JPH049042A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material contg. water-soluble dyes which lessen staining after photographic development processing by incorporating specific compds. into this material. CONSTITUTION:At least one kind of the compds. expressed by formula I and/or formula II are incorporated into this photosensitive material. In the formulas I, II, R<1>, R<2> denote a hydrogen atom, alkyl group, etc.; R<3> to R<6> denote a hydrogen atom; aryl group, etc.; R<7>, R<8> denote a hydrogen atom, alkyl group, etc.; L1 to L5 denote a methine chain; n1 denotes 0, 1; n2 denotes 0 to 2. The easy decoloration and/or flow-out is attained in the photographic development processing in this way and the staining after the processing is lessened.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to silver halide photographic materials containing dyes, and in particular, dyes useful as light-absorbing dyes (hydrophilic cob+-i (containing a layer) colored by dyes (5). This invention relates to silver halide photographic light-sensitive materials. It absorbs light,
It is well known that dyes are contained in the photosensitive layer (silver halide), and the hydrophilic n1-1 layer can be colored with these dyes. There is. The filter layer is usually located in the -1-4 layers of the photosensitive emulsion layers or between the emulsion layers, and has the role of converting the incident light that reaches the emulsion layer into light having a preferable spectral composition. In addition, for the purpose of improving the sharpness of photographic images, anti-halation +
1-layer is provided, and the interface between the emulsion layer and the support and the support 1.5-layer are provided.
A in body sound 11ij etc.] Absorbs harmful reflected light 1! -This,
Ha l/～su/,! It is often done to color the emulsion layer to absorb harmful reflected light and scattered light caused by silver halide grains, etc. There is. This)
1. Having good absorption spectrum characteristics in accordance with 1.
During photo development processing 6. - Completely bleached and easily eluted from silver halide (true exposure + A11), remaining color due to dyes after development processing; No staining, no negative effects such as fogging and desensitization on photographic emulsions. (a) Materials in solution: (c) "I') Must meet various conditions such as excellent stability over time in silver oxide photographic materials and no discoloration or fading.C) RejJJ [?, no. By now 1-1, the dye (go: 1
Many efforts have been made and a large number of dyes have been proposed.For example, U.S. Pat.
4L! Oxonol dyes described in Japanese Patent Publication No. 27, Japanese Patent Publication No. 1983-22nfiQ, and Japanese Patent Publication No. 55-1 (]0059), U.S. Patent No. 3,540.l'187
No. 3,344,325, U.S. Special Proclamation '1 No. 3.356.2] No. 4! II=:, Special Publication Show 31-1. Publication No. l'1578, Special It>1972
3623! ; Nolidene dye described in J Publication;
U.S. Pat. No. 2,439,747, U.S. Pat. ．． 845.
404■ Specifications such as sudyryl dyes are known. Please J7. The general method for these dyes is to dissolve them in water or an organic solvent that is miscible with water and add them to the five-layer constituent layer, but this method causes a decrease in sensitivity, gradation fluctuations, and fogging abnormalities. More or less undesirable phenomena will appear, and it will become more
There is a need to improve the layer. [Object 1-1 of the invention] The third object of the present invention is to also have good spectral absorption properties (te) and to be photographically inert in photographic light-sensitive materials and to be photographically developable. It is an object of the present invention to provide a silver halide photographic light-sensitive material containing a water-soluble dye that easily decolorizes and/or flows out during processing and causes very little contamination after processing. The above has been achieved by providing a silver halide photographic light-sensitive material characterized by containing at least one of the compounds represented by Form III and/or Form III. -Noshiro [I] [wherein rs', R2+i, hydrogen atom, al-tolu group, aryl 21., alkenyl group, cycloalkyl group,
Hete represents a L1 ring group. R1~I? '= represents a hydrogen atom, an ar-1-l group, an allyl group, an ar-5-nyl group, a cycloalkyl l1. Terocyclic group, -C00I-7-1-COR', -CONR7R',
-NR7fl', 5O71n', -So+n7, -SO
□Old? 711”, --11R'COl?'fJR'5O
zR8, -OR', ;u+, ho group, 2l:r1 group, halogen atom, cyano group. R' and R' do not represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heptad ring group. In addition, R'' and R5, R' and R6 each form a 19■ mouth (♂), and 2 and 1. represents n,
is 0. Imato: does not represent 2. 1-・Noshiro 1111 % expression % - Expresses the same meaning as Noshiro [I]. The present invention will be explained in further detail below. -・Noshiro [+] and −・Noshiro [I14 here, R~
・As the ar-1-l group represented by R', for example, methyl group, ethyl group, n-propyl group, 1SO-butyl group, etc.

