JPH05188517A - Silver halide photographic - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material small in drop of sensitivity even if a replenishing solution for a developing solution is decreased by incorporating a thiocyanate in a specified amount or less in the photosensitive material. CONSTITUTION:When the replenishing amount of the developing solution is <=20ml per 10X12 (inch), i.e., 251X302 (mm), the thiocyanate is contained in the surfaces of silver halide grains as SCN salt of 2X10<-3>mol/mol Ag or less. When the photosensitive material is processed with the developing solution reduced in the replenishing amount and containing >=6g/l as KBr, it is preferred to chemically sensitize the silver halide grains of this photosensitive material with a selenium compound. The thiocyanate to be used during preparation of the silver halide grains may be the metal or ammonium thiocyanates, preferably, a water-soluble salt, such as KSCN, NaSCN, and the like. The hardly water-soluble salt like AgSCN may be added in the form of fine particles, preferably, <=200nm, especially <=50nm, preferably, after a chemical sensitization stage and before a desalting stage.

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 particularly to a silver halide photographic light-sensitive material using a silver halide emulsion whose sensitivity does not easily drop when the developer replenishment amount is reduced.

[0002]

2. Description of the Related Art In recent years, it has been desired to reduce processing waste liquid from the viewpoint of protecting the global environment. The recently released CEPROS system of FUJIFILM Corporation (manufactured) also reflects this. However, it is desired to further reduce the amount of waste liquid, that is, the amount of replenisher liquid. On the other hand, in the medical field, especially in the X-ray application field, lowering the sensitivity must be avoided for the health of the patient.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a light-sensitive material which is less sensitive in sensitivity even when the amount of developing replenisher is reduced.

[0004]

The above-mentioned problem is that when the replenisher amount of the developer is 20 cc / 4 or less, the surface of the silver halide grains contains 2 × 10 ^-3 mol / mol Ag or more as SCN salt. It has been found that this can be achieved by processing the characteristic silver halide light-sensitive material. It is more preferable to chemically sensitize the silver halide of the light-sensitive material to be processed with a developer having a replenisher amount of KBr of 6 g / l or more, which is better achieved by the combined use of a silver halide light-sensitive material. It was

As the thiocyanic acid compound used in the preparation of the silver halide emulsion in the present invention, a water-soluble salt such as metal thiocyanate or NH ₄ SCN can be generally used. Care should be taken to use metal elements that do not adversely affect photographic performance, with KSCN, NaSCN, etc. being preferred. A poorly soluble salt such as AgSCN may be added in the form of fine particles. In this case, A
The size of the gSCN fine particles is preferably 0.2 μm or less in diameter, and particularly preferably 0.05 μm or less.

The thiocyanic acid compound may be added at any time during the emulsion preparation, but it is preferably added both before the desalting step and during the chemical sensitization. The amount of addition is 2.5 × 10 ⁻³ mol or more and less than 5 × 10 ⁻² mol, preferably 5 × 10 ⁻³ mol or more, per mol of silver halide, as the total amount added from the time of grain formation to the end of chemical sensitization. Less than × 10 ^-2 mol and 2.5 × 10 per mol of silver halide in the final light-sensitive material or emulsion as a result of being removed in the desalting step.
^-3 mol 2 × 10 ^-2 mol less, and particularly preferably 4 × 10 ^-3 content below mol to 1.5 × 10 ^-2 mol.

The method of adding the thiocyanic acid compound before the desalting step is the preferred method for the present invention. In this case, the thiocyanic acid compound may be added at any time during grain formation. The addition amount is preferably 1 × 10 ⁻³ mol or more and less than 5 × 10 ⁻² mol, and more preferably 2 × 10 ⁻³ mol or more and less than 2 × 10 ⁻² mol, per mol of silver halide.
2.5 × 10 ^-3 mol or more per mol of silver halide in the final sensitizing material or emulsion as a result of partial addition during chemical sensitization, if part is removed in the desalting step 2 Less than × 10 ^-2 mol, especially 4 × 10 ^-3 mol or more 1.5 ×
A content of less than 10 ^-2 mol is preferred. Further, the total amount of the thiocyanic acid compound attached to the surface of the silver halide grains contained in the final light-sensitive material or emulsion is 2 × 10 ⁻³ mol or more per mol of silver halide and 2 × 10 ^−2.
The amount of adhesion is preferably less than 2.5 mol, particularly 2.5 × 10 ⁻³ mol or more and less than 1 × 10 ⁻² mol. The thiocyanic acid compound added at the time of chemical sensitization may be used as a ligand of the gold sensitizer and added.

