols, etc. May be added and contained.

After the printing material is treated as described above to obtain a plate, various post-treatments can be carried out for the purpose of improving and improving printability. For example, for the purpose of improving ink receptivity, US Pat. Nos. 3,592,647 and 3,490,906.
No. 3161508, Japanese Patent Publication No. 46-109
No. 10, No. 48-29723, No. 51-15762.
No. 52-15762.

[0275]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 An internal latent image type silver halide emulsion A and a surface latent image type silver halide emulsion E were prepared by the following methods.

Emulsion A An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added in the presence of a 1,8-dihydroxy-3,6-dithiaoctane solvent while vigorously stirring the gelatin aqueous solution at 75 ° C. for 5 minutes. An octahedral silver bromide emulsion having an average grain size of 0.15 μm was obtained. After adjusting the pAg of the solution to 8.20,
To this emulsion were added 115 mg each of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of Ag, and the mixture was stirred at 75 ° C. for 5 minutes.
The chemical sensitization treatment was performed by heating for 0 minutes. Using the silver bromide grains thus obtained as a core, in the same manner as in the first precipitation environment, in the presence of ammonium iridium (IV) chloride, while controlling the pAg of the solution to be 7.50, 40 minutes Further growth was carried out by adding, and finally a cubic monodisperse core / shell silver bromide emulsion having an average grain size of 0.25 μm was obtained (Ir: 2.1 ×).
10 ^-8 mol / Ag mol). After washing and desalting, add 1 silver to this emulsion.
3.4 mg each of sodium thiosulfate and chloroauric acid (tetrahydrate) were added per mol, and the mixture was heated at 75 ° C. for 60 minutes for chemical sensitization treatment, and internal latent image type silver halide emulsion A was obtained.
Got

Emulsion E (Comparative Example) A cubic silver chlorobromide emulsion (AgCl) having an average particle size of 0.3 μ was added simultaneously to a mixed aqueous solution of sodium chloride and potassium bromide and an aqueous solution of silver nitrate at 50 ° C. over 11 minutes. ₉₈ Br
₂ ) was prepared. This emulsion was washed with sedimentary water, and sodium thiosulfate and chloroauric acid (tetrahydrate) were added at 60 ° C. for chemical sensitization to prepare surface latent image type emulsion E.

Production of a lithographic printing plate A matting layer containing silica particles having an average particle size of 5 μm was provided on one side of a polyester film support which had been subjected to subbing treatment, and carbon black was included on the opposite side of the photographic gelatin. A halation-preventing subbing layer containing 20% by weight of silica powder having an average particle size of 7 μm;
15 nucleating agents (2.5 × 10 ⁻⁶ mol / Ag mol) and VI
-1 nucleation accelerator (8.8 × 10 ⁻⁴ mol / Ag mol) and sensitizing dye I-1 (2.0 × 10 ⁻³ mol / Ag mol)
And emulsion A was coated. The gelatin of the undercoat layer is 3.1
g / m ² , the emulsion layer gelatin is 1.3 g / m ² , and the coated silver amount is 1.
It was 3 g / m ² . The hardener for the undercoat layer and emulsion layer is 2,
4-dichloro-6-hydroxy-s-triazine was used. A polyvinyl alcohol solution containing PdS nuclei, which are physical development nuclei, was applied onto this emulsion layer and dried to prepare a lithographic printing plate sample 1A. Also planographic printing plate sample 1
The sensitizing dyes shown in Table 1 were used instead of the sensitizing dye I-1 of A, and lithographic printing plate samples 2A to 16A were prepared. A lithographic printing plate sample 17E was prepared by using Emulsion E instead of Emulsion A of lithographic printing plate sample 1A, and removing the nucleating agent and nucleation accelerator.

These planographic printing plate samples 1A to 17E
Through a 633 nm interference filter with a high-intensity photometer at 10 ^-6 seconds to expose a halftone dot image having an area of 5% to 95% of a gray contact screen of 100 to 200 lines / inch, and a developing solution (X) is exposed. At 30 ° C. for 30 seconds.

