JPH0667334A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material causing no trouble to the fixability and residual color even when subjected to very rapid processing, free from roller marks and scuff blackening and having stability independently of a change in the compsn. of a developing soln. CONSTITUTION:This silver halide photographic sensitive material has at least one silver halide emulsion layer contg. silver halide particles having 0.6mol% or a lower silver iodide content and contains a compd. represented by the formula in the emulsion layer and/or other hydrophilic colloidal layer. In the formula, each of R1 and R2 is H, alkyl, etc., these groups may be substd., a halogen, alkyl, etc., are used as one or more substituents, in the case of two or more substituents, they may be different from each other and M is H, an alkali metal atom, etc.

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, which has excellent suitability for rapid processing, improves the generation of roller marks and the residual color of a sensitizing dye when processed by an automatic processor, and is processed. The present invention relates to a photographic light-sensitive material whose photographic performance does not easily change even when the liquid composition changes.

[0002]

2. Description of the Related Art In recent years, in the developing process of photographic light-sensitive materials (hereinafter referred to as "light-sensitive materials"), rapid processing at high temperature by an automatic developing machine has rapidly spread, and the processing time of various light-sensitive materials has been greatly shortened. In order to achieve rapid processing, a developing solution for achieving sufficient sensitivity in a short time, a photosensitive material that develops rapidly and gives a sufficient degree of blackening in a short time, and dry in a short time after washing with water. Characteristics are required. Techniques utilizing tabular grains are described in US Pat. Nos. 4,439,520 and 4,425,425 for the purpose of improving the viewpoints described above. Further, in JP-A-63-305343 and JP-A-1-77047, development progress and sensitivity / fogging ratio are improved by controlling the development start point of a silver halide grain having a (111) plane near the apex of the grain. Techniques for doing so are disclosed. Further, JP-A-58-111933 discloses a photographic element for radiography which has a high covering power by using tabular grains and swelling the hydrophilic colloid layer to 200% or less, and does not require addition of a hardening film during processing. Is disclosed. These known techniques are excellent techniques for improving the development progress of the light-sensitive material and have high utility value. However, shortening the processing time of each process of development, fixing, and water washing lowers the photographic sensitivity and increases the residual silver and residual hypo due to the deterioration of the fixability and water washability.
The preservation of the completed image will be seriously hindered. Also,
In the case of a light-sensitive material that has been spectrally sensitized with a sensitizing dye, the problem of residual color also comes to the surface. The problems other than the photographic properties are limited to the improvement by modifying the silver halide emulsion, and when the processing speed is shortened to a certain level or more (specifically, for example, when the developing / fixing time becomes 10 seconds or less, respectively). ) Ultimately, it results in a problem of film quality. That is, the thickness of the hydrophilic colloid layer regulates fixing and residual color, which is an obstacle to speeding up.

In this regard, Japanese Patent Laid-Open No. 64-7333
3, JP-A-64-86133, JP-A-1-10524
4, JP-A-1-158435, JP-A-1-15843
6, JP-A-63-221341 describes the amount of gelatin on the side having a hydrophilic colloid layer including a silver halide emulsion layer of 2.
A means for achieving a rapid treatment with a total treatment time of 20 seconds or more and less than 60 seconds, which is prepared in the range of 0 to 3.5 g / m ² , is disclosed. However, in these prior arts, as a result of reducing the amount of gelatin, there were problems such as blackening of scratches and marked deterioration of roller marks. Scratch blackening refers to a phenomenon in which, when the film is handled, rubbing between the films or rubbing the film with another substance causes scratching blackening after development processing. The roller mark is a phenomenon in which pressure is applied to the photosensitive material due to fine irregularities on the surface of the transport roller when the photosensitive material is processed by an automatic developing machine, and spot-like density unevenness occurs.

As a technique for improving such a defect by reducing the coating amount of gelatin, Japanese Patent Laid-Open No. 4-1288 has been proposed.
No. 32 discloses a light-sensitive material technique in which the silver iodide content of silver halide grains contained in a photosensitive emulsion layer is 0.6 mol% or less. By reducing the silver iodide content, the blackening of the scratches and the roller marks have been improved, and the total processing time can be further shortened, but on the other hand, the photographic properties are likely to change due to changes in the developer composition. There was a new drawback. For example, when iodine ions are accumulated in the developing solution, sensitization and fog are caused, and when the fixing solution is mixed in the developing tank, the low-sensitivity softening becomes severe.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is that there is no problem in fixability and residual color even when subjected to rapid processing, there is no problem in roller mark and scratch blackening performance, and the developer is Another object of the present invention is to provide a light-sensitive material that realizes stable photographic performance even when the composition changes.

[0006]

The objects of the present invention have been achieved by the following. In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver iodide content of the silver halide grains is 0.6 mol% or less, and the emulsion layer and / or the hydrophilic colloid layer of the silver halide photographic light-sensitive material is represented by the following general formula (I). A silver halide photographic light-sensitive material containing a compound. General formula (I)

[0007]

[Chemical 2]

In a particularly preferred embodiment, in the above silver halide photographic light-sensitive material, the average size of silver halide grains contained in the emulsion layer is less than 0.25 μm ³ . Hereinafter, a specific configuration of the present invention will be described in detail.

