JPH075629A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material improved in resistance to residual dye stains, stability after coating, running stability, highlight reproducibility, and enlargement characteristics. CONSTITUTION:The silver halide photographic sensitive material has on a support at least one silver halide emulsion layer and a hydrophilic colloidal layer containing an immobilized dye between the support and the emulsion layer, and this hydrophilic colloidal layer contains gelatin having an isoelectric point of >=6.5 as a hydrophilic colloid, and di- or poly-valent metal ions in an amount of >=1000ppm, and an anionic polymer. The emulsion comprises silver chloride or silver chlorobromide containing >=60mol% silver chloride. The photosensitive material is processed with a developing solution replenished by <=200ml/m<2>. It is preferred that this emulsion is sensitized with a selenium compound. It contains, for example, the compound represented by the formula. It is preferred that it contains a tetrazolium compound or a hydrazine derivative.

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, and more specifically, a silver halide having improved residual color, storability after coating, running stability, reproducibility of bright pigment, and stretchability. It relates to a photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, the demand for rapid processing of silver halide photographic light-sensitive materials has become extremely strict in the printing industry in order to cope with the increase in information volume and speed as part of the information industry. On the other hand, in order to improve the workability and stability, rapid access development, which is a drawback of the so-called lith development which has been conventionally used in the development of a photosensitive material for printing, is improved.

However, in terms of dye stain (remaining colorability) after treatment, storability after coating, running stability, etc., it is not yet at a satisfactory level and further improvement is desired.

On the other hand, in the line drawing photographing process of printing plate making, characters,
Various originals with different densities and line widths such as illustrations and halftone dots are pasted. Therefore, images having different densities and line widths are mixed in the original document, and there is a strong demand for a plate-making camera, a photographic light-sensitive material, or an image forming method for finishing these original documents with good reproduction. Further, in catalogs and posters, so-called expansion and contraction of halftone pictures, such as enlargement and reduction, are performed, and in plate making using enlarged halftone dots, the number of lines becomes rough and blurred points are taken. Therefore, in order to enhance the reproducibility of halftone, a photosensitive material having a wide exposure latitude is required.

[0005]

In order to solve the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material having the following characteristics.

Good dye immobilization and less residual color after treatment Good dye immobilization, less spreading to adjacent layers during coating, less sensitivity reduction, and good post-coating storage stability Running Excellent stability Excellent light reproducibility and good stretchability

[0007]

The above object of the present invention is achieved by a silver halide photographic light-sensitive material having the following characteristics.

A silver halide photograph having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer containing a dye immobilized between the emulsion layer and the support. In the light-sensitive material, the weight ratio of the dye to the hydrophilic colloid is 0.4 or less, and the coating amount of the hydrophilic colloid is 0.6 g / m ² or more.

A silver halide photograph having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer containing a dye immobilized between the emulsion layer and the support. In the light-sensitive material, the hydrophilic colloid is gelatin having an isoelectric point of 6.5 or more.

A silver halide photograph having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer containing a dye immobilized between the emulsion layer and the support. In the photosensitive material, divalent or higher valent metal ions are present in the dye-containing hydrophilic colloid in an amount of 1000 ppm or more,
Moreover, the coating amount of the hydrophilic colloid in the dye layer is 0.6 g / m ² or more.

A silver halide photograph having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer containing a dye immobilized between the emulsion layer and the support. In the light-sensitive material, the adjacent layer of the dye-containing hydrophilic colloid layer has a pH of 6.5 or less and divalent or higher valent metal ions are present in an amount of 1000 ppm or more based on the hydrophilic colloid of the adjacent layer.

A silver halide photograph having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer containing a dye immobilized between the emulsion layer and the support. In the light-sensitive material, the hydrophilic colloid layer contains an anionic polymer, and the emulsion has a silver chloride content of
It is 60 mol% or more of silver chloride or silver chlorobromide, and the developer replenishing amount during processing is 200 ml / m ² or less.

The above emulsion is preferably selenium sensitized.

It has at least two silver halide emulsion layers and at least one hydrophilic colloid layer on a support, and contains the compound represented by the general formula [D] (Formula 1).

A silver halide photograph having at least two silver halide emulsion layers on a support and a hydrophilic colloid layer containing a dye immobilized between the emulsion layers and the support. A silver halide photographic light-sensitive material containing a compound represented by the above general formula [D] in the light-sensitive material. It is preferable that each of the silver halide photographic light-sensitive materials 1 to 3 contains a tetrazolium compound or a hydrazine derivative.

The present invention will be specifically described below.

In the present invention, the immobilization is to improve the adsorptivity, to form a solid fine particle dispersion, an aluminum salt,
Alternatively, it means fixing as a silver salt or the like by preventing diffusion to other layers. In the solid fine particle dispersion, the compound is solid fine particles (preferably an average particle size of 10 μm or less, more preferably 1.0 μm).
m or less), it is dispersedly contained in the photographic constituent layer, and is stably present in the light-sensitive material in a water-insoluble state, but becomes water-soluble at a pH (for example, 8 or more) during the development processing after exposure, Elute in the processing solution.