[”
Building lX + building block, n -ζ methyl group, n
-HexyJ, 5, n-octyl, 1, n-conityl, 4-syl%, n-F; etc. The substituent groups for groups such as
1, li1 heptad substituent and 1. For example, halogen source P (
For example, C; l, each atom such as chlorine, bromine, 31 atoms, fluorine, etc.), aryl group (for example), x, -l group, -naphthyl group, etc.), ring (e.g., pyrrolidyl group, pyridyl w, etc.), sulfo group, sulfinic acid group, carbo 1
-nru group, di)1-1 group, hydroxyl group, mercapto group, amino W (e.g., 7mino group, diethylamino group, etc.), al-1-l:! -l-・'no group (e.g., methyloxine group, ethyloxy group, n-butyloxo group, n-ictyloxy group, isopropyloxy group, etc.), aryloxy group ()J, nyloxy group, naphthyloxy group groups), carbamoyl W, (e.g. aminocarbonyl groups,
Methylcarbamoyl n-pentylcarba 1,000-f J9,
fercarbamoylhenzaamyl group, n-ocdylamito group, etc.), sulfamoyl group (e.g., C,l sulfamoyl group, methylsulfan n-phdelsulfamyl group, etc.), sulfonamide group (e.g., methanesulfonamide 1 group, n-heptanesulfone group, etc.) Amino 1 group, -, Zensulfonami 11-J Chijiri.Sumo-゛1';-ru!Aj (IPU dogpomethylsulfinyl group 1o, 1,000 methylsulfinyl group, etc.;)- Arylcarbonyl groups such as rusulph, inyl group, fluorocarbonyl group, -!shi group, etc.), alkylcarbonyl group (e.g., methyloxycarbonyl group, hydroxyl group, etc.), '/carbonyl group, 2-hydethyloxycarbonyl group, TI
, R group, etc.), aryl-1-dicarbonyl group (e.g. phenyl-(゛xyloxycarbonyl)1-,!n, naphthyloxycarbonyl group, etc.), aryl-l-thio J,u (e.g. methyl 1,000, (-o group, n-person, xylthio method, etc.), ryolthio group (for example) di-nylthio group,
naphthylthio group, etc.), alkylcarbonyl group (e.g. acetyl group, ethylcarbonyl group, n-butylcarbonyl group, 0-octyl sulfonyl group, etc.), arylcarbonyl group (e.g. -ndzyl group, P meta) 'Sulbonamide ＼nzoyl group, p-carboxyhenduyl group, naphthoyl group, etc.), Soano 7 milk, +:y L1 radical group (e.g. methylureido group, phenyluredo group 1 group, etc.), 1,000
Examples include ureido groups (eg, methylthiourete group, phenylthioureido group, etc.). The aryl group represented by R'-R11 is 1.;1,
Examples include soenyl group and naphthyl group. These groups include those having substituents, and the substituents include:
Examples include the alkyl groups represented by R1 to R11, or the groups mentioned above as substituents for the alkyl groups represented by R1 and R11. The cycloalkyl group represented by R1-R8 is,
Schifjil propyl viscous, Socrobentyl group, Cyclo-,
Examples include xyl group. These groups include those having a substituent, and examples of the substituent include εJ, the alkyl group represented by R'-R', and the groups listed in 7 as the substituent of the alkyl group. Examples of the alkenyl group represented by R' to R11 include a vinyl group, an alkenyl group, a 1-propenylbutadienyl group, and a 2-pentenyl group. These groups include those having IJ substituents, and the 'I4' substituents include those listed above as substituents for the alkyl groups represented by R' to RIl. The heterocyclic group 2 represented by R1-R8 is, for example, a pyridyl group (2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 5-sulfo-2-pyridyl group, 5-carboxy-2-pyridyl group). , 3,5 dik1 colo-2-pyridyl group, 416-dimethyl2-=pyridyl group, 6-hy1
