JPH07110537A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the gradation difference between intrinsic sensitivity range and color sensitizing range by using a specific platelike silver halide particle at the time of adsorbing plural sensitizing dyestuffs. CONSTITUTION:In a photographic sensitive material provided with a silver halide emulsion layer on a supporting body, at the time of adsorbing the plural sensitizing dyestuffs, the silver halide particle is prepared so that platelike AgClxBryIz have (100) face for >=60% of total silver halide particles. Where, (x)=80-100mol%, (y)=0-20mol%, (z)=0-20mol%, preferably 0-2mol%. A platelike AgClxBryIz preferably have (100) face for >=70% of total silver halide particles. The platelike silver halide particle preferably have 0.5-10mum diameter and >=3 the ratio of diameter/thickness. The coefficient of variation of diameter distribution of the platelike particle is preferably <=20%.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photographic light-sensitive material using a silver halide emulsion for photography. In particular, it relates to a photographic light-sensitive material having a small difference in gradation between the intrinsic sensitivity region and the color sensitization region.

[0002]

2. Description of the Related Art Conventionally, in order to reduce the gradation difference between the intrinsic sensitivity range and the color sensitization range, the temperature and stirring conditions during the addition of the sensitizing dye have been adjusted. When the sensitizing dye is used, it is almost ineffective.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material in which the difference in gradation between the intrinsic sensitivity range and the color sensitization range is reduced when a plurality of sensitizing dyes are used. .

[0004]

For the purpose of the present invention,
In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, when adsorbing a plurality of sensitizing dyes, the tabular AgCl _x Br _y I _{z in which the} silver halide grains have 60% or more of (100) faces It has been found that a silver halide photographic light-sensitive material characterized by the following is effective. However, x = 80 to 100 mol%, y = 0 to 20 mol%, z = 0 to 20 mol%. Preferably z = 0 to 2 mol%
Is. It is preferably tabular AgCl _x Br _y I _z having 70% or more of (100) plane. The tabular AgClB
There are no particular restrictions on how to make rI, but it is not possible to use the method described in JP-A-51-88.
No. 017, Japanese Patent Publication No. 64-8323, European Patent 0534
395A1, Japanese Patent Application No. 4-77261, Japanese Patent Application No. 4-2.
No. 14109, No. 4-194614, No. 5-9625.
Methods such as No. 0 and No. 5-117624 are used.

As the plurality of sensitizing dyes, for example, any combination of sensitizing dyes represented by the following general formulas (I) to (IV) can be used. However, the total addition amount is preferably 1 × 10 ⁻⁴ mol or more per mol of silver halide.

[0006]

[Chemical 1]

Where R₁, R₂Are each replaced or non-placed
A substituted alkyl group, a substituted or unsubstituted alkenyl group,
Or represents a substituted or unsubstituted aryl group, and at least
Also R ₁And R₂Either is a sulfo group or a carboxyl group
including. R₃Represents an alkyl group. X^-Is the charge of the molecule
Represents the counterion necessary for neutralizing
Represents a number. Z₁And Z₂May each have a substituent
Non-metal atom required to complete benzene ring or naphtho ring
Represents a group. Incidentally, R₁, R₂Is a sulfo group or carboxyl
When it contains a group, R-SO₃M group or R-C
Salts may be formed in the form of OOM groups, where M is a hydrogen atom,
Potassium metal atom (eg Na, K, etc.) or ammonium
Represents a group.

[0008]

[Chemical 2]

R in the general formula (II)₁Through R_FourEach also replace
Or unsubstituted alkyl group, substituted or unsubstituted alkyl group
Represents a alkenyl group or a substituted or unsubstituted aryl group
And R ₃And R_FourAt least one of the
Contains a boxyl group. Z₁, Z₂, X, n are represented by the general formula (I)
Follow the same definition as each of.

