JPH06186665A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material not causing the deterioration of image quality due to a residual color, etc., even when very rapidly developed. CONSTITUTION:This silver halide photographic sensitive material having at least one silver halide emulsion layer on the substrate contains a water-soluble or water-dispersible reactive compd. having two or more isocyanato groups blocked with a hydrogensulfite in the silver halide emulsion layer and/or a layer on the emulsion layer and a sensitizing dye whose wavelength peak is within the range of 550-800nm in the emulsion layer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having improved residual color.

[0002]

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

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

[0004]

In order to solve 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 color even when it is developed extremely rapidly. is there.

[0005]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer and / or an upper layer thereof. Contains at least two or more isocyanate groups with a water-soluble or water-dispersible reactive compound blocked with bisulfite, and the emulsion layer contains a sensitizing dye having a wavelength peak from 550 nm to 800 nm. This is achieved by the characteristic silver halide photographic light-sensitive material.

The present invention will be specifically described below.

The free isocyanate compound used in the present invention contains at least two free isocyanate groups, at least two of the free isocyanate groups are blocked with bisulfite, and all remaining free isocyanate groups are The compound is blocked with the blocking agent of.

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 polymer, Sulfite and bicarbonate are used.

The polymer containing at least two free isocyanate groups can be easily synthesized by a conventionally known polyaddition method. In this case, however, 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%.

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

Further, as the bisulfite salt which is blocked with a compound having one or more active hydrogen groups and anionic salts in the same molecule, if necessary, sodium bisulfite, potassium bisulfite, ammonium bisulfite and the like can be mentioned. 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 kinds of groups, an amino group, a hydroxyl group and a sulfonic acid group, and a carboxylic acid group, can be mentioned. The aminosulfonic acids can be sulfanilic acid. , N-phenylaminomethanesulfonic acid, taurine methyltaurine, aminocarboxylic acids, such as glycine, alanine, glutamic acid, aminobenzoic acid, diaminobenzoic acid and hydroxy acids, glycolic acid, lactic acid, malic acid, salicylic acid and the like. To be Since they are used as a mixture with the bisulfite,
It is used as a lithium salt, sodium salt, potassium salt, ammonium salt or the like.

Specific blocking synthesis methods are described in, for example, Japanese Patent Publication No. 55-39254 and Japanese Patent Publication No. 53-17642. The reactive urethane compound used in the present invention is commercially available, for example, from Dai-ichi 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.
From Nippon Polyurethane Industry Co., Ltd., Coronate 2507, 2515,
Also from Koyo Sangyo Co., Ltd., AX-35, 36 and Nippon Shokubai Chemical Industry
Examples include K-1000 series from Co., Ltd.

Specific examples of the compounds will be given below, but the present invention is not limited to these.

[0015]

[Chemical 1]

[0016]

[Chemical 2]

[0017]

[Chemical 3]

[0018]

[Chemical 4]

The addition amount of the isocyanate compound of the present invention is 1.0 × 10 ^-5 to 2 × 10 ^-3 mol / g of gelatin. Below this addition amount, no effect is obtained, and the addition amount is further exceeded. Then, the degree of hardening increases and the sensitivity remarkably decreases. A more preferable addition amount is 5.0 × 10 ^-5 to 1 × 10 ^-3 mol
/ Per 1 g of gelatin.

The wavelength peak according to the present invention is 550 nm to 800 nm
The sensitizing dyes in 1 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 the formulas [2a] to [2e] are highly effective.

[0021]

[Chemical 5]

[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 inner 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 are each a non-metal atom group necessary for forming a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a natetoselenazole ring or a quinoline ring. Represents a lower alkyl group (eg, methyl group, ethyl group, etc.),
Alkoxy group (eg, methoxy group, ethoxy group, etc.), hydroxyl group, aryl group (eg, phenyl group), alkoxycarbonyl group (eg, tomexycarbonyl group),
It may be substituted with a halogen atom (eg, chlorine atom, bromine atom, etc.). R ₁ and R ₂ are a lower alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, etc.), an alkyl group having a sulfo group (eg, β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, sulfoalkoxyalkyl group (eg, sulfoethoxyethyl group, sulfopropoxyethyl group), etc., alkyl group having a carboxyl group (eg, β-
Carboxyethyl 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 that is usually used in cyanine dyes (for example, halogen ion, benzene sulfonate ion, p-toluene sulfonate ion, etc.). m represents 1 or 0, and in the case of an inner salt, m = 0.