With regard to the compounds of general formula (I), R ₁
And R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or a heterocyclic group. These groups may be substituted, and as a substituent, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a carbamoyl group, an amide group, a cyano group, a nitro group, an amino group, a sulfonyl group, an acyl group, an alkylthio group. , An arylthio group,
It represents an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonylamino group, and an allyloxycarbonylamino group. Two or more of these substituents may be substituted, and when two or more are substituted, they may be the same or different. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group, or a group capable of becoming a hydrogen atom or an alkali metal atom under alkaline conditions.

More specifically, R ₁ and R ₂
Is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms (eg, methyl group, propyl group, hexyl group, dodecyl group, isopropyl group, etc.), cycloalkyl group having 3 to 20 carbon atoms (eg, cyclopropyl group, A cyclohexyl group), an aromatic aryl group having 6 to 20 carbon atoms (eg, phenyl group, naphthyl group, etc.), 7 to 7 carbon atoms.
The 20 aralkyl groups (eg, benzyl group, phenethyl group, etc.), and the heterocyclic group specifically includes a 5-membered, 6-membered or 7-membered heterocycle containing at least one nitrogen, oxygen or sulfur atom. And further includes a condensed ring formed at an appropriate position (for example, a pyridine ring,
Quinoline ring, pyrimidine ring, isoquinoline ring, etc.).

The linear or branched alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group may be further substituted, specifically, a halogen atom (F, Cl, Br, etc.), an alkyl group ( Methyl group, ethyl group, isopropyl group, etc., alkoxy group (phenoxy group, etc.), carbamoyl group (unsubstituted carbamoyl group,
Dimethylcarbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamido group, benzamide group, etc.), cyano group, nitro group, amino group (unsubstituted amino group, dimethylamino group, etc.), sulfonyl group (methanesulfonyl group, p- Toluenesulfonyl group, etc., Acyl group (acetyl group, benzoyl group, etc.), Alkylthio group (Methylthio group, etc.), Arylthio group (Phenylthio group, etc.), Alkoxycarbonyl group (Methoxycarbonyl group, etc.), Aryloxycarbonyl group (Phenoxycarbonyl group, etc.) Groups), alkoxycarbonylamino groups (methoxycarbonylamino groups, etc.), allyloxycarbonylamino groups (phenoxycarbonylamino groups, etc.)
Can be raised. Two or more of these substituents may be substituted, and when substituting two or more, they may be uncle or different. An unsubstituted phenyl group is particularly preferable as R ₁ , and a hydrogen atom is particularly preferable as R ₂ .

M is a hydrogen atom, an alkali metal atom (for example, sodium atom, potassium atom, etc.), a quaternary ammonium group (for example, trimethylammonium group, dimethylbenzylammonium group, tributylammonium group, etc.) and M is a hydrogen atom under alkaline conditions. It represents a group that can be an alkali metal atom (eg, acetyl group, cyanoethyl group, methanesulfonyl group, etc.). Specific examples of the compound represented by formula (I) used in the present invention are shown below.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

[0015]

[Chemical 5]

The amount of the compound represented by the general formula (I) added is preferably 1 × 10 ^-6 mol to 1 × 10 ^-3 mol, and more preferably 5 × 10 ^-6 mol, per mol of silver. Is about 5 × 10 ⁻⁴ mol. The place of addition is a silver halide emulsion layer or another hydrophilic colloid layer, and the other hydrophilic colloid layer is a hydrophilic colloid layer on the side where the silver halide emulsion layer is present, such as a surface protective layer or an intermediate layer. Is. The timing of addition is not particularly limited, but in the case of addition to the silver halide emulsion layer, for example, the time from the end of chemical sensitization to coating is preferable. In the light-sensitive material of the present invention, the light-sensitive silver halide emulsion layer may be provided on one side of the support or may be provided on both sides of the support. The light-sensitive material of the present invention may have a hydrophilic colloid layer in addition to the silver halide emulsion layer, if desired, and it is preferable to provide a surface protective layer according to a known method. The amount of gelatin on the side having the hydrophilic colloid layer including the emulsion layer is preferably in the range of 2.0 g / m ² or more and less than 3.2 g / m ² , particularly 2.4 g / m ² or more and 3.0 g.
It is desirable to set in the range of less than / m ² . The melting time of the light-sensitive material of the present invention is preferably set to 8 minutes or more and 45 minutes or less. The measuring method of the melting time referred to in the present invention follows the method described in JP-A-63-221341.

Next, the emulsion grains used in the present invention will be described. The size of the particles used in the present invention is preferably 0.01 [mu] m ³ or more 1 [mu] m ³ as an average of the volume of each particle, a significant improvement effect is obtained in particular 0.03 .mu.m ³ or 0.25 [mu] m ³ or less. The silver halide grains in the emulsion may have a regular crystal form such as cubic or octahedral, spherical,
It may have an irregular crystal form such as a plate shape or a potato shape, and may be a mixture of particles of various crystal forms.

