JPH02153345A - Silver halide photographic sensitive material which has high sensitivity, degreases generation of fogging and has excellent preservable property with age - Google Patents

Abstract

PURPOSE:To enhance the sensitivity and preservable property with age of the photosensitive material and to decrease the generation of fogging by executing chemical maturation at the pAg value within a specific range and adding a pAg value increasing agent at the time of the maturation. CONSTITUTION:This photosensitive material contains the silver halide emulsion formed by subjecting the emulsion to the substantial chemical maturation at the pAg value within a 6.0 to 8.8 range and subjecting the emulsion to the process for adding a compd. (A) which forms a hardly soluble salt with silver ions to increase the pAg value before or during the chemical maturation to the emulsion. Thiocyanate (e.g. ammonium thiocyanate), etc., are usable as the pAg value increasing agent and can be added to the emulsion prior to the addition of a chemical sensitizer (e.g. sodium thiosulfate).

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, a silver halide photographic light-sensitive material that has high sensitivity, little fogging, and excellent storage stability over time. Regarding.

[Background of the invention]

Silver halide color photographic materials are required to have various performances, among which the most important are high sensitivity, high image quality, and improved storage stability over time.

In particular, increasing the sensitivity of the silver halide emulsion itself can be used not only as a technique for obtaining highly sensitive photographic materials, but also as a technique for obtaining high-quality photographs using silver halide emulsions with smaller grain sizes than before. It can also be used as a technique for obtaining photosensitive materials, and can be said to be an extremely effective technique.

Many methods are conventionally known for sensitizing silver halide photographic materials. Spectral sensitization using sensitizing dyes; Noble metal sensitization using salts of noble metals such as gold, platinum, and iridium; Sulfur sensitization using activated gelatin, sodium thiosulfate, thioacetamide, allylisothiourea, etc.; Colloidal selenium, selenourea Selenium sensitization using monovalent tin salts, polyamines,
Reduction sensitization using a hydrazine derivative; development acceleration using a polyionium salt of nitrogen, phosphorus or sulfur, or polyalkylene glycol are known. In the actual photographic industry, silver halide photographic materials are produced by appropriately combining these sensitizing techniques depending on the purpose, but a technology that is fully satisfactory in terms of storage stability over time has not yet been established. .

In order to improve these drawbacks, attempts have been made to add various fog suppressants to light-sensitive materials.

In particular, U.S. Pat. No. 1,758,576 and U.S. Pat.
No. 62, No. 2.697,040, No. 2,697.09
No. 9, No. 2,824,001, No. 2,476.536
Mercapto compounds described in British Patent No. 2,843.491, British Patent No. 3,251,691, British Patent No. 403.789, British Patent No. 893.428, Japanese Patent Publication No. 58-9939, etc. are effective in suppressing the above-mentioned fog. is effective, but the sensitivity has not reached a sufficiently satisfactory level due to deterioration of sensitivity, fog, etc. due to storage over time.

As described above, it has been extremely difficult to obtain a silver halide emulsion with high sensitivity, little fogging, and good storage stability over time.

[Purpose of the invention]

SUMMARY OF THE INVENTION In view of the above problems, it is an object of the present invention to provide a silver halogenide photographic light-sensitive material that has high sensitivity, low fog, and improved storage stability over time.

[Structure of the invention]

As a result of various studies in order to solve the above-mentioned object of the present invention, it has been found that the object can be solved by chemical ripening under the following environment.

That is, the purpose of the present invention is to achieve substantial chemical ripening with a pAg value of 6.
．． I) A silver halide emulsion that has undergone a process of increasing the Ag value by adding a compound that forms a poorly soluble salt with silver ions before or during chemical ripening. This was achieved using a silver halide photographic material characterized by having at least one photosensitive layer having the following characteristics.

The present invention is based on the following findings discovered by the present inventors. In other words, it is well known among those skilled in the art that the pAg setting when chemically ripening an emulsion has a sufficient effect on how the chemical ripening takes place.
A sensitization method in which ripening is carried out at a temperature of about .about.5 has been known for a long time. However, if the pAg is simply set low and chemical ripening is carried out, although the chemical ripening is completed in a short time, the fog becomes unstable, for example, fog increases due to storage over time, or if the same chemical ripening is applied. There may be problems with reproducibility over time. If, as a countermeasure, an antifoggant or the like is used in combination, other problems will arise as described above, and it will not be a fundamental solution.

However, after various studies by the present inventors, pA
Even if pAg is less than 8.8, adding a compound that forms a poorly soluble salt with silver ions during chemical ripening can reduce pAg.
If chemical ripening is performed within the pAg value range of 6.0 to 88 through the process of increasing the pAg value, a higher u' pAg value can be obtained.
It has been found that a silver halide photosensitive material with higher sensitivity, lower fog, and better storage stability over time can be obtained than when chemical ripening is carried out at a lower temperature.