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

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

Examples of the compound represented by the above general formula [2a].

[0028]

[Chemical 6]

[0029]

[Chemical 7]

[0030]

[Chemical 8]

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

The sensitizing dye of the present invention can be directly dispersed in the 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.

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

The sensitizing dye of the present invention is described in US Pat.
776, British Patent 742112, French Patent 2065662, Japanese Patent Sho
It can be easily synthesized with reference to No. 40-2346.

[0035]

[Chemical 9]

In the formula, R and R ₁ are each an alkyl group (having 1 to 10 carbon atoms, preferably having 1 to 5 carbon atoms) [eg methyl group, ethyl group, 3-propyl group, 4-butyl group, 3-
Butyl group, 5-benzyl group, etc.], substituted alkyl group [having 1 to 10, preferably 1 to 5 carbon atoms in the alkyl portion, for example, an alkyl group containing a sulfo group (preferably an alkyl radical (moiety) Having 1 to 4 carbon atoms] [eg, sulfoalkyl group {eg, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, etc.], hydroxy, acetoxy or alkoxy (number of carbon atoms of alkyl radical Is 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-
3- (3′-sulfopropoxy) propyl group, etc.}, sulfoaralkyl group {eg, p-sulfophenethyl group, p-sulfobenzyl group, etc.]], an alkyl group containing a carboxyl group (preferably an alkyl radical (moiety)) C1-4), [eg, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2- (2-carboxyethoxy) ethyl group, p-carboxybenzyl group, etc.], aralkyl group [eg Benzyl group, phenethyl group, phenylpropyl group, phenylbutyl, alkyl-substituted aralkyl group (for example, p-methylphenethyl, p-tolylpropyl, etc.), alkoxy-substituted aralkyl group (for example, p-methoxyphenethyl, etc.), halogen-substituted aralkyl group ( For example, p-chlor-phenethyl, m-chlor-phenethyl, etc.)], aryloxya Kill group (for example, phenoxyethyl group, phenoxypropyl group, phenoxybutyl group, alkyl- or alkoxy-substituted aryloxyalkyl group (for example, p-methylphenoxyethyl group, p-methoxyphenoxypropyl group, etc.), etc.), aryl group (preferably Having 4 to 15 carbon atoms, such as phenyl group,
Pyridyl group and the like], substituted aryl group [having an aryl moiety having 4 to 15 carbon atoms is preferable, and a substituent of a substituted alkyl group is used as the substituent. For example, p-methylphenyl group, p-methoxyphenyl group, etc.] and 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 are each an alkyl group [preferably having 1 to 5 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, etc.] is represented.

Z represents a group of non-metal atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus with a nitrogen atom, and examples of the heterocyclic nucleus include a thiazole nucleus [eg 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 [eg 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], oxazole nucleus [eg 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 nuclei (for example, 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 Fluoromethylbenzimidazole, 1-ethylnaphtho [1,2-d] imidazole, etc.), pyridine nucleus (eg, pyridine, 5-methyl-2-pyridi, 3-methyl-4-pyridine, etc.) and the like. Of these, a thiazole nucleus and an oxazole nucleus are advantageously used. More preferably, benzothiazole nucleus, naphthothiazole nucleus and naphthoxazole nucleus are advantageously used.

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

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

[0045]

[Chemical 14]

[In the formula, X represents -S- or -Se-, and R ₅
Represents an organic group having a water-soluble group, and any 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, one water-soluble group contained in any of R _{1 to} R ₄ in the general formula has a π value of -4.5 according to the Hansch method.
The above values are 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 a carboxyl group, a sulfamoyl group, a methoxymethyl group, and an organic group carrying a carbamoyl group.

Particularly preferred is an organic group carrying a carboxyl group or a sulfamoyl group. Examples of preferred substituents having a π value of -4 or more include a carboxyl group and an organic group carrying a sulfone group.