[0010]

[Chemical 3]

[In the formula, Z ₅ and Z ₆ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group. Q
₅ represents an atomic group necessary for forming a 5-, 6- or 7-membered ring. R _4, R ₅ represents an alkyl group. L ₃₂ ,
L ₃₃ , L ₃₄ , L ₃₅ , L ₃₆ , L ₃₇ , L ₃₈ , L ₃₉ and L ₄₀ represent a methine group or a substituted methine group. Further, it may form a ring with another methine group, or may form a ring with an auxochrome. n ₈ and n ₉ represent 0 or 1. M ₅ represents a charge neutralizing counterion, and m ₅ is a number of 0 or more necessary for neutralizing the charge in the molecule. ]

[0012]

[Chemical 4]

[In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group. R ₃ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. L ₁ ,
L ₂ , L ₃ and L ₄ represent a methine group or a substituted methine group, and L ₂ and L ₃ may be linked to each other to form a ring. V is a hydrogen atom, a lower alkyl group, an alkoxy group,
It represents an alkylthio group, a halogen atom or a substituted alkyl group. Z ₁ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. X ₁ represents an acid anion. m, p and q each independently represent 1 or 2. However, q is 1 when the dye forms an inner salt. ]

These dyes may be added at any of grain formation, chemical sensitization step and coating, or they may be added together or separately. Further, these dyes may be used by being dissolved in a solvent such as methanol, or may be used by being dispersed in gelatin in a microcrystalline state. Specific examples of the general formulas (I) and (II) of the present invention are shown below, but the present invention is not limited thereto.

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

The emulsion of the present invention is preferably selenium sensitized. Here, the selenium sensitization is performed by a conventionally known method. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added at a high temperature,
It is preferably carried out by stirring the emulsion at 40 ° C. or higher for a certain period of time. Selenium sensitization using the unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Specific examples of the unstable selenium sensitizer include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenamides,
There are selenocarboxylic acids and esters, and selenophosphates. Particularly preferred unstable selenium compounds are shown below.

I. Colloidal metal selenium II. Organic selenium compound (selenium atom is double-bonded to carbon atom of organic compound by covalent bond) a isoselenocyanate, for example, aliphatic isoselenocyanate such as allyl isoselenocyanate b selenourea (enol type For example, methyl, ethyl, propyl, isopropyl, butyl, hexyl octyl, dioctyl, tetramethyl, N- (β-carboxyethyl) -N ′, N′-dimethyl, N, N-dimethyl, diethyl, dimethyl, etc. Aliphatic selenoureas; aromatic selenoureas having one or more aromatic groups such as phenyl and tolyl; heterocyclic selenoureas having heterocyclic groups such as pyridyl and benzothiazolyl c selenoketones, for example, selenacetone, Selenoacetophenone, selenoketo having an alkyl group bonded to> C = Se , Selenobenzophenone, etc. d selenoamides, for example, selenoacetamide, etc. e, selenocarboxylic acids and esters, for example, 2-selenopropionic acid, 3-selenobutyric acid, methyl-3-selenobutyrate, etc. III. Other a selenides, for example, diethylselena Id, diethyl diselenide,
Triphenylphosphine selenide, etc. b Selenophosphates, for example, tri-p-tolylselenophosphate, tri-n-butylselenophosphate, etc.

Preferred types of labile selenium compounds have been described above, but are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and have no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, such a broad concept of unstable selenium compounds is advantageously used. Japanese Examined Sho 46-
4553, JP-B-52-34492 and JP-B-5
Selenium sensitization using the non-labile selenium sensitizer described in JP-A-2-34491 can also be used. Examples of the non-unstable selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diaryl selenides, diaryl diselenides, 2-thioselenazolidinediones, and 2-selenooxolidines. Thion and derivatives thereof are included. Japanese Examined Japanese Patent Publication Sho 52-38408
The non-labile selenium sensitizers and thioselenazolidinedione compounds described in JP-A No. 1994-1999 are also effective.

These selenium sensitizers are dissolved in water or an organic solvent such as methanol and ethanol alone or in a mixed solvent and 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 type, and two or more types of the above selenium sensitizers can be used in combination. A combination of an unstable selenium compound and a non-unstable selenium compound is preferred. 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 preferably 1 mol of silver halide. Per 1 x 10 ^-8
It is more than a mole. More preferably 1 × 10 ⁻⁷ mol or more 1
× 10 ⁻⁵ mol or less. The temperature of chemical ripening when a selenium sensitizer is used is preferably 45 ° C. or higher. More preferably, it is 50 ° C. or higher and 80 ° C. or lower. pAg and p
H is arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9.

