JP2537614B2 - Silver halide photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more specifically to a silver halide photographic light-sensitive material sensitized with a novel sensitizing dye to improve photographic characteristics. Regarding materials.

[Prior Art] It is well known that generally, when a sensitizing dye is added to a photosensitive silver halide emulsion, the photosensitive wavelength region of the silver halide emulsion is expanded and optically sensitized.

A large number of compounds have been known as optical sensitizing dyes used for such a purpose, and for example, "The Theory of the Photographic Process", 4th edition, written by TJ James, (1977). (McMillan, NY), 194 to 234, cyanine dyes, merocyanine dyes, xanthene dyes, and the like are known.

When these sensitizing dyes are usually applied to silver halide emulsions, they must satisfy not only the widening of the photosensitive wavelength range of silver halide emulsions but also the following conditions.

(1) The spectral sensitization region by dye sensitization is appropriate.

(2) The sensitization efficiency is good and a sufficiently high sensitivity can be obtained.

(3) No adverse interaction with other additives such as stabilizers, antifoggants, coating aids, color formers, etc.

(4) The occurrence of fogging can be suppressed.

(5) It is difficult for the sensitivity to decrease with time.

(6) The coating liquid has excellent stability over time.

The above conditions (1) to (6) have important meanings when preparing a silver halide emulsion. That is, the sensitizing dyes used in the visible wavelength region light-sensitive silver halide emulsions can be the cyanine dyes, merocyanine dyes, etc., but most of the cyanine dyes and merocyanine dyes do not always have sufficient sensitizing efficiency. Not only was the desired sensitivity obtained, but it was often accompanied by the occurrence of fogging, and there was nothing satisfactory that it caused a decrease in sensitivity with time.

[Object of the Invention] An object of the present invention is to firstly provide a silver halide photographic light-sensitive material having high sensitivity and capable of suppressing the occurrence of fogging, and secondly, to cause deterioration of sensitivity with time. It is to provide a difficult silver halide photographic light-sensitive material, and thirdly to provide a silver halide photographic light-sensitive material excellent in stability over time of a coating solution.

[Structure of the Invention] As a result of various investigations by the present inventors, the above-mentioned object is at least one of the silver halide emulsion layers in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support. Halogen characterized in that silver halide grains contained in one layer are spectrally sensitized with a compound represented by the following general formula [I], general formula [II] and / or general formula [III] It has been found that what can be achieved with a silver halide photographic light-sensitive material.

General formula [I] General formula [II] General formula [III] In the formula, Z ₁ , Z ₂ , Z ₃ and Z ₄ each represent a non-metal atom group necessary for forming a 5- or 6-membered heterocycle, and the heterocycle includes, for example, a thiazole nucleus (eg, thiazole, 4
-Methylthiazole, 4-phenylthiazole, 4,5-
Dimethylthiazole, 4,5-diphenylthiazole, etc.), benzothiazole nucleus (for example, benzothiazole,
4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-
Bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-methoxycarbonylbenzothiazole, 5-carboxybenzothiazole, 5-phenethyl Benzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,6
-Dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, etc.), naphthothiazole nucleus (for example, naphtho [2,1-d] thiazole, naphtho (1,2-d)) Thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-
Ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole, etc., thiazoline nucleus (eg thiazoline, 4-methylthiazoline, 4-nitrothiazoline etc.), oxazole nucleus (eg oxazole, 4
-Methyloxazole, 4-nitroxazole, 5-
Methyloxazole, 4-phenyloxazole, 4,5
-Diphenyloxazole, 4-ethyloxazole and the like), benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5 -Methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-
Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole and the like, naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-]
d] oxazole, 5-nitronaphtho [2,1-d] oxazole etc.), oxazoline nucleus (eg 4,4-dimethyloxazoline etc.), selenazole nucleus (eg 4-methylselenazole, 4-nitroselenazole, 4-phenyl) Selenazole, etc., benzoselenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole,
6-nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, etc.), naphthoselenazole nucleus (for example, naphtho [2,1-d] selenazole, naphtho [1,2]
-D] selenazole, etc., 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-dianoindolenine, 3,3- Dimethyl-6-nitroindolenine, 3,3
-Dimethyl-5-nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine, etc., imidazole nucleus (e.g. 1 -Alkylimidazole, 1-alkyl-4-phenylimidazole, 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1-alkyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole , 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5-trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-alkyl -6-chloro-5-trifluoromethylbenzimi Zole, 1-alkylnaphtho [1,2-d] imidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylimidazole, 1-arylbenzimidazole, 1- Aryl-5-chlorobenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole, 1-arylnaphtho [1,2-d ] Imidazole and the like, and the aforementioned alkyl has 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, isopropyl,
An unsubstituted alkyl group such as butyl, a hydroxyalkyl group (eg, 2-hydroxyalkyl, 3-hydroxypropyl, etc.) and the like are preferable. Particularly preferred are methyl group and ethyl group. The aforementioned aryl represents phenyl, halogen (eg chloro) substituted phenyl, alkyl (eg methyl) substituted phenyl, alkoxy (eg methoxy) substituted phenyl and the like. ), A pyrrolidine nucleus (eg, 2-pyrrolidine, etc.), a pyridine nucleus (eg, 2-pyridine, 4)
-Pyridine, 5-methyl-2-pyridine, 3-methyl-
4-pyridine and the like), quinoline nucleus (eg 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-nitro-2-quinoline, 8-fluoro- 2-quinoline, 6-methoxy-
2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6-ethoxy-4-
Quinoline, 6-nitro-4-quinoline, 8-chloro-4
-Quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4-quinoline, isoquinoline, 6-nitro-1-isoquinoline, 3,4-dihydro-1-isoquinoline, 6-nitro -3-isoquinoline etc.), imidazo [4,5-b] quinoxaline nucleus (1,3-tylimidazo [4,5-b] quinoxaline, 6-chloro-1,3
-Diallylimidazo [4,5-b] quinoxaline etc.),
It represents an oxadiazole nucleus, a thiazoazole nucleus, a tetrazole nucleus, a pyrimidine nucleus and the like.