Particularly preferred is an organic group carrying a sulfone group.

The present invention will be specifically described below.

R ₁ , R ₂ , R ₃ and R ₄ other than the above-mentioned organic group having a water-soluble group are hydrogen, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, It represents an aryl group or a substituted aryl group. R ₆ and R ₇ are the same or different and each is hydrogen, a hydroxy group, a halogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an alkoxy group, a substituted alkoxy group, an alkylthio group. , Substituted alkylthio group, arylthio group, substituted arylthio group, aryl group, substituted aryl group, acyl group, substituted acyl group, acyloxy group, substituted acyloxy group, alkoxycarbonyl group, substituted alkoxycarbonyl group, alkylsulfonyl group, substituted alkylsulfonyl group , 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 an atom necessary for completing 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 here is the so-called Hansch
Known as a method, it means a substituent having a π value smaller than 0.

The π value here indicates a parameter of hydrophobicity in the so-called structure-activity relationship. Generally, a value greater than 0 is hydrophobic, and a parameter smaller than 0 is considered to be hydrophilic. . In addition, this parameter actually changes somewhat due to the effect of other substituents, but in this patent, J. Med. Chem. 16, 1207 (1973) and J.
The so-called Han described in Med. Chem. 20, 304 (1977).
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 at the smallest π value is used.

Specific examples of the dye represented by the general formula of the present invention are shown below, but the dyes are not limited to these.

[0055]

[Chemical 15]

[0056]

[Chemical 16]

[0057]

[Chemical 17]

[0058]

[Chemical 18]

[0059]

[Chemical 19]

[In the formula 2d, 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 each represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. X is a counter ion and L ₁ ~
L ₅ represents a methine group, m and n are 0,
Represents 1 and 2. R ₁ and R ₂ in the general formula [2d] are R in the general formula [2a].
_{1 has} the same meaning as R ₂ . More specifically, Z ₁ and Z ₂ each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. Specific examples of Z ₁ and Z ₂ include, for example, an oxazoline ring, an oxazole ring, a benzoxazole ring, a benzisoxazole ring, a naphthoxazole ring, a thiazoline ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazoline ring, and selenazole. Ring, naphthoselenazole ring, tellurazole ring, benzoterrazole ring, naphthoterrazole ring, pyridine ring, quinoline ring,
There are a benzoquinoline ring, an indolenine ring, a benzoindolenine ring, a benzimidazole ring, a pyrroline ring, etc., and these heterocycles and condensed benzene rings and naphthalene rings have alkyl groups, aryl groups, alkoxy groups (eg, methoxy, ethoxy, etc.). , Propoxy, etc.), hydroxy group, carboxy group, alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), halogen atom (eg, fluorine, chlorine, bromine, iodine, etc.) and the like. . X represents a counter ion, R ₁ , R ₂ and Z
_{If 1} , Z ₂ does not have an acid substituent, an acid anion (eg, alkylsulfate ion such as methylsulfate, ethylsulfate,
(Thiocyanate ion, toluenesulfonate ion, halogen such as chlorine, bromine, iodine, etc., perchlorate ion, etc.), and when one acid substituent is present, X is not present because it forms an inner salt. When two or more are present, they represent a cation such as an alkali metal atom (eg, sodium, potassium, etc.), 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 alkyl group and aryl group as described above. Further, they may be linked to each other to form a 5- or 6-membered ring. May be formed), and m and n represent 0, 1, and 2.

Typical examples of the sensitizing dye represented by the general formula [2d] of the present invention are shown below, but the scope of the present invention is not limited thereto.

[0062]

[Chemical 20]

[0063]

[Chemical 21]

[0064]

[Chemical formula 22]

[0065]

[Chemical formula 23]

[0066]

[Chemical formula 24]

The infrared sensitizing dye used in the present invention may be any dye, for example, US Pat. No. 2,875,058 and US Pat. No. 3,457,0.
78, U.S. Patent 3,582,344, U.S. Patent 3,615,632, U.S. Patent 3,695,888, U.S. Patent 4,011,083, U.S. Patent 4,
Specific examples of the infrared sensitizing dye (2e) used in the present invention, which are dyes known in US Pat. No. 515,888 and US Pat. No. 4,536,473, are shown below, but the present invention is limited to these infrared sensitizing dyes. It is not limited.