With respect to the composition of the silver halide grains of the present invention, if the silver iodide content is 0.6 mol% or less, silver iodobromide,
It may be any of silver bromide, silver iodochlorobromide, silver chlorobromide, silver iodochloride, and silver chloride, but silver iodobromide is preferable in order to achieve high sensitivity, and is high in a laser imager or the like. Silver iodochlorobromide and silver chlorobromide are suitable as light-sensitive materials for illuminance exposure. The silver iodide content needs to be 0.6 mol% or less, preferably 0.01 mol% as the average of individual grains, based on the total silver amount.
It is preferably not less than 0.5 mol% and more preferably not less than 0.1 mol% and less than 0.4 mol%. The silver iodide distribution between individual grains may be uniform or uniform.

The use of monodisperse emulsions is a preferred embodiment for the present invention. A method for producing a monodisperse emulsion is known, and for example,
J. Photo. Sci. 12, 242-251 (1963),
Japanese Patent Publication No. 48-36890, Japanese Patent Publication No. 52-16364
No. 5, JP-A-55-142329, JP-A-57-179.
The technique described in No. 835 and the like can be appropriately used.
The emulsion of the present invention may be a core / shell type emulsion. The core / shell type emulsion is known from JP-A-54-48521.

Tabular grains are preferably used in the present invention. Regarding tabular grains, RESEARCH DISCLOSURE 22
Volume 5 Item 22534, 20-58, January issue (198
3) and JP-A Nos. 58-127921 and 58-
No. 113926, JP-A-58-113927, JP-A-58-113928, and US Pat. No. 4,439,520 can be referred to. The projected area diameter of the tabular emulsion of the present invention is preferably 0.3 to 2.0 μm, and particularly preferably 0.5 to 1.2 μm. Particle thickness is 0.05-0.3μ
m, particularly 0.1 to 0.25 μm, is preferable, and the aspect ratio is preferably 3 or more and less than 20, and particularly preferably 4 or more and less than 8. Among the tabular grains, monodisperse tabular grains are particularly useful grains. Details of the structure and manufacturing method of the monodisperse tabular grains referred to in the present invention are described in JP-A-63-1516.
18, as described in JP-A-1-158426.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention. For example, the additives described in the following relevant parts can be used. Item This section 1) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column 16 line, Japanese Patent Application No. 3-105035. 2) Antifoggant JP-A-2-68539, page 10, lower left column, line 17 and stabilizer to page 11 upper left column, line 7 and page 3 lower left column, line 2 to page 4 lower left Column. 3) Color improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, left lower column, line 20; JP-A-3-94249, page 6, lower left column, line 15 to Page 11, upper right column, line 19 4) Spectral sensitizing dye JP-A-2-68539, page 4, lower right column, line 4 to page 8, lower right column. 5) Surfactant JP-A-2-68539, page 11, upper left column, line 14 or from antistatic agent, page 12, upper left column, line 9 6) Matting agent, slipping agent JP-A-2-68539, page 12, upper left column, line 10 or plasticizer, same upper right column, line 10; page 14, lower left column, line 10 to right lower column, line 1 . 7) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 8) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 9) Support 10) Crossover JP-A-2-264944, page 4, upper right column, line 20 or cut method, page 14 upper right column. 11) Dyes and mordants JP-A-2-68539, page 13, lower left column, line 1 to page 14, lower left column, line 9 No. 3-24537, page 14, lower left column to page 16, lower right column. 12) Polyhydroxy JP-A-3-39948, page 11, upper left column to the same, first benzenes, page 2, lower left column, EP Patent No. 452772A. 13) Layer structure JP-A-3-198041. 14) Development processing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, left lower column, line 15 and JP-A-2-115837, page 3, lower right column, line 5 From page 6, upper right column, line 10 Next, the present invention will be described more specifically by way of examples.

[0022]

【Example】

Example 1 Preparation of emulsions 1-5 (octahedral grains of uniform composition) 25 g of inert gelatin, 0.76 g of potassium bromide, 50
% Ammonium nitrate (10 cc) and 25% aqueous ammonia solution (5.5 cc) were dissolved in 1 liter of distilled water and kept at 52 ° C. with stirring. 600 cc of a silver nitrate aqueous solution having a concentration of 0.98 mol / liter was added thereto over 50 minutes. One minute after starting the addition of the aqueous silver nitrate solution, control the mixed aqueous solution of potassium bromide and potassium iodide (total halogen concentration of bromine and iodine: 0.98 mol / liter) so that the pAg becomes constant at 9.2. While adding. Silver iodobromide grains having different compositions were prepared by changing the mixing ratio of potassium bromide and potassium iodide. After the addition of the aqueous silver nitrate solution and the aqueous halogen solution was completed, potassium thiocyanate (2N
30 cc of solution) was added. After 3 minutes, the mixture was cooled to 35 ° C., washed by the flocculation method, 30 g of inert gelatin was added, and then the temperature was raised to 40 ° C. and adjusted to pH 6.5 and pAg 8.2. The obtained emulsion has an equivalent spherical diameter of 0.6.
It consisted of octahedral grains of 2 μm (= 0.125 μm ³ ), and its coefficient of variation was 17%.