PB when adding thiocyanate compound
r is particularly important, and when it is too low, the amount of the thiocyanic acid compound attached to the silver halide grains is remarkably reduced, and when it is too high, fog occurs, which is not preferable. A preferable pBr that can be utilized during grain formation in the presence of a thiocyanate compound is 2.0 or more and 4.5 or less, and particularly 2.3
It is preferably not less than 4.0 and not more than 4.0.

[Method of Quantifying Thiocyanic Acid Compound in Sensitive Material and Emulsion] In order to achieve the effect of the present invention, the amount of thiocyanic acid compound in the finally obtained finished emulsion or sensitive material is determined by the following method. You can check (the model of the centrifuge and ion chromatography that was actually used,
See the examples for details such as measurement conditions).

1. Determination of thiocyanate ion in emulsion before coating 1% KB in emulsion containing 1.5 × 10 ^-2 mol of silver halide
10 cc of aqueous solution was added and stirred at 40 ° C. for 30 minutes. The emulsion is centrifuged to completely separate the emulsion, and the supernatant is diluted 100 times. After the ultrafiltration of the diluted solution, the thiocyanate ion in the diluted solution is quantified by ion chromatography. For the quantification, a calibration curve prepared in advance using a thiocyanic acid compound aqueous solution is used.

2. Determination of thiocyanate ion on the surface of silver halide grains in the emulsion before coating: To an emulsion containing 1.5 × 10 ^-2 mol of silver halide, 10 cc of distilled water was added and stirred at 40 ° C. for 30 minutes. This emulsion is centrifuged to completely decompose the emulsion, and the supernatant is diluted 100 times. After ultrafiltration of the diluted solution,
The thiocyanate ion in the diluted solution is quantified by ion chromatography. For the quantification, a calibration curve prepared in advance using a thiocyanic acid compound aqueous solution is used. By subtracting the value thus obtained from the value of all thiocyanate ions in the emulsion previously obtained, the amount of thiocyanate ions attached to the target grain surface is obtained.

3. Quantification of thiocyanate ion in the product form of the sensitive material The target emulsion layer containing 1 g of silver was peeled from the sensitive material. 4
Immerse in 9 cc of distilled water. After adding 1 cc of 1% KBr aqueous solution to this solution, ultrasonic stirring is performed at 40 ° C. for 30 minutes. After centrifuging this solution, the supernatant is filtered. The filtered supernatant is diluted 10-fold and then the thiocyanate ion contained therein is quantified by ion chromatography. For the quantification, a calibration curve prepared in advance using a thiocyanic acid compound aqueous solution is used.

4. Quantitative determination of thiocyanate ion on the surface of silver halide grains in the product form sensitive material The target emulsion layer containing 1 g of silver was peeled from the sensitive material 5
Immerse in 0 cc of distilled water. This solution is ultrasonically stirred at 40 ° C. for 30 minutes. After centrifuging this solution, the supernatant is filtered. The filtered supernatant is diluted 10-fold and then the thiocyanate ion contained therein is quantified by ion chromatography. By subtracting the value thus obtained from the previously obtained value of thiocyanate ions in the photosensitive material, the amount of thiocyanate ions attached to the target particle surface is obtained. Even in the case of a multi-layer coated product light-sensitive material, if this operation is performed after peeling layers by layer, accurate information on the emulsion of the target layer can be obtained.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is used by stirring the emulsion at a high temperature, preferably 40 ° C. or higher, for a certain period of time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-13489.
No. 2, JP-A-2-130976, Japanese Patent Application No. 2-22930.
It is preferable to use the compounds described in No. 0 and the like. Specific unstable selenium sensitizers include isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (eg,
2-selenopropionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium. And so on. The preferred types of labile selenium compounds are described above, but are not limiting. Speaking to a person skilled in the art as an unstable selenium compound as a sensitizer for a photographic emulsion, the structure of the compound is not so important as long as selenium is unstable,
It is generally understood that the organic portion of the selenium sensitizer molecule carries selenium and plays no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, the labile selenium compound having such a broad concept is advantageously used. Examples of the non-labile selenium compound used in the present invention include JP-B-46-4553 and JP-B-53-344.
The compounds described in JP-B No. 92 and JP-B-52-34491 are used. Examples of non-labile selenium compounds include selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof. Of these selenium compounds, the following general formulas (I) and (II) are preferable. General formula (I)