The present inventors have determined that the weight ratio of the dye and the hydrophilic colloid is 0.4 or less and the coating amount of the hydrophilic colloid is 0.6 g / m ² or more, or that the dye silver compound is used. It was found that the immobilization was improved by.

The dyes preferably used in the present invention include compounds represented by the following general formulas [1] to [6].

[0020]

[Chemical 2]

(In the formula, A and A ′ may be the same or different and each represents an acidic nucleus, Q represents an aryl group or a heterocyclic group, B represents a basic nucleus, and B ′ represents a heterocyclic group. And X and Y, which may be the same or different, each represents an electron-withdrawing group, L ₁ , L ₂ and L ₃ each represent a methine group, m represents 0 or 1, and n represents 0. 1
Or 2 and p represents 1 or 2. However, the dyes represented by the general formulas [1] to [6] have at least one group selected from a carboxy group, a sulfonamide group and a sulfamoyl group in the molecule. ) Examples of the aryl group represented by Q in the general formulas [1] and [4] include a phenyl group, a naphthyl group and a julolidyl group.
The heterocyclic ring represented by Q is, for example, pyridine,
Examples thereof include quinoline, isoquinoline, pyrrole, pyrazole, imidazole and indole.

The aryl group and the heterocycle include those having a substituent, and examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group,
Carboxy group, cyano group, hydroxy group, mercapto group, amino group, alkoxy group, aryloxy group, acyl group, carbamoyl group, acylamino group, ureido group,
Examples thereof include a sulfamoyl group and a sulfonamide group, and two or more kinds of these substituents may be combined. Preferably,
Alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, butyl group, 2-hydroxyethyl group, etc.), hydroxy group, halogen atom (eg, fluorine atom, chlorine atom, etc.), alkoxy group (eg, methoxy group) , Ethoxy group, methylenedioxy, 2-hydroxyethoxy group, n-butoxy group, etc.), substituted amino group (eg, dimethylamino group, diethylamino group, di (n-butyl) amino group, N-ethyl-N-hydroxy group) Ethylamino group, N-ethyl-N-methanesulfonamide ethylamino group, morpholino group, piperidino group, pyrrolidino group, etc.), carboxy group, sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (Eg, sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.) It may be combined.

The acidic nuclei represented by A and A'in the general formulas [1], [2] and [3] are preferably 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanin, hydantoin and thio. Hydantoin, oxazolone,
Examples include isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, and pyrazolopyridone.

The basic nucleus represented by B in the general formulas [3] and [5] is preferably pyridine, quinoline, oxazole, benzoxazole, naphthoxazole,
Examples include thiazole, benzthiazole, naphthothiazole, indolenine, pyrrole and indole.

The electron-withdrawing groups represented by X and Y in the general formulas [4] and [5] may be the same or different, and for example, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, Carboxy group, acyl group, alkylsulfonyl group, arylsulfonyl group,
A sulfamoyl group is mentioned.

The heterocycle represented by B'in the general formula [5] is
Examples include pyridine, pyridazine, quinoline, pyrrole, pyrazole, imidazole and indole.

L ₁ , L ₂ and L _{3 of the} general formulas [1] to [5]
The methine group represented by includes those having a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, isobutyl, etc.),
Aryl groups (eg phenyl, p-tolyl, p-chlorophenyl, etc.), C1-C4 alkoxy groups (eg methoxy, ethoxy, etc.), aryloxy groups (eg phenyl, etc.), aralkyl groups (eg benzyl) Groups, phenethyl groups, etc.), heterocyclic groups (eg pyridyl, furyl,
Thienyl, etc.), substituted amino groups (eg dimethylamino,
Tetramethyleneamino, anilino, etc.) and alkylthio groups (eg, methylthio group, etc.).

Next, specific examples of the dye used in the present invention will be given.

[0029]

[Chemical 3]

[0030]

[Chemical 4]

[0031]

[Chemical 5]

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

[0036]

[Chemical 10]

[0037]

[Chemical 11]

[0038]

[Chemical 12]

[0039]

[Chemical 13]

[0040]

[Chemical 14]

[0041]

[Chemical 15]

Further, in the present invention, immobilization can be achieved by a silver salt and a silver complex formed by the reaction of a dye and silver ion. A preferred dye capable of forming a silver salt of such a dye is, for example, Japanese Patent Application No. 3-
General formulas [I] to [V], general formulas [I '] to [V'], and general formulas [V] described on pages 6 to 58 of the specification of 358334.
Examples thereof include compounds represented by I]. More specific compounds include pages 12 to 22 and pages 28 to 36 of the same specification.
And those described on pages 40 to 57.