Q ₁ and Q ₂ represent a nonmetallic atom group necessary for forming a 5- or 6-membered heterocycle, and the heterocycle includes a rhodanine nucleus, a 2-thiohydantoin nucleus, and 2-thioxooxazolidine-4-.
On nucleus, 2-pyrazolin-5-one nucleus, barbituric acid nucleus, 2-thiobarbituric acid nucleus, thiazolidine-2,4-
There are a dione nucleus, a thiazolidin-4-one nucleus, an isoxazolone nucleus, a hydantoin nucleus, an indandione nucleus and the like.

W ₁ and W ₂ represent S, O or> N-R ₉ .

R < ₂ >, R < ₄ >, R <_7> , R < ₈ > and R < ₉ > are bonded to the nitrogen atom contained in these nuclei, and are a hydrogen atom, preferably having 1 to 1 carbon atoms.
18, more preferably 1 to 7, and particularly preferably 1 to 4 alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group,
Octyl group, dodecyl group, octadecyl group, etc. Substituted alkyl group (eg aralkyl group (eg benzyl group, 2
-Phenylethyl group etc.), hydroxylalkyl group (eg 2-hydroxyethyl group, 3-hydroxypropyl group etc.), carboxyalkyl group (eg 2-carboxyethyl group, 3-carboxpropyl group, 4-carboxybutyl group, carboxy) Methyl group, etc., alkoxyalkyl group (eg 2-methoxyethyl group, 2- (2-
Methoxyethoxy) ethyl group, etc.), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group,
3-sulfobutyl group, 4-sulfobutyl group, 2- [3-
Sulfopropoxy] ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group), sulfatoalkyl group (for example, 3-sulfatopropyl group, 4-sulfatobutyl group, etc.), heterocycle Substituted alkyl groups (eg 2- (pyrrolidin-2-one-
1-yl) ethyl group, tetrahydrofurfuryl group, 2-
Morpholino group, 2-acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group, etc.), allyl group, aryl group (for example, phenyl group, 2
-Naphthyl group), substituted aryl group (eg 4-carboxyphenyl group, 4-sulfophenyl group, 3-chlorophenyl group, 3-methylphenyl group etc.), heterocyclic group (eg 2-pyridyl group, 2-thiazolyl group) etc.), or represents the _{CH 2) i Y (CH 2} ) j (CF 2) k R 10. Here, Y is an oxygen atom or -CONH- (however, the carbon atom of -CONH- is
CH ₂ ) is bonded to the _i side), i and k are integers of 1 to 10, and j is an integer of 0 to 4. R ₁₀ is a hydrogen atom,
It represents a lower alkyl group or a fluorine atom.