Immediately after the development processing, the solution was treated with a neutralizing solution having the following composition at 25 ° C. for 15 seconds, the excess solution was removed with a squeezing roller, and dried at room temperature.

<Developer (X)> Water 700 ml Potassium hydroxide 23 g Anhydrous sodium sulfite 50 g Hydroquinone 27 g 2-Mercaptobenzoic acid 1.5 g 2-Methylaminoethanol 10 g 2-Methylimidazole 2.0 g Uracil 5.0 g Water 1 Bring to liter (adjust to pH 11.0).

<Neutralization liquid> Water 600 ml Citric acid 11 g Sodium citrate 36 g Colloidal silica (20% liquid) 6 ml Ethylene glycol 6 ml Water is made up to 1 liter.

Further, the lithographic printing plate made with a contact screen was mounted on an offset printing machine, the desensitizing liquid described below was applied all over the plate surface, and printing was carried out using the following dampening liquid. The printing machine is A. B. An AV-Dick 350CD manufactured by Dick was used.

<Desensitizer> Water 550 ml Isopropyl alcohol 450 ml Ethylene glycol 50 g Compound A (Chemical formula 79) 1 g

[0286]

[Chemical 79]

<Moistening liquid> o-phosphoric acid 10 g nickel nitrate 5 g sodium sulfite 5 g ethylene glycol 100 g colloidal silica (20%) 28 g Water is added to make 2 liters.

Lithographic printing plate samples 1A to 16A and 17E
For, the resolution and printing durability were evaluated.

The resolution of the printing plate was evaluated on the printed matter. That is, when exposing a lithographic printing plate through a gray contact screen, 100, 133, 150, 175 and 200 lines / inch were used, and fine halftone dots (5% dots) could be reproduced firmly and clearly. Rating 1 (100 lines / inch) to rating 5 (200 lines / inch) depending on the number
It was expressed in 5 steps. Further, the printing durability according to the number of sheets in which printing became impossible due to the occurrence of background stains or the scattering of silver was evaluated according to the following criteria. The results are shown in Table 1.

Printing durability evaluation standard 1 2000 sheets or less 2 2001-4000 sheets 3 4001-6000 sheets 4 6001-8000 sheets 5 8001 sheets or more

[0291]

[Table 1]

As is clear from the results shown in Table 1, it was found that a good negative transfer image was obtained by using the sensitizing dye of the present invention, and the positive transfer showed better printability than the image.

Example 2 Lithographic printing plate samples 1A to 16A and 17E of Example 1.
From the negative transfer image in the same manner as in Example 1 except that each of them was developed with a developing solution (Y) at 30 ° C. for 30 seconds and then treated with a developing solution (Z) at 30 ° C. for 30 seconds. The following planographic printing plate was obtained, and the resolution, printing durability, and inking property were evaluated. The results are shown in Table 2.

Developer (Y) (Z) Water 700 ml 700 ml Potassium hydroxide 23 g 23 g Anhydrous sodium sulfite 50 g 50 g Hydroquinone 27 g 27 g 2-Mercaptobenzoic acid 1.5 g 1.5 g 2-Methylaminoethanol-10 g 2-Methylimidazole 2 0.0g 1.5g Uracil-15g Make up to 1 liter with water. (Adjust to pH 11.0) (Adjust to pH 11.0)

[0295]

[Table 2]

As is clear from Table 2, ordinary chemical development was carried out with a developer (Y) containing no silver halide solvent to obtain a developer (Z) containing a large amount of silver halide solvent and having a strong dissolving power. By carrying out the diffusion transfer development with two baths, better results can be obtained as in Example 1.

Example 3 Internal latent image type silver halide emulsions B to D were prepared by the following method.

