JP3341123B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material having an improved residual color.

[0002]

2. Description of the Related Art In recent years, the consumption of silver halide photographic light-sensitive materials has been steadily increasing. For this reason, the number of developed silver halide photographic materials has been increased, and it has been required to speed up the development processing, that is, to increase the processing amount within the same time. The above tendency is also seen in the field of printing plate making. That is, since the immediacy of information and the increase in the number of times of information are rapidly increasing, it is necessary to carry out a printing and plate making operation in a short time and in a larger amount. In order to satisfy the demands of the printing plate making industry, it is necessary to promote the simplification of the printing process and to perform the photographic processing of the printing plate making film more quickly.

However, if the processing time is shortened, there is a problem that the deterioration of the residual color, particularly the deterioration from the red sensitivity having a wavelength peak of 550 nm to the infrared sensitivity is remarkable.

[0004]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material which does not deteriorate in image quality due to residual colors or the like even when developed very quickly. is there.

[0005]

Means for Solving the Problems The object of the present invention is to provide any one of the above [2a] to [2d] on a support .
A sensitizing dye or an infrared sensitizing dye [2e-
1] have a <br/> silver halide emulsion layer containing one selected from - [2e-15], said silver halide emulsion layer及beauty
At least one layer 2 or more isocyanate groups is added Burokkin grayed water-soluble or water-dispersible reactive urethane compound bisulphite in the form selected from the top of its
This is achieved by a silver halide photographic light-sensitive material characterized in that it is formed.

Hereinafter, the present invention will be described specifically.

The reactive urethane compound according to the present invention comprises:
Compounds containing at least two free isocyanate groups, wherein at least two of the free isocyanate groups are blocked by bisulfite, and all remaining free isocyanate groups are blocked by other blocking agents.

As the blocking agent, a compound having at least one active hydrogen capable of reacting with a free isocyanate group and an anionic group in the same molecule, for example, oxybenzoic acid, phenolsulfonic acid, glycolic acid, lactic acid, malic acid, heavy acid Sulfites and bicarbonates are used.

The urethane compound containing at least two free isocyanate groups can be easily synthesized according to a conventionally known polyaddition method. However, in this case, the molar ratio of isocyanate group / active hydrogen group can be freely selected to be 1 or more, but it is preferable that the content of free isocyanate group in the obtained urethane compound is 1 to 30% by mass .

Next, blocking of free isocyanate groups is carried out with an aqueous bisulfite solution.

The bisulfite to be blocked with a compound having at least one active hydrogen group and an anionic salt in the same molecule, if necessary, includes sodium bisulfite, potassium bisulfite, ammonium bisulfite and the like. As a compound having at least one active hydrogen group and an anionic salt-like group or an anionic salt-forming group in the same molecule,
As described above, aminosulfonic acids, aminocarboxylic acids and hydroxyacetic acid, such as those having two types of groups, an amino group, a hydroxyl group and a sulfonic acid group, and a carboxylic acid group.Examples of aminosulfonic acids include sulfanilic acid. As N-phenylaminomethanesulfonic acid, taurine methyltaurine, aminocarboxylic acids, glycine, alanine, glutamic acid, aminobenzoic acid, diaminobenzoic acid and hydroxy acids include glycolic acid, lactic acid, malic acid, salicylic acid, etc. Can be Since they are used by mixing with the bisulfite,
Used as lithium salt, sodium salt, potassium salt, ammonium salt and the like.

Specific examples of the synthesis method for blocking are described in, for example, JP-B-55-39254 and JP-B-53-17642. The reactive urethane compound used in the present invention is commercially available from, for example, Daiichi Kogyo Seiyaku Co., Ltd. under the trade name of Elastron. For example, the following products are available depending on the type of raw material polyol (polyester polyol, polyether polyol, etc.).

Elastron H-3, E-37 (polyester type), Elastron C-9, F-29, C-52, CT-7, H-
38, A-42, BAP, W-11, (polyether type), and Elastron R-24, S-24, KS-18, etc.
Coronate 2507, 2515, from Nippon Polyurethane Industry Co., Ltd.
Also AX-35, 36 and Nippon Shokubai Chemical Industry from Koyo Sangyo Co., Ltd.
K-1000 series from K.K.

Next, specific examples of the compounds will be given, but the present invention is not limited to them.