The present invention will be described in more detail below.

In the present invention, chemical ripening refers to sensitizing silver halide grains using a chemical sensitizer when forming a silver halide emulsion.

In the present invention, chemical ripening can be achieved by any chemical sensitization means, and the chemical sensitizer used is not particularly limited.

Chemical sensitizers that can be advantageously used in the present invention include noble metal sensitizers, sulfur sensitizers, selenium sensitizers and reduction sensitizers.

As the sulfur sensitizer, in addition to activated gelatin, sulfur compounds such as sodium thiosulfate, thiourea, and allyl inthionoanate can be used.

As selenium sensitizers, active and inactive selenium compounds can be used.

Reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives.

As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, platinum, etc. may be used.

As a chemical sensitizer that can more fully exhibit the objectives and effects of the present invention, a combination of a noble metal sensitizer and a sulfur sensitizer is preferred.

The amount of the chemical sensitizer added when chemically ripening the silver halide emulsion according to the present invention can be appropriately set depending on the silver halide grains used.

Next, the substantial chemical ripening referred to in the present invention will be explained.

The chemical ripening start step refers to a step of adding a chemical sensitizer, and in this step, the time when the chemical sensitizer is added is the time to start chemical ripening.

The chemical ripening described above can also be stopped by methods known in the art. As a method to terminate chemical ripening,
Methods such as lowering the temperature, lowering the pH, and using a chemical ripening stopper are known, but in consideration of the stability of the emulsion, it is preferable to use a chemical ripening stopper. Examples of the chemical aging stopper include halides (e.g., potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (e.g., 4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene, etc.) are known. These compounds may be used alone or in combination.

The time when these operations for terminating chemical ripening are performed is the end of chemical ripening.

In the present invention, the term "substantial chemical ripening time" refers to the time between the start of chemical sensitization and the end of chemical sensitization.

The pAg value when applying substantial chemical ripening is 6.0 to 8.
．． 8, but its preferred value is 7.0 to 8.2.
It is more preferably within the range of 7.4 to 8.0. The pAg value during substantial chemical ripening preferably satisfies the above conditions for at least 1/3 of the substantial chemical ripening time, particularly for at least 2/3 of the first half of this substantial chemical ripening time. It is preferable to satisfy the following.

Next, the [compound that forms an H-soluble salt with silver ions] (hereinafter abbreviated as pAg value increasing agent) referred to in the present invention will be explained.

As a pAg value increasing agent, pAg [li, 0 to 8.8
There are no particular limitations, however, as long as it is a compound other than halide ions that increases the pAg value by at least O,Q2 (preferably 0.05) or more when chemical ripening is carried out between Particularly preferred compound groups include thioanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate; selenocyanates such as sodium selenoneanate and ammonium selenocyanate; carbonates such as sodium carbonate and potassium carbonate; sodium sulfite,
Examples include sulfites such as potassium sulfite. Among these, the most preferred compound group is thiocyanate.

The amount of these pAg value increasing agents added varies depending on the composition, grain size, crystal habit, etc. of the silver halide emulsion used.
Usually preferably 0.000 per mole of silver halide
5 to 1.0 g, more preferably 0.001 to 0.0 g.
5g, particularly preferably 0. '005~0.2g.

The pAg value increasing agent may be added either before or after the start of the actual chemical ripening, but if it is after the start, it is preferably added in the first half of the actual chemical ripening time. Particularly preferred is the case where it is added prior to the addition of the chemical sensitizer.

The silver halide color photographic light-sensitive material of the present invention may contain various other components in addition to the above-mentioned essential components.

In the present invention, the silver halide emulsion includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
Any materials used in ordinary silver halide emulsions, such as silver chloroiodobromide and silver chloride, can be used, but silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred. .

The photosensitive silver halide grains used in the above silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are prepared, or they may be grown by various commonly used methods.

Further, the silver halide grains may be changed in halogen composition by using a conversion method at any step of their formation.

The silver halide grains described above can contain various metal elements inside the grains and/or on the grain surfaces, and can also be provided with reduction sensitizing nuclei by placing them in a suitable reducing atmosphere.

Further, the silver halide emulsion may be one in which unnecessary soluble salts are removed after the growth of silver halide grains is completed, or it may be one in which unnecessary soluble salts are still contained.

In the present invention, the silver halide grains in the silver halide emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is primarily formed inside the grains. Further, it may be in any crystal form.

The average grain size of the silver halide grains is 0.05 to 3.
It is preferably 0 μm, more preferably 0.1 to 20 μm.

In the present invention, the silver halide emulsion is
Any particle size distribution can be used. That is, an emulsion with a wide grain size distribution (referred to as a "polydisperse emulsion") may be used, or an emulsion with a narrow grain size distribution (referred to as a "monodisperse emulsion") may be used.

