JPH0450836A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material which fogs less, is improved in stability with lapse of time and has no adverse influence on photographic characteristics by providing at least one layer of photographic constituting layers contg. a dispersion dispersed with at least one kind of specific oil-soluble compds. CONSTITUTION:At least just one layer of the photographic constituting layers contg. the dispersion dispersed with at least one kind of the oil-soluble compds. expressed by formula I is provided on a base. In the formula I, R1 to R4 respectively denote a hydrogen atom, alkyl group, etc.; X1, X2 respectively denote an oxygen atom or sulfur atom; L1, L2 and L3 respectively denote a methine group; n denotes 0, 1 or 2 positive integer; M denotes a hydrogen atom or univalent metal atom. The silver halide photographic sensitive material which fogs and stains less and is improved in the stability with lapse of time is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a silver halide photographic material containing a filter dye.

[Prior Art] Silver halide photographic materials are required to have high image quality characteristics such as excellent sharpness and color reproducibility.

Furthermore, in recent years, in order to compete with the immediacy of competing electrophotographic materials, shortening of processing time, ie, suitability for ultra-rapid processing, has become even more necessary. In order to achieve the high image quality characteristics and ultra-rapid processing suitability required of such photographic materials, the industry is making efforts to further reduce the film thickness of photographic materials and to optimize silver halide and additive compound materials. It has been done.

Incidentally, it is well known that dyes are incorporated into silver halide photographic materials for the purpose of improving image quality or adjusting silver halide emulsion sensitivity. It is used.

Recently, dyes aimed at replacing yellow colloidal silver in color photographic materials (hereinafter referred to as "YC dyes"), dyes for cross-over cut layers in X-ray photographic materials, and dyes intended to replace yellow colloidal silver in printed photographic materials, and Its uses are expanding, including dyes for dyeing photosensitive emulsion layers.

Depending on the purpose of use, the dyes used for these purposes: 1. have a good absorption spectrum; 2.11
3. It does not diffuse from the colored layer to other layers. 3. It does not affect the photosensitive silver halide emulsion photographically. 4. It is stable in the silver halide photographic light-sensitive material. 5. It is easy to add. The following properties are required: 6. It is stable in the emulsion coating solution and does not affect the solution viscosity; 7. It does not leave any color after processing.

A large number of dyes have been proposed in the past for the purpose of satisfying these desired properties, such as U.S. Patent No. 3.540.
．． No. 887, No. 3.544.325, No. 3,56
No. 0214, Japanese Patent Publication No. 31-10578, and Japanese Patent Publication No. 5
Benzylidene dyes were proposed in No. 1-3623, etc., and British Patent No. 506.385 and Japanese Patent Publication No. 39-2206
9@ is oxonol dye, U.S. Patent No. 2.493.7
No. 47 includes merocyanine dye, U.S. Patent No. 1,845,
No. 404 proposes styryl dyes and the like.

Also, JP-A No. 1-196040, JP-A No. 1-196041
No. 1 discloses heterocyclic type arylidene dyes.

The general method is to dissolve these dyes in water or an organic solvent that is miscible with water and add them to the photographic constituent layers. It spreads to Therefore, in order to achieve the original purpose, it is necessary to add as much winter dye as will diffuse into other layers, which may cause undesirable phenomena such as decreased sensitivity, gradation fluctuations, and fogging abnormalities in both the white layer and other layers. It will appear.

In particular, when photosensitive materials are stored over time, fogging and desensitization occur significantly, and if the amount used is reduced to avoid these problems, the original light absorption effect will no longer be achieved.

To solve this problem, dyes with suppressed diffusion properties that dye specific layers are also known. Examples of diffusion-resistant dyes include U.S. Pat. Nos. 2,538,008 and 2,539,0
Specifications of No. 09 and No. 4.420.555, Japanese Unexamined Patent Publication No. 1983
No. 1-204630, No. 61-205934, No. 62
-32460, 62-56958, 62-92
9494, No. 62-222248, No. 63-4014
No. 3, No. 63-184749, No. 63-31685
Yellow dyes are described in each publication of No. 2. Also,
These dyes are similar to Carey lea silver, which is commonly used in color photographic elements.
The yellow colloidal silver called 5ilver absorbs not only the blue light region but also part of the long wavelength side, which reduces green sensitivity and increases the fogging of adjacent layers. There are many suggestions for saving money.

[Problems to be Solved by the Invention] Although these drawbacks can certainly be improved to some extent by using the above-mentioned diffusion-resistant dyes, storage stability is poor and desensitization occurs over time. In addition, a new problem has arisen in that the bleaching properties are insufficient, causing color staining. In order to improve these problems, new diffusion-resistant dyes are required.