[0015]

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[0016]

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[0017]

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[0018]

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The addition amount of the isocyanate compound of the present invention is 1.0 × 10 ^-5 to 2 × 10 ^-3 mol / g of gelatin. No effect is obtained below this addition amount, and the addition amount exceeds this addition amount. Then, the degree of hardening increases and the sensitivity is remarkably reduced. A more preferable addition amount is 5.0 × 10 ⁻⁵ to 1 × 10 ⁻³ mol.
/ G of gelatin.

The wavelength peak according to the present invention is 550 nm to 800 nm.
Sensitizing dyes are effective with general compounds such as cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxanol dyes. The sensitizing dyes of formulas [2a] to [2e] have a large effect.

[0021]

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Wherein Y ₁ and Y ₂ each represent a nonmetallic atomic group necessary for forming a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring or a quinoline ring. These heterocycles may be substituted with a lower alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom.

R ₁ and R ₂ each represent a lower alkyl group, an alkyl group having a sulfo group or an alkyl group having a carboxyl group. R ₃ represents a methyl group, an ethyl group, or a propyl group. X ₁ represents an anion. n ₁ and n ₂ are
Represents 1 or 2. m represents 1 or 0, and in the case of an internal salt, m = 0. Next, the general formula [2a] will be described in more detail.

In the above general formula [2a], Y ₁ and Y ₂ each represent a nonmetallic atom group necessary for forming a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a natetoselenazole ring or a quinoline ring. And these heterocycles are a lower alkyl group (eg, a methyl group, an ethyl group, etc.),
An alkoxy group (for example, a methoxy group, an ethoxy group, etc.), a hydroxyl group, an aryl group (for example, a phenyl group), an alkoxycarbonyl group (for example, a tomexicarbonyl group),
It may be substituted with a halogen atom (for example, chlorine atom, bromine atom, etc.). R ₁ and R ₂ are a lower alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), an alkyl group having a sulfo group {eg, a β-sulfoethyl group, a γ-sulfopropyl group, a γ-sulfobutyl group, δ-sulfobutyl group, sulfoalkoxyalkyl group (for example, sulfoethoxyethyl group, sulfopropoxyethyl group) and the like; and alkyl group having a carboxyl group (for example, β-
Carboxylethyl group, γ-carboxypropyl group, γ-
Carboxybutyl group, δ-carboxybutyl group, etc.). R ₃ represents a methyl group, an ethyl group, or a propyl group.
X ₁ represents an anion (for example, a halogen ion, a benzenesulfonate ion, a p-toluenesulfonate ion, etc.) usually used for a cyanine dye. m represents 1 or 0, and in the case of an internal salt, m = 0.

Next, the configuration of the present invention will be described more specifically.

First, the above general formula [2a] used in the present invention
Specific examples of the compound represented by are shown below. However, the compounds used in the present invention are not limited to these.

An example of the compound represented by the general formula [2a].

[0028]

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[0029]

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[0030]

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The sensitizing dye of the present invention is contained in a silver halide photographic emulsion in an amount of preferably from 1 mg to 2 g, more preferably from 5 mg to 1 g, per mol of silver halide.

The sensitizing dye of the present invention can be directly dispersed in an emulsion. These can be first dissolved in an appropriate solvent, for example, 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.

The sensitizing dyes of the present invention may be used alone or in combination of two or more. Further, sensitizing dyes other than the present invention can be used in combination. When a sensitizing dye is used in combination, it is preferable that the total content is the above content.

The sensitizing dye of the present invention is disclosed in US Pat.
776, UK Patent 742112, French Patent 2065662, Tokubo Akira
It can be easily synthesized with reference to 40-2346.

[0035]