Chemical sensitization is more effective when carried out in the presence of a silver halide solvent. Examples of the silver halide solvent that can be used in the present invention include US Pat.
271,157, 3,531,289, 3,574,628, and JP-A-54-1019, 5
(A) Organic thioethers described in JP-A-4-158917, JP-A-53-82408 and JP-A-55-7773.
No. 7, 55-2982 and the like (b) thiourea derivatives, and (c) the thiocarbonyl group described in JP-A No. 53-144319 (c) sandwiched between an oxygen or sulfur atom and a nitrogen atom. Silver halide solvent having
(D) imidazoles described in No. 100717,
(E) Sulfite, (f) thiocyanate and the like. Particularly preferred solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol per mol of silver halide.

The silver halide photographic emulsion of the present invention has higher sensitivity when combined with gold sensitization in chemical sensitization.
A low fog can be achieved. It is preferable to use sulfur sensitization together if necessary. Sulfur sensitization is usually carried out at a high temperature, preferably 40 ° C, by adding a sulfur sensitizer.
This is done by stirring the emulsion for a certain period of 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,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like can be mentioned. Other US Patent No. 1,57
4,944, 2,410,689, 2,2
78, 947, 2, 728, 668, and 3,
501,313, 3,656,955, German Patent 1,422,869, Japanese Patent Publication No. 56-2
The sulfur sensitizers described in JP-A-4937, JP-A-55-45016 and the like can also be used. The sulfur sensitizer may be added in 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 size of silver halide grains, but is not less than 1 × 10 ⁻⁷ mol per mol of silver halide and 5 × 10 ^−5. It is preferably not more than mol.

As the gold sensitizer for the above-mentioned gold sensitization, the oxidation number of gold may be +1 valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. Representative examples include chloroauric acid salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyl trichlorogold and the like. The amount of the gold sensitizer added varies depending on various conditions, but as a guide, it is preferably 1 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁵ mol or less per mol of silver halide.

At the time of chemical ripening, there is no particular limitation on the timing and order of addition of the silver halide solvent and the gold sensitizer used in combination with the selenium sensitizer or tellurium sensitizer. (Preferred) or the above compounds can be added at the same time during the progress of chemical ripening, or at different addition points. In addition, upon addition, an organic solvent capable of mixing the above compound with water or water,
For example, it may be added after being dissolved in a single liquid or a mixed liquid of methanol, ethanol, acetone and the like.

The method of reduction sensitization used in the present invention includes, as so-called reduction sensitizers, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, Reduction sensitization can be performed using a silane compound or a polyamine compound. Further, the pH of the emulsion is 7 or more or the pAg is 8.3.
It is possible to carry out reduction sensitization by keeping it below and aging. Further, reduction sensitization can be performed by introducing a single addition portion of silver ions during grain formation. However, it is preferable to carry out reduction sensitization using ascorbic acid and its derivative or thiourea dioxide in order to reduce the influence on grain formation and crystal growth and to carry out controlled reduction sensitization. The amount of the reduction sensitizer used depends on the type of the reducing agent, but varies from 10 ^-7 mol to 10 ^-2.
A mol / mol Ag amount is preferably used. Reduction sensitization is
It may be carried out anywhere during grain formation, and may be carried out at any time after grain formation and before chemical sensitization.

The tellurium sensitizers used in the present invention include US Pat. Nos. 1,623,499 and 3,320.
069, 3,772,031, British Patent No. 23
No. 5,211, No. 1,121,496, No. 1,29
5,462, 1,396,696, Canadian Patent No. 800,958, Journal of Chemical Society Chemical Communication (J. Chem.S.
oc.Chem.Commun.) 635 (1980), ibid 1102 (1979), ibid
645 (1979), Journal of Chemical Society Perkin Transactions (J.Chem.Soc.Perki
n Trans.) 1,2191 (198) and the like are preferably used.

