JPH06175366A - Planographic printing material - Google Patents

Abstract

PURPOSE:To obtain a planographic printing material having high sensitivity and IR sensitivity with which a negative transfer silver picture is obtd. by silver salt diffusion transfer method, by using such a silver halide emulsion that is an inner latent image-type emulsion and contains a specified sensitizing coloring matter. CONSTITUTION:This printing material has at least a silver halide emulsion layer and a physical development nucleus layer on a supporting body and is used to obtain a negative transfer silver picture by silver salt diffusion transfer method. The silver halide emulsion is an inner latent image-type emulsion and contains a sensitizing coloring matter having the sensitizing max. in >=670nm wavelength region. Thereby, the silver halide emulsion is sensitized in a near IR or IR region to have the sensitizing max. at >=670nm, preferably between 680nm and 800nm wavelength. Thus, the emulsion has IR sensitivity and can be exposed to semiconductor laser light of the like as the light source. This enables direct printing. As for the sensitizing coloring matter, tricarbocyanine coloring matter and/or 4-quinoline nucleus-contg. dicarbocyanine coloring matter are preferable.

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. Specifically, it relates to a red-sensitive or infrared-sensitive silver salt lithographic printing material. More specifically, the present invention relates to a silver salt lithographic printing material for silver salt diffusion transfer, which has excellent photographic characteristics, little generation of background stain, and improved ink inking property and printing durability.

[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-
No. 26019, JP-A No. 61-173247 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
6, No. 3,761,276, and No. 3,795,677. This product has a high sensitivity, but has the drawback that it is difficult to reverse with a developer containing a silver halide solvent.

JP-A-55-69551 describes a negative image forming method by a peeling type diffusion transfer method using an internal latent image type emulsion. However, the developing solution described here is a viscous developing solution containing hydroxyethyl cellulose having a pH of 13.1, and there is no mention of an activator process or a conventional process containing substantially no developing agent. It is not intended for lithographic printing materials.

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.

Under these circumstances, various types of silver salt diffusion transfer methods can be applied, high sensitivity, stable processing, and a negative transfer silver image having excellent printing characteristics can be obtained. Printing materials are desired.

Further, 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, it is considered that there is an advantage that it is easy to correspond to an output machine such as an image setter whose negative output is the main force. However, a negative type lithographic printing material has not yet been practically used, and as described above, a material satisfying the sensitivity and printing characteristics has not been obtained so far.

Among them, the semiconductor lasers are particularly small and inexpensive, easily modulated, and have a long life. Therefore, a lithographic printing material capable of obtaining a negative type silver image corresponding thereto is desired. The oscillation wavelength range of the semiconductor laser is 670 nm
As described above, it is necessary to sensitize the emulsion layer of the lithographic printing material to the wavelength region of 670 nm or more, particularly 680 nm or more in the near infrared or infrared.

When near-infrared or infrared sensitization is performed in the wavelength range of 670 nm or more, particularly 680 nm or more, the sensitizing dye is likely to change, which may deteriorate the storage stability of the light-sensitive material. It is remarkable in a lithographic printing material using a type emulsion, and a method of stabilizing the same is highly desired.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a highly sensitive and infrared-sensitive lithographic printing material for obtaining a negative transferred silver image by utilizing a silver salt diffusion transfer method. . Furthermore, it is intended to have high resolution, excellent printing durability, and excellent ink receptivity so that it can be applied to various processing systems.

[0011]

Such an object is achieved by the following constitutions (1) to (3). (1) In a lithographic printing material utilizing a silver salt diffusion transfer method having at least a silver halide emulsion layer and a physical development nucleus layer on a support, the silver halide emulsion is an internal latent image type emulsion and has a size of 670 nm or more. A lithographic printing material containing a sensitizing dye having a maximum sensitizing wavelength in the above wavelength range to obtain a negative transfer silver image. (2) The sensitizing dyes are tricarbocyanine dyes and 4
The lithographic printing material of (1) above, which is one or more of quinoline nucleus-containing dicarbocyanine dyes. (3) The tricarbocyanine dye is represented by the following chemical formula 5 or 6, and the 4-quinoline nucleus-containing dicarbocyanine dye is represented by the following chemical formula 7. Printing material.

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

[In the formula 5, R ₁₁ and R ₁₂ each represent an alkyl group, which may be the same or different. R ₁₀ represents a hydrogen atom, a methyl group, a methoxy group or an ethoxy group. D represents an atomic group necessary for completing a divalent ethylene bond. Z and Z ₁ each represent a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ₁ represents an acid anion, and r is 1 or 2
Represents In Chemical formula 6, R ₁₁ and R ₁₂ each represent an alkyl group, which may be the same or different.
R ₁₃ and R ₁₄ each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group or a benzyl group,
These may be the same or different. R ₁₅ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group,
A benzyl group or a group represented by Chemical formula 8 (in Chemical formula 8, W
₁₁ and W ₁₂ each represent an alkyl group or an aryl group,
W ₁₁ and W ₁₂ are connected to each other to form a 5- or 6-membered nitrogen-containing compound.