The high isoelectric point gelatin which can be used in the present invention may be either lime-treated or acid-treated, but acid-treated gelatin has less swelling and reticulation. It is preferable in terms of improving the quality. See Arthur Weiss, "The Macromolecular Chemistry of
Gelatin "(Academic Press, published 1964).

In order to obtain high isoelectric point acid-treated gelatin, the treatment is carried out by immersing pig skin, bone or gelatin in a dilute acid solution such as hydrochloric acid, sulfuric acid, sulfurous acid and phosphoric acid or a mixture thereof. It is common. As a concrete example,
On page 186 of the above-mentioned "The Macromolecular Chemistry of Gelatin", a method for producing acid-treated pig skin gelatin is described.

In addition, esterified gelatin (such as methyl esterification) and amidated gelatin (such as aminoethyl amidation) can be mentioned from the viewpoint of decreasing the carboxylic acid group to raise the isoelectric point.

For esterification, see H. Fraenkel-Conr.
at, HS Olcott, J. Biol. Chem., 161, 259 (1945), hydrochloric acid-methanol method, J. Bello, Biochim. Biopys.
Acta., 20, 426 (1956), J. Bello, HCA Riese.
JR Vinograd, J. Phys. Chem., 60, 1299 (1956), thionyl chloride-methanol method, AW Kenchington, B
iochem. J., 68, 458 (1958), sulfuric acid-methanol method, E. Klein, E. Moioar, E. Roche, J. Photogr. Sc
i., 19, 55 (1971), Yasumasa Chominami, Hiroto Otaki, Harukazu Toyota, "Leather Chemistry" 28, 33 (1982).

Regarding the amidation, DG Hoare, DE K
Examples include amidated gelatin using a water-soluble carbodiimide described in oshland Jr., J. Am. Chem. Soc., 88, 2057 (1966).

The isoelectric point of gelatin which can be used in the present invention is preferably 6.5 or more, more preferably
6.8 or higher.

As the divalent or higher valent metal ion used in the present invention, for example, Ca ²⁺ , Ba ²⁺ , Mg ^{2+ and the} like are preferable.

The anionic polymer used in the present invention is not particularly limited, but those having a carboxy group or a sulfo group and having a number molecular weight of 2000 to 10000 are preferable.

The formula (1) of the present invention will be described in more detail.

R ₃ is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a heterocyclic group such as pyridyl, furyl or thiophenyl. Can be mentioned. Examples of the substituent on R ₃ include an alkyl group, an alkoxy group, an alkylthio group, an acylamino group, a sulfonic acid amide group, and a halogen atom. R ₄ , R ₅ and R ₆ are
They may be the same or different, and a hydrogen atom or R
It represents a substituent represented by ₃ , but is preferably a hydrogen atom. R ₂ represents, for example, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, a sulfonic acid amide group, or a halogen atom. R ₁ and R ₂ and two R ₂ are
They may together form a ring, in which case the number of ring members is preferably 5 to 7. m and n preferably represent 0, 1 or 2. A and A'represent a hydrogen atom or a group which can be removed with an alkali. In that case, a hydrolyzable group such as an acyl group, an alkoxycarbonyl group and a sulfonyl group is preferable, and a hydrogen atom is particularly preferable. B
The group represented by is-(B) n- after the hydroquinone mother nucleus is oxidized by the oxidized form of the developing agent during development to become a quinone form.
It represents a divalent group capable of releasing DI and further releasing DI, and may have a timing adjusting function.
It may be a redox group that reacts with another molecule of oxidized developer to release DI. Here, when n is 0,
It means a case where DI is directly bonded to the hydroquinone mother nucleus, and when n is 2, it represents a combination of two or more of the same or different B, but n is preferably 0.

When B is a divalent linking group having a timing adjusting function, examples thereof include general formulas (T-1) to (T-6) and (R-6) described in JP-A-4-438. -1) ~
The thing of the structure represented by (R-3) is mentioned.

The development inhibitor preferred as DI is a compound having a development inhibitory property when cleaved, but is decomposed into a compound which does not substantially affect the photographic performance after it is dissolved in the developing solution. (Or change) properties, for example, US Pat. No. 4,447,563, JP-A-6
0-218644, 60-221750, 60-233650, or 61
The development inhibitors described in No. 11743 can be mentioned.

Specific examples of the compounds used in the present invention are listed below, but the present invention is not limited to these.

[0056]

[Chemical 16]

[0057]

[Chemical 17]

[0058]

[Chemical 18]

[0059]

[Chemical 19]

[0060]

[Chemical 20]

A synthesis example of the above compound (1) is shown below, but the compound used in the present invention can be easily synthesized by the same method.