Specific tellurium sensitizers include colloidal tellurium and telluroureas (eg, allyl tellurourea,
N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N ', N'-dimethyl tellurourea, N, N'-dimethylethylene tellurourea, N,
N'-diphenylethylene tellurourea), isotellocyanates (for example, allyl isotellurocyanate), telluroketones (for example, telluroacetone, telluroacetophenone), telluroamides (for example, telluroacetamide, N, N-dimethyl tellurobenzamide), tellurohydrazide. (For example, N, N ′, N′-trimethyltelurobenzhydrazide), telluroester (for example, t-butyl-t-hexyltelluroester), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropyl). Phosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride) and other tellurium compounds (eg negatively charged tellurium described in British Patent 1,295,462). Doion containing gelatin, Potassium nitrosium telluride, Potassium nitrosium tellurocyanate diisocyanate, tellurocarbonyl penta isethionate, sodium salt, allyl tellurocyanate)
Etc.

In the present invention, it is preferable to use a noble metal sensitizer such as gold, platinum, palladium or iridium together. In particular, it is preferable to also perform gold sensitization agent include chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and the like, per mol of silver halide, 10 ^{- About 7} to 10 ^-2 mol can be used.

In the present invention, it is also preferable to use a sulfur sensitizer together. Specific examples thereof include known unstable sulfur compounds such as thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylurea, allylthiourea), and rhodanines. 1 mol of silver halide About 10 ^-7 to 10 ^-2 mol can be used per unit.

The tabular silver halide grains of the present invention preferably have a diameter / thickness ratio of 3 or more, more preferably 5 or more and 100 or less, still more preferably 5 or more and 50 or less (particularly preferably 7 or more). 20 or less). Here, the diameter of a silver halide grain means the diameter of a circle having an area equal to the projected area of the grain. In the present invention, the tabular silver halide grains have a diameter of preferably 0.5 to 10 µ, more preferably 0.5 to 5.0 µ, and particularly preferably 1.0 to 4.0 µ.
Is. In general, tabular silver halide grains are tabular having two parallel planes, and therefore "thickness" in the present invention means a distance between two parallel planes constituting the tabular silver halide grain. Represented.

There are no particular restrictions on various other additives used in the light-sensitive material of the present invention, and for example, JP-A-2-
It is possible to use the materials described in the following relevant parts of Japanese Patent No. 68539. Item This section 1. Silver halide emulsion 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. Antifoggant / stability Page 10, left lower 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 lower left column, line 10 to right lower 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. Dye / mordanting agent, page 13, lower left column, line 1 to page 14, lower left column, line 9 11. Development processing method JP-A-2-03037 Gazette, page 16, upper right column, line 7 to page 19, lower left column, line 15 Japanese Patent Application Laid-Open No. 2-115837, page 3, lower right column, line 5 to page 6, upper right column, line 10 Next, examples will be shown to further describe the present invention.

[0034]

EXAMPLES The present invention will now be described in more detail by way of examples, but the embodiments of the present invention are not limited thereto. Example 1 Preparation of AgCl _99.2 Br _0.8 particles 1200 mL of an aqueous gelatin solution (containing 18 g of deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g, pH 4.3) was placed in a reaction vessel, and the temperature was kept at 43 ° C. While Ag-1 solution (100 mL of AgNO ₃ 20
g, the gelatin 0.8 g, containing HNO ₃ 1N solution 0.2 mL) and X-1 solution (NaCl6.9G in 100 mL, the gelatin 0.8 g, containing NaOH 1N solution 0.3 mL)
Was co-added at 12 mL at 24 mL / min. After stirring for 2 minutes, Ag-2 solution (2 mL of AgNO ₃ in 100 mL)
g, the gelatin 0.8 g, HNO ₃ containing 1N solution 0.2 mL) and X-2 solution (KBr1.4G in 100 mL, the gelatin 0.8 g, containing NaOH1N solution 0.2 mL) and 3
Only 19 mL was simultaneously mixed and added at 1 mL / min. After stirring for 2 minutes, Ag-1 solution and X-1 solution were simultaneously mixed and added at 36 mL at 48 mL / min. NaCl-1 solution (Na in 100 mL
20 mL of Cl (containing 10 g) was added to adjust the pH to 4.8 and the temperature was raised to 75 ° C. After aging for 20 minutes, the temperature was lowered to 60 ° C. and the pH was adjusted to 5.0, and then the silver potential 11
At 0 mV, Ag-3 solution (containing 10 g of AgNO _{3 in} 100 mL) and solution X-3 (containing 3.6 g of NaCl in 100 mL) were used as C.I. D. J. (controlled double jet) was added. The flow rate at the start of addition is 7 mL / min and 0.1 mL / min
The flow rate was accelerated and added in increments of 400 minutes, and 400 mL of Ag-3 solution was added. Add a precipitating agent, lower the temperature to 30 ° C, wash with settling water, add an aqueous gelatin solution, pH 6.2 at 38 ° C, pC
The emulsion was adjusted to 3.0 and Emulsion-A was prepared.