[0016]

[Chemical 8]

It is also possible to form an elementary ring. ) Is represented. D ₁ and D ₂ each represent a hydrogen atom, and D ₁ and D
₂ and it is also possible to make a bivalent ethylenic bonds jointly. Z and Z ₁ each represent a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ₁ represents an acid anion, and r represents 1 or 2. In Chemical formula 7, R ₁₆ and R ₁₇ each represent an alkyl group, which may be the same or different. R ₁₈ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group or a benzyl group, and these may be the same or different. V ₁ represents a hydrogen atom, a lower alkyl group, an alkoxy group or a halogen atom. Z ₂ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle.
X ₁₁ represents an acid anion, and p, q and r ₁ are each 1
Or represents 2. ]

In the above, the preferred configurations are (4) to (7) below. (4) The sensitizing dye in the above (1) to (3) is 680
It has maximum sensitivity in the wavelength range of nm to 800 nm. (5) In any one of (1) to (4) above, a compound represented by the following chemical formula 23 is further contained. (6) In any one of (1) to (5) above, further contain a compound represented by the following chemical formula 27. (7) In any one of (1) to (6) above, further contain one or more of the nucleating agents represented by Chemical Formulas 33 and 34 below.

[0019]

Specific Structure The specific structure of the present invention will be described in detail below. The lithographic printing material of the present invention is 670 nm or more,
Preferably, it contains a sensitizing dye having a sensitizing maximum in a wavelength range of 680 nm or more. Therefore, the silver halide emulsion of the present invention is near-infrared or infrared sensitized so as to have a maximum sensitization in a wavelength range of 670 nm or more, preferably 680 nm or more and 800 nm or less.

As a result, it becomes infrared-sensitive, and exposure using a semiconductor laser or the like as a light source can be performed. As a result, a direct printing plate can be obtained.

As the above-mentioned sensitizing dye, a tricarbocyanine dye and / or a dicarbocyanine dye containing a 4-quinoline nucleus is particularly preferable. This is because it is particularly advantageous in terms of sensitivity, sharpness, printing durability, and the like.

Among the tricarbocyanine dyes used in the present invention, those particularly useful are those represented by Chemical formulas 5 and 6.

In each of Chemical formulas 5 and 6, R ₁ and R ₂ may be the same or different and each is an alkyl group (preferably having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, Propyl group, butyl group, pentyl group, heptyl group, etc.), substituted alkyl group (as a substituent, for example, carboxy group, sulfo group, cyano group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxy Carbonyl group (C8 or less, for example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.), alkoxy group (C7 or less, for example, methoxy, ethoxy,
Propoxy group, butoxy group, benzyloxy group, etc.),
Aryloxy group (for example, phenoxy group, p-tolyloxy group, etc.), acyloxy group (having 3 or less carbon atoms,
For example, acetyloxy group, propionyloxy group, etc.), acyl group (having 8 or less carbon atoms, such as acetyl group, propionyl group, benzoyl group, mesyl group, etc.),
Carbamoyl group (for example, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), An alkyl group (having 6 or less carbon atoms in the alkyl portion) substituted with an aryl group (eg, phenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, d-naphthyl group, etc.). However, two or more of these substituents may be combined and substituted with an alkyl group. } Is represented.

In Chemical formula 5, R ₁₀ represents a hydrogen atom, a methyl group, a methoxy group or an ethoxy group.

In Formula 6, R ₁₃ and R ₁₄ are each a hydrogen atom, a lower alkyl group (eg, methyl group, ethyl group, propyl group, etc.), a lower alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.). ), A phenyl group, and a benzyl group.

In Chemical Formula 6, R ₁₅ is a hydrogen atom, a lower alkyl group (eg, methyl group, ethyl group, propyl group, etc.), a lower alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), phenyl group. , A benzyl group, and a group represented by Chemical formula 8. In chemical formula 8,
W ₁₁ and W ₁₂ are each a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms in the alkyl moiety, preferably 1 to 4,
For example, it represents a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, a phenylethyl group), an aryl group (for example, a phenyl group, a naphthyl group, a tolyl group, a p-chlorophenyl group, etc.), and W ₁₁ and W ₁₂ are It is also possible to combine with each other to form a 5- or 6-membered nitrogen-containing heterocycle.

In the chemical formula 5, D is a divalent ethylene bond,
For example, it represents an atomic group necessary for completing ethylene or triethylene, and this ethylene bond has one, two or more appropriate groups, for example, an alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group). Group, propyl group, isopropyl group, butyl group, etc.), halogen atom (for example, chlorine atom, bromine atom, etc.), or alkoxy group (having 1 to 4 carbon atoms, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, Butoxy group etc.) and the like.

In the chemical formula 6, D ₁ and D ₂ each represent a hydrogen atom. However, D ₁ and D ₂ jointly work on the above D
It is also possible to make a divalent ethylene bond having the same meaning as.

In each of Chemical formula 5 and Chemical formula 6, Z and Z ₁ represent a group of nonmetal atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, for example, a thiazole nucleus [eg benzothiazole, 4 -Chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole,
6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-
Ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5
-Phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole,
5,6-dimethylbenzothiazole, 5-hydroxy-
6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, 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 benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,1-d] Selenazole, naphtho [1,2-d] selenazole, etc.], oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzene Oxazole, 6-hydroxy-benzoxazole, 4,6-dimethyl-benzoxazole, 5-ethoxy benzoxazole, naphtho [2,
1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, etc.], quinoline nucleus [eg, 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2] -Quinoline, 6-methyl-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-
2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 8-fluoro-4-quinoline, etc.], 3,3-dialkylindolenine nucleus (for example,
3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine,
3,3-dimethyl-5-methylindolenine, 3,3-
Dimethyl-5-chloroindolenine, etc., imidazole nucleus (for example, 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl -5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole,
1-methyl-5-cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-methyl-5-
Fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-
5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-
Ethylnaphtho [1,2-d] imidazole, etc.), pyridine nucleus (eg, pyridine, 5-methyl-2-pyridine,
3-methyl-4-pyridine etc.) and the like. Of these, a thiazole nucleus and an oxazole nucleus are advantageously used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used.