Therefore, an object of the present invention is to provide a diffusion-resistant filter dye that satisfies the above requirements, has less fogging and staining, and
The object of the present invention is to provide a silver halide photographic material that has improved stability over time and exhibits good photographic properties.

[Means for Solving the Problems] The inventors of the present invention have conducted intensive studies in view of the above-mentioned problems, and as a result, the above-mentioned objects have been achieved by the present invention. That is, the present invention provides a silver halide photographic light-sensitive material having at least one photographic constituent layer containing a dispersion in which at least one oil-soluble compound represented by the general formula [I] is dispersed on a support. It is in.

In the general formula [■], R1 to R4 each represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group. X+ and X2 each represent an oxygen atom or a sulfur atom. L+, L2 and L3 each represent a methine group, and n represents a positive integer of 0, 1 or 2. M represents a hydrogen atom or a -valent metal atom. ] The present invention will be explained in more detail below.

In the general formula [I], examples of the alkyl group represented by the dimension 81 to 8 include methyl group, ethyl group, n-propyl group, 1so-propyl group, t-butyl group, n-pentyl group, n-hexyl group. group, n-octyl group, 2-ethylhexyl group, n-dodecyl group, 0-pentadecyl group,
Examples include eicosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. These groups include those having substituents, such as halogen atoms (for example, chlorine, bromine, iodine, and fluorine M'4 atoms), aryl groups (for example, phenyl groups, naphthyl groups, etc.), and heterocycles. groups (e.g. pyrrolidyl group, pyridyl group, etc.), carboxyl group, nitro group, hydroxyl group, mercapto group, amine group (e.g. Amim L diethylamino group, etc.), alkyloxy group (e.g. methyloxy group, ethyloxy group, n-butyloxy group) , n-octyloxy group, isopropyloxy group, etc.), aryloxy group (phenyloxy group, naphthyloxy group, etc.), carbamoyl group (e.g. aminocarbonyl group, methylcarbamoyl group,
n-penpurcarbamoyl group, phenylcarbamoyl group, etc.), amide group (e.g. methylamide group, benzamide group, n-octylamide group, etc.), sulfamoyl group (e.g. methylsulfamoyl group, phenylsulfamoyl group, n-butylsulfamoyl group) famoyl group, etc.), sulfonamide group (e.g. methanesulfonamide group, n-hebutanesulfonamide group, benzenesulfonamide group, etc.), sulfinyl M (e.g. methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, octyl Alkylsulfinyl groups such as sulfinyl groups, arylsulfinyl groups such as phenylsulfinyl groups), alkyloxycarbonyl groups (e.g. methyloxycarbonyl groups, ethyloxycarbonyl groups, 2-hydroxyethyloxycarbonyl groups, n-octyloxycarbonyl groups, etc.) 〉、
Aryloxycarbonyl group (e.g. phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, n-hexylthio group, etc.), arylthio group (e.g. phenylthio group, naphthylthio group, etc.), alkylcarbonyl groups (e.g. acetyl group, ethylcarbonyl group, n-butylcarbonyl group, n-octylcarbonyl group, etc.), arylcarbonyl group (e.g. benzoyl group, p-methanesulfonamidobenzoyl group, p-carboxybenzoyl group, naphthoyl group, etc.) , a cyano group, a ureido group (eg, methylureido group, phenylureido group, etc.), a thioureido group (eg, methylthioureido group, phenylthioureido group, etc.), and the like.

In the general formula [I], examples of the aryl group represented by R1 to R4 include a phenyl group and a naphthyl group. These groups include those in which the above-mentioned groups listed as substituents for the alkyl groups represented by R1 to R4 are directly substituted as substituents.

Examples of the aralkyl group represented by R1 to R4 in the general formula [I] include alkyl groups substituted with substituted or unsubstituted phenyl groups.

These groups include the alkyl group represented by R1-R1, or those in which the above-mentioned groups listed as substituents for the alkyl group represented by R1-R4 are directly substituted as substituents.

Examples of the alkenyl group represented by R1 to R% in the general formula [E] include vinyl group, allyl group, 1-propenyl group, 1,3-butadienyl group, 2-pentenyl group, 2-dodecenyl group, etc. . These groups are the alkyl groups represented by R1-R1, or R1-R+
The substituent of the alkyl group represented by the above includes those directly having the group listed above as a substituent.