Example 2 Preparation of AgCl ₉₇ Br ₃ grains Emulsion B was prepared in the same manner as Emulsion A except that 1.3 g of AgBr fine particles (0.02 μ) were added before washing with water.

Comparative Example 1 AgCl ₉₇ Br ₃ was prepared by using the method disclosed in JP-A-4-6546.
Emulsion-C having a (100) plane of 17% and an aspect ratio of 4.4 was prepared.

Example 3 Emulsions A, B and C were heated to 40 ° C. and phenoxyethanol (1.5 g) and a thickening agent were added to the emulsion at 56 ° C.
After the temperature was increased to 735 mg of sensitizing dye I-4 having the following structure
Then, 8 mg of sensitizing dye II-9 was added.
Minutes later, 3.3 mg of sodium thiosulfate and selenium compound-I
2 mg and chloroauric acid 2.6 mg and potassium thiocyanate 1
10 mg was added and the mixture was aged for 60 minutes and then rapidly solidified by cooling. Emulsions T-A to T-C were prepared in this manner. Emulsions S-A to S-C were prepared in exactly the same manner except that the sensitizing dye II-9 was not added. Table 1 shows the prepared emulsions.

[0038]

[Table 1]

Preparation of Coating Sample A coating sample was prepared by adding the following chemicals per mol of silver halide to prepare a coating solution.・ Gelatin (including Gel in emulsion) 108 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 Adjust the amount added so that the swelling rate will be 230% -Compound-I 34 mg-Compound-II 4.8 g-Compound-III 15 mg

[0040]

[Chemical 9]

[0041]

[Chemical 10]

Dye Emulsion A was added to the above coating solution so that Dye-I was 10 mg / m ² per side.

[0043]

[Chemical 11]

(1) Preparation of Dye Emulsion A 60 g of the above dye-I and the following high boiling point organic solvent-I
62.8 g, -II 62.8 g and ethyl acetate 333
g was melted at 60 ° C. Next, 65 cc of 5% aqueous solution of sodium dodecyl sulfonate, 94 g of gelatin and 581 of water.
cc was added, and the mixture was emulsified and dispersed at 60 ° C. for 30 minutes with a dissolver. Next, 2 g of the following compound-IV and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, using Asahi Kasei's ultrafiltration lab module ACP1050,
The mixture was concentrated to kg, and 1 g of the compound-IV was added to prepare a dye emulsion A.

[0045]

[Chemical 12]

The surface protective layer was prepared and prepared so that each component had the following coating amount.・ Gelatin 0.78 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.080 g / m ²・ 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.015 g / m ² coating aids -I 0.013 g / m ² and coating aids -II 0.045 g / m ² and coating aids -III 0.0065 g / m ² and coating aids -IV 0.003 g / m ² · Coating aid-V 0.001 g / m ² · Compound-V 1.7 mg / m ² · Compound-IV 100 mg / m ² · Polymethylmethacrylate (average particle size 3.7 μm) 0.087 g / m ² · Proxel ( Adjusted to pH 7.4 with NaOH) 0.0005 g / m ²

[0047]

[Chemical 13]

Preparation of Support (1) Preparation of Dye Dispersion B for Undercoat Layer Dye-II below was ball-milled by the method described in JP-A-63-197943.

[0049]

[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. 400 ml of zirconium oxide (ZrO ₂ ) beads (2 mm diameter) were added and the contents were milled for 4 days. After this, 160 g of 12.5% gelatin was added.
After defoaming, the ZrO ₂ beads were removed by filtration.
Observation of the obtained dye dispersion showed that the particle size of the crushed dye had a wide range of diameters from 0.05 to 1.15 μm, and the average particle size was 0.37 μm. Further, centrifugation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D was obtained. (2) Preparation of support Corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm, and the first undercoat liquid having the following composition was applied so that the coating amount was 4.9 cc / m ^2. It was applied with a wire bar coater and dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used had a dye-I content of 0.04 wt%. * Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158cc * 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41cc * Distilled water 801cc * The latex solution contains the following compounds as emulsifying dispersants in an amount of 0.4 wt% based on the latex solids.