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In the formula, R and R ₁ are each an alkyl group (having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms) [for example, a methyl group, an ethyl group, a 3-propyl group, a 4-butyl group, 3-
Butyl group, 5-bentyl group etc.), substituted alkyl group [alkyl group having 1 to 10, preferably 1 to 5 carbon atoms, for example, an alkyl group containing a sulfo group (preferably an alkyl radical (moiety) [For example, a sulfoalkyl group {eg, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, etc.], hydroxy, acetoxy or alkoxy (carbon number of alkyl radical) Are preferably 1 to 4) and an alkyl group substituted with a sulfo group {eg, 2-hydroxy-3-sulfopropyl group, 2- (sulfopropoxy)
Ethyl group, 2-acetoxy-3-sulfopropyl group, 3-methoxy-2- (3-sulfopropoxy) propyl group, 2- [2- (3
-Sulfopropoxyethoxy) ethyl group, 2-hydroxy-
Such as 3- (3'-sulfopropoxy) propyl group, sulfoaralkyl group (eg, p-sulfophenethyl group, p-sulfobenzyl group, etc.), alkyl group containing carboxyl group (preferably alkyl radical (moiety) C1 to C4), [for example, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2- (2-carboxyethoxy) ethyl group, p-carboxybenzyl group, etc.], aralkyl group [for example, Benzyl group, phenethyl group, phenylpropyl group, phenylbutyl, alkyl-substituted aralkyl group (eg, p-methylphenethyl, p-tolylpropyl, etc.), alkoxy-substituted aralkyl group (eg, p-methoxyphenethyl, etc.), halogen-substituted aralkyl group ( For example, p-chloro-phenethyl, m-chloro-phenethyl, etc.), aryloxya A kill group (for example, a phenoxyethyl group, a phenoxypropyl group, a phenoxybutyl group, an alkyl- or alkoxy-substituted aryloxyalkyl group (for example, a p-methylphenoxyethyl group, a p-methoxyphenoxypropyl group, etc.), an aryl group (preferably Those having 4 to 15 carbon atoms, for example, a phenyl group,
A pyridyl group or the like] or a substituted aryl group [the aryl moiety having 4 to 15 carbon atoms is preferable. As the substituent, a substituent of a substituted alkyl group is used. For example, p-methylphenyl group, p-methoxyphenyl group, etc.] and an allyl group.

At least _one of R and R ₁ represents an alkyl group containing a sulfo group or an alkyl group containing a carboxyl group.

R ₂ and R ₃ each represent an alkyl group (preferably having 1 to 5 carbon atoms). For example, a methyl group, an ethyl group, a propyl group, etc.].

Z represents a group of non-metallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus together with a nitrogen atom. Examples of the heterocyclic nucleus include a thiazole nucleus [for example, thiazole, 4-methylthiazole, 4-phenylbenzothiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 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-trifluoromethylbenzo Thiazole, 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 (e.g., 4-methylselenazole, 4-phenylselenazole, benzoselenazole, 5-chlorobenzo) Selenazole nucleus, 5-
Methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,1-
d) selenazole, naphtho (1,2-d) selenazole and the like, an oxazole nucleus (e.g., oxazole, 4-methyloxazole, 4-ethyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole), Benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5-hydroxy Benzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5 - Butoxy benzoxazole, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, etc.], quinoline nucleus [for example, 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-diethyl Indolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-chloroindolenine Etc.), imidazole nucleus (eg, 1-methylimidazole, 1-ethylimidazole, 1-methyl-4-phenylimidazole, 1-phenylimidazole, 1-ethyl-4-phenylimidazole, 1-methylbenzimidazole, 1-ethyl Benzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1 -Alkyl-5-meth Cibenzimidazole, 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-tri Examples thereof include fluoromethylbenzimidazole, 1-ethylnaphtho [1,2-d] imidazole, and the like, and a pyridine nucleus (for example, pyridine, 5-methyl-2-pyridi, 3-methyl-4-pyridine, and the like). Of these, thiazole nuclei and oxazole nuclei are preferably used advantageously. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, and a naphthoxazole nucleus are advantageously used.

Next, typical examples of the dye represented by the general formula [2b] are shown below.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046] [wherein, X represents -S- or -Se-, R ₅
Represents an organic group having a water-soluble group, and _{one of} R _{1 to} R ₄ represents an organic group having a water-soluble group. R ₆ , R ₇
Represents the same or different group as R _{1 to} R ₄ . In a preferred embodiment of the present invention, the π value of one water-soluble group of any of R _{1 to} R ₄ in the general formula according to the Hansch method is −4.5.
The value is smaller than 0 and the π value of the water-soluble group of R ₁ is −4 or less. Preferred examples of the substituent having a π value of −4.5 or more and less than 0 include an organic group carrying a carboxyl group, a sulfamoyl group, a methoxymethyl group, and a carbamoyl group.

Particularly preferred are organic groups carrying a carboxyl group or a sulfamoyl group. Preferred examples of the substituent having a π value of -4 or more include an organic group carrying a carboxyl group and a sulfone group.

Particularly preferred is an organic group carrying a sulfone group.