[0015]

[Chemical 1]

In the formula, Z ₁ and Z _{2, which} may be the same or different, each represents an alkyl group (for example, a methyl group,
Ethyl group, t-butyl group, adamantyl group, t-octyl group), alkenyl group (eg, vinyl group, propenyl group), aralkyl group (eg, benzyl group, phenethyl group), aryl group (eg, phenyl group, penta) Fluorophenyl group, 4-chlorophenyl group, 3-nitrophenyl group, 4-octylsulfamoylphenyl group, α-
Naphthyl group), heterocyclic group (for example, pyridyl group, thienyl group, furyl group, imidazolyl group), -NR ₁ (R ₂ ),-
It represents an OR ₃ or -SR _4. R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group.
Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ . However, R ₁ and R ₂ are a hydrogen atom or an acyl group (for example, acetyl group, propanoyl group, benzoyl group, heptafluorobutanoyl group, difluoroacetyl group, 4-nitrobenzoyl group, α-naphthoyl group, 4-trifluoro group). Methylbenzoyl group). In formula (I), Z ₁ is preferably an alkyl group, an aryl group or —NR ₁ (R ₂ ).
And Z ₂ represents —NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅
R ₆ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group. In the general formula (I), more preferably N, N-dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-
Dialkyl-arylselenoamide, N-alkyl-N
Represents an aryl-arylselenoamide. General formula (II)

[0017]

[Chemical 2]

In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, -OR ₇ , -NR ₈ (R ₉ ), -SR. ₁₀ , -Se
R ₁₁ , X and a hydrogen atom are represented. R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. , X represents a halogen atom. In the general formula (II), Z ₃ , Z ₄ , Z ₅ , Z ₇ , Z ₈ ,
The aliphatic group represented by Z ₉ , Z ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl group, ethyl group, n-
Propyl group, isopropyl group, t-butyl group, n-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group, A propargyl group, a 3-pentynyl group, a benzyl group, a phenethyl group). In the general formula (II), Z ₃ , Z ₄ , Z ₅ ,
The aromatic group represented by Z ₇ , Z ₈ , Z ₉ , Z ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, a phenyl group,
Pentafluorophenyl group, 4-chlorophenyl group, 3
-Sulfophenyl group, α-naphthyl group, 4-methylphenyl group). In the general formula (II), Z ₃ , Z ₄ ,
The heterocyclic group represented by Z ₅ , Z ₇ , Z ₈ , Z ₉ , Z ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Represents a heterocyclic group (eg, pyridyl group, thienyl group, furyl group, thiazolyl group, imidazolyl group, benzimidazolyl group). In the general formula (II), the cations represented by R ₇ , R ₁₀ and R ₁₁ represent an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Represents In formula (II), preferably Z ₃ , Z ₄ or Z ₅
Represents an aliphatic group, an aromatic group or -OR ₇ , and R ₇ represents an aliphatic group or an aromatic group. In formula (II), it is more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate. Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the invention is not limited thereto.

[0019]

[Chemical 3]

[0020]

[Chemical 4]

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

[0025]

[Chemical 9]

[0026]

[Chemical 10]

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, or in Japanese Patent Application Nos. 2-264447 and 2-2.
No. 64448 is added at the time of chemical sensitization. It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one kind, and the selenium sensitizers described above
One or more species can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and the like. It is 1 × 10 ⁻⁸ mol or more per mol. It is more preferably 1 × 10 ⁻⁷ mol or more and 1 × 10 ⁻⁵ mol or less.
The temperature of chemical ripening when the selenium sensitizer is used is preferably 45 ° C. or higher. More preferably 50 ° C or higher and 80 ° C
It is below. pAg and pH are arbitrary. For example p
The effect of the present invention can be obtained in a wide range of H from 4 to 9. It is more effective to perform selenium sensitization in the presence of a silver halide solvent.

As the silver halide solvent which can be used in the present invention, US Pat. Nos. 3,271,157, 3,531,289, 3,574,628 and JP-A-54- (A) Organic thioethers described in 1019, 54-158917 and the like, JP-A-53-824.
No. 08, No. 55-77737, No. 55-2982 and the like (b) thiourea derivatives, JP-A-53-144
(C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, and (d) described in JP-A No. 54-100717.
Examples include imidazoles, (e) sulfites, (f) thiocyanates and the like.