In Chemical Formulas 5 and 6, X ₁ represents an acid anion. In Chemical formula 5 and Chemical formula 6, r represents 1 or 2.

Among the 4-carboline nucleus-containing dicarbocyanine dyes used in the present invention, particularly useful ones are represented by Chemical Formula 7. In Chemical formula 7, R ₁₆ and R ₁₇ have the same meanings as R ₁₁ and R _{12 in} Chemical formula 5 and Chemical formula 6, respectively.

R ₁₈ has the same meaning as R _{13 in} Chemical formula 6. However, R ₁₈ is preferably a lower alkyl group or a benzyl group.

V ₁ is a hydrogen atom, a lower alkyl group (eg, methyl group, ethyl group, propyl group), an alkoxy group (eg, methoxy group, ethoxy group, butoxy group),
Represents a halogen atom (eg, fluorine atom, chlorine atom, etc.) and a substituted alkyl group (eg, trifluoromethyl group, carboxymethyl group, etc.).

Z ₂ has the same meaning as Z and Z _{1 in} Chemical formulas 5 and 6. X ₁₁ has the same meaning as X ₁ in Chemical formula 5 and Chemical formula 6.

P, q and r ₁ each represent 1 or 2.

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

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

[0042]

[Chemical 14]

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

[0046]

[Chemical 18]

[0047]

[Chemical 19]

[0048]

[Chemical 20]

[0049]

[Chemical 21]

[0050]

[Chemical formula 22]

The infrared sensitizing dye used in the present invention is 5 × 10 ^-7 mol to 5 × 10 ^-3 mol, preferably 1 × 10 ^-6 mol to 1 × 10 ^-3 mol per mol of silver halide. It is contained in the silver halide photographic emulsion in a molar ratio of from 2.times.10.sup.- ⁶ mol to 5.times.10.sup.- ⁴ mol.

The infrared sensitizing dye used in the present invention can be directly dispersed in an emulsion. Further, these may be first dissolved in a suitable solvent such as 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. As a method of adding the infrared sensitizing dye, as described in US Pat. No. 3,469,987, the dye is dissolved in a volatile organic solvent, and this solution is dispersed in a hydrophilic colloid, As described in JP-B-46-24185, a method of adding this dispersion to an emulsion, a water-insoluble dye is dispersed in an aqueous solution emulsion without being dissolved, and this dispersion is added to the emulsion. Method:
As described in U.S. Pat. No. 3,822,135, a method in which a dye is dissolved in a surfactant and this solution is added to an emulsion: as described in JP-A-51-74624, a compound for red-shifting Method of dissolving by using this solution and adding the solution to the emulsion: a method of dissolving the dye in a substantially water-free acid and adding the solution to the emulsion as described in JP-A-5080826 Are used. Other,
U.S. Pat. Nos. 2,912,343 and 33, 33 are added to the emulsion.
42605, 2996287, 3429835.
The methods described in No. etc. are also used. The infrared sensitizing dyes described above may be evenly dispersed in the silver halide emulsion before coating on a suitable support, but of course they may be dispersed at any stage in the preparation of the silver halide emulsion. it can.

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, US Pat. Nos. 3,703,377, 2,688,545 and 339.
No. 7060, No. 3615635, No. 3628964
No., British Patent Nos. 1242588 and 1293862.
No. 4, Japanese Patent Publication No. 43-4936, No. 44-14030,
43-10773, U.S. Pat. No. 3,416,927,
JP-B-43-4930, U.S. Pat. No. 3,615,613.
No. 3615632, No. 3617295, No. 36
The sensitizing dyes described in 35721 and the like can be used.

In the present invention, the compound represented by the following chemical formula 23 can be used for the purpose of further enhancing the supersensitizing effect and / or enhancing the storage stability.

[0055]

[Chemical formula 23]

In the formula 23, --A ₀ --represents a divalent aromatic residue, which is a --SO ₃ M group [wherein M represents a hydrogen atom or a cation imparting water solubility (eg sodium, potassium, etc.). . ] May be included.

-A ₀ -is, for example, -A in Chemical formula 24 and Chemical formula 25.
Those selected from _1- or -A ₂ -of Chemical formula 26 are useful. However R _19, R _20, when the R ₂₁ or R ₂₂ contains no -SO ₃ M is, -A ₀ - is -A ₁ - is selected from the group consisting of.

[0058]

[Chemical formula 24]

[0059]

[Chemical 25]

[0060]

[Chemical formula 26]

In Chemical formulas 24 and 25, M is a hydrogen atom,
Alternatively, it represents a cation that imparts water solubility.

