JPH05232631A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material for use in printing small in residual dye stains and superior in safelight operation safety and adapted to ultrahigh-speed processing. CONSTITUTION:This silver halide photographic sensitive material has at least one hydrophilic colloidal layer on a support, and this hydrophilic colloidal layer contains a dye in a dissolved state, and this dye is insoluble in water in a pH of <=7.0 in a coated state and soluble in water in a pH of >=8.5, and this hydrophilic colloidal layer is formed by lowering the pH of the layer to the insoluble range of the dye immediately before coating with this layer. It is preferred to incorporate fine particles giving surfaces dyeable with this dye on the hydrophilic colloidal layer colored with this dye.

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 light-sensitive material for printing, and more particularly to a silver halide photographic light-sensitive material suitable for ultra rapid processing.

[0002]

BACKGROUND OF THE INVENTION In recent years, silver halide photographic light-sensitive materials for printing have been demanded to be processed quickly because of the demand for shortening delivery time. When such ultra-acceleration is performed, various problems arise, but above all, the problem of decolorization of the filter dye appears.
Generally, silver halide photographic light-sensitive materials are often used with filter dyes for preventing halation, irradiation, etc., and these are decolorized during processing. However, in the ultra-rapid processing, there is a problem that these dyes are poor in decolorization. Therefore, when the amount of the dye is reduced, the effect of preventing irradiation is insufficient, leading to a decrease in sharpness, and when an antihalation layer is provided below the emulsion layer, the dye diffuses to other layers, and the sensitivity decreases,
Problems such as safelighting also occur.

To solve these problems, Japanese Patent Laid-Open No. 62-70830,
No. 55-33172 discloses a means for fixing a decolorizable water-soluble dye to a target layer during photographic processing by using a basic polymer mordant. This type of mordanting technology has a relatively low filter density (for example, the absorption peak absorbance is 0.2 or less).
In some cases, the object can be achieved to some extent, but in a system that requires a sufficiently high filter concentration, there is a problem in coatability and decolorization of the layer, and its versatility is not always sufficient.

On the other hand, in JP-A-63-197943, by using a fine crystal dispersion of a dye, the degree of immobilization of the dye in a specific layer is excellent and the filter layer is adjusted to a high concentration. Even in such a case, a technique having excellent decolorizing property is disclosed.

However, these techniques have not been sufficiently effective in the ultra-rapid treatment which is required recently.

[0006]

SUMMARY OF THE INVENTION With respect to the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material for printing, which has improved safelight property and greatly improved residual color in ultra-rapid processing. is there.

[0007]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, wherein the hydrophilic colloid layer is in a coated state.
Contains a dye that is water-insoluble at a pH of 7.0 or less and substantially water-soluble at a pH of 8.5 or more, and the pH of the layer is insoluble in the dye immediately before coating the hydrophilic colloid layer. It is achieved by a silver halide photographic light-sensitive material for printing, which is formed by reducing the area.

In the above light-sensitive material, it is preferable that the hydrophilic colloid layer colored with a dye contains fine particles for providing a surface on which the dye can be colored.

The present invention will be specifically described below.

The dye of the present invention is required to have the property that it is water-insoluble at pH ≦ 7.0 and the molecule is substantially water-soluble at pH 8.5 or higher. The dye that can be used in the present invention is preferably selected from the group consisting of compounds represented by the following general formulas [1] to [5] and may be used alone or in combination.

[0011]

[Chemical 1]

(In the formula, A and A'may be the same or different, each represents an acidic nucleus, B represents a basicity, X and Y may be the same or different, and each is an electron withdrawing group. R represents a hydrogen atom or an alkyl group, R ₁ and R ₂ each represent an alkyl group, an aryl group, an acyl group or a sulfonyl group, and R ₁ and R ₂ are linked to form a 5- or 6-membered ring. R ₃ and R ₆ each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkoxy group or a halogen atom, and R ₄ and R ₅ represent a hydrogen atom or R ₁ and R ₄ or R ₂ and R _{5 respectively.} Represents a group of non-metal atoms necessary for bonding to form a 5- or 6-membered ring, L ₁ , L ₂ and L ₃ each represent a methine group, m represents 0 or 1 and n represents 0, represents 1 or 2, p represents 0 or 1, when p is 0, R ₃ is hydroxy or carboxy And it represents a sill radicals R ₄ and R ₅ represents a hydrogen atom.