In the general formula [E], the heterocyclic group represented by R1-R4 includes a pyridyl group, an oxasilyl group, a thiazolyl group, an imidazolyl group, a furyl group, a thienyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, a purinyl group, and an isocyclic group. Examples include oxacylyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc., and these heterocyclic groups are substituted with alkyl groups represented by R1 to R4, or alkyl groups represented by R1 to R4. It includes those that directly have the above-mentioned groups as substituents.

In the general formula [I], R1 to R=+ may each be the same group or different groups, but it is preferable that the total number of carbon atoms in R1 to R4 is 15 or more.

In the general formula [I], the methine group represented by L+, L2, or L3 may be substituted, and examples of such substituents include halogen atoms such as chlorine, bromine, and fluorine atoms, such as methyl groups, Alkyl groups such as ethyl group, isopropyl group, aryl group such as phenyl group, naphthyl group, alkyloxy group such as methyloxy group, ethyloxy group, isopropyloxy group, aryloxy group such as phenoxy group, naphdyloxy group, etc. Examples include groups.

In the general formula [I], examples of the monovalent metal atom represented by M include a sodium atom and a potassium atom.

In the present invention, the oil-soluble compound refers to a compound having a solubility of 11/2 or less at 25°C when distilled water with a pl-t of 6 to 7 is used, preferably a solubility of 0.1 fl/ffi or less. .

Specific examples of the compound represented by the general formula [I] of the present invention are listed below, but the present invention is not limited thereto.

Next, an example of synthesis of the compound of the present invention will be shown, but other compounds may also be used. Compounds can also be easily synthesized by a similar method.

112 spaces below; Compound (1) 19.1a, Compound (2>4.6(1
, pyridine 39 and dimethylformamide 100d were heated at 40°C and reacted for 5 hours. 300 ml of reaction mixture
The mixture was added to the water in step d to make it slightly acidic, and extracted with ethyl acetate 150112. After washing twice with saturated brine, it was dried over anhydrous sodium sulfate.

Ethyl acetate was concentrated, and Compound 32 was isolated and purified by column chromatography to obtain 9.9 g of crystals (yield: 52%). The product compound 32 was confirmed by 'H-Nuclear Magnetic Resonance Vector (NMR) and FAB quality spectrometer (FAB/MS).

The compound of the present invention is used in silver halide photographic materials so that the optical density is in the range of 0.05 to 30 depending on the purpose.

The method of dispersing the compound according to the present invention in a photosensitive material is as follows: (1) dispersing the compound in an oil, that is, substantially water-insoluble and having a boiling point of about 1
A method in which a solution dissolved in a high boiling point solvent of 60°C or higher is added to a hydrophilic colloid solution and dispersed. This high boiling point solvent is
For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl phosphate, etc.), as described in U.S. No. R+2,322,027. butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate) , trimesate esters (eg, tributyl trimesate), etc. can be used. Also, organic solvents with a boiling point of 30°C to about 150°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and water. It is also possible to use a solvent that is easily soluble in, for example, an alcohol such as methanol or ethanol.

``Specific examples of other usable high boiling point organic solvents are described in U.S. Pat. No. 2,533,514, U.S. Pat.

(2) A method in which a hydrophilic polymer is used in place of the high-boiling point solvent or in combination with the high-boiling point solvent in (1) above. This method is described, for example, in U.S. Pat. No. 3,619,195, West German Pat.
No. 957.467.

(2) A method in which a compound is dissolved in a water-miscible solvent and then an aqueous latex is gradually added to this solution to obtain a dispersion in which the compound is contained in latex particles. This method is described, for example, in JP-A-51-59943.

■ A method in which a compound is dissolved in a water-miscible solvent, and then this solution is mixed with water containing a surfactant and dispersed in water. This method is described, for example, in JP-A-53-139532.

In addition, hydrosil, a lipophilic polymer described in Japanese Patent Publication No. 51-39835, may be added to the hydrophilic colloid dispersion obtained above.

Gelatin is a typical hydrophilic colloid, but any other conventionally known colloid used for photography can be used.

In the present invention, photographic constituent layers include photosensitive layers such as blue-sensitive emulsion layers, green-sensitive emulsion layers, red-sensitive emulsion layers, intermediate layers, protective layers, filter layers, antihalation layers, and anti-irradiation layers, or non-photosensitive layers. Indicates gender.

The compound of the present invention is preferably contained in the non-photosensitive layer, particularly preferably in the filter layer.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any of the conventional silver halide emulsions can be used.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and its counterpart hydrophilic colloid layer can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of a light-sensitive material for color photography.

Furthermore, by coupling a colored coupler having a color correction effect with a competing coupler and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a carrier, a silver halide solvent,
Compounds that release photographically useful fragments such as toning agents, hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers, and sensitizers are used.

A photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, etc., but these layers and/or emulsion layers contain substances that may flow out of the photosensitive material during development. Alternatively, a bleaching dye may be included.

A formalin scavenger-1 fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventive agent, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.

As the support for the photosensitive material, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain an image using the photosensitive material of the present invention, commonly known photographic processing can be performed after exposure.

[Example 1] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example-1 In all of the following Examples, the amount added in the silver halide photographic material is based on the weight per 112 unless otherwise specified.
g). In addition, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic element sample 1-1 was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample 1-1 (comparison) (1-(C-1) 11i: Antihalation layer Black colloidal silver U absorbent (UV-1) Colored coupler (CC-1) Colored coupler (CM-2) High boiling point layer *(○1f-1> Gelatin 2nd layer; Intermediate layer (1, L, <) U■ Absorber (UV-1) High boiling point solvent (Oil-1) Gelatin 3rd layer; Low sensitivity red-sensitive emulsion layer Silver bromide emulsion (El!+-'l) Silver iodobromide emulsion (Em-2) Sensitizing dye (S-1) (RL) Sensitizing dye (S-2) Sensitizing dye (S-3) 0 .01 1.5 0.8 2.5X10-now (mol/mol silver) 2.5X10-4 (mol/mol silver) o, 5xio→ (mol/mol silver) 0.05 > 0.05 0.002 0.5 1.5 2.0 Cyan coupler (C-1) Cyan coupler (C-2> Cyan coupler (C-4) Colored cyan coupler (CC-1 DIR compound (D-1) High boiling point layer ts (○1f-1) Gelatin 4th layer; High sensitivity red-sensitive emulsion 11 (RH) Silver iodobromide emulsion (
E-13) Sensitizing dye (S-1) 2.0X10→ (mol/silver 1 mol) Sensitizing dye (S-2) 2. Ox 1O
-4 (mol/silver 1 mol) Sensitizing dye (S-3) 0.1x10→(
0.10 cyan coupler (C-4) 0.25 colored cyan coupler (CC-1) 0.015 DIR compound (D -2) 0.050.2 1.5 0.5 High boiling point solvent <0il-1) Gelatin 5th layer; Intermediate layer (1, L, -2) Gelatin 6th layer; Low-sensitivity green-sensitive emulsion layer (GL ) Silver iodobromide emulsion (Em-1) Sensitizing dye (S-4) 1.0 5×10→ (mol/silver 1 mol) Sensitizing color jl! 1 (S-5) 1x10
→〈mol/silver 1 mol) Magenta coupler (M-1) 0.5 colored magenta coupler (CM-1) DIR compound (D-3
) DIR compound (D-4) High boiling point solvent (Qil-2) Gelatin 7th layer; Intermediate layer ([, L, -3) Gelatin 8th layer: High-sensitivity green-sensitive emulsion layer (GH) 0.01 0. 02 0.020 0.3 1.0 0.8 Silver iodobromide emulsion (El-3) 1.3 Sensitizing dye (S-6) 1.5x10-rumor (mol/silver 1 mol) Sensitizing dye ( S-7) 2.5x10-4
(Mole/1 mole of silver) Sensitizing dye (S-8) 0.5x10-4
(Mole/1 mole of silver) Magenta coupler (M-2) 0.05 magenta coupler (M-3) 0.15 colored magenta coupler (CM-2) DIR compound (D-3) High boiling point solvent (0+l-3> Gelatin 9th layer; Yellow filter layer (YC) Yellow colloid silver stain inhibitor (SC-1) High boiling point solvent (Oil-3) Gelatin 10th layer; Low sensitivity blue-sensitive emulsion layer (BL) 0.05 0.01 0.5 1.0 0.1 0.1 0.8 Silver iodobromide emulsion (E--1) Silver iodobromide emulsion (Es-2) Sensitizing dye (S-10) Yellow coupler (Y-1 ) Yellow coupler (Y-2) DIR compound (D-2) High boiling point solvent (Oil-3) Gelatin No. 1111, high sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (El-4) Silver iodobromide emulsion (Em -1) Sensitizing dye (S-9) (BH) Sensitizing dye (S-10) Yellow coupler (Y-1) Yellow coupler (Y-2) High boiling point solvent (Oil-3) Gelatin 0.25 0. 25 X1O-4 (mol/silver 1 mol) 0.5 0.1 0.01 0.3 1.0 0.50 0.20 Mol) 0.30 0.05 0.15 1.1 121i; 1st Preservation II (PRO-1) Fine grain silver iodobromide emulsion 0.4 (average grain size 0.08
μ, Aa 12 mol%) Uv absorber (UV-1)
0.10Uv absorber (UV-2)
0.05 high boiling point solvent (Oil-1)
0.1 High boiling point solvent (Oil-4) 0
．． 1 formalin scavenger (MS-1) 0.5 formalin scavenger (H8-2>0.2 gelatin
1.0 13th layer; 2nd protection 11
1i (PRO-2) Surfactant (Su-1)
0.005 alkali soluble matting agent
0.05 (average particle size 2 μm) Polymethyl methacrylate 0.05 (average particle size 3 μm) Cyan dye (A I C-1) 0.00
5 Magenta dye (AIM-1) 0.01 Slip agent (WAX-1) 0.04 Gelatin 0.6 In addition to the above composition, each layer also contains coating aid 5u-2, dispersion aid 5u-3, and hardening agent. Membrane agent H-1 (40B10 gelatin), stabilizer 5tab-
1. Antifoggant AF-1 was added.