[0051]

[Chemical 15]

A second undercoat layer having the following composition was applied to each of the above-mentioned first undercoat layers on one side so that the coating amount would be the amount described below, and on both sides at 155 ° C. by a wire bar coater system. It was applied and dried.・ Gelatin 80 mg / m ²・ Dye dispersion B (as dye solid content) 8 mg / m ²・ Coating aid-VI 1.8 mg / m ²・ Compound-VII 0.27 mg / m ²・ Mat agent Average particle size 2 0.5 μm polymethylmethacrylate 2.5 mg / m ²

[0053]

[Chemical 16]

Preparation of Photographic Material The above emulsion layer and surface protective layer were coated on both sides of the prepared support by the simultaneous extrusion method. The amount of silver coated on one side was 1.6 g / m ² .

Each sample was evaluated as follows. [Processing by automatic developing machine] The drying zone of the CEPROS-M (manufactured by Fujifilm Corporation) automatic developing machine was modified (the upper four rollers of the drying zone were set to 80 ° C and the temperature of the drying zone was changed). It was possible to dry to dry for 30 seconds by changing the linear velocity by changing the linear velocity. The average processing amount of the photosensitive material per day is about 200 sheets in terms of the size of quarter cut.
The processing liquid and its supplement are as follows.

Development Treatment Preparation of Concentrated Solution <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 to 4500 ml.

Parts agent B tetraethylene glycol 750 g 3-3'-dithiopishydrocinnamic acid 3 g glacial acetic acid 75 g 5-nitroindazole 4.5 g 1-phenyl-3-pyrazolidone 67.5 g Water to add 1000 ml

Parts agent C Potassium bromide 15 g Potassium metabisulfite 120 g Add water 750 ml

<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 container 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, 54 g of acetic acid and 5 parts of potassium bromide were used as a starter in the developing tank.
300 ml of an aqueous solution containing 5.5 g was added. Insert the above treatment agent container upside down and insert it into the perforation blade of the treatment solution stock tank mounted on the side of the automatic processing machine to break the sealing film of the cap and transfer each treatment agent in the container to the stock tank. Filled. These processing agents were filled in the developing tank and fixing tank of the developing machine at the following ratios by operating the pumps installed in the developing machine. In addition, the sensitive material is 2 in quarter size conversion.
Every time five sheets were processed, the stock solution of the treating agent and water were mixed at this ratio and filled in the treating tank of the automatic developing machine.

Developing solution Part agent A 60 ml Part agent B 13.4 ml Part agent C 10 ml Water 116.6 ml pH 10.50 Fixing solution concentrate 80 ml Water 120 ml pH 4.62 The washing tank was filled with tap water.

[Exposure] (1) Exposure A: Each sample of the photographic material was exposed for 0.05 seconds from both sides using X Ray Orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd. The key was evaluated. (2) Exposure B: Each sample of the photographic material was 2854 with a double-sided exposure meter
Light having a color temperature of K was exposed through a bandpass filter of 420 nm for 0.05 seconds to evaluate the gradation.

[0063]

[Table 2]

Example 4 The following additives were added to Emulsions A to C per mol of silver halide to prepare emulsion coating solutions. (Formulation of emulsion coating solution) a. Spectral sensitizing dye (A-1) described in Table 3 b. Spectral sensitizing dye (B-3) described in Table 3 c. Supersensitizer [III] 300 mg d. Shelf life improving agent [IV-1] 1 × 10 ⁻³ Morpho. Polyacrylamide (molecular weight 40,000) 10 g f. Trimethylolpropane 1.6 g. Polystyrene sulfonate Na 1.2 g H. Poly (ethyl acrylate / methacrylic acid) latex 12 g Re. N, N'-ethylenebis- (vinyl sulfone acetamide) 3.0 g Lu. 1-phenyl-5-mercapto-tetrazole 50mg

[0065]

[Chemical 17]