[0062]

[Chemical 21]

1) Synthesis of 1-A To 50 g of 2,5-dimethoxyaniline, 400 ml of acetonitrile and 26 ml of pyridine were added, and further ethyl isothiocyanate 2 was added.
8.5 g was added and the mixture was heated under reflux for 5 hours. After completion of the reaction, aqueous hydrochloric acid solution was added to the reaction mixture, the mixture was extracted with ethyl acetate, washed with water, concentrated and dried to obtain 47 g of the title compound.

2) Synthesis of 1-B To 30 g of 1-A obtained above was added 500 ml of 47% hydrobromic acid, and the mixture was heated under reflux for 4 hours. After completion of the reaction, water was added to the reaction mixture, extracted with ethyl acetate, washed with water, concentrated and dried to obtain 13 g of the title compound.

3) Synthesis of 1-C To 10 g of 1-B obtained above, 400 ml of ethanol and 11 g of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone were added, and the mixture was stirred at room temperature for 2 hours. did. After the reaction was completed, the precipitated crystals were separated by filtration, washed with ethanol and dried to obtain 8 g of the title compound.

4) Synthesis of Exemplified Compound (1) 400 g of ethyl acetate was added to 4 g of 1-C obtained above, and 5
-Mercapto-1- (4-nitrophenyl) tetrazole 5g, p
-Toluenesulfonic acid monohydrate (0.1 g) was added, and the mixture was stirred at 50 ° C for 2 hours. After completion of the reaction, water was added, the mixture was extracted with methylene chloride, washed with water, concentrated and dried to obtain 3.5 g of the title compound.

The compound of the general formula [1] of the present invention is 1.0 × 1
0 ^{-8 to} 1.0 × 10 ^-2 mol / m ² , preferably 1.0 × 10 ^-7 mol / m ²
Used within the range of.

The compound of the present invention can be used by dissolving it in a suitable water-miscible organic solvent such as alcohols, ketones, dimethylsulfoxide, dimethylformamide, methylcellosolve and the like.

It is also possible to add it as an emulsified dispersion using an already known oil. Alternatively, the compound powder can be dispersed in water by a ball mill, a colloid mill, an impeller disperser, or ultrasonic waves according to a method known as a solid dispersion method.

Next, examples of the tetrazolium compound used in the present invention include known compounds such as those described on pages 28 to 31 of Japanese Patent Application No. 5-016552.

Further, the hydrazine derivative used in the present invention is described, for example, in Japanese Patent Application No. 5-043861, pp. 7-
It is described on page 19, and specific compounds include H-1 to H-40 described on pages 12 to 18 of the same specification.

Further, the nucleation accelerator preferably used when a hydrazine derivative is used is described on pages 21 to 27 of the same specification, and specific compounds are described on the same page.
2-1 to 3-6 described on pages 23 to 27 are mentioned.

Next, for the silver halide emulsion used in the light-sensitive material of the present invention, various preparation methods including various sensitizing methods known in the art of silver halide photographic light-sensitive materials and various additives can be used.

In the present invention, a monodisperse emulsion is preferred. As the monodisperse silver halide grains in the monodisperse emulsion, the weight of silver halide contained within the grain size range of ± 20% centering on the average grain size r is 60% or more of the total weight of silver halide grains. Some are preferable, particularly preferably 70% or more, further preferably 80% or more.

The monodisperse emulsion of the present invention has a monodispersity index defined by (standard deviation of grain size / average grain size) × 100 = monodispersity index of 20 or less, more preferably 15 or less. is there.

The silver halide photographic light-sensitive material of the present invention comprises at least two silver halide emulsion layers, and the silver chloride content thereof is 60 mol% or more of silver chloride or silver chlorobromide.

Various additives can be used in the light-sensitive material of the present invention depending on the purpose. These additives are described in more detail in Research Disclosure, Vol. 176, Item.
17643 (December 1978) and Volume 187 Item 18716 (November 1979)
Month).

In the present invention, various known flexible supports used for silver halide photographic light-sensitive materials may be coated on one side or both sides. The support may be colored with a dye or pigment. It may be black for the purpose of shading. The surface of these supports is generally subbed to improve adhesion with emulsion layers and the like.

In the silver halide photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method or the like can be used.

Various known techniques can be used for the processing in the present invention, but the developing time is preferably within 30 seconds,
The development, fixing, washing and drying steps that are processed within 20 seconds will be described.

A combination of a dihydroxybenzene chain and 1-phenyl-3-pyrazolidones is most preferable in that a developing agent used in the black-and-white developing solution used in the present invention can easily obtain good performance. Of course, in addition to this, a p-aminophenol-based developing agent may be contained.

LFA Meson, "Photographic Processing Chemistry," Focal Press (1966), pages 226-229, US Pat. Nos. 2,193,015 and 2,5.
92,364, JP-A-48-64933 and the like may be used.