1-1 Average grain size: 0.46 μm, average silver iodide content: 7.0%.

Monodisperse surface low silver iodide emulsion 1-2 Average grain size: 0.30μ, average silver iodide content: 2.0%.

Monodisperse emulsion with uniform composition Em-3 Average grain size 0.81μ, average silver iodide content 7.0%.

Monodisperse surface-lowered silver-containing emulsion E■-4 Average grain size is 0.95μ, average silver iodide content is 8.0%.

S-9 S-10 M-3 M-2 I C-1 M-1 No.

UV-1 caHs(t) UV-2 CH2=CH6O2CH20CHISO2CH=C)!
2IC-1 AIM-1 AX-1 L11 ■ NaO,5-C-COOCH2 (CF, CI" 2),
IC-C00CH2 (CF, CF2)5Hu-2 NuO=S CC○OC,H,.

CH2COOCm)I　7 u-3 C,H.

(Preparation of Samples 1-2 to 1-9) In place of the yellow colloidal silver in the 9th layer, dyes shown in Table 1 were added to a high boiling point solvent (Oil-3), a color stain inhibitor (SC-
1> and the surfactant Alkanol
Multilayer color photographic elements 1-2 to 1-9 were prepared in the same manner as in Example 1-1.

Further, in Samples 1-1 to 1-9, the dye additives used were each set to 0.3 Q/f.

Comparative dyes 1 to (comparative dye-1) (comparative dye-2) in the prepared samples 1-2 to 1-4 Cz Hs Here! Yamabukuro □ NHSO, (CHl), CH.

Each of the samples 1-1 to 1-9 thus prepared was subjected to wedge exposure using white light, and then subjected to the following development treatment.

Processing step A (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Wash 3 minutes 15 seconds Fix
Wash with water for 6 minutes and 30 seconds
Stabilized for 3 minutes and 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75Q anhydrous sodium sulfite 4.250 hydroxylamine 1/2III11 acid salt 2.0g Anhydrous potassium carbonate 31.50 Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.59 Potassium hydroxide 1. Add OQ water and add 1
Set to 1.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt ioo, o g Nigelenediaminetetraacetic acid diammonium salt 10.00 Ammonium bromide 150.0 Q Glacial acetic acid
Add 10.0d water and 1i
and adjusted to pl-1-6,0 using ammonia water.

[Fixer ammonium cothiosulfate 175. OQ anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 12, and adjust to pl-1-6.0 using acetic acid.

[Stabilizer 1 Formalin (37% aqueous solution) 1.5d Konidax (Konica ■l1l) 7.5112
Add water and 1! shall be.

In addition, 4-amino-3-
Methyl-N-ethyl-N-(β-hydroxyethyl)-
A processing solution excluding aniline and sulfate is prepared, and color development is performed using this, followed by bleaching and bleaching in the same manner as processing step A.
Fixation and stabilization treatments were applied. (Referred to as processing step B) The influence of dyes on fogging was evaluated as follows.

(Shadow on fog 1) ΔDB2 - Difference between the minimum yellow density in processing step A and the minimum yellow S degree in processing step B of each sample (1-1 to 1-9) Also, evaluate the storage stability over time of the photosensitive material After forced storage at 55° C. and 80% relative humidity for 3 days, the above processing step A8 was carried out, and the decrease in sensitivity of the blue-sensitive emulsion layer was expressed as ΔSs and compared.

55°C 80% r 1. 686 after storage for 8.3 days = sensitivity of blue-sensitive emulsion layer, sensitivity of blue-sensitive emulsion layer before forced storage 100 (%) However, the sensitivity of the blue-sensitive emulsion layer (minimum Expressed as the reciprocal of the exposure level of 11 degrees in 10, 3).