Hereinafter, the present invention will be described specifically.

R ₁ , R ₂ , R ₃ and R ₄ other than the above-mentioned organic group having a water-soluble group are hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, Represents an aryl group or a substituted aryl group. R ₆ and R ₇ are the same or different and are each hydrogen, hydroxy, halogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, alkoxy, substituted alkoxy, alkylthio , Substituted alkylthio, arylthio, substituted arylthio, aryl, substituted aryl, acyl, substituted acyl, acyloxy, substituted acyloxy, alkoxycarbonyl, substituted alkoxycarbonyl, alkylsulfonyl, substituted alkylsulfonyl Represents a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a carboxy group or a cyano group, or R ₆ and R ₇ together represent the atoms necessary to complete a carbocyclic ring system; the ring system, R ₆ and R ₇ respectively Nitsu The same or different one or more substituents selected from the substituents shown Te can be supported.

The water-soluble group referred to herein is a so-called Hansch
It refers to a substituent having a value of π known as a modulus that is smaller than 0.

The π value here indicates a parameter of hydrophobicity in a so-called structure-activity relationship. Generally, a value larger than 0 is hydrophobic, and when the parameter is smaller than 0, it is considered hydrophilic. . Also, this parameter actually varies somewhat due to the effects of other substituents, but in this patent, J. Med.Chem. 16, 1207 (1973) and J.
Med.Chem. 20, 304 (1977), a so-called Han
The π value known as the sh method is used as it is.

In the case of an ionizable substance such as a quaternary ammonium group or a carboxyl group, the π value in the state where the π value is the smallest is used.

The following are specific examples of the dye represented by the general formula of the present invention, but the present invention is not limited thereto.

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[Wherein R ₁ and R ₂ may be the same or different, and R ₃ represents a heterocyclic group. Z ₁ and Z ₂ may be the same or different and represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. X is a counter ion, and L ₁ to
L ₅ represents a methine group, m and n each represent 0,
1 and 2 are represented. R ₁ and R ₂ in the general formula [2d] are the same as those in the general formula [2a].
₁ has the same meaning as R _2. More specifically, Z ₁ and Z ₂ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. Specific examples of Z ₁ and Z ₂ include, for example, an oxazoline ring, an oxazole ring, a benzoxazole ring, a benzoisoxazole ring, a naphthoxazole ring, a thiazoline ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazoline ring, and a selenazole. Ring, naphthoselenazole ring, tellurazole ring, benzotellurazole ring, naphthotellurazole ring, pyridine ring, quinoline ring,
There are a benzoquinoline ring, an indolenine ring, a benzoindolenine ring, a benzimidazole ring, a pyrroline ring and the like, and an alkyl group, an aryl group, an alkoxy group (for example, methoxy, ethoxy) , Propoxy, etc.), a hydroxy group, a carboxy group, an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.) and a halogen atom (eg, fluorine, chlorine, bromine, iodine, etc.). . X represents a counter ion, R ₁ , R ₂ and Z
_{If 1} and Z ₂ do not have an acid substituent, acid anions (eg, alkyl sulfate ions such as methyl sulfate and ethyl sulfate,
Thiocyanate ion, toluenesulfonic acid ion, halogen such as chlorine, bromine and iodine, perchlorate ion, etc.), and when there is one acid substituent, X is not present because an inner salt is formed. When two or more are present, they represent cations such as an alkali metal atom (eg, sodium, potassium, etc.) and an organic ammonium (eg, triethylammonium, tributylammonium, pyridinium, etc.). L _{1 to} L ₅ are each a methine group (this methine group may be substituted with an alkoxy group in addition to the above-mentioned alkyl group and aryl group. Further, they are linked to each other to form a 5- or 6-membered ring. And m and n represent 0, 1, and 2, respectively.

Next, representative examples of the sensitizing dye represented by the general formula [2d] of the present invention will be given, but the scope of the present invention is not limited thereto.

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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The infrared sensitizing dye used in the present invention may be any dye, for example, US Pat. No. 2,875,058, US Pat.
No. 78, US Patent 3,582,344, US Patent 3,615,632, US Patent 3,695,888, US Patent 4,011,083, US Patent 4,
No. 515,888 and US Pat. No. 4,536,473. Specific examples of the infrared sensitizing dye (2e) used in the present invention are shown below, but the present invention is limited to these infrared sensitizing dyes only. It is not limited.