Emulsions 1 to 5 were subjected to the following chemical sensitization. 6
First, 0.02 mg of thiourea dioxide while stirring at 0 ° C.
Was added and held for 20 minutes for reduction sensitization.
Next, 0.1 mol of 0.03 μm AgI fine particles was added and
4-hydroxy-6-methyl-1,3,3
120 mg of a, 7-tetraazaindene and 240 mg of the sodium salt of the sensitizing dye anhydro-5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) -oxacarbocyanine were added. Subsequently, sodium thiosulfate 1.5 mg and triphenyl-phosphinic acid selenide 3
mg, chloroauric acid 2.6 mg and potassium thiocyanate 20
25 mg was added and cooled to 35 ° C. 25 minutes later. Emulsions 1 to 5 were thus obtained. The silver iodide contents of Emulsions 1 to 5 are summarized in Table 1.

Preparation of Emulsion Layer Coating Solution The following chemicals were added to chemically sensitized emulsions 1 to 5 per mol of silver halide to prepare coating solutions.・ 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg ・ trimethylolpropane 9 g ・ dextran (average molecular weight 39,000) 18.5 g ・ potassium polystyrene sulfonate (average molecular weight 60) 10,000) 1.8g

[0025]

[Chemical 6]

Snowtex C (manufactured by Nissan Chemical Industries, Ltd.) 29.1 g Gelatin The amount of gelatin in the emulsion layer was adjusted to 1.6 g / m ² .・ Hardener (1,2-bis (vinylsulfonyl hydrophilic acetoamide) ethane of hydrophilic colloid) 8 × 10 ^-3 mol per 100 g of ratin

Preparation of Coating Solution for Surface Protective Layer A coating solution for surface protective layer was prepared and prepared so that each component had the following coating amount. Gelatin 0.60 g / m ² · Sodium polyacrylate (average molecular weight 400,000) 0.023 g / m ² · polymethylmethacrylate (average particle size 3.7μm) 0.087g / m ² · Proxel 0.0005 g / m ²

[0028]

[Chemical 7]

(PH adjusted to 7.4 with NaOH)

Preparation of Photographic Material A biaxially stretched polyethylene terephthalate film having a thickness of 185 μm was preliminarily coated with an undercoat layer on both sides. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0031]

[Chemical 8]

The emulsion layer and the surface protective layer were coated on both sides of the support by the coextrusion method. The coated silver amount per one side was 2.15 g / m ² . Photographic materials 1 to 1
I got 0.

Table-1 ------------------ ------- Photographic material Emulsion No. Silver iodide Content Exemplified compound (3) of the present invention (mole%) (mg / Ag 1 mole) ----------------------------. ---- 1 Ratio 1 0.1 Not added 2 Ratio 2 0.2 Not added 3 Ratio 3 0.4 Not added 4 Ratio 4 0.6 Not added 5 Ratio 5 0 6.8 No addition 6 The present invention 1 0.1 17 7 The present invention 2 0.2 17 8 The present invention 3 0.4 179 The present invention 4 0.6 17 10 The ratio comparison 5 5 0.8 17 -------- −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

Evaluation of standard photographic performance Photographic materials 1 to 10 were 0.05 from both sides using a direct medical fluorescent intensifying screen HR-4 manufactured by Fuji Photo Film Co., Ltd.
Giving second exposure. After exposure, the following processing was performed to evaluate the sensitivity. The sensitivity was represented by the ratio of the reciprocal of the exposure amount giving a density of 1.5 in addition to the fog, with the photographic material 1 as 100. For the fog, the net fog value by the developed silver after subtracting the base density was used.

<Automatic processor> CEPROS manufactured by Fuji Photo Film Co., Ltd. (The speed of the film transfer can be increased by changing the rotation speed of the drive motor)

Preparation of Concentrated Solution <Developer> Parts Agent A-potassium hydroxide 270 g-potassium sulfite 1125 g-sodium carbonate 450 g-boric acid 75 g-diethylene glycol 150 g-diethylenetriamine pentaacetic acid 30 g-1- (N, N-diethylamino) ethyl -5-Mercaptotetrazole 1.5g Hydroquinone 405g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 30g Water was added to 4500 ml

Parts agent B ・ Tetraethylene glycol 750 g ・ 3,3′-Dithiobishydrocinnamic acid 3 g ・ Glacial acetic acid 75 g ・ 5-Nitroindazole 4.5 g ・ 1-Phenyl-3-pyrazolidone 67.5 g Water was added. 1000 ml

Parts agent C-potassium bromide 15 g-potassium metabisulfite 120 g Water added 750 ml

<Fixer> Ammonium thiosulfate (70 wt / vol%) 3.0 liters • Ethylenediaminetetraacetic acid / 2 sodium dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N, N- Diethylamino) ethyl 15 g-5-mercaptotetrazole-Tartaric acid 48 g-Glacial acetic acid 675 g-Sodium hydroxide 225 g-Sulfuric acid (36 N) 58.5 g-Aluminum sulfate 150 g Water was added to 6000 ml, pH 4.68.