The results obtained are not shown in Table 1.

Table 1 As shown in Table 1, the fog in the blue-sensitive layer of the sample of the present invention is improved compared to the case where yellow colloidal silver is used.

On the other hand, comparative dyes -1, -2 or =3 (samples 1-2 to 1-
In 4), a decrease in the sensitivity of the blue-sensitive layer due to storage is observed.

In contrast, it can be seen that the samples using the dye of the present invention have less influence on fog and have good storage stability.

Example 2 Sample 2-1 was prepared as a comparative sample of a multilayer color light-sensitive material by sequentially coating each layer having the following composition on a subbed triacetylcellulose film support from the support side.

The coating amount of each component is expressed as 0/f.

(Sample 2-1) No. 111 (Antihalation layer) Ultraviolet absorber (UV-1) 0.3 Ultraviolet absorber (UV-2) 0.4 High boiling point lj
A (Oil -1) 1.0 black colloidal silver 0.24 gelatin
2.0 Second layer (intermediate layer) 2.5-di-t-octylhydroquinone high boiling point solvent (
Oil-1>0.2 gelatin
10 Third layer; low sensitivity red-sensitive silver halide emulsion layer A(]Br1 (l I 4.0 mol%, average grain size 0) spectrally sensitized by red sensitizing dyes (S-2, S-11) .25μ)0.
5 Coupler (C-5) 0.1 mol High boiling point solvent (Oil-3) 0.6 Gelatin 1.3 4th layer; High sensitivity red-sensitive silver halide emulsion layer Red sensitizing dye (S-2,8- 1
1) spectrally sensitized by A(13r 1 (A(+1 2 mol%, average particle size 06 μ)) 0.8 coupler (C-5) 0.2 mol High boiling point solvent (Oil-3) 1.2 gelatin
18 5th layer (intermediate layer) 2.5-di-t-octylhydroquinone 0.1 High boiling point solvent (Oil-4) 0.2 Gelatin 0.9 6th layer (low sensitivity green-sensitive silver halide emulsion layer) AQ 3r r (Ao 1 4 mol%, average particle size 0.25μ) coupler spectrally sensitized with green sensitizing dyes (S-12 and S-13)
(M-4>0.04 molar coupler (M
-5) 0.01 mol high boiling point solution 11! (
○1f-1) 0.5 gelatin
1.4 7th layer (high sensitivity green-sensitive silver halide emulsion layer) green sensitizing dye (S-12, S-13)
A(I Br 1 (Ao I 2 mol %, average particle size 0.6 μ) spectrally sensitized by A(I Br 1 (Ao I 2 mol %, average particle size 0.6 μ) 0.9 coupler (M-4 > 0.10 mol coupler (M-5 > 0.02 mol high boiling solvent) (Oil-1) 1.0 gelatin
1.5 8th layer (middle@) 9th layer same as 5th layer (yellow filter layer) Yellow colloidal silver 0.1 Gelatin 0.92.5-G-t-
Octylhydroquinone 0.1 High boiling point solvent (Oif -4>0.2 101t (Low sensitivity blue sensitive silver halide emulsion layer) Aa Br spectrally sensitized by blue sensitizing dye (S -14)
I (Afll 1 4 mol%, average particle size 0.35μ) 0.
6 Kabra (Y-2) 0.3 mol High boiling point solvent (Oil-1') 0.6 Gelatin 1.3 No. 111i1
(High sensitivity blue-sensitive silver halide emulsion 1m) Blue sensitizing dye (
A (13r 1 (AgI 2-E %, average particle size 0.9μ) 0.
9 Coupler (Y-2) 0.5 mol High boiling point solvent (○1t-1) 1.4 Gelatin 2,1 12th layer; 1st protective layer Ultraviolet absorber (UV-1) 0.3 Ultraviolet absorber ( UV-2) 0.4 high boiling point solvent (
Off -1) 0.6 gelatin
1.22.5-di-t-octylhydroquinone 0.1 Thirteenth layer: second protective layer average grain size (r) 0.08μ■, non-photosensitive layer made of silver iodobromide containing 1 mol% of silver iodide Silver halide emulsion with fine grains 0.8 polymethyl methacrylate particles (diameter 1.5 μm+) Surfactant (Su-1
> Gelatin 0.7 In addition to the above composition, a gelatin hardening agent (H-1) and a surfactant were added to each layer.