[0068]

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[0069]

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[0070]

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The above-mentioned infrared sensitizing dye used in the present invention is preferably used in an amount of from 5 × 10 ⁻⁷ mol to 1 mol of silver halide.
5 × 10 ^-3 mol, more preferably 1 × 10 ^-6 mol to 1 × 10 ^-3 mol
Mol, particularly preferably 2 × 10 ^-6 mol to 5 × 10 ^-4 mol, in the silver halide photographic emulsion.

The silver halide emulsion used in the light-sensitive material of the present invention may be any silver halide emulsion which is commonly used in silver halide emulsions, and may contain at least 50 mol% of silver chloride. Preferably, the particle size is 0.2 μm or more and 0.5 μm or less.

The amount of gelatin on the emulsion layer side was 2.8 g / m ² or less,
Preferably it is 2.5 g / m ² or less. In addition, various techniques known in the art, in particular, the technique of a photosensitive material for printing plate making can be used for the photosensitive material in the present invention, and various known techniques can also be applied to the processing. [Examples] Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 A container containing gelatin, sodium chloride and water, heated at 40 ° C., was charged with an aqueous solution of silver nitrate and 6 × per mole of silver halide.
^10-7 moles of potassium hexachloroiridate and 4 ×
Silver bromochloride particles containing 35 mol% of silver bromide by adding a mixed aqueous solution of potassium bromide and sodium chloride to which 10 ^-8 mol of potassium hexabromorhodate is added by a double jet method (broad distribution) 12%, cubic, particle size 0.33μm)
The pH was adjusted while maintaining H3.0pAg7.7, and after returning to pH 5.9, desalting was carried out by a conventional method.

This emulsion was subjected to gold sensitization and sulfur sensitization, and sensitizing dyes represented by the general formulas [2a] to [2e] shown in Table 1 were added in an amount of 240 mg per mol of silver halide and 200 mg of a compound A, and Further, 70 mg of 1-phenyl-5-mercaptotetrazole per mole of silver halide, 4-hydroxy-6-methyl-1,3,
After ripening was stopped by adding 1.2 g of 3a, 7-tetrazaindene and gelatin, 4 g of hydroquinone, 3 g of potassium bromide, 5 g of saponin, and 5 g of styrene-maleic acid were used per mole of silver halide. 2 g of a polymer and 3 g of a polymer latex of ethyl acrylate are added.
After adding the amount shown in Table 1 as a hardening agent, 3.5 g of silver was placed on a subbed polyethylene terephthalate support.
/ M ² as the amount of gelatin is in Table 1, a protective film as gelatin 500g of an aqueous solution of potassium bromide 10 g, 1-decyl-2- (3-isopentyl) succinate-2-sulfonic acid soda 4g was added 100 g of amorphous silica having an average particle size of 5 μm was added and dispersed, and gelatin was dispersed in an emulsion layer of 2.0 g / m ² , and a protective layer was formed.
The emulsion layer and the protective layer were simultaneously coated at a concentration of 1.0 g / m ² .

[0076]

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The sample thus obtained was treated with the following developing solution and fixing solution using a conventional roller type automatic developing machine under the following conditions, and the residual color was evaluated.

The residual color was evaluated in 10 steps, 10 being the best, 1-4 being unusable, and 5 or more being the usable level. The results are shown in Table 1.

Processing conditions (process) (Temperature) (Time) Current image 35 ° C 12 seconds Fixed 34 ° C 12 seconds Water washing Normal temperature 12 seconds Drying 50 ° C 10 seconds Developer formulation (Composition A) Pure water (Ion exchange water) 150ml Disodium salt of ethylenediaminetetraacetic acid 2.0g Diethylene glycol 50.0g Potassium sulfite (55% w / v aqueous solution) 100ml Potassium carbonate 50.0g Hydroquinone 15.0g 5-Methylbenzotriazole 200mg 1-Phenyl-5-mercaptotetrazole 30.0 mg Potassium hydroxide, amount to make pH after use 10.4 Potassium bromide 4.5 g (Composition B) Pure water (ion exchange water) 3.0 ml Diethylene glycol 50.0 g Disodium ethylenediaminetetraacetate 25.0 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-phenyl-3-pyrazolidone 700 mg When using a developer, dissolve the above-mentioned composition A and composition B in 500 ml of water in this order and finish to 1 liter. .