In the present invention, "development time" and "fixing time" are the time from the immersion of the photosensitive material to be processed in the developing tank solution of the developing machine to the immersion of the next fixing solution, respectively. Next washing tank liquid (stabilizing liquid)
Say the time to soak. What is "washing time"?
It means the time of immersion in the washing tank liquid. In addition, the "drying time" is usually 35 ℃ ~ 100 ℃, preferably 40 ℃ ~ 80 ℃, the drying zone where the hot air is blown is installed in the automatic developing machine, Say.

The development temperature and time are about 25 ° C. to 50 ° C. and 30 seconds or less, preferably 30 ° C. to 40 ° C. and 6 seconds to 20 seconds.

The fixing solution is an aqueous solution containing thiosulfate,
It has a pH of 3.8 or higher, preferably 4.2 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which have thiosulfate ion and ammonium ion as essential components, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 6 mol / l. In addition, various additives commonly used in fixing solutions can be used.

The fixing temperature and time are preferably about 20 ° C. to about 50 ° C. for 6 seconds to 1 minute, more preferably 30 ° C. to 40 ° C. for 6 seconds to 30 seconds, and further preferably 30 ° C. to 40 ° C. for 6 seconds. ~ 15 seconds.

In the present invention, the light-sensitive material is subjected to washing with water or stabilization after fixing with the actual solution. For the washing or stabilizing treatment, any method known in the art can be applied, and water containing various additives known in the art can also be used as washing water or a stabilizing solution. Washing or stabilizing bath temperature and time is preferably 0 ° C to 50 ° C for 6 seconds to 1 minute,
6 to 30 seconds at 15 ℃ to 40 ℃ is more preferable, and further 15 ℃
6 to 15 seconds at -40 ° C is preferred.

According to the method of the present invention, the developed, fixed and washed photographic material is dried by squeezing the washing water, that is, the squeeze roller method. Drying is about 40 ℃ ~ 100
The drying time may be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 1 minute, more preferably
It is about 5 to 30 seconds at 40 ° C to 80 ° C.

In the present invention, the line speed is 1000 mm
/ Min or more, preferably 1500 mm / min or more, more preferably
1800 mm / min or more.

According to the method of the present invention, the so-called Dry to Dry processing time until development, fixing, washing and drying is 100 seconds or less, preferably 60 seconds or less, more preferably 50 seconds or less. is there.

Here, "dry to dry" means that from the moment the tip of the photosensitive material to be processed enters the film inserting portion of the automatic developing machine,
It is the time until it is processed and the tip comes out of the machine.

[0092]

EXAMPLES The effects of the present invention will be illustrated by the following examples.

Example 1 Three layers of a dye-containing layer, a silver halide emulsion layer and a protective layer were coated on one side on the polyethylene terephthalate film having the undercoat described in Example 1 of JP-A-59-19941. A backing layer was applied to the other side.

[Dye-Containing Layer and Emulsion Lower Layer] General Formula [1]
As the solid disperse dyes of [3] to [3], the solid disperse dyes shown in Table 1 were dissolved in an alkali with an aqueous sodium acetate solution. Next, the amount of gelatin when applied to this solution was 0.6 g / m ² , and 10 mg of sodium p-dodecylbenzenesulfonate as a surfactant was used.
/ m ² and composed manner was added, the pH of the solution was adjusted to 5.8 with citric acid, the emulsion layer was simultaneously coated with the emulsion protective layer. The amount of dye added was 0.3 g / m ² .

[Preparation Method of Emulsion (A)] Liquids A and B shown below
A silver chlorobromide emulsion was prepared by using the solutions of liquids C, D and D.

<Solution A> Ocein gelatin 17 g Polyisopropylene-polyethyleneoxy disuccinate sodium salt 10% aqueous ethanol solution 5 ml Distilled water 1280 ml <Solution B> Silver nitrate 170 g Distilled water 410 ml <Solution C> Sodium chloride 45.0 g Potassium bromide 27.4g 6 Iridium chloride salt 200μg Polyisopropylene oxydisuccinate sodium salt 10% ethanol solution 3ml Ocein gelatin 11g Distilled water 407ml After keeping solution A at 40 ℃, add sodium chloride so that the EAg value becomes 160mV. Was added. Next, as in JP-A-57-92523
Solution B and solution C were added by the double jet method using the mixing stirrer described in No. 57-92524. As shown below, the addition flow rate was gradually increased over the entire addition time of 80 minutes while the EAg value was kept constant.

The EAg value was 160 mV, and 3 ml /
The EAg value was changed to 120 mV with 1 l of aqueous sodium chloride solution, and this value was maintained thereafter until the mixing was completed.

In order to keep the EAg value constant, the EAg value was controlled using a 3 mol / l sodium chloride aqueous solution.

[0099] A metal silver electrode and a double junction type saturated Ag / AgCl reference electrode were used to measure the EAg value (the double junction disclosed in JP-A-57-197534 was used for the electrode configuration).