In Chemical Formula 23, R ₁₉ , R ₂₀ , R ₂₁ , and R ₂₂ are each a hydrogen atom, a hydroxy group, or a lower alkyl group (the number of carbon atoms is preferably 1 to 8. For example, methyl group, ethyl group, n -Propyl group, n-butyl group, etc.),
Alkoxy group (1-8 carbon atoms are preferred.
For example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, naphthoxy group, o-troxy group, p-sulfophenoxy group, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.), Heterocyclic nuclei (eg morpholinyl group, piperidyl group etc.), alkylthio groups (eg methylthio group, ethylthio group etc.), heterocyclylthio groups (eg benzothiazolylthio group, benzimidazolyl group, phenyltetrazolylthio group etc.), arylthio groups ( For example, 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, - hydroxyethylamino group, di - (beta-hydroxyethyl) amino group, beta-sulfoethylamino group), an arylamino group or a substituted arylamino group (e.g. anilino group,, o-sulfoanilino group,
m-sulfoanilino group, p-sulfoanilino group, o-toluidino group, m-toluidino group, p-toluidino group, o
-Carboxyanilino group, m-carboxyanilino group,
p-carboxyanilino group, o-chloroanilino group, m
-Chloroanilino group, p-chloroanilino group, p-aminoanilino group, o-anisidino group, m-anisino group,
p-anisidino group, o-acetaminoanilino group, hydroxyanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc., heterocyclylamino group (for example, 2-benzothiazolylamino group,
2-pyrazyl-amino group), a substituted or unsubstituted aralkylamino group (eg, benzylamino group, o-anisylamino group, m-anisylamino group, p-anisylamino group, etc.), aryl group (eg, phenyl group, etc.),
Represents a mercapto group. R ₁₉ , R ₂₀ , R ₂₁ , and R ₂₂ may be the same or different from each other. −A ₀ − is −A ₂ −
At least one of R ₁₉ , R ₂₀ , R ₂₁ , and R ₂₂ has at least one sulfo group (which may be a free acid group or may form a salt). Need to be present.

W represents -CH = or -N =, preferably -CH = is used.

Next, specific examples of the compound contained in Chemical formula 23 used in the present invention will be given. However, the present invention is not limited to these compounds.

(II-1) 4,4'-bis [4,6-di (benzothiazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (II-2) 4,4'-bis [4,6-di (benzothiazolyl-2-amino) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (II-3) 4,4'-bis [4 , 6-di (naphthyl-2
-Oxy) pyrimidin-2-ylamino] stilbene-
2,2'-Disulfonic acid disodium salt (II-4) 4,4'-bis [4,6-di (naphthyl-2)
-Oxy) pyrimidin-2-ylamino] bibenzyl-
2,2'-Disulfonic acid disodium salt (II-5) 4,4'-bis (4,6-dianilinopyrimidin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (II-6) ) 4,4'-Bis [4-chloro-6- (2-naphthyloxy) pyrimidin-2-ylamino] biphenyl-2,2'-disulfonic acid disodium salt (II-7) 4,4'-bis [ 4,6-Di (1-phenyltetrazolyl-5-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (II-8) 4,4'-bis [4,6 -Di (benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (II-9) 4,4'-bis (4,6-diphenoxypyrimidin-2-ylamino) ) Su Reuben 2,2'-disulfonic acid disodium salt (II-10) 4,4'-bis (4,6-diphenyl-thio-2-ylamino) stilbene-2,2'-
Disulfonic acid disodium salt (II-11) 4,4'-bis (4,6-dimercaptopyrimidin-2-ylamino) biphenyl-2,2'-disulfonic acid disodium salt (II-12) 4,4 ' -Bis (4,6-dianilino-triazin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (II-13) 4,4'-bis (4-anilino-6-hydroxy-triazine-2 -Ilamino) stilbene-
2,2'-Disulfonic acid disodium salt (II-14) 4,4'-bis (4-naphthylamino-6)
-Anilino-triazin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt

Among these specific examples, (II-1) to (II
-12) is preferable, and particularly (II-1), (II-2),
(II-3), (II-4), (II-5) and (II-7) are preferable.

The compound of Chemical formula 23 is the silver halide 1 in the emulsion.
It is advantageously used in an amount of about 0.01 to 5 g per mole. Moreover, you may use 1 or more types or 2 or more types together. The ratio (weight ratio) of the infrared sensitizing dye and the compound represented by Chemical formula 23 is preferably such that the range of 1/1 to 1/100 of infrared sensitizing dye / compound represented by Chemical formula 23 is used. In particular, a range of 1/2 to 1/50 is advantageously used.

The compound represented by Chemical formula 23 used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It can also be dissolved and added 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. Also, Japanese Patent Laid-Open No. 50-
It can also be dispersed and added to the emulsion by the method described in JP-A-80119.

In the present invention, the compound of the following chemical formula 27 can be used in combination. By using the compound of Chemical formula 27, storability is improved.

[0070]

[Chemical 27]

In the formula 27, Z ₃ represents a non-metal atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, for example, thiazolium compounds {eg thiazolium, 4-
Methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium,
5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,1-d] thiazolium, etc.}, oxazolium {for example Oxazolium, 4-methyloxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-d] oxazolium}, etc., Imidazoliums (for example, 1-methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium,
1-ethyl-5,6-dichlorobenzimidazolium,
1-allyl-5-trichloromethyl-6-chloro-benzimidazolium, etc.), selenazolium [for example, benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazo And naphtho [1,2-d] selenazolium] and the like. R ₂₃ represents a hydrogen atom, an alkyl group (having 8 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group) and an alkenyl group (eg an allyl group). R ₂₄ represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.). X
₂ is an acid anion (for example, Cl ⁻ , Br ⁻ , I ⁻ , ClO
₄ ^- represents a p- toluenesulfonic acid ion). Z ₃
Among them, thiazolium compounds are preferably used advantageously.
More preferably, a substituted or unsubstituted benzothiazolium or naphthothiazolium is advantageously used.

Specific examples of the compound represented by Chemical formula 27 are shown below. However, the present invention is not limited to only these compounds.

[0073]

[Chemical 28]

[0074]

[Chemical 29]

[0075]

[Chemical 30]

[0076]

[Chemical 31]

[0077]

[Chemical 32]

The compound of formula 27 is advantageously used in an amount of about 0.01 to 5 g per mol of silver halide in the emulsion. The ratio (weight ratio) of the infrared sensitizing dye to the compound represented by Chemical formula 27 is preferably in the range of 1/1 to 1/300 of the infrared sensitizing dye / compound represented by Chemical formula 27. The range of 1/2 to 1/50 is advantageously used.