0x-2-pyridyl group, 2,3,5.6-titrafluoro-4-pyridyl group, 3-=draw-2-pyridyl group, etc.), ``gisazolyl group (5-sulfo-2-henzokyridyl group, 2 benzoxazolyl group, 2-oxazolyl group, etc.), thiazolyl group (5-sulfo-2-benzthiazolyl group, 2-benzthiazolyl group, 2-thiazolyl group, etc.), imidazolyl group (1-methyl-2imidazulyl group, l -methyl-5-sulfo-2benzimidazolyl group, etc.), furyl group (3-furyl group, etc.), pyrrolyl group (3-
bisylyl group, etc.), thienyl group (2-thienyl group, etc.),
Pyrazinyl group (2-pyrazinyl group, etc.), pyrimidinyl group (2-pyrimidinyl group, 4-chloro-2-pyrimidinyl group, etc.), pyridanyl group (2-pyridazinyl group, etc.), purinyl group (8-purinyl group, etc.), isoxazolyl group (3 −
iso1ki4Jzolyl (etc.), selenazuryl group (5-sul'p212lenaduryl w, etc.), sulporanil, )i
T! (3 sulforanyl group, etc.), piperidinyl, 44 (I
methyl-3-piperidinyl group, etc.), vinzolyl group (
3-vinzolyl, etc.), te-1-razolyl (1-methyl
5 Te1raduryl group, etc.). These groups include those having a substituent, and examples of the substituent include the alkyl groups represented by C11, R1 to R11 above, and the groups listed as substituents for the alkyl group. Examples of the halogen atom represented by R1-R1' include chlorine, bromine, and sosodine atoms. A ring can be formed by R1R', r<'LHR', examples of these rings include Hensen's ring, -nophthyl ring, birituru ring, -y-enyl ring, etc. I can get it. These rings may further have a substitution W. As the substituent, R of (:l, -Noshiro El] and [Il]
Alkyl group represented by '-R8 and position 1 of the alkyl group
Listed as m Jl. Examples of the water-soluble group possessed by Noshiro [+] and/or [I] include sulfo group, carboxyl group, sulfinyl group, hydroxyl group, sulfonyl group, bosphinyl group,
Examples include runonitoside 4 and the like, with sulfo groups and carboxyl groups being preferred. Specific compounds of the present invention are listed below, but the present invention is not limited thereto. Hi H3 (JI3 03Na SO, Na CHzCIIzSOaK (lI2cH2sOJ CIIzCI12SO3Na CHzCIIzSOJa CI. 0°C Cl1zCII, 5OJa CH2CH2SO3Na The skeleton of the dye compound of the present invention is various. For example, Large Organic Chemistry Volume 14 Heterocyclic Compounds 1 p,
444-490 (1st grade, 1 no: 1, supervised by Yu Asakura Shoten) and the methods described in its references. Specific synthesis examples of dye compounds are shown below, but other dye compounds of the present invention can be similarly synthesized easily. (Synthesis Example I) Synthesis of Compound Example No. 47 C1l. 5.3 g of compound (1), 2.8 g of compound (2), and 3 g of trimedelamine were added dropwise at the temperature of dimethylformamide. After stirring at room temperature for 7 hours, the rough adjustment was made.