Preparation of Treatment Solution The above treatment concentrate was filled into a replenisher container of CEPROS. The developer replenisher container is one in which parts A, B and C are connected together by the container itself. The developing and fixing tanks of the automatic processor are filled with the processing agents having the following mixing ratios. Developer Part A 60 ml Part agent B 13.4 ml Part agent C 10 ml Water 116.6 ml (pH 10.50) Fixer concentrate Concentrate 80 ml Water 120 ml (pH 4.62) The washing tank was filled with tap water.

Development temperature 35 ° C. Fixing temperature 35 ° C. Water washing temperature 15 ° C. Drying temperature 50 ° C. Processing speed 30 seconds with Top to Top Photographic fog and sensitivity results are summarized in Table 2.

Evaluation of Photographic Performance when Iodine Ions Accumulate in the Developer Under the conditions for evaluating the standard photographic performance described above, KI was added at a rate of 20 ml / liter in the developer in the developing tank of the automatic processor. After addition, the photographic performance was evaluated in the same manner. The results of fog and sensitivity are summarized in Table 2.

Evaluation of photographic performance when fixing solution is mixed in the developing solution Under the conditions for evaluating the standard photographic performance described above, 4 cc / fixing solution in the fixing tank was added to the developing solution in the developing tank of the automatic developing machine. It was added at a rate of 1 liter and the photographic performance was evaluated in the same manner. The results of fog and sensitivity are summarized in Table 2.

Evaluation of Roller Marks Photographic materials 1 to 10 were uniformly exposed in a size of 10 × 12 inches to a density of 1.0, and then processed under the same conditions as in the evaluation of standard photographic performance. However, the carrying roller of the developing tank and the crossover roller from the developing to the fixing used at this time were intentionally fatigued rollers.
The roller surface had irregularities of up to ± 10 μm. Some photographic materials after processing had many fine spots. This state was sensory-evaluated in the following four stages, and the results are summarized in Table-2. ◎ ... Almost no spots are observed. ○… Slightly spotted, but practically not noticeable. B: Spots occur, but they do not occur on a roller with little fatigue. Acceptable level. ×… Many spots. Even rollers with less fatigue are generated and cannot be put to practical use.

Table 2 ------------------ Photographic Material No. Standard Photographic Performance KI Accumulation state Fixing fluid mixed state Roller sensitivity Fog sensitivity Fog sensitivity Fog mark -------------------------------------------------------------------------- --------------------------------- 1 comparison 100 0.020 120 0.055 80 0.080 ◎ 2 comparison 110 0.025 130 0.060 95 0.085 ◎ 3 comparison 110 0.030 135 0.070 100 0.080 ○ 4 comparison 110 0.030 125 0.065 105 0.055 △ 5 comparison 110 0.035 120 0.060 100 0.050 × 6 Invention 95 0.015 105 0.020 100 0.015 ◎ 7 Invention 105 0.020 110 0.025 110 0.020 ◎ 8 Invention 100 0.030 110 0.030 100 0.030 △ 9 Comparison 100 0.030 105 0.030 100 0.030 × −−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−

The experimental results in Table 2 show that the developer used in this experiment did not contain a processing hardener, and the roller mark deteriorated as the silver iodide content of the grains increased. In practice, photographic materials 5 and 10 having a silver iodide content of 0.8 mol% cannot be used practically. On the other hand, as the silver iodide content decreases, the photographic performance when the fixing solution is mixed in the developing tank is more desensitized and the fog increases. However, the photographic materials 6 to 9, which are a combination of the compound of the present invention and the silver iodide content, have practically no problem with the roller mark, and the development in which the sensitivity and fog are small even when the developing solution is mixed with the fixing solution and the KI is accumulated. It can be seen that even a liquid is a very stable light-sensitive material with little fluctuation in sensitivity and fogging. The effect of the present invention is clear from this embodiment.

Example 2 Photographic materials 11 to 18 were prepared in the same manner as in Example 1.
However, in the preparation of the monodisperse octahedral emulsion, the grain size was changed by adjusting the temperature during preparation and the addition amount of the 25% aqueous ammonia solution. Further, as the compound of the present invention, the exemplified compound (8) was used instead of the exemplified compound (3). Table 3 shows the silver iodide contents, grain sizes, and addition amounts of the exemplary compound (8) of the present invention in the photographic materials 11 to 18.

Photographic materials 11 to 18 were evaluated in the same manner as in Example 1 and the results are summarized in Table-4. Although not shown in Table 4, the roller marks of the photographic materials 11 to 18 were all in the range of ⊚ to ◯, and there was no problem.