[0068]

[Chemical 25]

[0069]

[Chemical formula 26]

[0070]

[Chemical 27]

The above infrared sensitizing dye used in the present invention is preferably 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
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.

As the silver halide emulsion used in the light-sensitive material of the present invention, any silver halide used in ordinary silver halide emulsions can be used, but it may contain silver chloride in an amount of 50 mol% or more. The particle size is preferably 0.2 μm or more and 0.5 μm or less.

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

Example 1 A container containing gelatin, sodium chloride and water heated to 40 ° C. was placed in an aqueous solution of silver nitrate and 6 × per mol of silver halide.
10 ^-7 mol hexachloroiridate potassium salt and 4 ×
A silver chlorobromide grain containing 35 mol% of silver bromide was added by adding a mixed aqueous solution of potassium bromide and sodium chloride to which 10 ^-8 mol of potassium hexabromorhodate was added by the double jet method (the distribution is wide). 12%, cubic, grain size 0.33 μm)
It was adjusted while maintaining H3.0pAg7.7, returned to pH 5.9, and then desalted by a conventional method.

This emulsion was gold-sensitized and sulfur-sensitized by adding 240 mg of the compounds of the general formulas [2a] to [2e] shown in Table 1 per mol of silver halide and 200 mg of the compound of A as a sensitizing dye, Furthermore, 70 mg of 1-phenyl-5-mercaptotetrazole per mole of silver halide, 4-hydroxy-6-methyl-1,3,
After 1.2 g of 3a, 7-tetrazaindene and gelatin were added to stop the ripening, 4 g of hydroquinone, 3 g of potassium bromide, 5 g of saponin, and styrene-maleic acid were added per mol of silver halide. 2g of polymer and 3g of 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 added on the polyethylene terephthalate support that had been subjected to undercoating.
/ 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 used as an emulsion layer of 2.0 g / m ² and a protective layer.
The emulsion layer and the protective layer were simultaneously coated so as to have a concentration of 1.0 g / m ² .

[0076]

[Chemical 28]

The sample thus obtained was processed with the following developing solution and fixing solution in an ordinary roller type automatic developing machine under the following conditions, and the residual color was evaluated.

The residual color is evaluated by dividing it into 10 stages, 10 being the best, 1 to 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 ℃ 12 seconds Settlement 34 ℃ 12 seconds Water wash Normal temperature 12 seconds Dry 50 ℃ 10 seconds Developer formulation (composition A) Pure water (Ion-exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2.0 g Diethylene glycol 50.0 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50.0 g Hydroquinone 15.0 g 5-Methylbenzotriazole 200 mg 1-Phenyl-5-mercaptotetrazole 30.0 mg Potassium hydroxide, the amount to bring the pH after use to 10.4 Potassium bromide 4.5g (Composition B) Pure water (ion-exchanged water) 3.0ml Diethylene glycol 50.0g Ethylenediaminetetraacetic acid disodium salt 25.0mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 700 mg When using the developer, dissolve the above composition A and composition B in 500 ml of water in this order and make up to 1 liter. .

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240 ml Sodium sulfite 17.0 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g Acetic acid (90% w / v Aqueous solution) 13.6 ml (Composition B) Pure water (ion exchanged water) 17.0 ml Sulfuric acid (50% w / v aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% w / v aqueous solution) 26.5 g When using the fixing solution, the above composition A and composition B were dissolved in this order in 500 ml of water, and the solution was made up to 1 liter. Of this fixer
The 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 0.01% aqueous solution of potassium hexabromorhodate salt 1.0 ml solution C water 3.8 l silver nitrate 1,700 g In solution A kept at 40 ° C., while maintaining pH 3 and pAg 7.7, solution B and solution C were functional at the same time. To 60 minutes, continue stirring for 10 minutes, adjust the pH to 6.0 with aqueous sodium carbonate solution, add 2 liters of 20% magnesium sulfate aqueous solution and 2.55 liters of 5% polynaphthalene sulfonic acid aqueous solution, and add emulsion to 40 Flocculate at ℃, decant and wash with water to remove excess salt of the aqueous solution. Then, 3.7 liters of water is added thereto to disperse it, and 0.9 liters of a 20% aqueous magnesium sulfate solution is added again to similarly remove excess salt from the aqueous solution. Add 3.7 l of water and 141 g of gelatin to it, 55
Disperse at ℃ for 30 minutes. With this, 35 mol% of silver bromide,
Grains with a silver chloride content of 65 mol%, an average of 0.25 μm and a monodispersity of 9 are obtained.