5 (1 mp, 1.00 mn of ethanol and potassium oxalate A J g to t (t) of cold liquid C ~ The reaction solution was slowly added and salted out. The crude crystals obtained by filtration were dried. It was dissolved in 35 ml of water and then added to a previously prepared solution consisting of 20 Or+1 methanol, 50 ml of ethanol, and 5 g of 111 IM potassium to perform salting out.This purification procedure was repeated every three times. The parent peak of the product was identified as r+1 and 7 in the mass spectrum. Yield: 13.1 g, yield 52% (Synthesis Example 2) Synthesis of Compound No. I [':l+,. To a solution consisting of 5.5 g of compound (3), 2.6 g of compound (41), and dimethylpolyamyl (!) was added dropwise trimethylamine rl g at room temperature. After stirring at room temperature for 5 hours, The reaction solution was slowly added to a pre-adjusted solution consisting of 200 mff of methanol, 200 mff of ethanol, and 3 g of potassium acetate, and salting out was carried out. ml, then 200 ml of pre-prepared methanol, 200 ml of ethanol,
and 3 g of potassium acetate, and salting out was carried out. By repeating this purification operation three times, the target compound was obtained. The product is 7 and the parent peak is confirmed by mass spectrometry. Yield: 12.8g Yield: 48% (Synthesis Example 3) Synthesis of compound N033 SO, Na SO3Na SO3Na compound (5
) 5.5 g, compound (4) 2.6. and dimethylporumami F' 60 m 1. Add 3 g of trimethylamine dropwise to the solution consisting of at room temperature. 6 at 40-50°C
After stirring for an hour, add 200 mL of methanol, 200 mL of ethanol, and 200 mL of ethanol, which had been adjusted to approximately U5. The reaction solution was slowly added to a solution containing 2 g of potassium acetate and 3 g of potassium acetate, and salt IF was performed. Crude ♀1 obtained by filtration
! Dissolve one item in 50 mff of dry water, then add 200 m of methanol (2
was added to a solution consisting of 300 mj2 of ethanol and 3 g of potassium acetate to perform salting out. By repeating this purification operation three times, a "uniform compound" was obtained.
4% In the photographic material of the present invention, oxonol dyeing represented by gijki-・Noshiro [I] and [rl]
When it is contained in a silver genide photographic emulsion, it can be used as an ionization prevention dye, and when it is contained in a non-photosensitive hydrophilic layer, it can be used as a filter dye. Alternatively, 1. It can also be used as an antihalation dye.Also, depending on the usage (2), it may be used in combination with the 2-1 dyes, or it may be used in combination with other dyes. In order to incorporate the dye according to Invention 111 into a silver halide photographic light-sensitive emulsion layer or other hydrophilic colloid layer (11), it can be easily carried out by a conventional method. The organic and inorganic alkali salts of Dye 1'1 are dissolved in water to make an aqueous dye solution with a concentration of y1, which is added to the coating liquid and coated by a known method to contain the dye in the photographic material. The content of these dyes varies depending on the purpose of use, but in general, the content of these dyes is 1 per nr area of the photosensitive material.
It is applied and used in an amount of ~800 mg. Supports for the photographic material of the present invention include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyolefin films such as polyethylene, polystyrene films, polyamide films, polycarbonate films, Halique paper, polyolefin-coated paper, Examples include polypropylene synthetic paper, glass plate metal, and the like, and these supports are appropriately selected depending on the intended use of the photographic material. Hydrophilic colloids in the photographic material of the present invention include gelatin, derivative gelatin such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein, and alginic acid, and synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone. , cellulose derivatives such as carboxymethyl cellulose, etc., and these can be used alone or in combination. The silver halide emulsion in the photographic material of the present invention includes:
Any compounds commonly used in silver halide photographic emulsions are included, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. The silver halide emulsion used in the photographic material of the present invention is