Table -3 ------------------------------------- Photographic Material Emulsion No. Grain Size Iodine Silver halide content Exemplified compound (8) of the present invention (μm ³ ) (mol%) (mg / Ag 1 mol) -------------------------. −−−−−−−−−−−− 11 Comparison 6 0.270 0.25 Not added 12 Comparison 7 0.125 0.25 Not added 13 Comparison 8 0.065 0.25 Not added 14 Comparison 9 0.035 0.25 Not added 15 Present invention 6 0.270 0.25 20 16 present invention 7 0.125 0.25 20 17 present invention 8 0.065 0.25 20 18 present invention 9 0.035 0.25 20 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−

Table -4 --------------------------------------- Photographic material No. Standard photographic performance KI Accumulation state Mixing state of fixer Sensitivity Fog Sensitivity Fog Sensitivity Fog --------------- Fog --------------------------- Comparison 160 0.055 180 0.080 135 0.075 12 Comparison 110 0.025 130 0.060 95 0.080 13 Comparison 80 0.020 100 0.040 55 0.035 14 Comparison 55 0.015 75 0.030 25 0.035 15 Invention 145 0.035 160 0.040 135 0.040 16 Invention 100 0.020 105 0.020 100 0.020 17 Invention 75 0.015 80 0.015 75 0.015 18 Invention 50 0.010 50 0.010 50 0.010 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−

From the results shown in Table 4, the particle size was 0.25.
[mu] m ³ or more in the photographic material 11 and 15 has a large desensitization of photographic properties due to the addition of the compound of the present invention, KI accumulated developer in sensitivity and graininess material change suppression is less than 0.25 [mu] m ³ of fog Is insufficient compared to. Further, even in the development with the fixing solution mixed, the effect is less than that of the particle-sensitive material in which the desensitization and the suppression of fog are less than 0.25 μm ³ . From this experiment, it can be seen that the effect of the present invention is remarkable when the particle size is less than 0.25 μm ³ .

Example 3 Preparation of Tabular Grain Emulsion a To 1 liter of water was added 6 g of potassium bromide and 6 g of low molecular weight gelatin having an average molecular weight of 20,000 obtained by enzymatically treating an alkali-treated gelatin, and the mixture was placed in a container kept at 55 ° C. While stirring, an aqueous solution of 5.56 g of silver nitrate and an aqueous solution of 9.4 g were added over 45 seconds by the double jet method. Subsequently, 20 g of gelatin having a normal molecular weight was added, the temperature was raised to 62 ° C., and an aqueous solution of 11.11 g of silver nitrate was added over 12 minutes. Next, 6 cc of 25% NH ₃ aqueous solution was added, and after 5 minutes, 5.6 cc of 100% acetic acid aqueous solution was added to neutralize. Then, an aqueous solution of 150 g of silver nitrate and a mixed aqueous solution of potassium bromide and potassium iodide were added over 25 minutes by the control double jet method while keeping the potential at pAg 8.5.
The flow rate at this time was linearly accelerated so that the flow rate at the end of addition was 8 times the flow rate at the start of addition. When 23 minutes have passed since the start of this accelerated flow rate addition, K ₃ IrCl ₆ was added to 5 times.
× 10 ⁻⁵ g was added. After the addition by the control double jet method for 25 minutes was completed, 15 cc of 2N potassium thiocyanate solution was added. After this, the temperature is 35 ℃
To 40 ℃ after removing soluble salts by sedimentation method.
The temperature is raised to 41 g of gelatin and phenoxyethanol.2.
5 g was added and the pH was adjusted to 5.95 with NaOH. Thus, tabular grains a were prepared. The obtained emulsion had a silver iodide content of 1.1 mol% and an average projected area diameter of 0.
63 μm (standard deviation 9.2%), average thickness is 0.10.
The aspect ratio was 6 at 5 μm.

Preparation of Tabular Grain b 6 g of potassium bromide and 6 g of low molecular weight gelatin having an average molecular weight of 20,000 obtained by enzymatically treating an alkali-treated gelatin with 6 g were added to 1 liter of water and stirred in a container kept at 55 ° C. An aqueous solution of 5.56 g of silver nitrate and an aqueous solution of 9.4 g were added over 45 seconds by the double jet method. Subsequently, 20 g of gelatin having a normal molecular weight was added, the temperature was raised to 62 ° C., and an aqueous solution of 11.11 g of silver nitrate was added over 12 minutes. Next, 6 cc of 25% NH ₃ aqueous solution was added, and after 5 minutes, 5.6 cc of 100% acetic acid aqueous solution was added to neutralize. Thereafter, an aqueous solution of 150 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by the control double jet method while maintaining the potential at pAg of 8.8. The flow rate at this time was linearly accelerated so that the flow rate at the end of addition was 8 times the flow rate at the start of addition. At 23 minutes after the start of the accelerated flow rate addition, 5 × 10 ⁻⁵ g of K ₃ IrCl ₆ was added.
After the addition by the control double jet method for 25 minutes was completed, 15 cc of 2N potassium thiocyanate solution was added. Thereafter, 0.25 mol of a silver iodide fine grain emulsion having an average diameter of 0.03 μm was added. Lower the temperature to 35 ° C,
After removing soluble salts by the precipitation method, the temperature was raised to 40 ° C., 41 g of gelatin and 2.5 g of phenoxyethanol were added, and the pH was adjusted to 5.95 with NaOH. Thus, tabular grains b were prepared. The obtained emulsion had a silver iodide content of 0.255 mol% and an average projected area diameter of 0.62 μm.
m (standard deviation 9.0%), the average thickness was 0.10 μm, and the aspect ratio was 6.2.