The silver halide photographic emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization. Sulfur sensitization usually involves adding a sulfur sensitizer,
It is carried out by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. For sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate,
Examples include rhodanine. Other US Patents 1,5
74,944, 2,410,689, 2,
278, 947, 2,728,668, 3,501,313, 3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-
The sulfur sensitizers described in JP-A-24937, JP-A-55-45016 and the like can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature and large size of silver halide grains, but it is 1 × 10 ^-7 mol or more and 5 × 10 ^-4 mol per mol of silver halide. The following are preferred.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 or +3, and a gold compound usually used as a gold sensitizer can be used. Representative examples are chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate ,. Pyridyl trichloro gold etc. are mentioned. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ mol per mol of silver halide. At the time of chemical ripening, it is not necessary to particularly limit the timing and order of addition of a silver halide solvent and a selenium sensitizer or a sulfur sensitizer and / or a gold sensitizer which can be used in combination with a selenium sensitizer. Alternatively, for example, the above compounds may be added at the same time as the initial (preferably) chemical ripening or during the progress of chemical ripening, or at different addition points. In addition, at the time of addition, the above compound may be dissolved in water or an organic solvent capable of mixing with water, for example, a single liquid or a mixed liquid of methanol, ethanol, acetone or the like and added.

In the present invention, the antifoggant and the low illuminance irregularity improving agent described in JP-A-64-0531 and JP-A-02-000837 can be used.

The silver halide grains used in the present invention may have any form, but tabular grains are preferred. The aspect ratio of the tabular grains used in the present invention is given by the ratio of the average value of the diameter of a circle having an area equal to the projected area of the individual tabular grains and the average value of the individual tabular grains and the thickness. Be done. A preferable particle morphology is an aspect ratio of 4 or more and less than 20, more preferably 5 or more and less than 10. Further, the thickness of the particles is preferably 0.3 μm or less, and particularly preferably 0.2 μm or less. The tabular grains are preferably present in an amount of 80% by weight, more preferably 90% by weight or more, based on the total grains. The silver halide that can be used in the silver halide emulsion may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride and the like. Preferred are silver iodobromide (I = 0 to 10 mol%), silver bromide, and silver chlorobromide. The AgI distribution may be high inside or outside. In the process of silver halide grain formation or physical ripening, cadmium salt,
Zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt, etc. may be present together. If necessary, chemical sensitization can be performed.

One of the features of the present invention is that the amount of the replenisher in the developing process is 20 cc / 4 or less, which is an extremely small amount. With respect to the amount of replenisher, particularly the amount of developer replenisher, heretofore, replenishment of 25 cc / 4 or more has been conventionally performed. In this area, it is possible to obtain almost constant photographic properties even with conventional photographic light-sensitive materials in terms of the amount of KBr accumulated when running, the consumption of dihydroxybenzenes (for example, hydroquinone) during development, and the consumption due to air oxidation. You can However, when the development processing is attempted in the area of 20 cc / 4 cutting or less, the change in photographic property is too large with the conventional photosensitive material. It is very important from the ecological point of view and from the cost point of view to keep the area below 20cc / 4 cut. On the contrary, the above object can be achieved by obtaining a light-sensitive material having the technical features of the present invention. In the present invention, as a matting agent, US Pat.
No. 101, No. 2701245, No. 4142894,
Homopolymers of polymethylmethacrylate or copolymers of methylmethacrylate and methacrylic acid as described in JP-A-4396706, organic compounds such as starch, and fine particles of inorganic compounds such as silica, titanium dioxide, sulfuric acid, and strontium barium can be used. The particle size is preferably 1.0 to 10 μm, and particularly preferably 2 to 5 μm.

The combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is most preferable for the developing agent used in the developing solution used in the present invention because good performance can be easily obtained. Of course, in addition to this, a p-aminophenol-based developing agent may be contained. Hydroquinone is particularly preferable as the dihydroxybenzene developing agent used in the present invention. Methyl-p-aminophenol is preferred as the p-aminophenol-based developing agent used in the present invention. The developing agent is preferably used usually in an amount of 0.01 mol / liter to 1.2 mol / liter. As the preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite,
Examples include lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite. The sulfite is preferably 0.2 mol / liter or more, particularly preferably 0.4 mol / liter or more. The upper limit is preferably 2.5 mol / liter. The pH of the developer used in the present invention is 9
Those in the range from 1 to 13 are preferred. More preferably, the pH is in the range of 10 to 12. The alkaline agent used for setting the pH includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.
JP-A-62-186259 (borate), JP-A-60-9
3433 (eg, sucrose, acetoxime,
A buffering agent such as 5-sulfosalicylic acid), a phosphate or a carbonate may be used.

As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, Organic solvent such as ethanol and methanol: 1-phenyl-5
Mercapto-tetrazole, 2-mercapto-benzimidazole-5-sulfonic acid sodium salt and other mercapto-based compounds, 5-nitroindazole and other indazole-based compounds, 5-methylbenztriazole and other benztriazole-based compounds such as antifoggants If desired, it may further contain a toning agent, a surfactant, an antifoaming agent, a water softening agent, an amino compound described in JP-A-56-106244 and the like. Particularly, in order to maintain stable photographic performance even if the amount of the replenisher is reduced as in the present invention, the amount of KBr in the developer replenisher is preferably 6 g / liter or more. In the present invention, a silver stain preventing agent is used in the developer, for example, JP-A-56-24347, JP-B-56-46585,
US 4254215, JP-B-62-4702, JP-B-62-4703, JP-A-58-203439, JP-A-62-56959, JP-A-62-178247.
The compounds described in US Pat. No. 3,318,701 can be used.

The development processing time in the present invention is Dry to Dr.
It is preferable that y is 20 to 60 seconds, particularly 30 to 45 seconds. The treatment temperature is 25 to 50 ° C., especially 30 to 40
C. is preferred. Of these, the development time is 4
It is preferably 10 seconds.

There are no particular restrictions on other various additives used in the light-sensitive material of the present invention and other techniques relating to development processing conditions. For example, those described in the following relevant parts of JP-A-2-68539 can be used. Can be used. Item This section 1. Silver halide emulsion and JP-A-2-68539, page 8, lower right column, line 6 from the bottom, or from its production, page 10 upper right column, line 12 2. Chemical sensitization method, page 10, upper right column, line 13 to lower left column, line 16 3. Anti-foggant / stability Page 10, lower left column, line 17 to page 11, upper left column, line 7 and agent, page 3, lower left column, line 2 to page 4, lower left column 4. Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column, 5. Surfactants / antistatics Page 11, upper left column, line 14 to page 12, upper left column, line 9 Antistatic agent 6. Matting agent, slip agent, page 12, upper left column, line 10 to upper right column, line 10 14th plasticizer, page 10, lower left column, line 10 to lower right column, line 1 7. Hydrophilic colloid, page 12, upper right column, line 11 to left lower column, line 16 8. Hardener, page 12, lower left column, line 17 to page 13, upper right column, line 6 9. Support, page 13, upper right column, lines 7 to 20 10. Dyes / mordanting agents, page 13, lower left column, line 1 to page 14, lower left column, line 9 11. Development method JP-A-2-03037 Gazette, page 16, upper right column, line 7 to page 19, lower left column, line 15 And JP-A-2-115837, page 3, lower right column, line 5 to page 6, upper right column, line 10

[0038]

【Example】

Example 1 Preparation of tabular grains 6 g of potassium bromide and 7 g of gelatin were added to 1 liter of water, and 37 cc of silver nitrate aqueous solution (4.00 g of silver nitrate) and 5.9 g of potassium bromide were stirred into a container kept at 55 ° C. 38 cc of an aqueous solution containing P was added by the double jet method in 37 seconds. Then, after adding 18.6 g of gelatin, 70
The temperature was raised to ° C and 89 cc of an aqueous silver nitrate solution (9.8 g of silver nitrate) was added over 22 minutes. Here, 7 cc of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 6.5 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 153 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by the control double jet method while maintaining the pAg at 8.5. Next, the pBr was adjusted to 2.8 using an aqueous solution of silver nitrate, and then a 2N potassium thiocyanate solution was added (however, with ion chromatography, the first
It was controlled so that it became a table). After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Monodispersed pure silver bromide tabular grains having an average projected area diameter of 1.10 µm, a thickness of 0.165 µm and a variation coefficient of diameter of 18.5% were obtained.
After this, the soluble salts were removed by the sedimentation method. 40 again
The temperature was raised to 0 ° C., 30 g of gelatin, 2.35 g of phenoxyethanol, and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and pH was adjusted to 5.90 and pAg was adjusted to 8.25 with caustic soda and silver nitrate solution. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. However, AgI fine particles before and after chemical sensitization were adjusted to 0.
05% was added. First, 0.043 mg of thiourea dioxide was added, and the mixture was held as it was for 22 minutes for reduction sensitization. Next, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene 20mg and sensitizing dye