Various manufacturing methods including the conventional manufacturing method, such as the method described in Japanese Patent Publication No. 46-7772, or the method described in U.S. Pat. No. 2,592,250, i.e., the solubility A so-called conversion emulsion is formed by forming an emulsion of silver salt grains that are larger than silver oxide and consisting of at least some silver salts, and then converting at least a part of these grains into silver bromide salts or silver iodobromide salts. Alternatively, it can be produced by a production method such as a production method of a Lippmann emulsion made of finely divided silver halide having an average grain size of 0.1 μm or less. This silver halide emulsion may contain chemical sensitizers such as sulfur sensitizers such as thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyane 1, cystine, and active or inactive selenium sensitizers. , gold compounds such as potassium chloroaurate, oryctotrichloride, potassium aurinthiocyanate-1,2-aurothiahenzthiazole methyl chloride, etc., palladium such as ammonium chlorocoparatate, sodium chloropalatite, etc. The compound can be sensitized using noble metal sensitizers such as platinum compounds, ruthenium compounds, rhodium compounds, iridium compounds, etc., such as potassium chlorooleate, or combinations of such sensitizers. In addition to chemical sensitization, this emulsion can also be reduced sensitized with a reducing agent, such as triadurs, imidazoles, azaindenes, Hen's thiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof. It can also be stabilized with thioethers,
A sensitizing compound of the quaternary ammonium salt type or polyalkylene oxide type may be contained. The photographic emulsion used in the photographic material of the present invention may be spectrally sensitized with a sensitizing dye, if necessary. Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merostyryl dyes,
Various sensitizing dyes such as Nutrep-1-cyanine can be used, and one or more sensitizing dyes can be used in combination. In the photographic material of the present invention, in the photographic emulsion layer and other hydrophilic colloid layers, glycerin, a dihydroxyalkane such as 15-bentanediol, an ester in the ethylene bisglycol layer, bis-ethoxydiethylene glycol succinate, obtained by emulsion polymerization, It can contain a wetting agent such as a water-dispersible particulate polymer compound, a plasticizer, a film property improver, etc. In addition, an aldehyde compound, an N-notyrol compound such as N,N'-dimethylol urea, a mucohalogen acids, divinyl sulfones, active halogen compounds such as 24-dichloro-6-hydroxy-5-triazine, dioxane derivatives,
Hardening agents such as isocyanin-1, carbonimide 1, ribonin, polyalkylene glycol 1, polyalkylene glycol ether alkyl sulfonate, alkyl, zenesulfonate, al-1 diphthalate, etc. Contains surfactants such as sulfonate salts, as well as photographic additives such as optical brighteners, antistatic agents, anti-soothing agents, ultraviolet absorbers, and stabilizers. - can. In the photographic material of the present invention, a color coupler may be included in the photographic emulsion layer, and the coupler may be either a 4-equivalent or a 2-equivalent coupler, such as a color 1 coupler for mass 4-equivalent or 13 (a cup that releases a development inhibitor:
;−'゛ζ may be present. As a yellow forming coupler,
Open-chain getmethylene compounds such as acylacetate 1-amide, magenta-forming couplers and L7, pyrazurone compounds, cyan-forming couplers 1-L. In this case, phenolic or naphyl-based compounds are usually preferred.
There are 1. [Examples] Next, the present invention will be explained by examples, but the present invention is not limited by these examples. Example 1 Add 3.5 g of gelatin to distilled water 35 rn Q, dissolve it, knead, add 5 mff of an aqueous solution containing 2. Dubonin water) mixture]. 2 5 mi!
and 1% formalin aqueous solution 0. 7 5 m 1. After that, water was added to make the total amount 50 mff. This dye t1 aqueous solution was applied onto an acetyl cellulose support and dried to prepare samples 1 to 78, respectively, and treated with a model fatigue solution in which the following dyes were accumulated. Each sample was prepared using sodium hydroxide (pl + -
1 0. 4) for 30 seconds under stirring at 30'C, washed with water for 15 seconds in a water bath containing a dye at a concentration of (11 molar extinction coefficient), and dried. The visible spectrum of each sample was measured before and after immersion, and the elution rate was determined from the absorbance at the maximum absorption wavelength, which is shown in Table 16. G E,44, Hydroxide Sui・Liu J, is the absorbance before immersion in an aqueous solution, and E2 is the absorbance after immersion. In addition, the sample was immersed in a developer having the following composition for 30 seconds at 30°C (11 molar extinction coefficient) containing a molar concentration of dye.