For addition of solutions B and C, a variable flow rate roller tube metering pump was used. During the addition, it was confirmed by observing with an electron microscope that no new grains were found in the system due to sampling of the emulsion. Further, during the addition, the pH value of the system was controlled with a 3% nitric acid aqueous solution so as to keep it constant at 3.0.

After the addition of solutions B and C, the emulsion was ripened for 10 minutes in Ostwald, desalted and washed in a conventional manner, and then 600 ml of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) and a compound [ 15 ml of a 1% aqueous solution of the mixture of A], [B] and [C] was added and dispersed by stirring at 55 ° C. for 30 minutes and then adjusted to 750 ml to obtain emulsion A.

[0102]

[Chemical formula 22]

The emulsion A thus obtained was sensitized with gold and sulfur, and 1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, followed by sensitization. Dye A
300 mg per mol of silver halide contained in the emulsion,
Sensitizing dye B was added in an amount of 100 mg per mol of silver halide contained in the emulsion.

Next, the following tetrazolium compound T-1 (360 mg) per mol of silver halide, p-sodium dodecylbenzenesulfonate (300 mg), a styrene-maleic acid copolymer (2 g) and a styrene-butyl acrylate-acrylic acid copolymer were used. 15 g of latex (average particle size of about 0.25 μm)
In addition, gelatin was coated on the support so that the amount of gelatin was 1.8 g / m ^{2 for the} emulsion layer and the amount of Ag was 4.0 g / m ² . At that time, a protective layer of bis- (2-ethylhexyl) sulfosuccinate 10 mg / m ^{2 as} a spreading agent, formalin 15 mg / m ² as a hardener, and a gelatin amount 1.0 g / m ² containing glyoxal 8 mg / m ² Simultaneous multilayer coating was performed.

[0105]

[Chemical formula 23]

A backing layer described below was provided on the side opposite to the emulsion layer with the support interposed therebetween.

Gelatin 60 g Dyes A to C 100 mg / m ² Saponin 2 g Glyoxal 1 g

[0108]

[Chemical formula 24]

It was made up to 1 liter with pure water, 2 g / m ^{2 of} gelatin was added, and the same protective layer as the emulsion protective layer was coated so that the gelatin content was 1 g / m ² .

As shown in Table 1, samples were prepared by adding a dye or dye silver and changing the weight ratio of the dye and the hydrophilic colloid, and using these samples, the immobilization rate was measured by the following method.

(Measurement Method of Immobilization Rate) Each coated sample was 5%.
The sample was immersed in a gelatin solution at 35 ° C. for 2 minutes, and then the absorbance of the sample was measured with a commercially available spectrophotometer. It was expressed as a relative value when the absorbance before immersion was 100%. The closer to 100%, the higher the immobilization rate.

For the dye silver in the table, 0.1 ml of dye and 10.1 g (0.1 ml) of triethylamine were dissolved in 1000 ml of water, 10 ml of a 1 mol / l silver nitrate aqueous solution was dropped with stirring, and the resulting precipitate was filtered. After washing with water and drying, the desired dye silver was prepared.

[0113]

[Table 1]

From the results in Table 1, it is clear that all the samples of the present invention have a high immobilization rate. Further, as a result of examining the case of adding the hydrazine derivatives H-1, H-2, and H-3, the same results as in the case of the tetrazolium compound were obtained.

[0115]

[Chemical 25]

Example 2 In the same manner as in Example 1, a sample in which the weight ratio of the dye and the hydrophilic colloid was changed and the gelatin isoelectric point of the hydrophilic colloid was changed was prepared as shown in Table 2, and the sample was left by the following method. The color was measured.

(Measurement of Residual Color) The unexposed sample was processed under the following prescription and conditions, and five samples of each sample were overlaid and visually evaluated for residual color by five levels. In the evaluation, 5 is good with almost no residual color, and 1 is poor with many residual color,
3 is the lower limit practically.

<Development processing conditions> (Process) (Temperature) (Time) Tank capacity (l) Image 28 ° C 30 seconds 20 Fixed 28 ° C 30 seconds 20 Washing 18 ° C 20 seconds 15 Drying 40 ° C 20 seconds Each The process includes so-called wading transport time until the next process.
Dry to Dry time is 100 seconds.

<Developer formulation> (Composition A) Pure water (ion-exchanged water) 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200mg 1-Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount to make the pH of the used solution 10.4 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) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 700 mg butylamine diethanolamine 15 g When the developer was used, the above composition A and composition B were dissolved in 500 ml of water in this order to make 1 liter.

<Fixer Solution Formulation> (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90% w / w Aqueous solution) 13.6 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% w / w aqueous solution) 4.7 g Aluminum sulfate (aqueous solution with an Al ₂ O ₃ equivalent content of 8.1% w / w) 26.5 g Fixer At the time of use, the above composition A and composition B were dissolved in 500 ml of water in this order to make 1 liter and used. Of this fixer
The pH was about 4.3.