Sensitizing dye 5-11 Sensitizing dye 5-12 Sensitizing dye S-13 Sensitizing dye 5-14 Coupler C-5 Coupler M-4 C! Coupler M-5 (Produced by Samples 2-2 to 2-9) Next, in place of the yellow colloidal silver in the 9th layer, dyes shown in Table 2 were added to the high-boiling pre-layer! l! Multilayer color photographic elements 22 to 2-9 were prepared in the same manner as Sample 2-1 except that Sample 1 (Oil-4) and 2°5-dioctylhydroquinone were dissolved in ethyl acetate and dispersed and coated with gelatin.

Further, in Samples 2-1 to 2-9, the additive base of the dye used was each 0.3 g/f.

The samples 2-1 to 2-9 thus obtained were exposed to white light using a wedge, and then subjected to the following development treatment.@ Processing process Processing time Processing temperature First development 6 minutes 38°C Washing with water 2 minutes 38 ℃ anti
2 minutes 38℃ color development 6 minutes 38℃ adjustment 2 minutes 38℃ bleaching
White 6 minutes 38℃
fixed if 4 minutes 3
Wash with water at 8℃ 4 minutes 38℃
Stable 1 minute Dry at room temperature
The composition of the treatment liquid used in the drying step is as follows.

! 1. Sodium tetrapolyphosphate 2 g Sodium sulfite 20 g Hydroquinone
Monosulfonate 30 (] Sodium carbonate (monohydrate) 30 Ql-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone
20 Potassium Bromide 2.5
g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) Add 2 ounces of water and add trilotrimethylenephosphonic acid 6-sodium salt 3 g 1st chloride
Tin (dihydrate) 1g p-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid
15. Q Add water
1000tR color developer Sodium tetrapolyphosphate 3g Sodium sulfite 7q Sodium 3F14 acid (dihydrate) 36g Potassium bromide
1g potassium iodide (0.1% solution 812) 901
g Sodium hydroxide 8 g Citrazic acid 1.5 g N-ethyl-
N-β-Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 11 g2. Add 2-ethylenedithiogetanol 1 g water
1000mR1 Toyo1 Sodium sulfite 12 Q Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4d Glacial acetic acid
Add 31i2 water
1000 Dai bleaching solution Sodium ethylenediaminetetraacetate (dihydrate) 2Q Ammonium iron(III) ethylenediaminetetraacetate (dihydrate)
Add 120 fil ammonium bromide 100g water
10001Qti Ammonium thiosulfate ao g Sodium sulfite 50 Sodium bisulfite 5g Add water
1oooI+21 Presentation 1 Formalin (37% by weight) 51g Konidax (manufactured by Konica Corporation) Add 5mN water and 10001L2 Each developed sample was exposed to blue light to obtain the maximum density (D-aX) and minimum density (Dg*in). Established.

Further, each sample was stored at 55° C. and 80% relative humidity for 4 days and then exposed and processed as described above, and the decrease in sensitivity of the blue-sensitive emulsion layer was expressed as ΔS8 and compared.

Sensitivity of the blue-sensitive emulsion layer of 688- after storage at 55°C, 80% R, H for 4 days xloo (%) Sensitivity of the blue-sensitive emulsion layer before forced storage It is expressed as the reciprocal of the exposure amount.

Table 2 As shown in Table 2, the sample of the present invention has a higher maximum concentration than when using yellow colloidal silver. In addition, samples using comparative dyes had large minimum densities and showed a decrease in the sensitivity of the blue-sensitive layer during storage, whereas samples using compounds of the present invention had small minimum densities and could not maintain sufficient maximum densities. It also had good storage stability.

Example 3 [Preparation of 11 g of silver halide emulsion (E+a-A)] The amounts of additives used in the preparation of emulsion 14 below are per mole of silver halide unless otherwise specified.

A solution containing a silver nitrate solution, potassium bromide, and sodium chloride was added to an inert gelatin aqueous solution using a double jet method.
H6,0Sl)l 6.0 and a temperature of 50° C.17) A were added while maintaining the conditions for producing a silver halide emulsion.

Next, desalting and washing with water were performed by a conventional method to prepare a silver chlorobromide emulsion El-A.

The grain characteristics of emulsion El-A are that the average grain size is 0.47μ11 [3
The r content was 60 mol%, the coefficient of variation was 0.09, and the shape was cubic.

Using the above emulsion, sensitize to red sensitivity as shown below,
Multilayer silver halide photographic material samples 3-1 to 3-7 were prepared and subjected to the following treatments, and the safelight properties of each were evaluated as shown below.

Multilayer silver halide photographic material sample 3-1 was prepared by sequentially coating the following seven layers on polyethylene resin-coated paper. Note that the amounts of additives shown below are per 1f unless otherwise specified.