After washing with water for 15 seconds in a water tank, it was dried. The visible spectrum of each sample was measured before and after immersion in the developer, and the decolorization rate was determined from the absorbance at the maximum absorption wavelength. The results are shown in Table 1. 1 go, 1 e. is the absorbance before immersion in the developer, and E4 is the absorbance after immersion in the developer. (Composition of developer) Metol 3. Og trisulfite, (anhydrous) 4 5. 0 g
Carbonic acid 1 liter (monohydrate) 8 0. 0
g Potassium bromide 2.0g
Add 1 g of dye (molecular weight) x (101 molar extinction coefficient) g water and make 1p. shall be. In addition, comparative dyeing t・1 is as follows. Comparative Dye A Comparative Dye B Comparative Dye C Comparative Dye Comparative Dye E Comparative Dye F Comparative Dye G As is clear from Table 1, the sample of the present invention showed extremely high values for both the elution rate and the dehydration rate, and The exemplified dyes are easily eluted from the gelatin layer and exhibit superior decolorizing properties compared to comparative dyes. Example 2 Color photosensitive materials for printing were prepared as described in (1) below, and after these samples were imagewise exposed, they were processed using the following color developer and bleach-fix solution to form each dye image. We measured the performance related to (1) Preparation of sample A paper support whose surface was coated with polyethylene containing anacouse-type titanium oxide as a white pigment was pretreated with gelatin subbing, and then the following layers were sequentially coated to prepare a sample. . Layer 1: Blue-sensitive silver chlorobromide emulsion layer Silver chlorobromide emulsion containing 5 mol % of silver chloride, and the following yellow coupler (Y-1) and 2.5 g Ler
Coating was carried out using an emulsified dispersion prepared by melting t-octylhydroquinone and dioctyl phthalate. Layer 2: First intermediate layer was coated using an emulsified dispersion prepared by dissolving tert-octylhydroquinone in dioctyl phthalate. Third layer: Green-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 15 mol% of silver chloride, and the following magenta coupler (M-1) and 2.5-di-te
rt-ocdylhydroquinone to dioctyl phthalate-1
An emulsified dispersion prepared by melting the liquid and an aqueous dye solution shown in Table 3 below were added and coated. Layer 4: Second intermediate layer Ultraviolet absorber (UV-1) and 2,5-diter
An emulsified dispersion prepared by dissolving L-octylhyquinone in dioctyl phthalate and an aqueous dye solution shown in Table 3 were added for coating. Layer 5: Red-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 25 mol% of silver chloride, and the following cyan coupler (C-1) and 2,5 ter
Coating was performed using an emulsified dispersion prepared by dissolving t-octylhydroquinone in dioctyl phthalate. N6: A protective layer mainly containing gelatin and a hardening agent was applied. (Y-1) rρ (UV-1) Amount of each component in the sample (mg amount per 100c+i)
are shown in Table 2. (M-1) rρ Based on the layer structure C, 2, the dyes in the green-sensitive silver chlorobromide emulsion layer and layer 4 (intermediate layer) were changed. The samples shown in Table 4 were prepared by changing the dyes in the red-sensitive silver chlorobromide emulsion layer and the layer 71 (intermediate layer). 1
It was 1. ■Process 1'1 of the fogged unexposed samples using the treated lens frame shown below, and measure the magenta and cyan densities of the resulting samples using a Densitonork type Turf D-, -1, 22. went. ■Residual color contamination In order to investigate the degree of color contamination due to residual color of the dye after development processing in sample Q, N-ethyl-N-β methanesulfonamide in the color developing solution used in the processing step in 1
A solution was prepared without using ethyl-j(-methyl-4-aminoaniline sulfate) and the same test as in (■) was conducted.The results are shown in Table 3.
and shown in Table 4. Processing step (38°C) 17 Color development 2 minutes 30 seconds Bleach-fixing 1 minute Water Washing 1 minute Drying 60-80°C The composition of each processing solution is as follows. [Color developer] 1 ton 1 ton Zyl alcohol 1 Liconitanolamine sulfate II] Quizinoamine potassium bromide chloride Tosu J Potassium sulfite 2 minutes 800 mE 15 m! 1,0 g 2.0g 1.5g 1,0t: 2.0g N-ethyl-N-β-methanesulfonamide 4-aminoaniline sulfate 4.5g 1,1 Diposponic acid ((i0% aqueous solution) Potassium carbonate J7, WhiLex BB (50% water?1112 children 1
( ) (Fluorescent brightener, manufactured by Sumitomo Chemical) ], 5 ml 2 g d Add pure water to make IC 20% potassium hydroxide J, or 10
Adjust the pH to 0.1 with % dilute sulfuric acid. (Bleach-fix solution) Pure water 600 ml Iron(III) ethylenediaminetetraacetate Ammonia 11 5 g Ethylenecyaminetetraacetic acid 2 Sodium salt Ammonium thiosulfate Bisulfite I/Ryu 1, Sourium metabisulfite Lithium ethylenediaminetetraacetic acid Sodium thorium bromide color developing solution Adjust to 1 by adding pure water. Each number of dyes is 1
It shows the coating it (mg) per 0.00 cm. The desired whiteness for a color photosensitive material for printing requires a fog of 0.005 or less, and the samples of the present invention satisfy this requirement. Table-3 and Table-
It is clear from 4. Furthermore, color contamination due to residual color of the dye, which is observed in samples containing calibration dyes, is hardly observed in the samples of the present invention. It has been found that the dye according to the present invention has very little adverse effect on the emulsion. Example 3 Undercoating was done! - Sample 170 was prepared as a comparative sample of a multilayer color light-sensitive material by sequentially coating each layer having the following composition on a cellulose cellulose film support from the support side. The coating amount of each component is expressed in g/m''. 1st layer (antihalation layer) Ultraviolet absorber U-10,3 Ultraviolet absorber U-20,4 High boiling point solvent 0-1 1.0 black colloid' silver 0.24 Gelatin 2.0 2nd layer (intermediate layer) 2.5-di-octylhydroquinone 0.1 High boiling point solvent 0-1 0.2 Geladin
1.0 Third layer: low sensitivity red-sensitive silver halide emulsion layer red sensitizing dye (S-1, 5-2)
AgBr1 (Ig+ 4.