[0039]

[Chemical 11]

400 mg was added. Further, 0.83 g of calcium chloride was added. Succeedingly, the sensitizers listed in Table 4, 2.6 mg of chloroauric acid, and potassium thiocyanate 9 were added.
0 mg was added and after 40 minutes it was cooled to 35 ° C. In this way, preparation of tabular grains T-1 was completed.

Preparation of Coating Samples Coating samples 1 to 13 were prepared by adding the following chemicals to 1 mol of silver halide of T-1 to prepare coating solutions.・ Gelatin (including Gel in emulsion) 65.6 g ・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 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%.

[0042]

[Chemical 12]

The surface protective layer was prepared and prepared so that each component had the following coating amount. Contents coating weight Gelatin 0.966 g / m ² · sodium polyacrylate surface protective layer (average molecular weight 400,000) 0.023 - 4-hydroxy-6-methyl-1,3,3a, 7- Tetoraza indene 0. 015

[0044]

[Chemical 13]

-Polymethylmethacrylate (average particle size 3.7 μm) 0.087-Proxel (adjusted to pH 7.4 with NaOH) 0.0005

Preparation of Support (1) Preparation of Dye D-1 for Undercoat Layer The following dye was ball milled by the method described in JP-A-63-197943.

[0047]

[Chemical 14]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 4
00 ml (2 mm diameter) was added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. Observation of the resulting dye dispersion showed that the crushed dye had a wide range of particle diameters from 0.05 to 1.15 .mu.m, with an average particle size of 0.37 .mu.m. Further, a centrifugation operation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D-1 was obtained. (2) Preparation of support Corona discharge treatment was performed on a biaxially stretched 183 μm-thick polyethylene terephthalate film, and the first undercoat liquid having the following composition was applied so that the coating amount was 5.1 cc / m ^2. It was applied with a wire bar coater and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0049]

[Chemical 15]

Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79 cc

[0051]

[Chemical 16]

2,4-Dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc distilled water 900.5 cc A second undercoat having the following composition on the above-mentioned first undercoat layers. Layers are coated on each side so that the coating amount is as described below, and 150 ° C on both sides by the wire bar coater method.
It was applied and dried.・ Gelatin 160 mg / m ²・ Dye Dispersion D-1 (26 mg / m ² as a solid dye component)

[0053]

[Chemical 17]

Matting Agent Preparation of Polymethyl Methacrylate 2.5 mg / m ² Photographic Material with Average Particle Diameter 2.5 μm The above emulsion layer and surface protective layer were coated on both sides of the prepared support by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² .

(Quantification of thiocyanate compound) It was determined according to 1 and 2 (quantification of thiocyanate ion in the emulsion before coating) of the thiocyanate compound. That is, to an emulsion containing 1.5 × 10 ^-2 mol of silver halide, 10 cc of a 1% KBr aqueous solution (when quantifying thiocyanate ion in the emulsion) or distilled water (when quantifying thiocyanate ion in the binder) is used. In addition, the mixture was stirred at 40 ° C for 30 minutes. Then, centrifugation was performed at 10,000 rpm for 10 minutes using Hitachi Centrifuge 20RP-5. The supernatant was diluted 100 times and then subjected to ultrafiltration using an air press 30 manufactured by Tosoh Corporation. Next, the chromatographic measurement of the filtrate was performed using the CP system manufactured by Tosoh Corporation below. Column: TS IC-Anion SW Column temperature: 40 ° C. Detector: UV detector (210 nm) Eluent: 7.5 mM Na ₂ HPO ₄ and 7.5 mM NaH ₂ PO ₄
An aqueous solution (pH 7.0) containing 0.5 ml / min of calibration curve; 0.1 ppm to 10 ppm of potassium thiocyanate aqueous solution was prepared.