The results are shown in Table 2.

[0122]

[Table 2]

The results in Table 2 show that the samples of the present invention have extremely good residual color.

Example 3 In Example 1, 2 was added to the dye-containing hydrophilic colloid.
A sample was prepared in exactly the same manner as in Example 1 except that Ca ²⁺ as a valent metal ion was added as shown in Table 3, and the immobilization rate was evaluated in the same manner.

The results are shown in Table 3.

[0126]

[Table 3]

From the results shown in Table 3, it can be seen that the sample of the present invention in which the hydrophilic colloid contains Ca ²⁺ ions in an amount of 1000 ppm or more has an excellent immobilization rate.

Example 4 In Example 3, the layer adjacent to the dye-containing hydrophilic colloid layer was
Samples were prepared in the same manner as the samples of Example 3 except that the pH was changed as shown in Table 4, and these samples were evaluated for thermostorability by the following method.

(Evaluation of Thermostorability) The sample was put in a thermostat at 40 ° C. for 3 days to examine the sensitivity fluctuation. The relative sensitivity after the thermo was measured when the sensitivity after coating was 100. still,
Regarding the sensitivity, the sample was brought into close contact with a step wedge, exposed to 3200 ° K tungsten light for 5 seconds, and developed under the conditions described in Example 2 above.

The results are shown in Table 4.

[0131]

[Table 4]

From the results shown in Table 4, the samples of the present invention in which the dye-containing hydrophilic colloid has a Ca ²⁺ ion content of 1000 ppm or more and the pH of the adjacent layer of the hydrophilic colloid layer is 6.5 or less have thermostorability. It turns out to be excellent.

Example 5 In the silver chlorobromide prepared in Example 1, the silver chloride content was changed as shown in Table 5, and the dye-containing hydrophilic colloid layer was further treated with the following anionic polymers as shown in Table 5. 100m
A sample was prepared in the same manner as in Example 1 except that g / m ^{2 was} contained.

Further, in carrying out the developing solution treatment described in Example 2, the developing solution replenishment amount was changed as shown in Table 5 to carry out the running treatment. Running processor is GR-2
7 (manufactured by Konica Corporation) was used so that the total area of the treated samples would be 150 m ² . Exposure has a blackening rate of almost 80
It was set to be%.

With respect to the sample thus treated, the residual color before and after running was evaluated by the above method. The results are shown in Table 5.

[0136]

[Chemical formula 26]

[0137]

[Table 5]

Example 6 Silver chlorobromide having a silver chloride content of 70 mol% was used in the same manner as the sample prepared in Example 5, and N, N-dimethylselenourea was added to silver when chemically sensitizing gold and hypo. 10 mg per mole
Was added. Dyes and anionic polymers were added as shown in Table 6.

The same running treatment as in Example 5 was performed,
The sensitivity after running was evaluated as a relative value, with the sensitivity of the new solution as 100. The results are shown in Table 6.

[0140]

[Table 6]

From the results shown in Table 6, it can be seen that the selenium-sensitized sample of the present invention containing the anionic polymer shows little deterioration in sensitivity due to running even when the replenishing amount is small.

Example 7 A sample was prepared by adding the compound represented by the general formula [1] to the silver halide emulsion as shown in Table 7 except that the dye-containing hydrophilic colloid layer was excluded from the photosensitive material of Example 1. Created.
The Gothic line width of the obtained sample was measured by the following method.

(Evaluation of Brightness / Gogo Reproducibility) The obtained sample was C-
The line width of the Gothic body was measured with an 880F (Dainippon Screen Co., Ltd.) scanner when the exposure was adjusted so that the Mincho body was 50 mm. The closer to 50 mm, the better the light reproducibility.

The results are shown in Table 7.

[0145]

[Table 7]

From the results in Table 7, it is understood that the sample of the present invention to which the compound represented by the general formula [1] is added has better reproducibility.

Example 8 A sample was prepared by adding the general formula [1] as in Example 7 and further providing a dye-containing hydrophilic colloid layer as in Example 1 as shown in Table 8. The hydrophilic colloid layer was coated such that gelatin was 0.6 g / m ² and dye was 200 mg / m ² .

Using these samples, the stretch-extending characteristics were evaluated.

(Evaluation of stretchability) Using a scanner SG-808 (II) manufactured by Dainippon Screen Co., Ltd. and a photosensitive material RSDII manufactured by Konica Corporation, a transmission image of a person consisting of halftone dots and halftone% are stepped. Created a step wedge that was changed.
The number of screen lines at this time was 150 lines / inch, and a manuscript was prepared. Dainippon Screen Co., Ltd.
The above original is stretched to Fine Zoom C-880F made by 1
The sample was exposed to light by setting it to 20%. At this time, the exposure was performed so that 95% of the step wedge of the original became 5%. The filter of the present invention was installed between the original and the light source.