0 mol%, average grain size 0.25μ) 0.5 Coupler C-10, 1 mol High boiling point solvent 0-2 0.6 Gelatin 1.3 4th layer: High sensitivity red-sensitive silver halide emulsion layer Red sensitization Dye (II, S~
2) AgBr1 (＾gr
2 mol%, average particle size 0.6 μ) 0.8 Coupler C-10, 2 mol High boiling point solvent 0-2 1.2 Gelatin 1.8 5th layer [intermediate layer] 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 (S-3,5-4
) was spectrally sensitized by Ag1lrl (4g14
Mol%, average particle size 0.25μ) 0.6 Coupler C-20.04 mole Coupler C-30.01 mole High-boiling solvent 0-3 0.5 Gelatin 1.4 7th layer (high-sensitivity green-sensitive silver halide Emulsion layer) Green sensitizing dye (S-3,
ΔgBrl (Ag
I 2 mol%, average particle size 0.6 μ) 0.9 Coupler C-20, 10 mol Coupler C-30, 02 mol High-boiling solvent 0-3 1.0 Gelatin 1,5 8th layer (intermediate layer) 5th 9th layer (yellow filter layer) same as layer Yellow colloidal silver 0.1 Gelatin 0.92.5-di-L-octylhydroquinone 0.1 High boiling point solvent 0-1
0.2 10th layer (low sensitivity blue-sensitive silver halide emulsion layer) AgBr1 spectrally sensitized with blue sensitizing dye (S-5) (8g 14 mol%, average grain size 0.35 u) 0.6 Coupler C-4Q, 3 mol High boiling point solvent 0-3 0.6 Gelatin 1.3 11th layer (high sensitivity blue-sensitive silver halide emulsion layer) Blue sensitizing dye (S'-
5) spectrally sensitized by 8gllrT (8g+
2 mol%, average particle size 0.9 μ) 0.9 Coupler C40.5 mol High boiling point solvent o -31.4 Gelatin 2.1 12th layer: 1st protective layer purple) Ray absorber U-10.3 Ultraviolet absorber U-20.4 High boiling point solvent 0-30.6 Gelatin 1,22.5
-Jj'-Octylhydroquinone UV absorber U UV absorption scraping 0.1 13th layer; 2nd protective layer Average grain size (7) 0.08 μIn Non-photosensitive layer made of silver iodobromide containing 1 mol% of silver iodide Fine grain silver halide emulsion
Silver amount 0.3 Polymethyl methacrylate-1/particles (diameter 1.5 μm) Surfactant-1 Gelatin 0.7
In addition to the above composition, gelatin hardeners 1 and 2 and a surfactant were added to each layer. In addition, tricresyl bosphene 1. was used as a coupler solvent. Sensitizing dye S Sensitizing dye S Sensitizing dye S Coupler C-1 Sensitizing dye S Coupler C-2 Sensitizing dye S Coupler C-3 (C11□), SO, I+ ・N (Czlls) + Coupler C-4 C. Gelatin hardening agent-1 Gelatin hardening agent-2 1hc-CtlS (hclhOclhsO2clI-C
lh surfactant-1 Na03S-CIICOOCl12 (CF2CF2)
3+1C1hCOOf:th (ChCh) 311z
lls cg++s After adding 0.01 g/n (0.01 g/n) of the compound of the present invention to the 13th layer (second protective layer) of Sample 57 to prepare the samples shown in Table 5, the following evaluations were performed. Fog] After storing the unexposed sample at 55°C for 17 days, the increase in maximum blue density (Δ
Dmax) is expressed as a relative value with sample 57 set as 100. [Processing process] Process Processing time Processing temperature First development
6 minutes 38°C water washing 2
Minutes 38°C inversion 2 minutes 38°C color development 6 minutes
38°C adjustment 2 minutes
38°C bleaching 6 minutes
38°C fixation 4 minutes
Wash with water at 38°C 4 minutes 3
The composition of the treatment liquid used in the second treatment step of "C stable 1 minute drying at room temperature" is as follows. [First developer] Sourium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone
2g potassium bromide 2.