However, the general formulas [1], [2], [3],
The compound represented by [4] or [5] has a dissociative group having a pka in the range of 4 to 11 in a mixed solution of water and ethanol in a volume ratio of 1: 1 at least once in one molecule. .. ) The general formulas [1], [2], [3], [4] and [5] will be described in detail. The acidic nucleus represented by A or A ′ is preferably 2-pyrazolin-5-one, rhodan,
Represents hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbituric acid, thiobarbituric acid, indandione, pyrazolopyridine or hydroxypyridine.

The basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, thiosazole, benzoxazole, naphthoxazole or pyrrole.

A group having a dissociative proton having a pAa (acid dissociation constant) in the range of 4 to 11 in a mixed solution of water and ethanol in a volume ratio of 1: 1 is a dye molecule having a pH of 7 or less than pH 7. There is no particular limitation on the kind and the substitution position to the dye molecule, as long as it is water-insoluble and has a pH8 or pH8 or more to make the dye molecule substantially water-soluble, but is preferably a carboxy group, a sulfamoyl group or a sulfonamide. And a hydroxy group, and more preferably a carboxyl group. The dissociative group is not only directly substituted on the dye molecule, but also a divalent linking group (eg, alkyl group, phenylene group)
May be substituted via. Examples via a divalent linking group include 4-carboxyphenyl, 2-methyl-3-carboxyphenyl, 2,4-dicarboxyphenyl, 3,5-dicarboxyphenyl, 3-carboxyphenyl, 2,5 -Dicarboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl, 2,4,6-trihydroxyphenyl, 3-benzenesulfonamidophenyl, 4- (p-siamid (Sulfonamido) phenyl, 3-hydroxyphenyl, 2-hydroxyphenyl, 4-
Hydroxyphenyl, 2-hydroxyphenyl-4-carboxyphenyl, 3-methoxy-4-carboxyphenyl, 2-
Methyl-4-phenylsulfamoylphenyl, 4-carboxybenzyl, 2-carboxybenzyl, 3-sulfamoylphenyl, 4-sulfamoyl, 2,5-disulfamoylphenyl, carboxymethyl, 2-carboxyethyl, 3-
Examples thereof include carboxypropyl, 4-carboxybutyl, 8-carboxyoctyl and the like.

The alkyl group represented by R, R ₃ or R ₆ is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isoamyl and n-octyl groups. ..

The alkyl group represented by R ₁ and R ₂ has 1 carbon atom.
~ 20 alkyl groups (such as methyl, ethyl, n-propyl, n-butyl, n-octyl, n-octadecyl, isobutyl, isopropyl) are preferred, substituents (for example, halogen atoms such as chlorine, bromine, nitro group, Cyano group, hydroxy group, carboxy group, alkoxy group (for example, methoxy, ethoxy), alkoxycarbonyl group (for example,
Methoxycarbonyl, i-propoxycarbonyl), aryloxy group (for example, phenoxy group), phenyl group,
An amide group (eg, acetylamino, methanesulfonamide), a carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl), a sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].

An aryl group, a phenyl group or a naphthyl group represented by R ₁ or R ₂ is preferable, and a substituent [as the substituent is mentioned as a substituent which the alkyl group represented by R ₁ and R ₂ has. Groups and alkyl groups (eg methyl, ethyl) are included. ] May be included.

The acyl group represented by R ₁ or R ₂ has 1 carbon atom.
The acyl groups of 10 to 10 are preferable, and examples thereof include acetyl, propionyl, n-octanoyl, n-decanoyl, isobutanoyl, benzoyl and the like. Examples of the alkylsulfonyl group or arylsulfonyl group represented by R ₁ or R ₂ include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl,
The amount of benzenesulfonyl, p-toluenesulfonyl, o-carboxybenzenesulfonyl and the like can be mentioned.