The silver halide emulsion described above may be a mixture of two or more silver halide emulsions formed separately.

The silver halide color photographic light-sensitive material of the present invention can be applied to, for example, color negative and positive films, color photographic paper, and the like.

Further, when the silver halide photographic light-sensitive material of the present invention is used for color purposes, it may be for monochrome use or for multicolor use. In order to perform subtractive color reproduction, multicolor silver halide photographic materials usually contain a silver halide emulsion layer containing magenta, yellow, and cyan couplers as photographic couplers, and a non-light-sensitive layer. has a structure in which layers are laminated on a support in an appropriate number and order, but the number and order of layers can be arbitrarily set depending on the important performance and purpose of use.

Known photographic additives can be used in the silver halide photographic emulsion of the present invention.

Examples of known photographic additives include Research Disclosure's RD-17643 and RD- shown in the table below.
Examples include compounds described in 18716.

V' lower / 6 / white additive chemical sensitizer sensitizing dye development accelerator antifoggant stabilizer color stain inhibitor image stabilizer ultraviolet absorber filter dye brightener hardener coating aid surfactant plasticizer Slip agent Static inhibitor Mantle agent Binder RD-17643RD-18716 Page Classification Page Classification 23 III 648- Upper right 23
1V 648 right-upper right 29 Xn
648- Upper right 24 Vl
649- Bottom right //
//25 ■ 65
0 25 ■ 25 ~ 26 ■ 649 right ~ 650 left //
//2
4 V 26 X 651 right 26-27 XI 650 right 26-27
n 650 right 27 ff
650 Right Left - Right 27 ■ A dye-forming coupler is used that forms a dye through a coupling reaction with an oxidized form of (e.g.). The dye-forming coupler is typically selected for each emulsion layer to form a dye that absorbs light in the light-sensitive spectrum of the emulsion layer, and a yellow dye-forming coupler for the blue-sensitive emulsion layer or a green-sensitive dye for the blue-sensitive emulsion layer. A magenta dye-forming coupler is used in the emulsion layer or a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Compounds that release photographically useful fragments such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included.

Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The old R couplers and old R compounds used include those in which an inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, which prevents the coupling reaction from occurring. These include those (referred to as timing DIR couplers and timing DIR compounds) in which the inhibitor is bonded such that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction at the base circle. Also, depending on the purpose, inhibitors that can be dispersed after release and those that are not so dispersible can be used alone or in combination.

Colorless couplers (also referred to as competitive couplers) that undergo a coupling reaction with the oxidized product of the aromatic primary amine developer but do not form dyes can be used in combination with dye-forming couplers.

As the yellow dye-forming coupler, known anruacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

Specific examples of yellow couplers that can be used include U.S. Pat. No. 2,875,057, U.S. Pat.
, No. 408, 194, No. 3,551,155, No. 3,
No. 582.322, No. 3,725,072, No. 3,8
91,445, West German Patent No. 1,547,868, West German Patent Application No. 2,219,917, West German Patent No. 2,261.361
No. 2,414.006, British Patent No. 1,425,0
No. 20, Special Publication No. 51-10783, Japanese Patent Publication No. 47-26
No. 133, No. 48-73147, No. 50-6341, No. 50-87650, No. 50-123342, No. 50-130442, No. 51-21827, No. 51
-102636, 52-82424, 52-1
No. 15219, No. 58-95346, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolopenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, intazolone couplers, and the like can be used.

Specific examples of magenta coloring couplers that can be used include U.S. Pat. No. 2,600.788, U.S. Pat.
3.062,653, 3,127,269, 3,311,476, 3,419,391, 3
, No. 519,429, No. 3,558.319, No. 3,
No. 582.322, No. 3,615,506, No. 3,8
No. 34.908, No. 3,891,445, West German Patent 1
, No. 810,464, West German Patent Application (OLS) 2,4
No. 08,665, No. 2,417,945, No. 2.41
No. 8.959, No. 2.424.467, Special Publication No. 1977-
No. 6031, JP-A-49-74027, JP-A No. 49-74
No. 028, No. 49-129538, No. 50-6023
No. 3, No. 50-159336, No. 51-20826, No. 51-26541, No. 52-42121, No. 5
No. 2-58922, No. 53-55122, Special No. 1987
-110943 etc. are mentioned.

As the Noan dye-forming coupler, a known 7-enol or naphthol coupler can be used.

For example, phenolic couplers substituted with an alkyl group, anruamino group, or ureido group, naphthol couplers formed from a 5-aminonaphthol skeleton, diisomeric naphthol couplers with an oxygen atom introduced as a leaving group, etc. Ru.

Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Pat. No. 3,779,763, U.S. Pat.
No. 60-225155, No. 60422853,
No. 59-185335, U.S. Patent No. 3.488.193
No. 60-237448, No. 53-52423,
No. 54-48237, No. 56-27147, Equity 4
9-1.1572, Patent No. 61-3142, Patent No. 61.
9652-3, 61-39045, 61-50
No. 136, No. 61-99141, No. 61-10554
Examples include those described in No. 5.

Examples of light-sensitive materials to which the silver halide photographic light-sensitive material of the present invention can be applied include various color and black-and-white light-sensitive materials. For example, color photosensitive materials such as color negative film, color reversal film, color photographic paper, color positive film, color reversal photographic paper, direct positive film, heat development film, silver dive ring film, X-ray photography, squirrel film, etc. It can be used in photosensitive materials for black and white photography such as micro photography, general photography, and black and white photographic paper.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Multilayer color photographic element sample 10 was prepared by sequentially forming each layer of IIFR as shown below on a triacetyl cellulose film support from the support side.

・) The amount added in a silver halide photographic light-sensitive material is the weight (g) per 1 m2 unless otherwise specified. In addition, silver halide and colloidal silver are shown after conversion.

Layer structure of sample No. 1 First layer; antihalation layer (HC-1) black colloidal silver 0.20 UV absorber (UV-1
) 0.20 high boiling point solvent (OIQ-
1) 0.20 gelatin
1.5 Second layer: Intermediate layer (IL-1) UV absorber (UV-1) 0.01
High boiling point solvent (OiC-1) 0.01
Gelatin 1.5 3rd layer: low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.9 Silver iodobromide emulsion (Em-2) 0.6 Sensitizing dye (S -1 ) 2.5x 10-' (mol/1 mol of silver) 2.5X 10-' (mol/1 mol of silver) 0.5X 10-' (mol/1 mol of silver) Sensitizing dye (S-3) Sensitization Dye (S-2) / Uncoupler (C-1) Cyan coupler (C-2) Colored / Uncoupler (CC DIR compound (D-1) High boiling point solvent (OiQ-)) Gelatin 4th layer; High sensitivity red Sensitive emulsion layer (RH) Silver iodobromide emulsion (
Em-3) Sensitizing dye (S-1) 2, OX 10-' (mol/silver 2, OX 10-' (mol/silver 0, IX 10-' (mol/silver 1.0 0.05 1) 0.05 0.002 0.5 1.5 Sensitizing dye (S-2) Sensitizing dye (S-3) Cyan coupler (C-2) Uncoupler (C-3) Colored cyan coupler (CC-1) DIR Compound (D-2) High boiling point solvent (OIQ-1) Ceratin 2.0 1 mol) 1 mol) 1 mol) 0.015 0.25 0.015 0.05 0.3 1.5 5th layer; middle Layer (IL-2) Gelatin 6th layer, low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.5 1.0 Sensitizing dye (S-4) 5X10-' (mol/ Silver 1 mol) Sensitizing dye (S-5) I X 10-' (mol/
1 mole of silver) Magenta coupler (M-1) 0.5 colored magenta coupler (CM-1) DIR compound (D-3
DIR compound (D-4) High boiling point solvent (044-2) Gelatin 7th layer; Intermediate layer (IL-3) Gelatin 8th layer: High-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (En+- 3) Sensitizing dye (S-6) 1.5X 10-'0.0
1 O2O3 0,020 0,4 1,0 0,8 1,3 (mol/silver 1 mol) Sensitizing dye (S-7) 2.5x 10-' (mol/silver 1 sensitizing dye (S-8) ) 0.5X 10-' (mol/silver l Magenta coupler (M-2) Magenta coupler (M-3) Colored magenta coupler (CM-2) 0.05 mol) mol) 0.15 DIR compound (D-3) ) High boiling point solvent (Oi12-3) Gelatin 9th layer: Yellow filter layer (yc) Yellow colloid silver stain inhibitor (SC-1) High boiling point solvent (OIQ-3) Gelatin 10th layer: Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (
Em-1) Silver iodobromide emulsion (Em-2) 0.05 0.0I O15 1,0 0,1 0,1 0,1 0,8 0,25 0,25 Sensitizing dye (S-10) 7 X 10-' (mol/silver yellow coupler (Y-1) Yellow coupler (Y-2) DLR compound (D-2) High boiling point solvent (OiQ-3) Gelatin 11th layer; High sensitivity blue-sensitive emulsion layer ( BH) Silver iodobromide emulsion (
Em-4) Silver iodobromide emulsion (Em=1) Sensitizing dye (S-9) lXl0-' (mol/silver sensitizing dye (S-40) 3 X 10-' (mol/silver yellow coupler (Y -1:) Yellow coupler (Y-1 High boiling point solvent (0112-3) Gelatin 12th layer; First protective layer (PRO-1) Fine grain silver iodobromide emulsion 1 mol) 0.5 0.1 0. 01 O83 1,0 0,4 0゜3 1 mol) 1 mol) 0.30 0.05 0.1 1.1 (Average particle size 0.08 μmAg12 mol%) UV absorber (
OV-1) UV absorber (UV-2) High boiling point solvent (OiQ, -1) High boiling point solvent (Oi12-4) Formalin scavenger (O3-1) Formalin scavenger (O5-2) Seratin No. 13 Layer: #2, protective layer (PRO-2) surfactant (,
5U-1) Alkali-soluble matting agent (average particle size 3 μm) Gelatin 0.4 0.05 0.1 0.1 0.5 0.2 0.005 1.10 0.6 Ea+-1: Average particle Diameter 0.46 μm 1 average iodine silver 7.
0 mol%, monodisperse surface silver-containing emulsion εm-
2: Average grain size 0.30 μΦ, average silver iodide content 2.0 mol%, monodisperse and uniform composition emulsion 3: Average grain size 0.8
1/7 m Em Average silver iodide content...7.0 mol % Monodisperse surface paper silver iodide-containing emulsion Em-4: Average grain size 0.95/7 m.