5g Potassium thiocyanate 1.2g
Potassium iodide (0.1% solution) 2ml Add water to 1000ml9゜
Reversal solution] Nitrilotrimethylenephosphonic acid, 6-sodium salt 3g Stannous chloride (dihydrate) Igp-aminophenol 0.1g Sodium hydroxide 8g Add glacial acetic acid water [Color developer] Sodium tetrapolyphosphate 3g Sulfite Sodium 7g Reithrium tertiary phosphate (dihydrate) 3 G IN Potassium bromide J. 1g Potassium iodide (
0.1% solution) 90mQ sthorium hydroxide 3g citrazine acid
1.5g N-ethyl-N-β-sonotanesulfonamidoethyl 3-methyl-4-aminoaniline.
Sulfate 1g 2.2-Ethylene dithiodiethanol 1g Add water to 1000ml [adjustment solution] Solutonium sulfite 12g ethylenediaminetetraacetic acid Solulithium (dihydrate) g 1,000-glycerin 0.4ml1
15mfV. Add 1,000 d d 1,000 glacial acetic acid water [bleaching solution] Sodium ethylenediaminetetraacetate (dihydrate) g Iron ethylenediaminetetraacetate (■1) Ammonium (dihydrate) 120g 20g Ammonium bromide 100g add water
10100O. [Fixer] Ammonyl thiosulfate J・80) 7 Sodium sulfite 5g Sodium bisulfite 5g Add water
10100O [Stabilizing liquid] Formalin (37% by weight) 5 mρ Konidanx (manufactured by Konica Corporation) 5 Add purified water 1000 m 11 Table-5 Comparative dye ■] Comparative dye ■ As is clear from the results in Table 5, the present invention The dyes used have little effect on emulsion properties. That is, it can be seen that it is inactive with respect to emulsions. [Effects of the Invention] The present invention provides general formula [I] and/or -
Since it contains the oxonol dye represented by the formula [+1], the obtained silver halide photographic light-sensitive material has good spectral absorption characteristics and does not have any adverse effect on the emulsion. It has the excellent effect of being easily decolorized and/or washed out during photographic processing, resulting in extremely little contamination after processing.

Claims (1)

[Claims] 1. A silver halide photographic material containing at least one compound represented by the general formula [I] and/or the general formula [II]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R^1 and R^2 represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group. R^3 to R^6 are a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, a heterocyclic group, -C
OOR^7-, -COR^7, -CONR^7R^8,
-NR^7R^8, -SO_2R^7, -SOR^7,
-SO_2NR^7R^8, -NR^7COR^8, -
NR^7SO_2R^8, -OR^7 represents a sulfo group, a nitro group, a halogen atom, or a cyano group. R^7 and R^8 represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, a cycloalkyl group, or a heterocyclic group. Further, R^3 and R^5, and R^4 and R^6 can each form a ring. L_1 to L_5 represent methine chains, n_1 represents 0 or 1, and n_2 is
Represents 0, 1 or 2. ] General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 to R^6, L_1 to L_5, n_1, n
_2 represents the same meaning as the general formula [I]. 2. A silver halide photographic material, wherein the compound represented by the general formulas [I] and [II] according to claim 1 has at least two water-soluble groups.