The alkoxy group represented by R ₃ or R ₄ is preferably an alkoxy group having 1 to 10 carbon atoms, such as mexy, ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy, isopropoxy and the like. A group can be mentioned.

Examples of the halogen atom represented by R ₃ or R ₄ include chlorine, bromine, fluorine and the like.

Examples of the ring formed by connecting R ₁ and R ₄ or R ₂ and R ₅ include a julolidine ring.

Examples of the 5- or 6-membered ring formed by R ₁ and R ₂ in succession include a piperidine ring, a morpholine ring and a pyrrolidine ring.

The methyl group represented by L ₁ , L ₂ or L ₃ is
Substituents (eg, methyl, ethyl, cyano, phenyl,
It may have a chlorine atom, hydroxypropyl).

The electron-withdrawing groups represented by X or Y may be the same or different and each is a cyano group, a carboxy group, an alkylcarbonyl group (an optionally substituted alkylcarbonyl group, for example, acetyl, propionyl, heptanoyl). , Dodecanoyl, hexadecanoyl, 1-oxo-7-
Chloroheptyl group etc.), arylcarbonyl group (which may be substituted arylcarbonyl group such as benzoyl, 4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl group etc.), alkoxycarbonyl group (which may be substituted alkoxycarbonyl group) There are, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2- (2-chloroethoxy) ethoxycarbonyl, 2- [2- (2-chloro) Etc.) ethoxy] ethoxycarbonyl group), an aryloxycarbonyl group (a substituted aryloxy group,
For example, phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl,
4-methoxyphenoxycarbonyl, 2,4-di- (t-amyl)
Phenoxycarbonyl group, etc., carbamoyl group (which may be substituted, such as carbamoyl group, ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2,4-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl) , 4-ethoxycarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl,
4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,
4-di- (t-amyl) phenylcarbamoyl, 2-chloro-3-
(Dodecyloxycarbonyl) phenylcarbamoyl, 3-
(Hexyloxycarbonyl) phenylcarbamoyl group, etc.), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl group, etc.), sulfamoyl group (which may be substituted sulfamoyl group, for example, sulfamoyl, methylsulfamoyl group, etc.) ..

Next, specific examples of the dyes used in the present invention will be listed, but the present invention is not limited thereto.

[0027]

[Chemical 2]

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

[0032]

[Chemical 7]

[0033]

[Chemical 8]

The dye used in the present invention is disclosed in JP-A-2-293740.
The compounds listed in I-1 to V-7 described in Nos. (5) to (16) can be used, and International Application Publication (WO) 88/0.
4794, European Patent (EP) 0274723A1, 276,
566, 299,435, JP-A-52-92716, 55-155350
No. 55, No. 55-155351, No. 61-205934, No. 48-8623, U.S. Patent Nos. 2,527,583, 3,486,897, 3,746,539,
It can be easily synthesized according to the method described in No. 3,933,798, No. 4,130,429, No. 4,040,841 and the like and the method.

The fine particles that provide a surface on which the dye of the present invention can be adsorbed are those that form a discontinuous solid phase different from the continuous phase of the hydrophilic colloid (hereinafter referred to as the binder), and are mixed and dispersed in the binder. Means something.

Next, the method for applying the filter dye layer of the present invention will be described.

The dye of the present invention needs to be dissolved in the state of the coating solution for the layer containing the dye, and therefore the pH of the coating solution for the filter dye layer is sufficient to substantially dissolve the contained dye. It is alkaline. In order to form the filter dye layer of the present invention, it is necessary to reduce the pH of the layer to the insoluble region of the dye containing layer just before coating the layer. Just before coating may be within 5 minutes from the time of coating. p
There is no restriction on how to reduce H. For example, after coating the filter dye layer and drying it once, an acidic coating solution (emulsion layer coating solution or acidic coating solution other than emulsion layer may be used)
May be applied to lower the pH of the filter dye layer by diffusion, or an acidic coating solution may be applied during the process from immediately after the application of the filter dye layer to the drying.
Further, the filter dye layer may be applied and once dried, and then soaked in an acidic liquid, or may be soaked in an acidic liquid in the process from immediately after the application of the filter dye layer to the drying. When and / or after applying the filter dye layer, the coating solution for reducing the pH of the layer to the insoluble region of the dye containing layer may be an adjacent layer, or may be a filter dye layer and an acidic coating solution layer. There may be an intermediate layer between.