(Evaluation of Photographic Performance) An X-ray orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd. was used to perform exposure for 0.05 seconds from both sides to evaluate the sensitivity. The automatic developing machine used in this experiment is a modification of the automatic developing machine FPM-9000 manufactured by Fuji Photo Film Co., Ltd. The processing steps are shown in Table 1 below.

[0057]

[Table 1]

The processing liquid is as follows. Development Treatment Preparation of Concentrated Liquid <Developer> Part Agent A Potassium hydroxide 270 g Potassium sulfite 1125 g Sodium carbonate 450 g Boric acid 75 g Diethylene glycol 150 g Diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamino) ethyl-5-mercaptotetrazole 1.5 g Hydroquinone 405 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 30 g Water was added 4500 ml Parts agent B Tetraethylene glycol 750 g 3,3'-Dithiobishydrocinnamic acid 3 g Glacial acetic acid 75 g 5-Nitroindazole 4 0.5 g 1-phenyl-3-pyrazolidone 67.5 g Water was added 1000 ml Parts agent C Glutaraldehyde (50 wt / wt%) 150 g Potassium bromide 15 g Potassium metabisulfite 1 750ml In addition to the 0g water

<Fixer> Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid / disodium dihydrate 0.45 g Sodium sulfite 225 g Boric acid 60 g 1- (N, N-dimethylamino) -ethyl-5 Mercapto tetrazole 15g Tartaric acid 48g Glacial acetic acid 675g Sodium hydroxide 225g Sulfuric acid (36N) 58.5g Aluminum sulphate 150g Water added 6000ml pH 4.68

Preparation of Processing Solution The above concentrated developer solution was filled in the following containers for each parts agent. In this container, the partial containers of the parts agents A, B and C are connected together by the container itself. Also,
The above fixing solution concentrate was also filled in the same kind of container.

First, 300 ml of an aqueous solution containing 54 g of acetic acid and 55.5 g of potassium bromide as a starter in the developing tank.
Was added. Put the above-mentioned treatment agent container upside down and insert it into the perforation blade of the treatment liquid stock tank mounted on the side of the automatic processing machine to break the sealing film of the cap and put each treatment agent in the container into the stock tank. Filled. The developing agent and the fixing tank of the developing machine were filled with the respective processing agents at the following ratios by operating the pumps installed in the developing machine. However, under the conditions A to C, the amount of developing replenisher per 4 runs was as shown in Table 2, and the concentrations of KBr and hydroquinone at that time were as shown in Table 3.

[0062]

[Table 2]

[0063]

[Table 3]

Developing solution Parts agent A 60 ml Parts agent B 13.4 ml Parts agent C 10 ml Water 116.6 ml pH 10.50

Fixing solution Concentrated solution 80 ml Water 120 ml pH 4.62 The washing tank was filled with tap water.

[0066]

[Table 4]

It can be seen that the sample of the present invention is effective.

[0068]

【Example】

Example 2 6.0 g of potassium bromide and gelatin 5.
0 g was added, and 30 cc of an aqueous silver nitrate solution (5.5 g of silver nitrate) and potassium bromide were stirred into a container kept at 55 ° C.
33cc of aqueous solution containing 4g was prepared by double jet method to 45
Added in seconds. Then, the temperature was raised to 62 ° C. and 60 cc of an aqueous silver nitrate solution (silver nitrate 11.1 g) was added over 12 minutes. Here, 6 cc of 25% aqueous ammonia solution was added, and the mixture was physically aged at the same temperature for 5 minutes, and then 5.6 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 150.0 g of silver nitrate and an aqueous solution of potassium bromide were added over 25 minutes by the control double jet method while maintaining pAg8. Next, 15 cc of 2N potassium thiocyanate solution and AgI fine particles having a diameter of 0.07 μm were added to the total silver amount of 0.1
Mol% was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, monodisperse tabular grains having a total silver iodide content of 0.1 mol%, an average projected area diameter of 0.60 µm, a thickness of 0.12 µm and a diameter variation coefficient of 16.8% were obtained. After this, the soluble salts were removed by the sedimentation method. The temperature was raised again to 40 ° C., 41 g of gelatin and 1.4 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 5.90 and pAg to 7.90 with caustic soda and silver nitrate solution. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, add 0.1 mg of thiourea dioxide 1
It was held for 0 minutes as it was for reduction sensitization. Next, 430 mg of the same sensitizing dye as in Example 1, dye- (I), was added. Subsequently, the sensitizers listed in Table 5 were added. Subsequently, chloroauric acid and potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. Preparation of tabular grains was thus completed.