Average silver iodide content: 8.0 mol%, monodisperse (width of distribution 14%) surface paper Silver iodide (0.5 mol%)-containing emulsion In addition to the above compositions, each layer contains Coating aid 5u-2, stabilizer 5tb-1, and antifoggant AF-1 were added to the solution.

Furthermore, a silver halide emulsion to be used in the 8th layer of Sample-1H was prepared under various chemical ripening conditions as shown in Table 1, and was replaced with the silver halide emulsion in the 8th layer of Sample-1ot. , Samples-102 to 110 were C, H.

(co2)+so3θ (C)11)1503)1 (CI(I), So, O (CI(,), So, e (CH2), So4゜ (CH2)I5OIH-N(C2H5)3C,Hl C2H.

(C)Iz)*5Oxe (CH2)Y5OJ-N(C21b:h(CI(2)+
SOhθ C, I+.

(CHz)3sOxNa C,H.

H Q Q C. 0 ■ ■ Cθ a M-1 Q M O Q ■ H H O1+ u Na01S Ccoocl12 (cF2cF2),.

CC00CH2(CF2CFz)aH u NaO,5-C-COoC,11,7 H2 COOC, H.

u ■ H B iQ V ■ f'lH c+hs(t) V-2 C21(S S S [(CH□ CtlSOzCHz)+CCt(2so2(C1b)2
N(C1l□)*5OJ0i(1- H C,H+5(t) lQ- IQ tab HF ■ 55° for each of the prepared samples 101 to 110
The sample left for one week under C160%RH conditions and the sample immediately after manufacture were exposed to wedge light using white light, and then subjected to the following development treatment.

Processing process (38°C) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water
Fixing for 3 minutes and 15 seconds. Washing for 6 minutes and 30 seconds. Stabilization for 3 minutes and 15 seconds. Drying for 1 minute and 30 seconds. The composition of the processing liquid used in each processing step is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2.5g potassium hydroxide 1.0g Add water to make IQ.

[Bleach solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100. g Ethylenediaminetetraacetic acid 2 ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml12 Add water to make IQ, and adjust to pH = 6°0 using aqueous ammonia.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Water was added to make IQ, and the pH was adjusted to -6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5
n+Q Konidanks (Konica) 7.
Add 5mff water to make 112.

For each sample obtained, the green (G) density was measured, and the relative sensitivity and fog density were determined.

The relative sensitivity was determined as the reciprocal of the exposure amount required to obtain a density of minimum density + 0.3, and sample 101 was set as 100, and the other samples (102 to 110) were expressed as relative sensitivities to sample -101. . These results are shown in Table-2.

As is clear from the results in Table 2, the samples using the emulsion chemically ripened under the conditions of the present invention have high sensitivity, less fog, and excellent storage stability over time. We were able to suppress the decrease in sensitivity. - Furthermore, when similar experiments were conducted with a blue-sensitive emulsion layer and a red-sensitive emulsion layer, similar results were obtained, confirming the effects of the present invention.

Example 2 A multilayer color photosensitive material sample 201 (comparison) was prepared by sequentially coating each layer having the composition shown below on a subbed triacetyl cellulose film support from the support side. Incidentally, the coating amount of each component is shown in g/m2.

However, silver halide is shown in the coating amount in terms of silver, and coupler is shown in the number of moles per 1 mole of silver.