In the coating method of the present invention, these methods may be appropriately combined and used, but JP-B-56-20534 and JP-A-63-63.
No. 54975, it is preferable to apply a very small amount of a hydrophilic colloid layer or a layer containing a very small amount of acidic water to a layer adjacent to the filter dye layer.

The coating amount of the hydrophilic colloid constituting the filter dye layer can be adjusted as necessary, but for the purpose of reducing the drying load in rapid processing, it is 1 g / side.
m ² or less, preferably 0.5 g / m ² or less, and particularly 0.3 g / m ² or less. Known compounds such as gelatin, dextran, and polyacrylamide can be used as the hydrophilic colloid.

The position where the filter dye layer is provided in the photographic element may be on the side closer to the support than the light-sensitive silver halide emulsion layer, and there is another layer for the purpose below the filter dye layer. However, it is especially preferred to utilize the subbing layer in the photographic element as the filter dye layer.

Generally, a photosensitive material for printing has at least one photosensitive silver halide emulsion layer on a support, and the silver halide contained in the silver halide emulsion layer has an average grain size of Fine particles with a size of 0.3 μm or less. As the silver halide, for example, a type having a multilayer laminated structure of at least two layers can be used. For example, silver chlorobromide grains may be used in which the core portion is silver chloride, the shell portion is silver bromide, conversely the core portion is silver bromide and the shell portion is silver chloride. At this time, iodine can be contained in any layer within 5 mol%. It may also be tabular grains. When preparing a silver halide emulsion, rhodium salt, osmium salt or ruthenium salt can be added to control sensitivity or gradation. When the rhodium salt is used, other inorganic compounds such as iridium salt, platinum salt, thallium salt, cobalt salt and gold salt may be used together.

In the silver halide photographic light-sensitive material for plate making, a so-called contrast adjusting agent such as a tetrazolium compound or a hydrazine compound is usually used in the light-sensitive silver halide emulsion layer. In addition, various known techniques used in the production of silver halide photographic light-sensitive materials are used. Incidentally, the details are described in, for example, Japanese Patent Application No. 2-10517.

In the present invention, the exposure for obtaining an image may be carried out by using a usual method. That is, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon,
Any of various known light sources such as an arc lamp, a carbon arc lamp, a xenon flash lamp, and a cathode ray tube flying spot can be used. The exposure time is 1/1000 second which is usually used in a camera to 1 second
An exposure shorter than 1000 seconds, for example, a 1/10 ⁴ to 1/10 ⁶ second exposure using a xenon flash lamp or a cathode ray tube can be used, and an exposure longer than 1 second can also be used. The spectral composition of the light used for exposure can be adjusted with a color filter as needed. Laser light can also be used for exposure.

There is no particular limitation on the method for developing the photosensitive material for plate-making used in the present invention, and any of those generally used for processing the photosensitive material for plate-making can be used.

The developing solution may contain any developing agent. As developing agents, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg
1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, and US Pat.
67,872, 1,2,3,4-heterocyclic compounds such as tetrahydroquinoline ring and indole ring condensed,
They can be used alone or in combination. The developing solution generally contains other well-known fence agents, alkali agents, pH buffers, antifoggants, etc., and further contains solubilizing agents, color toning agents, development accelerators, surfactants, defoaming agents, hard water if necessary. A softening agent, a hardener, a viscosity imparting agent, etc. may be included.

[0046]

EXAMPLES Specific examples of the present invention will be shown below, but the present invention is not limited thereto.

Example 1 A negative type silver halide light-sensitive material was prepared in the following manner as a light-returning light-sensitive material.

(Preparation of Emulsion) A silver chlorobromide emulsion having a silver bromide content of 2 mol% was prepared as follows.