The constitution of the coated sample is shown below. Composition on emulsion side A) Emulsion layer Coating amount 2.3 g / m ² Gelatin amount 2.5 g / m ² · Dextran (average molecular weight 39,000) 0.4 g / m ² · 2,6-bis (hydroxy) Amino) -4-diethylamino-1,3,5-triazine 1.46 mg / m ²

[0070]

[Chemical 18]

Ethyl acrylate / methacrylic acid copolymer latex (97/3) 0.30 g / m ² Sodium polystyrene sulfonate 0.037 g / m ² Snowtex C (Nissan Chemical Co., Ltd.) 0.35 g / M ²

B) Surface protective layer on emulsion side Gelatin 500 mg / m ² Dextran (average molecular weight 39,000) 0.1 g / m ² Sodium polyacrylate (average molecular weight 400,000) 18 mg / m ² Polymethylmethacrylate particles ( Average particle size 2.5 μm) 195 mg / m ²

[0073]

[Chemical 19]

Polypotassium-p-vinylbenzene sulfonate 0.6 mg / m ²

Composition of Back Surface a) Antihalation Layer-Gelatin 2.0 g / m ² Phosphoric Acid 5.2 mg / m ² Snowtex C (Nissan Chemical Co., Ltd.) Solid content 0.5 g / m ² Polystyrene potassium sulfonate (average molecular weight 600,000) 25 mg / m ² · Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3) 0.53 g / m ²

[0076]

[Chemical 20]

[0077]

[Chemical 21]

B) Surface protective layer on the back surface-Gelatin 1.0 g / m ² Polymethylmethacrylate (average particle size 3.5 μm) 20 mg / m ² (average particle size 0.7 μm) 81 mg / m ²

[0079]

[Chemical formula 22]

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 The simultaneous extrusion method was applied and dried simultaneously. For the back surface and hard film, 1,2-bis (vinylsulfonylacetamide) ethane was added to the antihalation layer and the emulsion layer,
After swelling at 25 ° C and 68% RH for 10 days, the swelling rate is 1 on the back side.
90% and the emulsion surface were adjusted to 230%.

(Evaluation of Sensitivity) The coated sample was caused to emit light in a CRT for medical multi-camera (light emitter P-45) so as to have a concentration gradient, and exposed for 1 second from the emulsion surface side. The treatment was performed under the same conditions A to C as in Example 1.

[0082]

[Table 5]

It can be seen that the sample of the present invention is effective.

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[Procedure amendment]

[Submission date] March 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction content]

(Quantification of thiocyanate compound) It was determined according to 1 and 2 (quantification of thiocyanate ion in the emulsion before coating) of the thiocyanate compound. That is, 1% KBr was added to an emulsion containing 1.5 × 10 ⁻² mol of silver halide.
10 cc of an aqueous solution (when quantifying thiocyanate ion in emulsion) or distilled water (when quantifying thiocyanate ion in binder) was added, and the mixture was stirred at 40 ° C. for 30 minutes. After this, Hitachi centrifuge 20RP-
Centrifugation was carried out for 10 minutes at 10,000 revolutions using the No.5. The supernatant was diluted 100 times and then subjected to ultrafiltration using an air press 30 manufactured by Tosoh Corporation. Next, the chromatographic measurement of the filtrate was performed using the CP system manufactured by Tosoh Corporation below. Measured value-from SCN
The salt was calculated. Column; TS IC-Anion SW column temperature; 40 ° C. detector; UV detector (210 nm) eluent; 7.5 mM Na ₂ HPO ₄ and 7.5 mM.
Solution containing NaH ₂ PO ₄ (pH 7.0) flow rate; 0.7 ml / min calibration curve; 0.1 ppm to 10 ppm potassium thiocyanate aqueous solution.

Claims (2)

[Claims] 1. In a silver halide photographic light-sensitive material developed with a developer having a developer replenisher amount of 20 cc / 4 or less, at least one emulsion layer contains S on the silver halide grain surface.
A silver halide photographic light-sensitive material characterized by containing 2 × 10 ⁻³ mol / mol Ag or more as a CN salt. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide is chemically sensitized with a selenium compound.