1st layer: antihalation layer UV absorber U-10,3 UV absorber U-20,4 High boiling point solvent O-11,0 Black colloidal silver 0.24 Gelatin 2.0 2nd layer, intermediate layer 25-G (-Octylhydroquinone 0.1 High boiling point solvent 0-1 0.2 Gelatin
l. 0 3rd layer Low sensitivity red-sensitive silver halide emulsion layer Red sensitizing dye (5-1) and (5-
2) spectrally sensitized silver iodobromide (Agl 4 mol%
Average particle size 0.25μm) 0.5
Coupler cp-l O,1 high boiling point solvent 0-2 0.6 gelatin
1.3 Fourth layer: Highly sensitive red-sensitive silver halide emulsion layer Red sensitizing dye (S-1) and (5-
2) spectrally sensitized silver iodobromide (Agl 2 mol%
average particle & 0.60 p m)
0.8 Coupler cp-10,2 High boiling point solvent 0-2 1.2 Gelatin 1.8 5th layer: Intermediate 1 2.5-Di[-octylhydroquinone 0.1
High boiling point solvent 0-1 0.2 Gelatin 0.9 6th layer: Low sensitivity green-sensitive silver halide emulsion layer Green sensitizing dye (5-3) and (
Silver iodobromide spectrally sensitized by 5-4) (Agl 4 mol% average particle size 025 μm) 06 Coupler Cp-20,04 Coupler Cp-30,01 High boiling point solvent 0-3 0.5 Gelatin 1.4 7th layer: high-sensitivity green-sensitive silver genide emulsion layer containing silver iodobromide (Agl 2
Mol% average grain m 0.60 p m)
0.9 Coupler Cp-20,10 Coupler CI)-30,02 High boiling point solvent o -31,0 Gelatin 1.5 8th layer:
9th layer same as 5th intermediate layer: yellow filter layer yellow colloidal silver 0.12.5
-D-L-octylhydroquinone 0.1 High boiling point solvent o-10,2 Gelatin 0.9 No. 10
Layer: Low-speed blue-sensitive silver halogenide emulsion layer Blue sensitizing dye (
Silver iodobromide spectrally sensitized by 5-5) (Ag 14 mol% average grain size 0.35 μm) 0.6
Coupler Cp-40,3 High boiling point solvent 0-3 0.6 Gelatin 1.3 11th layer: High sensitivity blue-sensitive silver halide emulsion layer Iodobromide spectrally sensitized with blue sensitizing dye (5-5) Silver (Ag 12 mol% average particle size 0.90 μm) 0.9
Coupler Cp-40,5 High boiling point solvent 0-3 1.4 Gelatin 2.1 12th layer: 1st protective layer Ultraviolet absorber U -10,3 Ultraviolet absorber U -20,4 High boiling point solvent 0-3 0 .62.5-
1 octyl hydroquinone 0.1 gelatin 1.2 13th layer: 2nd layer
Protective layer A non-photosensitive fine-grain silver halide emulsion consisting of silver iodobromide with an average grain size of 0.08 μm and containing 1 mol% of silver iodide.
0.3 Polymethyl methacrylate particles (diameter 1.5 μm) Blush active agent-1 Seratin 0.7 In addition to the above composition, gelatin hardening agent-1 and a surfactant were added to each layer.

Sensitizing dye S Sensitizing dye s-4 Sensitizing dye S C,H UV absorber Ultraviolet absorber Sensitizing dye S-2 Coupler cp Coupler cp Gelatin hardening agent - Surfactant Na0sS CHCOOCH, (CF=CF2)sH
C)1. C00CH2 (CF20F, ), +1 high boiling point solvent - C2H6 C2H.

The silver halide emulsion in the silver emulsion layer is heated at a temperature of 55% in the reaction tank.
It was kept at 0.degree. C. and subjected to chemical ripening using sodium thiosulfate and chloroauric acid.

The PAg value during chemical ripening was 9.2, and the product was aged for 90 minutes.

On the other hand, the conditions for chemical ripening of the silver halide emulsion of the first O layer are shown in Table 3.

Furthermore, various silver halide emulsions for use in the 10th layer of Sample-201 were prepared under the conditions shown in Table 3, and Sample-201
High boiling point solvent O to replace the silver halide emulsion in the first O layer of Sample 201 High boiling point solvent 0-3 For each of the photosensitive halogen prepared samples 201 to 207 except for the first O layer of sample 201, 55°C 160% R ，
The sample left for one week under H conditions and the sample immediately after manufacture were exposed to wedge light using white light, and then subjected to the following development treatment.

Processing process Development time Processing temperature First development
6 minutes 38°C water washing
2/1 reversal
211! /Color development 61111 adjustment 2tt
//Bleach 6
〃 〃arrival
41/ll water wash
4 tt tt low
Constant 1 tt Normal Wet Dry The composition of the treatment liquid used in the above treatment step is as follows.