An aqueous solution containing 23.9 mg of pentabromorhodium potassium salt, sodium chloride and potassium bromide per 60 g of silver nitrate and an aqueous solution of silver nitrate were stirred in an aqueous gelatin solution at the same time for 25 minutes at 40 ° C. and averaged. Each silver chlorobromide emulsion having a grain size of 0.20 μm was prepared.

After adding 200 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene as a stabilizer to this emulsion, it was washed with water and desalted.

20 mg of 6-methyl-4-hydroxy-
After addition of 1,3,3a, 7-tetrazaindene, it was sulfur sensitized. After sulfur sensitization, each necessary amount of gelatin was added, and 6-methyl-4-hydroxy-1,3,3a, 7 was added as a stabilizer.
The emulsion was prepared by adding tetrazaindene and then making up to 260 ml with water. (Preparation of latex (L) for emulsion addition) KMDS (dextran sulfate sodium salt) manufactured by Meito Sangyo Co., Ltd. was added to 40 liters of water.
Add 0.25 kg and ammonium persulfate 0.05 kg to the solution with a liquid temperature of 81
N-Butyl acrylate under nitrogen atmosphere with stirring at ℃
A mixture of 4.51 kg, styrene 5.49 kg and acrylic acid 0.1 kg was added over 1 hour, and then ammonium persulfate was added 0.00
After adding 5 kg and further stirring for 1.5 hours, the pH was adjusted to 6 with cooling and further with aqueous ammonia.

The obtained latex liquid was used as GF manufactured by Whotman.
A monodisperse latex (L) having an average particle size of 0.25μ was prepared by filtering with a / D filter and finishing with water to 50.5 kg.

The following additives were added to the above emulsion to prepare a silver halide emulsion coating solution as follows.

(Preparation of emulsion coating solution) After adding 9 mg of phenol as a bactericide to the emulsion solution, the pH was adjusted to 6.5 using 0.5N sodium hydroxide solution, and then 360 mg of the following compound (T) was added. , 5 ml of 20% saponin aqueous solution, 180 mg of sodium dodecylbenzenesulfonate, 5-methylbenztriazole per mol of silver halide
80 mg, 43 ml of the latex liquid (L) for adding the emulsion liquid, 60 mg of the following compound (M), and 280 mg of a styrene-maleic acid copolymer aqueous polymer as a thickener are sequentially added, and the mixture is made up to 475 ml with water. After finishing, an emulsion coating solution was prepared.

Next, an emulsion protective film coating solution was prepared as follows.

(Preparation of Coating Solution for Emulsion Protective Film) Pure water was added to gelatin and swelled and dissolved at 40 ° C. Then, the following compound (Z) as a coating aid was 32.7 mg / m ² , and the following was used as a filter dye. Was added as shown in Table 1.

Further, as a matting agent, amorphous silica having a particle size of 4 is used.
5 mg / m ² less than μm, 20 mg / m ² with particle size of 4 μm or more
m ^{2 was} added. The pH at that time was 8.7.

[0058]

[Chemical 9]

Next, a backing coating solution used for coating the backing lower layer was prepared as follows.

(Preparation of backing coating solution) Gelatin 36 g
Was swollen in water, heated and dissolved, and then 1.6 g of the following compound (C-1), 310 mg of (C-2), and (C-3) were used as dyes.
1.9 g, 2.9 g of the compound (N) as an aqueous solution was added,
Next, 11 ml of a 20% aqueous saponin solution and 5 g of the following compound (C-4) as a physical property modifier were added, and further 63 mg of the following compound (C-5) was added as a methanol solution. To this solution, as a thickener, 800 g of styrene-maleic acid copolymer water-soluble polymer was added to adjust the viscosity, pH was adjusted to 5.4 using an aqueous citric acid solution, and finally 144 mg of glyoxal was added, and 960 ml of water was added. To prepare a backing coating solution.

[0061]

[Chemical 10]

[0062]

[Chemical 11]

Next, a protective film coating solution for coating the protective film layer of the backing layer was prepared as follows.