The compound represented by Chemical formula 27 used in the present invention can be directly dispersed in an emulsion, and a suitable solvent (water, methyl alcohol, ethyl alcohol,
It is also possible to dissolve it in propanol, methyl cellosolve, acetone, etc.) or a mixed solvent containing a plurality of these 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 Chemical formula 27 may be added to the emulsion before or after the addition of the infrared sensitizing dye. Further, the compound of Chemical formula 27 and the infrared sensitizing dye may be separately dissolved, and these may be separately and simultaneously added to the emulsion, or may be mixed and then added to the emulsion. You may use together the compound of Chemical formula 23 and the compound of Chemical formula 27.

In the present invention, the nucleating agent used in combination with the internal latent image type emulsion is preferably at least one of the compounds represented by Chemical formulas 33 and 34.

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.

[0083]

[Chemical 33]

[0084]

[Chemical 34]

In the formula 33, Z ¹ represents a group of non-metal atoms 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 35 or Chemical formula 36. 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.

[0086]

[Chemical 35]

[0087]

[Chemical 36]

In the chemical formula 34, 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 37, 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 38 may be formed to include ²⁴ and the hydrazine nitrogen. Further, the above-mentioned groups may be substituted with a substituent, if possible.

[0089]

[Chemical 37]

[0090]

[Chemical 38]

The nucleating agent represented by Chemical formula 33 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.

[0092] 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 by 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 represented by R ¹ preferably has 1 to 1 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 is applicable, some have already been described so far, 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.

Here, X ¹ is an adsorption promoting group to 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 those mentioned as the substituents 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.
Examples thereof include benzotriazole and aminothiazole.

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 39 and the like are preferable.

[0107]

[Chemical Formula 39]

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 33, those having an adsorption promoting group on 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 33 are shown below, but the invention is not limited thereto.

[0111]

[Chemical 40]

[0112]

[Chemical 41]

[0113]

[Chemical 42]

[0114]

[Chemical 43]

[0115]

[Chemical 44]

[0116]

[Chemical formula 45]

The compounds described above are, for example, 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.

Next, the chemical formula 34 will be described in detail. In Chemical formula 34, 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, an 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 the adsorption of the compound represented by Chemical formula 34 on the surface of silver halide grains. X ² here
Has the same meaning as X ¹ in Chemical formula 33, 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 33. 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 34, a carbonyl group is most preferable.
Further, as Chemical Formula 34, those having an adsorption group to silver halide are more preferable. Particularly preferred adsorbing groups on silver halide are the mercapto group, the cyclic thioamide group and the nitrogen-containing heterocyclic group described in Chemical formula 33 above.

Specific examples of the compound represented by Chemical formula 34 are shown below. However, the present invention is not limited to the following compounds.

[0133]

[Chemical formula 46]

[0134]

[Chemical 47]

[0135]

[Chemical 48]

[0136]

[Chemical 49]

[0137]

[Chemical 50]

[0138]

[Chemical 51]

The method of synthesizing the compound represented by Chemical formula 34 used in the present invention is described in, for example, Research Disclosure magazine No. 15162 (November 1976, pp. 76-77), 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 33 and 34 may be contained in the photographic light-sensitive material, but any layer is preferable, but it is preferable that the compound is 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 33, 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 where it has a group promoting adsorption to 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 penzothiazolium.

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

(5) In the above (2), R ¹ 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 above (6), R ¹ is bonded to the heterocycle completed by Z to form a ring.

When the nucleating agent represented by Chemical formula 34 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 represented by X ² on the silver halide 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 33 and the compound of Chemical formula 34 can be used in combination.

As the nucleating agent, all compounds conventionally developed for the purpose of nucleating an internal latent image type silver halide are applicable. Two or more nucleating agents may be used in combination as described above. More specifically, examples of the nucleating agent include “Research Disclosure” (Resarc
h Disclosure) No. 22534 (January 50, 1983)
Pp. 54), and these are roughly classified into three categories: hydrazine compounds, quaternary heterocyclic compounds and other compounds.

The nucleating agent of Chemical formula 33 can be classified as a quaternary heterocyclic compound, and the nucleating agent of Chemical formula 34 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 the above-mentioned Research Disclosure (Resarch Disclosur).
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 of Chemical formulas 33 and 34 may be used in combination with the other nucleating agents described therein. Further, in the present invention, it is particularly preferable to use the nucleating agent of Chemical formula 33.

In the present invention, it is preferable to use a nucleating agent together with a 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. A nucleation accelerator useful in the present invention is represented by Chemical Formula 52.

[0165]

[Chemical 52]

In the chemical formula 52, A represents a group which adsorbs 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 mercaptobutanes, aryl mercaptans, alkenyl mercaptans and aralkyl mercaptans.

Y ¹ represents a divalent linking group consisting of an atom or a group of atoms 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 53.

[0171]

[Chemical 53]

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 52, preferred compounds are represented by Chemical formulas 54 to 59.