Nezumi'woikan'L Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone・
Sodium monosulfomonocarbonate (l hydrate) l-phenyl-4-methyl-4-hy3-pyrazolidone Potassium bromide Potassium thiocyanate Potassium iodide (0.1% solution) Add water and invert Liquid nitrilotrimethylene phosphone Acid / 6-sodium salt Stannous chloride (dihydrate) p-Aminephenol Sodium hydroxide Add glacial acetic acid water and add Sodium tetrapolyphosphate Sodium sulfite Sodium tertiary phosphate (dihydrate) 30g 0g Droxymethylg 2.5g 1.2g mff 000mQ g g O,Ig g 5mff 1000+n12 g g 6g g 1% solution) 90mQ g 1.5g Methanesulfonamide ethylaminoaniline sulfate 1g Potassium bromide Potassium iodide (0 Sodium hydroxide/N-ethyl dorazate-N-β 3-methyl-4 2,2-ethylenedithiogetanol Adjust by adding water Liquid sodium sulfite ethylenediaminetetraacetic acid sodium 2g Rum (dihydrate) g 0.4mff mC 1000mff g 1000mff Add thioglycerin glacial acetic acid water g Ethylenediaminetetraacetic acid iron (I[r) ammonium (2
water salt) 120g ammonium bromide Add 100g water
1000 mff fixing liquid Ammonium thiosulfate 80g Sodium sulfite 5g Sodium bisulfite 5g Add water
1000m12 Stable liquid formalin (37% by weight) 5mC
Conidax (manufactured by Konica Corporation) 5 m (2 by adding water, 10100 O obtained I; blue density was measured for each sample, and relative sensitivity and maximum color density (Dmax) were determined.

In addition, the relative sensitivity was determined by calculating the reciprocal of the exposure amount required to obtain a blue density of 0.5, and sample-201 was set as 100, and the other samples (202 to 207) were expressed as relative sensitivities to sample 201. .

These results are shown in Table-4.

As is clear from the results in Table 4, samples using emulsions chemically ripened under the conditions of the present invention have high sensitivity, exhibit excellent storage stability over time, and suppress sensitivity changes and decreases in maximum density. I was able to do that.

Furthermore, when similar experiments were conducted with a red-sensitive emulsion layer and a line-sensitive emulsion layer, similarly good results were obtained, confirming that the effects of the present invention are exerted regardless of the difference in color sensitivity. .

Example 3 Color reversal photosensitive material sample 3 was prepared by providing the following 1st to 11th layers on a paper support coated with polyethylene on both sides.
Created the old one. The coating amount of each component is shown in 67 m2. However, for silver halide, the coating amount is expressed in terms of silver.

1st layer (antihalation layer) Black colloidal silver -0,10 gelatin -1,5 2nd layer (1st red-sensitive layer) Cyan coupler C-1---0,080 horn
C-2---0.

16 Anti-fading agent A -1---0,12N
A-2---0.06 high point solvent 0-1---0.18 red sensitizing dye (
AgBr1 (Ag
l 3.0 mol%, average particle size 0.4 μm) 0.14 Gelatin -0,81 Third layer (second red-sensitive layer) Cyan coupler C-1---0,043//
C-2---0,085 Anti-fading agent A
-1---0,064// A -2-
--0,032 High boiling point solvent 0-1 ---
0.097 8 g Brl spectrally sensitized with red sensitizing dye (S-1,5-2) (All 3.0 mol%, average particle size 0.8 μm) 0.16 gelatin -0.98 4th layer (First intermediate layer) Color mixing prevention agent A N -1---0,020//
AN-2---0,060 high tinsel point solvent
O Gelatin 5th layer (first green-sensitive layer) Magenta coupler C Anti-fading agent A tt A high boiling point solvent
O Green sensitizing dye (S-3) AgBrl (8g1 3.0 mol%.

Gelatin 6th layer (second green-sensitive layer) Magenta coupler C- Anti-fade agent 8- No/A- High boiling point solvent 〇- Green sensitizing dye (S-3) Ag13rl (Agl 3.0 mol% gelatin --- 0,13 0,90 3---0,25 3---0,067 4---0,12 1---0,19 Spectrally sensitized average particle size 0.4 μm) --- 0,15 ---0,93 3 ---0,15 3 ---0,040 4-1-0,070 1-1-0,11 Average particle size 0.7 μm) 0.15 ---0.83 7th layer (second intermediate layer) Yellow colloidal silver -0,20 Color mixing inhibitor A N -1 ---0,014tt
AN2 -- 0.046 high boiling point solvent
0-2---0.096 gelatin
-0,90 8th layer (first blue sensitive layer) Yellow coupler C-4---0,24 anti-fading agent
A-1---0,096tt A
5 --0.048 high boiling point solvent o -
3--0,048 AgBr1 spectrally sensitized with blue sensitizing dye (S-4) (Agl 3.0 mol%, average particle size 0.4 μm) -0,15 Gelatin -0,95 @ 9 layers (Second blue sensitive layer) Yellow coupler C-4---0,32 anti-fading agent
A-1---0,13pt A-
5---0,064 High boiling point solvent 0-3-
--0.064 AgBr1 spectrally sensitized with blue sensitizing dye (S-4) (Ag 13.0 mol%, average particle size 0.
8/Z111)---0,13 Gelatin -0,93 10th layer (
Ultraviolet absorbing layer) Ultraviolet absorber U -1---0,45tt
[J-2-m-0,15 Color mixture prevention agent
A N -1---0,033 High boiling point solvent 0-
3---0.37 gelatin
~--1,87 Eleventh layer (protective layer) Gelatin -0,50 However, in addition to the above, it contains a surfactant, a hardener, and an anti-irradiation dye.