Preparation of tabular grains c To 1 liter of water was added 6 g of potassium bromide and 6 g of low molecular weight gelatin having an average molecular weight of 20,000 which had been enzymatically treated with an alkali-treated gelatin, and the mixture was stirred in a container kept at 55 ° C. An aqueous solution of 5.56 g of silver nitrate and an aqueous solution of 9.4 g were added over 45 seconds by the double jet method. Subsequently, 20 g of gelatin having a normal molecular weight was added, the temperature was raised to 62 ° C., and an aqueous solution of 11.11 g of silver nitrate was added over 12 minutes. Next, 6 cc of 25% NH ₃ aqueous solution was added, and after 5 minutes, 5.6 cc of 100% acetic acid aqueous solution was added to neutralize. After that, an aqueous solution of 150 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by the control double jet method while maintaining the potential at pAg of 8.8. The flow rate at this time was 8 times the flow rate at the start of addition It accelerated linearly so that. At 23 minutes after the start of the accelerated flow rate addition, 5 × 10 ⁻⁵ g of K ₃ IrCl ₆ was added. Two
After the addition by the control double jet method for 5 minutes was completed, 15 cc of 2N potassium thiocyanate solution was added. Then, the temperature is lowered to 35 ° C., the soluble salts are removed by the precipitation method, and the temperature is raised to 40 ° C.
g and phenoxyethanol (2.5 g) were added and the pH was adjusted to 5.95 with NaOH. The temperature was raised to 56 ° C. again, and a silver iodide fine grain emulsion having an average diameter of 0.03 μm was added to 0.2.
After adding 05 mol, the mixture was allowed to stand for 10 minutes. Thus, tabular grains c were prepared. The obtained emulsion had a silver iodide content of 0.051 mol% and an average projected area diameter of 0.62.
μm (standard deviation 9.0%), average thickness is 0.10 μm
The aspect ratio was 6.2.

The emulsions a to c were chemically sensitized as follows. While stirring at 56 ° C., 0.043 mg of thiourea dioxide was added and the mixture was held for 15 minutes for reduction sensitization. Next, 4-hydroxy-6-methyl-
160 mg of 1,3,3a, 7-tetraazaindene and sensitizing dye anhydro-5,5'-dichloro-9-ethyl-
350 mg of the sodium salt of 3,3'-di (3-sulfopropyl) -oxacarbocyanine were added. Subsequently, sodium thiosulfate and selenide triphenylphosphinic acid, chloroauric acid and potassium thiocyanate were used together for chemical sensitization. After the chemical sensitization was completed, the emulsion was cooled to obtain an emulsion.

(Preparation of Emulsion Layer Coating Solution) Tabular grains ac
The following chemicals were added to 1 mol of silver halide to prepare an emulsion layer coating solution. -2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72-Gelatin: Add gelatin so that the amount of gelatin coated in the emulsion layer is 2.5 g / m ² -Dextran (average molecular weight 3. 90,000) 18.5 g-Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g-Hardener 1,2-bis (vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling rate is 230%.

[0057]

[Chemical 9]

[0058]

[Chemical 10]

Snowtex C (manufactured by Nissan Chemical Industries, Ltd.) 9.6 g as solid content Dextran (average molecular weight 39,000) 5.8 g Exemplified compound of the present invention (3) Amount used in Table 5 The swelling ratio is the same as the one described in JP-A-58-111933.

(Preparation of Surface Protective Layer of Emulsion Layer) The surface protective layer of the emulsion layer was prepared and prepared so that each component had the following coating amount.・ Gelatin 0.97 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.018 g / m ²・ 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.003 g / m ²・ Polymethylmethacrylate (average particle size 2.5μm) 0.05g / m ²・ Proxel 0.0005g / m ²

[0061]

[Chemical 11]

The pH was adjusted to 7.2 with NaOH. The prepared emulsion layer coating solution and surface protective layer coating solution were simultaneously extruded on a polyethylene terephthalate film having a thickness of 183 μm which had been biaxially stretched and pre-coated with an undercoat layer. , Coated on one side. The amount of coated silver is 2.75.
It was adjusted to be g / m ² . The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0063]

[Chemical 12]

(Preparation of Antihalation Layer) An antihalation layer and a surface protection layer of the antihalation layer were coated on the side coated with the emulsion layer and the surface protection layer, and on the side opposite to the support. Each layer was prepared so as to have the following coating amount. (Antihalation layer) ・ Gelatin 1.5 g / m ²・ Phosphoric acid 5.2 g / m ²・ Snowtex C (Nissan Chemical Co., Ltd.) 0.5 g / m ² as solid content ・ Potassium polystyrene sulfonate (average molecular weight) 600,000) 25 mg / m ² · Polymer latex (Poly (ethyl acrylate / methacrylic acid) = 97/3)