The exposed sample was processed in an automatic developing machine using the developing solution and fixing solution according to the above formulation.

Gradation reproducibility of the shardy part of the sample obtained by adjusting the halftone dot% (highlight part) of the sample obtained by adjusting the exposure amount The 10-point evaluation was carried out in order from the best one. The case where the stretchability was excellent was set to 10, and the case where it was very inferior was set to 1. 5 is the practical lower limit.

The results are shown in Table 8.

[0153]

[Table 8]

From the results shown in Table 8, it can be seen that the samples of the present invention having the dye-containing hydrophilic colloid layer and containing the compound represented by the general formula [1] have excellent stretching properties.

[0155]

According to the present invention, a silver halide photographic light-sensitive material having the following characteristics can be provided.

Good fixation of dye and little residual color after treatment Good fixation of dye, little decrease in sensitivity without spreading to adjacent layers during coating, and good storage stability after coating Running in treatment Excellent stability Excellent light reproducibility and good stretchability

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03C 1/09 1/43

Claims (9)

[Claims] 1. A halogenation comprising a support having at least one silver halide emulsion layer and a hydrophilic colloid layer containing a dye immobilized between the emulsion layer and the support. In the silver photographic light-sensitive material, the weight ratio of the dye to the hydrophilic colloid is 0.4 or less, and the coating amount of the hydrophilic colloid is 0.6 g / m ² or more. 2. A halogenation having at least one silver halide emulsion layer on a support and a hydrophilic colloid layer containing a dye immobilized between the emulsion layer and the support. In a silver photographic light-sensitive material, the hydrophilic colloid has an isoelectric point
A silver halide photographic light-sensitive material characterized by being gelatin of 6.5 or more. 3. A halogenation comprising a support having at least one silver halide emulsion layer and a hydrophilic colloid layer containing a dye immobilized between the emulsion layer and the support. In the silver photographic light-sensitive material, metal ions having a valence of 2 or more are present in an amount of 1000 ppm or more with respect to the dye-containing hydrophilic colloid, and the coating amount of the hydrophilic colloid in the dye layer is 0.6 g / m ² or more. Silver halide photographic light-sensitive material. 4. A halogenation having at least one silver halide emulsion layer on a support, and a hydrophilic colloid layer containing a dye immobilized between the emulsion layer and the support. In a silver photographic light-sensitive material, the halogen adjacent to the dye-containing hydrophilic colloid layer has a pH of 6.5 or less and a metal ion having a valence of 2 or more is present in the hydrophilic colloid of the adjacent layer in an amount of 1000 ppm or more. Silver halide photographic light-sensitive material. 5. A halogenation having at least one silver halide emulsion layer on a support, and a hydrophilic colloid layer containing a dye immobilized between the emulsion layer and the support. In a silver photographic light-sensitive material, the hydrophilic colloid layer contains an anionic polymer, and the emulsion has a silver chloride content of 60.
A silver halide photographic light-sensitive material characterized by comprising a mol% or more of silver chloride or silver chlorobromide, and replenishing amount of a developing solution at the time of processing is 200 ml / m ² or less. 6. A silver halide photographic light-sensitive material, wherein the emulsion according to claim 5 is selenium-sensitized. 7. A support having at least two silver halide emulsion layers and at least one hydrophilic colloid layer,
A silver halide photographic light-sensitive material containing a compound represented by the following general formula [D]. [Chemical 1] [In the formula, R ₁ is R ₃ N (R ₅ ) C (S) N (R ₄ )-, R ₃ C (S) N (R ₄ )-, R ₃ OC
(S) N (R ₄ )-, R ₃ SC (S) N (R ₄ )-, R ₃ SC (O) N (R ₄ )-, R ₃ C (O) C
(O) N (R ₄ )-, R ₃ OC (O) C (O) N (R ₄ )-, R ₃ N (R ₅ ) C (O) C (O) N (R ₄ )
-, R ₃ N (R ₆ ) N (R ₅ ) C (O) N (R ₄ )-represents R ₃ is an alkyl group,
It represents an aryl group or a heterocyclic group, and R ₂ represents a substituent other than a hydrogen atom. B represents a group that releases DI after being separated from the hydroquinone mother nucleic acid product, DI represents a development inhibitor, m and n represent integers, and A and A ′ represent a hydrogen atom or a group removable by an alkali. . R ₁ and R ₂ and two R ₂
May together form a ring. ] 8. A halogenation comprising a support having at least two silver halide emulsion layers and a hydrophilic colloid layer containing a dye immobilized between the emulsion layers and the support. A silver halide photographic light-sensitive material, comprising a compound represented by the above general formula [D]. 9. The silver halide photographic light-sensitive material according to any one of claims 1 to 9, wherein the silver halide photographic light-sensitive material contains a tetrazolium compound or a hydrazine derivative.