Q CaH1r AN-1 H H AN-2 ■ Di-2-ethylhequinulfthalate di-isodecyl phthalate di-nonyl phthalate (CH3)3SO+e 2H5 (CH2)4SO3θ Used in each color-sensitive layer I; silver halide emulsion , Japanese Patent Publication No. 1983-
It was prepared by the method of Publication No. 178447 Example-1.

In addition, each emulsion in the photosensitive silver halide emulsion layer except the third layer of Sample-301 was desalted and washed with water, and then heated at 55°C in the presence of sodium thiosulfate, chloroauric acid, and ammonium thionarate. A 9.0i trowel was used for optimal chemical aging.

On the other hand, the conditions for chemical ripening of the silver halide emulsion in the third layer are shown in Table-
5.

Furthermore, various silver halide emulsions for use in the third layer of Sample-301 were prepared under the conditions shown in Table-5.
Each sample 3 was prepared by placing it on the third layer of silver halide emulsion.
For each of 01 to 310, those left for 5 days at 55 ° C 160% R, H conditions and those immediately after production,
After wedge exposure using white light, the following development process was performed. Processing time (processing temperature) First development (monochrome development) 1 minute 15 seconds (38°C) Water
Wash 1 minute 30
Second light fog 100ffux or more 1 second or more Second development (color development) 2 minutes 15 seconds (38°C) Water
Wash 4
5 seconds bleach fixing 2 minutes (38℃) water
Washing: 2 minutes and 15 seconds The composition of the treatment liquid used in the above treatment step is as follows.

(First developer) Potassium sulfite 3.0g Thio・
/Sodium annate 1.0g Sodium bromide 2.4g Potassium iodide
8.0mg potassium hydroxide (4
8%) 6, 2m124g 2g 4-Hydroquine methyl 1.5g Sulfo-Fuichi! -23,3g l,0Q (pH 9,65) Potassium carbonate Sodium bicarbonate l-Phenyl-4-methyl 3-pyrazolidone Add hydroquinone monowater (color development liquid) Benzyl alcohol ethylene glycol Potassium carbonate (anhydrous) Potassium hydroxide sodium sulfite 3.6-cythiaoctane-1,8-diol 14.6m
12 12.6mC 6g 1.4g 1.6g 0.24g Hydroquinylamine sulfate 2.6g4-N
-Ethyl-N-β-(methanesulfonamidoethyl)-
2-Methyl-p-phenyl diamine sesquisar 7-
Add 1~5.0g water
1.0Q (bleach-fix solution) 1.56 mol m solution of ammonium salt of ethylenediaminetetraacetate diiron complex 115ml 71 Sodium metabisulfite 15.4g Ammonium thiosulfate (58%) 126InQ5-Mercapto-
Add 1,2,4-triazole 0.4g water
1.0Q (pH=f3.5) For each sample obtained, the red reflection density was measured to determine the relative sensitivity and maximum color density (D max).

The relative sensitivity was determined by calculating the reciprocal of the exposure amount necessary to obtain a red reflection density of 1.7, and the sample 301 was set as 100, and the other samples 302 to 310 were expressed as relative sensitivities to the sample 301.

As is clear from the results in Table 6, the samples using the emulsion chemically ripened under the conditions of the present invention have high sensitivity and excellent storage stability over time, suppressing changes in sensitivity and decrease in maximum density. was completed.

〔Effect of the invention〕

According to the present invention, it has been possible to produce a silver halide photographic material which has high sensitivity, low fog, and improved storage stability over time.

Procedural amendment ■, Indication of case, 1988 Patent Application No. 308589 2, Title of invention Silver halide photographic light-sensitive material with high sensitivity, less fogging, and excellent storage stability over time

Claims (1)

[Claims] By performing substantial chemical ripening within the pAg value range of 6.0 to 8.8 and adding a compound that forms a sparingly soluble salt with silver ions before or during the chemical ripening, the pA
A silver halide photographic material comprising at least one photosensitive layer containing a silver halide emulsion that has undergone a process of increasing g-value.