Fixer formulation (composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240ml Sodium sulfite 17.0g Sodium acetate trihydrate 6.5g Boric acid 6.0g Sodium citrate dihydrate 2.0g Acetic acid (90% w / v) / v aqueous solution) 13.6 ml (aqueous composition B) pure water (ion-exchanged water) aqueous solution of 17.0ml sulfate (50% w / v) 4.7 g of aluminum sulfate (Al ₂ O ₃ in terms of content of 8.1% w / v) 26.5 g When the fixing solution was used, the above composition A and composition B were dissolved in 500 ml of water in this order, and finished to 1 liter. This fixer
pH was about 4.3.

[0081]

[Table 1]

From Table 1, it can be seen that the present invention has good residual color.

Example 2 (Preparation of emulsion) Solution A water 9.7 l Sodium chloride 20.0 g gelatin 105.0 g Solution B water 3.8 l sodium chloride 94.0 g gelatin 365.0 g potassium bromide 450.0 g 0.01% aqueous solution of potassium hexachloroiridate 28 ml 1.0 ml of 0.01% aqueous solution of potassium hexabromorhodate salt Solution C 3.8 l of water 1,700 g of silver nitrate The above solution B and solution C were simultaneously functionalized while maintaining pH 3 and pAg 7.7 in the above solution A kept at 40 ° C. After stirring for 10 minutes, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution, and 2 liters of a 20% aqueous magnesium sulfate solution and 2.55 liters of a 5% aqueous solution of polynaphthalenesulfonic acid were added. Flocculate at ℃, decant and wash with water to remove excess aqueous salts. Then, 3.7 liters of water are added thereto to disperse, and again 0.9 liter of a 20% aqueous magnesium sulfate solution is added again to remove excess salts of the aqueous solution. Add 3.7l of water and 141g of gelatin to it and add 55
Disperse at 30 ° C for 30 minutes. This gives 35 mol% of silver bromide,
Grains having a silver chloride content of 65 mol%, an average of 0.25 μm and a monodispersity of 9 are obtained.

To an emulsion adjusted to pH 5.5 and pAg 7 by adding 12 ml of a 1% aqueous solution of citric acid and 12 ml of an aqueous solution of 5% potassium chloride, 120 ml of an aqueous solution of 0.1% sodium thiosulfate, and 0.2% chloroauric acid The water solubility was increased by adding 80 ml and aging at 60 ° C. for the highest sensitivity.

The above emulsion was divided into 10 equal parts, and 1-phenyl-5-mercaptotetrazole was used as an antifoggant.
25 ml of 0.5% solution, 4-hydroxy-6-methyl as stabilizer
-1.3.3a. 180 ml of a 1% solution of 7-tetrazaindene and 400 ml of a 10% aqueous solution of gelatin were added to stop ripening. Then, as shown in Table 2, an infrared sensitizing dye was added, and pH and pAg were added. After the preparation of hydroquinone as an antifoggant
50 ml of a 20% saponin aqueous solution as a spreading agent.
50 ml of a 4% aqueous solution of a styrene-maleic acid polymer as a thickener and 30 g of a polymer latex of ethyl acrylate were added and stirred, and after 1 hour and 20 hours, the amount shown in Table 2 as a hardener was added. And the above emulsion was coated on a polyethylene terephthalate support having been subjected to undercoating.
4.2 g / m ² , and as a protective film, 100 ml of a 10% aqueous solution of potassium bromide was added to an aqueous solution of 500 g of gelatin, and 1-decyl-2- (3-isopentyl) succinate-2-sulfone was used as a spreading agent. Add 400 ml of 1% aqueous solution of acid soda,
Further, 100 g of amorphous silica having an average particle size of 3.5 μm was added and dispersed, and the emulsion layer and the protective layer were simultaneously coated so that the gelatin became 1.1 g / m ² .

[0086]

[Table 2]

[0087]

[Table 3]

Processing was performed in the same manner as in Example 1 thus obtained, and the residual color was evaluated.

<Developing solution formulation> Pure water (ion-exchanged water) Approx. 800 ml Potassium sulfite 60.0 g Disodium ethylenediaminetetraacetate 2.0 g Potassium hydroxide 10.5 g 5-methylbenzotriazole 300 mg Diethylene glycol 25.0 g 1-phenyl-4,4- Dimethyl-3-pyrazolidinone 300 mg 1-phenyl-5-mercaptotetrazole 60 mg Potassium bromide 3.5 g Hydroquinone 20.0 g Potassium carbonate 15.0 g Add pure water (ion exchange liquid water) to make up to 1 liter.