[0065]

[Chemical 13]

[0066]

[Chemical 14]

(Surface protection layer of antihalation layer) ・ Gelatin 0.66 g / m ²・ Polymethylmethacrylate (average particle size 3.5 μm) 65 mg / m ²

[0068]

[Chemical 15]

C ₈ F ₁₇ SO ₃ K 1.7 mg / m ² · potassium polystyrene sulfonate (average molecular weight 600,000) 2 mg / m ² · NaOH 2.5 mg / m ² antihalation layer and its surface protection layer It was simultaneously coated and dried by the simultaneous extrusion method. The swelling ratio of the antihalation layer and the surface protection layer was measured by the cryo-SEM method. 1
It was 30%. Photographic material 19-24 completed in this way
The contents of the above are summarized in Table-5.

Table-5 ------------------------------------- Photographic material Emulsion No. Silver iodide Content Exemplified compound (3) of the present invention (mole%) (mg / Ag 1 mole) ----------------------------. −−−−− 19 Comparison a 1.1 No addition 20 Comparison b 0.255 No addition 21 Comparison c 0.051 No addition 22 Comparison a 1.1 20 23 Invention b 0.255 20 24 present invention c 0.051 20 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

The CRT single-sided photosensitive material thus obtained was evaluated in the same manner as in Example 1. However, the exposure was performed with monochromatic light of 545 nm by an interference filter from the emulsion surface side, and the exposure time was set to 2 seconds. Sensitivity is photographic material 1
9 was displayed as 100. The results are summarized in Table-6.

Table-6 ---------------------------------------------- Photographic Materials Standard Photographic Performance KI Accumulation State Fixing liquid mixed roller Sensitivity Fog sensitivity Fog sensitivity Fog mark --------------- Mark -------------------------- Comparison 100 0.025 120 0.040 95 0.030 × 20 Comparison 100 10020 20 115 0.030 85 0.035 ◎ 21 Comparison 100 0.015 110 0.020 70 0.040 ◎ 22 Comparison 90 0.020 100 0.030 100 0.020 × 23 Present invention 95 0.015 100 0.020 100 0.015 ◎ 24 Invention 95 0.015 95 0.015 95 0.015 ◎ −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

From the results shown in Table 6, it was found that the effect of the present invention was remarkable also in the single-sided photosensitive material composed of tabular grains.

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[Procedure amendment]

[Submission date] October 14, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

<Fixer> Ammonium thiosulfate (70 wt / vol%) 3.0 liters • Ethylenediaminetetraacetic acid / 2 sodium dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N, N- Dimethylamino) ethyl 15g-5-Mercaptotetrazole-Tartaric acid 48g-Glacial acetic acid 675g-Sodium hydroxide 225g-Sulfuric acid (36N) 58.5g-Aluminum sulfate 150g Water was added to 6000ml, pH 4.68.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

Evaluation of Photographic Performance when Iodine Ions Accumulate in the Developer Under the conditions for evaluating the standard photographic performance described above, KI was added to the developer in the developing tank of the automatic processor at a rate of 20 mg / liter. After addition, the photographic performance was evaluated in the same manner. The results of fog and sensitivity are summarized in Table 2.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

The experimental results in Table 2 show that the developer used in this experiment did not contain a processing hardener, and the roller mark deteriorated as the silver iodide content of the grains increased. In practice, photographic materials 5 and 10 having a silver iodide content of 0.8 mol% cannot be used practically. On the other hand, as the silver iodide content decreases, the photographic performance when the fixing solution is mixed in the developing tank is more desensitized and the fog increases. However, the photographic materials 6 to 8, which are a combination of the compound of the present invention and the silver iodide content, have practically no problem with the roller mark, and the fluctuations in sensitivity and fog are small even in the development in which a fixing solution is mixed, and the development in which KI is accumulated is achieved. It can be seen that even a liquid is a very stable light-sensitive material with little fluctuation in sensitivity and fogging. The effect of the present invention is clear from this embodiment.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver iodide content of the silver halide grains is 0.6 mol% or less, and the emulsion layer and / or the hydrophilic colloid layer of the silver halide photographic light-sensitive material is represented by the following general formula (I). A silver halide photographic light-sensitive material containing a compound. General formula (I) In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group and a heterocyclic group. These groups may be substituted, and as a substituent, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a carbamoyl group, an amide group, a cyano group, a nitro group, an amino group, a sulfonyl group, an acyl group, an alkylthio group. Represents an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonylamino group, and an allyloxycarbonylamino group. Two or more of these substituents may be substituted, and when two or more are substituted, they may be the same or different. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group, or a group capable of becoming a hydrogen atom or an alkali metal atom under alkaline conditions. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
The silver halide photographic material according to claim 1, wherein the average size of silver halide grains contained in the emulsion layer is less than 0.25 µm ³ .