3. Preparation of Surface Protective Layer Coating Solution for Emulsion Layer The container was heated to 40 ° C., and additives were added in the following formulation to prepare a coating solution. (Formulation of coating solution for surface protection layer of emulsion layer) a. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g d. N, N'-ethylenebis- (vinyl sulfone acetamide) 2.2 g e. Polymethylmethacrylate fine particles (average particle size 2.0 μm) 2.7 g f. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0g Ji. Sodium polyacrylate 6.0 g Re. C ₈ F ₁₇ SO ₃ K 70 mg Nu. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) _4- SO ₃ Na 70 mg ru. 6 ml of NaOH (1N). Methanol 90 ml Wa. 1-phenyl-5-mercapto-tetrazole 80 mg Compound (V-1) 0.06 g

[0067]

[Chemical 18]

4. Preparation of Back Layer Coating Liquid A container was heated to 40 ° C., and additives were added in the formulation shown below to prepare a back layer coating liquid. (Prescription of back layer coating liquid) a. Gelatin 100 g b. Dye [II-1] 4.2 g c. Polystyrene sodium sulfonate 1.2 g d. Poly (ethyl acrylate / methacrylic acid) latex 5 g e. N, N'-ethylenebis- (vinyl sulfone acetamide) 4.8 g f. Compound [V-1] 0.06 g g. Dye [II-31] 0.3 g h. Dye [II-32] 0.05g

[0069]

[Chemical 19]

5. Preparation of Back Surface Protective Layer Coating Solution A container was heated to 40 ° C., and additives were added in the following formulation to prepare a coating solution. (Prescription of back surface protective layer coating liquid) a. Gelatin 100 g b. Polystyrene sodium sulfonate 0.5 g c. N, N'-ethylenebis- (vinyl sulfone acetamide) 1.9 g d. Polymethylmethacrylate fine particles (average particle size 4.0 μm) 4 g e. Sodium t-octylphenoxyethoxyethane sulfonate 2.0 g f. NaOH (1N) 6 ml. Sodium polyacrylate 2.4 g h. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 4.0g Li. C ₈ F ₁₇ SO ₃ K 70 mg Nu. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) _4- SO ₃ Na 70 mg ru. 150 ml of methanol. Compound [V-1] 0.06 g

6. Preparation of Photographic Material The coating solution for the back layer as described above was coated together with the coating solution for the surface protective layer of the back layer on one side of the polyethylene terephthalate support so that the total coating amount of gelatin was 3.0 g / m ² . Subsequently, the emulsion coating liquid and the surface protective layer coating liquid described above were applied to the opposite side of the support, and the total Ag coating amount was 2.6 g /
m ² and the amount of gelatin coated on the surface protective layer is 0.6 g / m ²
Was applied so that 7. Method of sensitometry The coated sample was subjected to sensitometry after keeping it at 25 ° C. and temperature and humidity of 60% RH for 7 days and after further lapse of 30 days at 23 ° and 50% RH. (1) Exposure C: exposure is FCR-7 manufactured by FUJIFILM Corporation
CR-LP414 semiconductor laser 780nm
Scanning exposure was performed at a wavelength of about 10 ⁻⁷ seconds. (2) Exposure D: Under the condition of exposure B, exposure was performed for about 10 ⁻⁶ seconds. The treatment was performed in the same manner as in Example 3. The results are summarized in Table 3.

[0072]

[Table 3]

As can be seen from Table 3, the sample of the present invention has a small change in gradation.

Claims (5)

[Claims] 1. A photographic light-sensitive material having at least one silver halide emulsion layer on a support, when adsorbing a plurality of sensitizing dyes, the silver halide grains have a tabular AgCl having a (100) face of 60% or more. _A silver halide photographic light-sensitive material characterized by being _x Br _y I _z . However, x = 80 to 100 mol% y = 0 to 20 mol% z = 0 to 20 mol% 2. The (100) plane according to claim 1, 70%
A silver halide photographic light-sensitive material, which is a tabular AgCl _x Br _y I _z having the above. 3. A silver halide photographic light-sensitive material according to claim 1 or 2, wherein the coefficient of variation of inter-grain distribution of sensitizing dye adsorption is less than 45%. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the tabular grains have an average aspect ratio of 3 or more. 5. A silver halide photographic light-sensitive material according to any one of claims 1 to 4, wherein the variation coefficient of the diameter distribution of the tabular grains is 20% or less.