To the emulsion adjusted to pH 5.5 and pH 7 by adding 12 ml of a 1% citric acid aqueous solution and 12 ml of a 5% potassium chloride aqueous solution, 120 ml of an aqueous solution of 0.1% sodium thiosulfate and 0.2% of chloroauric acid were added. 80 ml of water solubility was added and it was aged at 60 ° C for maximum 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.7- Tetrazaindene 1% solution 180 ml, gelatin 10% aqueous solution 400 ml were added to stop ripening, and then an infrared sensitizing dye was added as shown in Table 2 to adjust pH and pAg. Was prepared, and then 10% hydroquinone was added as an antifoggant.
% Solution of 50% and 19% of 20% saponin solution as a spreading agent.
50 ml of a 4% aqueous solution of styrene-maleic acid polymer as a thickener and 30 g of a polymer latex of ethyl acrylate are added and stirred, and after 1 hour and 20 hours, the amount shown in Table 2 as a hardening agent, respectively. On the polyethylene terephthalate support which has been subjected to the undercoating process.
4.2 g / m ² , and as a protective film, 100 g of 10% potassium bromide aqueous solution was added to 500 g of gelatin aqueous solution, and 1-decyl-2- (3-isopentyl) succinate-2-sulfone was used as a spreading agent. Add 400 ml of 1% aqueous acid soda solution,
Further, 100 g of amorphous silica having an average particle diameter of 3.5 μ was added and dispersed so that gelatin was 1.1 g / m ² , and the emulsion layer and the protective layer were simultaneously coated.

[0086]

[Table 2]

[0087]

[Table 3]

The residual color was evaluated by treating in the same manner as in Example 1 thus obtained.

<Developer formulation> Pure water (ion exchanged water) About 800 ml Potassium sulfite 60.0 g Ethylenediaminetetraacetic acid disodium 2.0 g Potassium hydroxide 10.5 g 5-Methylbenzotriazole 300 mg Diethylene glycol 25.0 g 1-Phenyl-4,4- Dimethyl-3-pyrazolidinone 300mg 1-Phenyl-5-mercaptotetrazole 60mg Potassium bromide 3.5g Hydroquinone 20.0g Potassium carbonate 15.0g Pure water (ion exchange water) is added to make 1 liter.

The developer pH was 10.8.

<Fixing solution composition> (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 % W / W aqueous solution) 13.6 ml (Composition B) Pure water (ion exchanged water) 17.0 ml Sulfuric acid (50% W / W aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% w / w aqueous solution) ) 26.5g The above composition A and composition B in 500 ml of water when using the fixer
Were melted in this order and finished to 1 liter before use. The pH of this fixer was about 4.3.

From the results shown in Tables 2 and 3, it can be seen that the samples of the present invention have good residual color.

Example 3 In Example 1, the blocked isocyanate compound of the present invention was put in the protective film and the same evaluation was carried out. The results are shown in Table 4.
Shown in.

[0094]

[Table 4]

As is clear from Table 4, the effect is obtained even if the blocked isocyanate compound is used in the upper layer other than the sensitizing dye addition layer.

[0096]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which does not deteriorate in image quality due to residual color even when it is developed extremely rapidly.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver halide emulsion layer and / or the upper layer thereof contains a water-soluble or water-dispersible reaction compound having at least two isocyanate groups blocked with bisulfite.
A silver halide photographic light-sensitive material characterized in that the emulsion layer contains a sensitizing dye having a wavelength peak of 550 nm to 800 nm.