(Preparation of coating solution for protective film of backing layer) After swelling 50 g of gelatin in water and dissolving with heating, 340 mg of 2-sulfonate-bis (2-ethylhexyl) succinate ester sodium salt was added, and 3.4 g of sodium chloride was added. In addition, 1.1 g of glyoxal and 540 mg of mucochloric acid were added. Spherical polymethylmethacrylate having an average particle size of 4 μm was added to this to a concentration of 40 mg / m ^2, and water was added to
After finishing to 000 ml, a coating solution for protective film was prepared.

At the time of coating, a liquid containing (CH ₂ = CHSO ₂ CH ₂ ) ₂ O and HCHO as a backing protective film hardener is mixed with the coating liquid immediately before coating to prepare an emulsion protective film and a hardener. A hardener solution obtained by adding citric acid to (CH ₂ = CHSO ₂ CH ₂ ) ₂ O and HCHO was mixed with the coating solution immediately before coating so that the pH of the emulsion protective film was 7.0 or less.

The compounds shown in Table 1 were added to the emulsion protective film.

As a support, a polyethylene terephthalate film (thickness 100 μm) provided with an undercoat layer of Example 1 of JP-A-59-19941 was used.

The amount of gelatin coated is 2.0 m for the backing layer.
g / m ² , backing protective layer 1.5 mg / m ² , emulsion layer 2.0 g / m ² , emulsion protective layer 1.0 g / m ² , and silver amount was 3.5 g / m ² .

The respective samples prepared above are shown below.
The evaluation was performed and the results are shown in Table 1. Safelight test Emulsion layer side of each sample using Toshiba Corporation
Irradiate to the side so that the illuminance is 400Lx, and
And the fog density is 0.04
The time was measured to be 5 or less.

Residual color test Five-level visual evaluation was carried out. (5) is colorless and (1) has a strong residual color. For general printing plate making, the residual color below (3) is a practically problematic level.

Development Processing Condition Process Temperature (° C) Time (sec) Development 28 30 Fixing 20 30 Washing with water Normal temperature 10 Drying 40 9 [Developer formulation] (Composition A) Pure water (ion-exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt Salt 2g Diethylene glycol 50g Potassium sulfite (55% W / V aqueous solution) 100ml Potassium carbonate 50g Hydroquinone 15g 5-Methylbenzotriazole 200mg 1-phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount to bring the pH of the solution to 10.9 Potassium bromide 4.5g (Composition B) Pure water (ion exchanged water) 3ml Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 25mg Acetic acid (90% aqueous solution) 0.3ml 5-Nitroindazole 110mg 1-Phenyl-3-pyrazolidone 500mg Water when using developer The above composition A and composition B in 500 ml
Were melted in this order and finished to 1 liter before use.

[Fixing solution formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (90% W / W aqueous solution)
8.1 ml (Composition B) Pure water (ion-exchanged water)
17 ml Sulfuric acid (50% W / W aqueous solution) 5.8 g Aluminum sulphate (Al ₂ O ₃ converted content is 8.1% W / W aqueous solution) 26.5 g When using the fixer, the above composition A and composition B are added in 500 ml of water in this order. It was melted and finished to 1 liter before use. PH of this fixer
Was about 4.3.

[0073]

[Table 1]

As can be seen from Table 1, Nos. 8, 9 and 13 have little residual color (stain) and are at a level without a problem, and have a safelight time of 16 minutes or more, which is satisfactory as a light-returning light-sensitive material. It is a level that can be done.

[0075]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material for printing which has less residual color and is excellent in safelight property and has suitability for ultra-rapid processing.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, wherein the hydrophilic colloid layer has a pH of 7.0 or less and is water-insoluble and a pH of 8.5 or more when coated. It is formed by containing a dye which is substantially water-soluble in a dissolved state, and by reducing the pH of the hydrophilic colloid layer to the insoluble region of the contained dye immediately before coating the hydrophilic colloid layer. And a silver halide photographic light-sensitive material for printing. 2. The silver halide photographic light-sensitive material for printing according to claim 1, wherein the hydrophilic colloid layer colored with a dye contains fine particles for providing a surface on which the dye can be colored.