[0176]

[Chemical 54]

[0177]

[Chemical 55]

[0178]

[Chemical 56]

[0179]

[Chemical 57]

[0180]

[Chemical 58]

[0181]

[Chemical 59]

In the formula 54, Q ¹ is preferably an atom necessary for forming a 5- or 6-membered heterocyclic ring composed of at least one atom of 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, tetrazole,
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 = H or an alkali metal atom under alkaline conditions. Possible groups (eg acetyl, cyanoethyl, methanesulfonylethyl, etc.)
Represents

These heterocycles include a nitro group, a halogen atom (eg, chlorine atom, bromine atom, etc.), a mercapto group, a cyano group, and a 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 ( For example, methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (eg, unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (eg, unsubstituted sulfamoyl group, methylsulfamoyl group, etc.). Moyl group, phenylsulfamoyl group, etc.), carbonamide group (eg, acetamide group, benzamide group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.) , Acyloxy groups (eg acetyl Alkoxy 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 are tetrazoles, triazoles, imidazoles, thiadiazoles and oxadiazoles. Y ¹ , R, t, and s each have the same meaning as in Chemical formula 52.

In the formula 55, Y ¹ , R, t, s, M ¹
Are synonymous with those of Chemical formula 52 and Chemical formula 54, and Q ² represents an atomic group necessary for forming a 5- or 6-membered heterocycle capable of forming with iminosilver. 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 56, M ¹ , R, Y ¹ and s have the same meanings as those of Chemical formula 54. X ⁵ represents an oxygen atom, a sulfur atom or a selenium atom, preferably a sulfur atom.

In Formula 57, 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 formula 54, respectively.

In Formula 58, R ³⁰ is-(Y ¹ ) _s -R
Represents However, M ¹ , R, Y ¹ and s are each
Synonymous with each of the four.

In Chemical Formula 59, 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 formula 58, respectively.

Specific compounds represented by Chemical Formula 52 of the present invention are shown below, but the compounds of the present invention are not limited to these.

[0193]

[Chemical 60]

[0194]

[Chemical formula 61]

[0195]

[Chemical formula 62]

[0196]

[Chemical formula 63]

[0197]

[Chemical 64]

[0198]

[Chemical 65]

[0199]

[Chemical formula 66]

[0200]

[Chemical formula 67]

[0201]

[Chemical 68]

[0202]

[Chemical 69]

The nucleation accelerator 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 in 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 contains silver halide grains whose surfaces are not pre-fogged and which form a latent image mainly 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 or (iodo) bromide or 20 mol% of bromine. The above is silver chlorobromide.

The average grain size of the silver halide grains (in the case of spherical grains or grains close to spheres, the grain size is represented by the grain size in the case of cubic grains, and the average size based on the projected area) is 2 μm or less. 0.1 μm or more is preferable, but 1 μm or less and 0.15 μm or less is particularly preferable.
That is all. The particle size distribution may be narrow or wide, but within the range of ± 40% of the average particle size (more preferably within ± 30%, most preferably within ± 30%) in terms of number of particles or weight in order to improve graininess and sharpness. (Preferably within ± 20%)
It is preferred to use in the present invention so-called "monodisperse" silver halide emulsions having a narrow grain size distribution such that 90% or more, especially 95% or more, of all the grains are contained in. Further, in order to satisfy the target gradation of the lithographic printing material which is a light-sensitive material, two or more kinds of monodisperse silver halide emulsions or grains of the same size having different grain sizes in emulsion layers 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, an octahedron, a dodecahedron and a 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 or other hydrophilic colloid layer of the present invention 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 mainly having a substantial light absorption in a range of 330 nm to 850 nm for improving 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, to 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.

[0219] 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 planographic 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 invention contains, for example, polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine compound 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 and 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 physical development nucleus layer 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 carbon black dye, International Publication WO88 / 04794, European Patent Publications EP0274723A1, 276566, 299435 and JP-A-52-92716. Issue 55-
155350, 55-155351, 61-2.
05934, 48-68623, US Patent 252
No. 7583, No. 3486897, No. 3746539
No. 3933798, No. 4130429, No. 40
40841, Japanese Patent Application No. 1-50874, and Japanese Patent Laid-Open No. 2-2
No. 82244, Japanese Patent Application No. 1-307363, Japanese Patent Application No. 2-
It is a hydrophilic colloid layer in which a solid fine particle dye or pigment disclosed in No. 310011 is dispersed. Further, in order to impart a printing plate suitability to the antihalation layer and the emulsion layer, fine powder of 1 to 10 μm such as silica can be added.

As a hydrophilic binder which can be advantageously used in the silver halide emulsion according to the present invention, there is gelatin, and a part or all of gelatin is a synthetic polymer such as polyvinyl alcohol or poly-N-vinylpyrrolidone. 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 can be used. 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.

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, bismuth, etc., or water-soluble metal salts thereof 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 a combination of these may be used. 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 photosensitive silver halide emulsion layer.

The support of the offset printing material according to the present invention includes, for example, 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 adhesion to the surface coated with the polyolefin, or for improving the printability.

In these regards, US Pat.
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.

A known surfactant may be added to the constituent layers of the offset printing material of the present invention, if necessary, alone or in 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 alkylamines, 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 its adjacent layers (undercoat layer, intermediate layer), etc., but it is most preferable to incorporate it in the antihalation layer. The alkaline aqueous solution used for development may also contain a developer.

Specific compounds of the developer include polyhydroxybenzenes such as hydroquinone, catechol, chlorohydroquinone, pyrogallol, bromohydroquinone, isopropylhydroquinone, tolhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5. -Dimethylhydroquinone, 2,3-dibromohydroquinone, 1,4-dihydroxy-2-acetophenone, 2,5-dimethylhydroquinone, 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, if necessary, a compound capable of forming a soluble silver complex salt with an unexposed portion of silver halide, which is called a complexing agent, may be contained in the constituent layers to advantageously promote physical development.

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 above-mentioned 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 is added directly to any layer or dissolved in gelatin or a synthetic polymer compound such as polyvinyl alcohol or polyalcohol. Examples thereof include vinylpyrrolidone, alkyl acrylates, sulfoalkyl acrylates described in US Pat. No. 3,488,708, and copolymers of acrylic acid.