Layer 1: 1.2 g of gelatin, 0.35 (1 (metallic silver equivalent, same hereinafter)) blue-sensitive silver chlorobromide emulsion (average grain size 0.
8 μm, silver bromide content 90 mol%) and 0.9 g of yellow coupler YC-1 and 2,5-di-t of 00150.
-Octylhydroquinone (hereinafter referred to as rHQ-IJ)
A layer containing dioctyl phthalate (hereinafter referred to as rDOPJ) in which dioctyl phthalate is dissolved.

112...0.7 (] of gelatin and 0.06Q of H
A cabinet containing DOP in which Q-1 was dissolved.

Layer 3: 1.250 gelatin, 0.350 green-sensitive silver chlorobromide emulsion (average grain size 0.45 μI, silver bromide content 7)
0 mol %) and 0.53 g of magenta coupler MC-3
and 0.12g of [A-1] and 0.2g of [A-21 and 0
．． A layer containing DOP in which HQ-1 of 015o is dissolved.

14...1.3Q gelatin and O, ogg HQ-
Contains DOP in which UV absorber (UV-1) of 1 and 0.50 is dissolved! li,.

Gelatin of I5...1.4 (), 0.3 g of red-sensitive silver chlorobromide emulsion (Em-A, sensitized appropriately at 57°C using sodium thiosulfate and chloroauric acid, Sensitive dye (S-1
) and 0.3 g of cyan coupler C
C-1 and 0.2g of CC-2 and 0.02i) of HQ-1
A layer containing DOP dissolved in

Layer 6...1. OQ gelatin and 0.032 (l H
Dissolve Q-1 and uv-i of 0.2a, 0.14g
(7) A layer containing DOP.

Layer 7... Silicon dioxide 0.003 (l and gelatin 0
．． A layer containing 5g.

As a hardening agent, [H-”l] was added at 51 (1
, [H-2] was added in an amount of 10 mq per 1 g of gelatin.

Furthermore, samples 3-2 to 3-7 were prepared in the same manner except that 71 g of the dye shown in Table 3 was added to layer 6 in the preparation of sample 3-1.
was created.

(A-1) (CC-2) (A-2) (MC-3) C! (YC-1) I (UV-13 (H-1) (H-2) (SS) (S-1) The following evaluations were performed on the obtained samples.

(1) Evaluation of Safelight Properties Safelight properties were determined by exposing to light through an interference filter with a center wavelength of 590+v, processing according to the processing steps shown below, and measuring the sensitivity of the red-sensitive layer.

Safelight evaluation C,H.

C2H.

[Color development process] [1 color development 38°C [2 color development 33°C] [3] Water washing 25-30°C [41 Drying 75-80°C [Processing solution composition] (Color developer) Benzyl alcohol ethylene glycol Potassium sulfite Potassium bromide Sodium chloride 3 minutes 30 seconds 1 minute 30 seconds 3 minutes Approximately 2 minutes 151β 51g 2, Og 1.3 g o, 2g Potassium carbonate 30. OQ hydroxylamine sulfate 3.0g polyphosphoric acid (
TPPS) 2.5Q3-methyl-4-
Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5
0 Fluorescent brightener (4,4'-diaminostilbensulfone derivative) 1.0! ;Potassium monohydroxide 2. Add OQ water to bring the total volume to 12, and adjust to 1) H-10,20.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetate dihydrate 60Ω ethylenediaminetetraacetic acid II 3a Ammonium thiosulfate (70% aqueous solution) 100d Ammonium sulfite (40% aqueous solution) 27.5d Potassium carbonate or glacial acetic acid 1) H=7 Adjust to .1 and add water to bring the total volume to 1.
Let it be i.

Table-3 *1 Comparative dye-1 Kyo2 Comparative dye-2 As shown in Table-3 above, the water-soluble dye of the comparative example shows a color sensitizing effect, but the compound of the present invention has no effect on the photographic emulsion layer. It can be seen that the safe light property has been improved.

[Effects of the Invention] As explained in detail above, by containing the oil-soluble compound of the present invention as a dispersion, there is less fog, the stability in the shed during storage is improved, and the halogen-free compound has no adverse effect on photographic properties. A silver oxide photographic material is provided.

Claims (1)

[Claims] A halogenated support comprising at least one photographic constituent layer containing a dispersion of at least one oil-soluble compound represented by the following general formula [I] on a support. Silver photosensitive material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 to R_4 each represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, or a heterocyclic group. X_1 and X_2 each represent an oxygen atom or a sulfur atom. L_1, L_2 and L_3 are each
It represents a methine group, and n represents a positive integer of 0, 1 or 2. M represents a hydrogen atom or a monovalent metal atom. ]