The pH of the developer was 10.8.

<Composition of Fixing Solution> (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17.0 g sodium acetate trihydrate 6.5 g nitric acid 6.0 g sodium citrate dihydrate 2.0 g acetic acid (90 aqueous solution of% W / W aqueous solution) 13.6 ml (composition B) pure water (ion-exchanged water) aqueous solution of 17.0ml sulfate (50% W / W) 4.7g of aluminum sulfate (Al ₂ O ₃ in terms of content of 8.1% w / w 26.5g When using fixer, the above composition A and composition B were added to 500ml of water.
And finished to 1 liter. The pH of the fixing solution was about 4.3.

The results of Tables 2 and 3 also show that the samples of the present invention have good residual colors.

Example 3 In Example 1, the same evaluation was performed by adding the blocked isocyanate compound of the present invention to the protective film. Table 4 shows the results
Shown in

[0094]

[Table 4]

As is clear from Table 4, the use of a blocked isocyanate compound in the upper layer other than the layer to which the sensitizing dye was added is effective.

[0096]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material in which image quality is not degraded due to residual colors and the like even when ultra-rapid development is performed.

Continuation of the front page (56) References JP-A-4-86821 (JP, A) JP-A-4-194921 (JP, A) JP-A-4-324855 (JP, A) JP-A-4-104138 (JP) , A)

Claims (1)

(57) [Claims] 1. The method according to any one of the following [2a] to [2d] on a support
Sensitizing dye represented by any selected general formula or infrared
One selected from sensitizing dyes [2e-1] to [2e-15]
It has a silver halide emulsion layer containing a Zureka, at least one layer selected from an upper layer of said silver halide emulsion layer及benefactor
And characterized in that two or more isocyanate groups Brocchi <br/> in g water-soluble or water-dispersible reactive urethane compound <br/> compounds bisulphite is formed is added to the Silver halide photographic light-sensitive material. [A] [Wherein Y ₁ and Y ₂ each represent a benzothiazole ring,
Nzoselenazole ring, naphthothiazole ring, naphthosele
Necessary to form a azole ring or a quinoline ring.
Represents a metal atom group, these heterocycles are a lower alkyl group,
Alkoxy group, aryl group, hydroxyl group, alkoxy
May be substituted with a cicarbonyl group or a halogen atom
No. R ₁ and R ₂ represent a lower alkyl group and a sulfo group, respectively.
With alkyl or carboxyl groups
Represents a hydroxyl group. R ₃ is a methyl group, an ethyl group, a propyl group
Represents X ₁ represents an anion. n ₁ and n ₂ are 1 or
2 is represented. m represents 1 or 0, and when it is an inner salt, m
= 0. ] [Of B] Wherein R and R ₁ are an alkyl group, a substituted alkyl,
Group, hydroxy group or acetoxy group or alkoxy group
Alkyl group substituted with sulfo group, sulfoaralkyl
Group, alkyl group including carboxyl group, aralkyl group,
Alkyl-substituted aralkyl group, alkoxy-substituted aralkyl
Group, halogen-substituted aralkyl group, aryloxyalkyl
Group, aryl group, substituted aryl group or allyl group,
And at least one of R ₁ and R ₁ is an alkyl containing a sulfo group.
And an alkyl group containing a carboxyl group or a carboxyl group. R ₂
And R ₃ each represents an alkyl group. Z together with the nitrogen atom
Necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus
Represents a group of metal atoms. ] [Of C] [Wherein, X represents -S- or -Se-, and R ₅ represents a water-soluble group.
Represents an organic group having, and one of either R ₁ to R ₄
Represents an organic group having a water-soluble group. R _6, R ₇ and R ₁ to R ₄
Represents the same or different groups. ] [Of D] [Wherein, R _1, R ₂ may be the same or different, R ₃
Represents a heterocyclic group. Z ₁ and Z ₂ may be the same or different
Atoms necessary to form a 5- or 6-membered nitrogen-containing heterocycle
Represents X is a counter ion, and L _{1 to} L ₅ are each
And m and n represent 0, 1, and 2, respectively. ] [Of] E [Formula F] [G]