When the offset printing material of the present invention is subjected to alkali activation treatment after exposure, it is possible to use treatment liquids containing various additives.

The main examples thereof are alkaline agents (eg, alkali metal or ammonium hydroxides, carbonates, phosphates), pH adjusting agents or buffers (eg, weak acids or weak bases such as acetic acid or sulfuric acid, or 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,
It may contain potassium thiocyanate, alkanolamines, cyclic imines, alkyl-substituted amino alcohols, thioureas, mesoions, thiosalicylic acid, thiosalicylic acid capable of forming thiosalicylic acid in an alkaline solution, such as 5-methylcarbamoylthiosalicylic acid.

When it is necessary to stop the development of the offset printing material according to the present invention after the 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 making, various post-treatments can be carried out for the purpose of improving and improving the 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.

[0259]

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

Example 1 Internal latent image type silver halide emulsions A to D, and
F, G and surface latent image type silver halide emulsion E were prepared.

Emulsion A An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to the aqueous gelatin solution in the presence of a 1,8-dihydroxy-3,6-dithiaoctane solvent with vigorous stirring 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, the mixture was added for 40 minutes in the same manner as in the first precipitation environment, but with control so that the pAg of the solution was 7.50. Average particle size of 0.25 μm
A cubic monodisperse core / shell silver bromide emulsion was obtained. Wash
After desalting, 3.4 mg each of sodium thiosulfate and chloroauric acid (tetrahydrate) were added to this emulsion per mol of silver.
A chemical sensitization treatment was performed by heating at 5 ° C. for 60 minutes to obtain an internal latent image type silver halide emulsion A.

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 particle size of 0.1 μm. It was After the pAg of the solution was adjusted to 8.0, 130 mg of sodium thiosulfate and 1 mol of Ag and chloroauric acid (tetrahydrate) were added to this emulsion, and the mixture was subjected to chemical sensitization treatment by heating at 75 ° C. for 60 minutes. It was Iridium (IV) chloride was used to further shell the silver bromide grains thus obtained as a core.
A mixed aqueous solution of ammonium chloride containing sodium chloride and potassium bromide and a silver nitrate aqueous solution were simultaneously added to give a pAg of 7.8.
It is allowed to grow further by heating for 60 minutes while controlling so that the average particle size is 0.4.
μm silver chlorobromide (Br 20 mol%) cubic monodisperse core /
A shell emulsion was obtained (2.1 × 10 ⁻⁸ mol of iridium /
Ag mol content). After washing with water and desalting, this emulsion was treated with 12 mg of sodium thiosulfate and chloroauric acid (4 mg each per mol of silver).
Aqueous salt) was added and the mixture was heated at 75 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion B.

Emulsion C In Emulsion B, a silver chlorobromide cubic monodisperse core / shell Emulsion C containing 5 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 at ℃ for 1 hour, settled, washed with water, size 0.33
A μm AgBr ₂₀ Cl _79.7 (I _0.3 ) silver (iodo) chlorochlorobromide emulsion was prepared (conversion type internal latent image emulsion).

Emulsion E (Comparative Example) A cubic silver chlorobromide emulsion (AgCl) having an average particle size of 0.3 μm 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.

Emulsions F and G Emulsion B was prepared by changing the composition and temperature of the halogen solution to be shelled to prepare a silver chlorobromide cubic monodisperse core / shell emulsion having Br of 50 mol% and Br of 70 mol%. Br
The one having 50 mol% was designated as Emulsion F and the one having Br of 70 mol% was designated as Emulsion G.

Preparation of lithographic printing plate A matting layer containing silica 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. On the other hand, an antihalation undercoat layer containing 20% by weight of silica powder having an average particle size of 7 μm, and NI-15
Nucleating agent (1.0 × 10 ⁻⁶ mol / Ag mol), and VI-1
Emulsion A containing the nucleation accelerator (2.2.times.10.sup.- ⁴ mol / Ag mol) and sensitizing dye I-1 (1.4.times.10.sup.- ³ mol / Ag mol) was coated.

The gelatin of the undercoat layer was 3.0 g / m ² , the gelatin of the emulsion layer was 1.3 g / m ² , and the coated silver amount was 1.4 g / m ² . For the undercoat layer and the emulsion layer, formalin was used as a hardener. On top of this emulsion layer, the physical development nuclei PdS
A polyvinyl alcohol solution containing nuclei was applied and dried to prepare a lithographic printing plate (1).

Further, using the emulsions B, C, D, F and G in place of the emulsion A of the lithographic printing plate (1), the lithographic printing plate (2),
(3), (4), (6) and (7) were produced. A lithographic printing plate (5) was prepared by using the emulsion E instead of the emulsion A of the lithographic printing plate (1) and removing the nucleating agent and the nucleation accelerator.

Each of the planographic printing plate samples (1) to (7) was passed through an interference filter of 780 nm with a high illuminance sensitometer at 10 ^-6 seconds to obtain 5 to 95% of a gray contact screen of 100 to 200 lines / inch. A halftone image having an area of 100% was exposed and processed with a developing solution (X) at 30 ° C. for 30 seconds.

Immediately after the development processing, the neutralizing solution was added at 25 ° C. for 1 hour.
It was treated for 5 seconds, excess liquid 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 40 g 2-Mercaptobenzoic acid 1.5 g 2-Methylaminoethanol 15 g 2-Methylimidazole 2.0 g Uracil 2.0 g Water 1 Bring to liter (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.