Emulsion B An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin at 75 ° C. for 5 minutes to obtain an octahedral silver bromide emulsion having an average grain size of 0.1 μm. It was P of solution
After adjusting the Ag to 8.0, this emulsion was treated with 130 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of Ag.
Was added and the mixture was heated at 75 ° C. for 60 minutes for chemical sensitization. The silver bromide grains thus obtained are used as a core for further shelling. A mixed aqueous solution of sodium chloride containing iridium (IV) chloride and potassium bromide and a silver nitrate aqueous solution are simultaneously added so that the pAg becomes 7.8. Controlled to 60 minutes for heating to further grow, and finally the average particle size 0.4μm
Silver chlorobromide (Br 80 mol%) cubic monodisperse core / shell emulsion was obtained (Iridium is 2.1 × 10 ⁻⁸ mol / Ag).
Molar content). After washing with water and desalting, 12 mg each of sodium thiosulfate and chloroauric acid (tetrahydrate) were added to this emulsion per mol of silver, and the mixture was heated at 75 ° C. for 60 minutes for chemical sensitization to give an internal latent image. A type silver halide emulsion B was obtained.

Emulsion C In Emulsion B, a silver chlorobromide cubic monodisperse core / shell emulsion C containing 20 mol% Br was prepared by changing the composition of the halogen solution to be shelled.

Emulsion D An aqueous solution of sodium chloride and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin at 50 ° C. for 10 minutes to prepare a cubic silver chloride emulsion having an average grain size of 0.3 μm. Add potassium bromide and potassium iodide solution to this emulsion,
After aging for 1 hour, settle, wash with water, size 0.33μ
An mBr AgCl ₂₀ Cl _79.7 (I _0.3 ) silver (iodo) chlorobromide emulsion was prepared (conversion type internal latent image emulsion).

Samples 1A, 5A, 6A and 1 of Example 1
0A, 11A, 14A, Emulsion A is the above Emulsion B
To D were prepared as shown in Table 3 to prepare lithographic printing plates, which were treated and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0302]

[Table 3]

It can be seen that the sensitizing dye of the present invention exhibits good printability even in emulsions of various halogen compositions, particularly silver (iodo) bromide bromide emulsions containing a large amount of Br.

Example 4 The sample of Example 3 was treated in the same manner as in Example 2 to examine the printability and the like. The results are shown in Table 4.

[0305]

[Table 4]

As in Example 2, it can be seen that the two-bath treatment exhibits better printability.

Example 5 Samples 1A, 5A of Example 1 and Samples 1B-a, 1B-b, 1C-a, 1C-b, 1D- of Example 3
a, 1D-b, a lithographic printing plate was prepared in the same manner as in Example 1 except that the compound of formula (1) was added to the emulsion layer as shown in Table 5, and processed and evaluated in the same manner as in Example 1. The results are shown in Table 5.
Shown in.

[0308]

[Table 5]

When the compound of the formula (1) is used in combination, the resolution,
It can be seen that the printing durability is improved.

[0310]

According to the present invention, it is possible to deal with high illuminance light sources such as He-Ne and semiconductor lasers. Further, it has excellent characteristics such as high resolution and printing durability.

Claims (1)

[Claims] 1. A lithographic printing material utilizing a silver salt diffusion transfer method, which comprises, on a support, at least one undercoating layer containing an antihalation layer, a silver halide emulsion layer and a physical development nucleus layer. The silver halide emulsion layer is an internal latent image type emulsion layer,
A lithographic printing material for obtaining a negative transfer silver image, which contains at least one of the sensitizing dyes represented by the following Chemical Formulas 1 and 2. [Chemical 1] [Chemical 2] [In Chemical Formula 1, Z and Z ₁ each represent an atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₁
And R ₂ each represent an alkyl group or an aryl group. Q ₁ and Q ₂ together represent the non-metallic atomic group necessary to complete the 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone nucleus. L, L ₁ and L ₂ each represent a methine group. n ₁ and n ₂ each represent 0 or 1. X ₁ represents an anion. m ₁
Represents 0 or 1, and when forming an intramolecular salt, m ₁
Is 0. In Chemical Formula 2, R ₁₁ and R _{12, which} may be the same or different, each represents an alkyl group, an aralkyl group, an alkenyl group or an aryl group, and R ₁₃ represents a heterocyclic group. Z ₁₁ and Z ₁₂ may be the same or different and each represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. X ₁₁ is a counterion, L
_{11 to} L ₁₅ each represent a methine group, and p and q each represent 0, 1 or 2. ]