The resolution of each of the planographic printing plates (1) to (7) was evaluated. The resolution of the lithographic printing plate is 100, 133, 150 for the gray contact screen,
Using 175 and 200 lines / inch, fine halftone dots (5% dots) were reproduced clearly and clearly. Evaluation 1 (100 lines / inch) to evaluation 5 (200
It is expressed in 5 steps (line / inch).

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.

<Desensitizing Solution> Water 550 ml Isopropyl alcohol 450 ml Ethylene glycol 50 g Compound A (Chemical Formula 70) 1 g

<Moistening liquid> o-phosphoric acid 10 g Nickel nitrate 5 g Sodium sulfite 5 g Ethylene glycol 100 g Colloidal silica (20% liquid) 28 g Water is added to make 2 liters.

[0278]

[Chemical 70]

As the printing machine, AB Dick 350CD manufactured by ABDick was used. 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 above results are summarized in Table 1.
Table 1 also shows the halogen composition and size of the emulsion.

Printing durability evaluation criteria 1 4000 sheets or less 2 4001 to 6000 sheets 3 6001 to 8000 sheets 4 8001 to 10000 sheets 5 10001 sheets or more

[0281]

[Table 1]

As can be seen from Table 1, it was possible to obtain an infrared-sensitive lithographic printing material capable of obtaining a negative transfer image of an acceptable level or more and exhibiting printability of an acceptable level or more.

Example 2 In each of the planographic printing plates (1) to (4), the compound of formula 23 was used as II-1, II-2, II-3, II-4, II-5, II-7.
Is added as shown in Table 2, and lithographic printing materials (1) to
Along with (4), 28 types of lithographic printing materials were prepared.
Further, these materials were subjected to a forced thermotest for 20 days at 40 ° C. together with the planographic printing materials (1) to (4). The samples before and after the forced thermotest were exposed and processed in the same manner as in Example 1 to examine the resolution. The results are shown in Table 2.

[0284]

[Table 2]

From Table 2, it is understood that the storability is improved by adding the compound of Chemical formula 23.

Example 3 II of the compound of Chemical formula 23 in planographic printing plate (1) -a of Example 2
-1, instead of -1, as the compound of Chemical formula 27, III-1, II
I-2, III-3, III-4, III-9, III-10, I
II-11, III-14, and III-16 were added as shown in Table 3 to prepare various planographic printing plates, which were evaluated in the same manner as in Example 2. Further, in the planographic printing plate (1) -a, a planographic printing material (1) -a10 in which III-1 was used in combination with II-1 was prepared and evaluated in the same manner.

The results are shown in Table 3.

[0288]

[Table 3]

From Table 3, it is understood that the storability is improved by adding the compound of Chemical formula 27. Also,
It can be seen that the combined use of the compound of 3 and the compound of 27 is also preferable. In Examples 1 to 3, the sensitizing dyes used in the lithographic printing plate were sensitizing dyes I-1 to I-15,
When treated in the same manner and evaluated in the same manner except that each of I-26 was changed, the same results as in Examples 1 to 3 were obtained.

[0290]

According to the present invention, an infrared-sensitive lithographic printing material capable of obtaining a negative transfer image can be obtained. In addition, storability can be improved. Further, it has high sensitivity, high resolution, and good printability.

Claims (3)

[Claims] 1. A lithographic printing material utilizing a silver salt diffusion transfer method having at least a silver halide emulsion layer and a physical development nucleus layer on a support, wherein the silver halide emulsion is an internal latent image type emulsion, 670
A lithographic printing material containing a sensitizing dye having a maximum sensitizing wavelength in the wavelength range of nm or more to obtain a negative transfer silver image. 2. The lithographic printing material according to claim 1, wherein the sensitizing dye is one or more of a tricarbocyanine dye and a 4-quinoline nucleus-containing dicarbocyanine dye. 3. The tricarbocyanine dye is represented by the following chemical formula 1 or 2, and the 4-quinoline nucleus-containing dicarbocyanine dye is represented by the following chemical formula 3. Lithographic printing material. [Chemical 1] [Chemical 2] [Chemical 3] [In Chemical Formula 1, R ₁₁ and R ₁₂ each represent an alkyl group, and these may be the same or different. R ₁₀ is
It represents a hydrogen atom, a methyl group, a methoxy group or an ethoxy group. D represents an atomic group necessary for completing a divalent ethylene bond. Z and Z ₁ each represent a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X
₁ represents an acid anion, and r represents 1 or 2. In Chemical formula 2, R ₁₁ and R ₁₂ each represent an alkyl group, which may be the same or different. R ₁₃ and R ₁₄ each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group or a benzyl group, and these may be the same or different. R ₁₅ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a group represented by Chemical formula 4 (In Chemical formula 4, W ₁₁ and W ₁₂ each represent an alkyl group or an aryl group, and W ₁₁ and W ₁₂ is connected to each other to form a 5- or 6-membered nitrogen-containing compound It is also possible to form a prime ring. ) Is represented. D ₁ and D ₂ each represent a hydrogen atom, and D ₁ and D ₂ may be combined to form a divalent ethylene bond. Z and Z ₁
Represents a group of non-metal atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ₁ represents an acid anion,
r represents 1 or 2. In Chemical formula 3, R ₁₆ and R
Each of _17's represents an alkyl group, which may be the same or different. R ₁₈ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group or a benzyl group,
These may be the same or different. V ₁ represents a hydrogen atom, a lower alkyl group, an alkoxy group or a halogen atom. Z ₂ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ₁₁ represents an acid anion, and p, q and r ₁ each represent 1 or 2. ]