R ₁ , R ₃ , R ₅ and R ₆ are preferably an alkyl group having 1 to 18 carbon atoms, more preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms, a substituted alkyl group (for example, an aralkyl group, a hydroxylalkyl group, Carboxyalkyl group, alkoxyalkyl group, sulfoalkyl group, sulfatoalkyl group, heterocycle-substituted alkyl group, 2-acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group, etc.), or CH ₂ ) _i Y (CH ₂ ) _j (CF ₂ ) _k R ₁₀ is represented. Specific examples of these groups are the above-mentioned R ₂ , R ₄ , R ₇ , R ₈ and R ₉
There are the same as those mentioned in the explanation. Further, here, Y, R ₁₀ , i, j, and k have the same meanings as described above.

However, at least one of R _{1 and} R ₂ is CH ₂ ) _i Y
(CH ₂ ) _j (CF ₂ ) _k R ₁₀ and at least one of R ₃ , R ₄ , R ₅ , and R ₉ is CH ₂ ) _i Y (CH ₂ ) _j (CF ₂ ) _k R ₁₀ Represents R ₆ , R ₇ , R ₈ , R
_At least one of ₉ represents CH ₂ ) _i Y (CH ₂ ) _j (CF ₂ ) _k R ₁₀ . Where Y,
R ₁₀ , i, j and k are as defined above.

 L₁, L₂, L₃, L_Four, L_Five, L₆, L₇, L₈, L₉, L_TenAnd L₁₁Is
Methine group or substituted methine group {alkyl group (eg methyl group
Group, ethyl group, etc., aryl group (eg phenyl group)
Etc.) or halogen atom (eg chlorine, bromine, etc.)
It may be replaced. Also, they bond to each other to form a ring
Good. } Is represented. X Represents an acid anion, specifically
Is halide anion, alkylsulfate anion, p-tolu
Ensulphonate etc. are mentioned. n₁, N₂, N₃And n_Four
Represents 0 or 1. l₁, L₂, L₃, L_FourAnd l_FiveIs 0,
Represents 1, 2 or 3. p represents 0 or 1.

Specific examples of the compound represented by the general formula [I], the general formula [II] and / or the general formula [III] are shown below.
The scope of the present invention is not limited to these.

[Exemplified compound] The compound represented by the above general formula [I], general formula [II] and / or general formula [III] (hereinafter referred to as the compound of the present invention) according to the present invention is, for example, by F. M. Hama,
Cyanine Soybean and Relayed Compounds (1964, published by Inter Science Publishers), Japanese Patent Publication Nos. 46-549, 46-18105, 46-1810
No. 6, No. 46-18108, No. 47-4085, No. 58-52574,
U.S. Patents 2,839,403, 2,839,404, 3,384,486
Those skilled in the art can easily synthesize the compound according to the synthetic method described in No. 3, No. 3,625,698, No. 3,480,439, No. 3,567,458 and the like. In addition, CH in the N position, which is a feature of the present invention
_{2) i Y (CH 2)} j (CF 2) a method of introducing the _k R ₁₀ can be easily carried out by a method described below.

Compounds in which Y is -CONH- are described in "Journal of the
Organic Kemisutoryi "(J.Org.Chem.), 26, 40
21 (1961), “Industrial and Engineering Chemistry” (Ind. & Eng. Chem.), 48 , 209
A fluorinated alkylamine compound synthesized according to the method described in (1956) and the like was used to derive a ω-halogenalkylcarboxylic acid amide compound, and subsequently, JP-A-61-29.
4429 and the above-mentioned known method.

 Compounds in which Y is an oxygen atom are "industrial and
・ Engineering Chemistry "(Ind. & Eng.Che
m.),48, 445 (1956), Zh.Vsses.Khim.O-va.,twenty two
(4), 469 (1977), Khim.Prom-st.Ser.Reakt.Osobo.C
According to the method described in hist.Veshchestva, 1979, 55 etc.
Synthesized fluorinated alkyloxy alcohol, or fluorine
Using fluorinated alkyloxyalkyl halide compounds
Japanese Patent Application No. 61-68285 and synthesis by the above-mentioned known method
Can be.

The compound (sensitizing dye) of the present invention is 1 × 10 ^-8 mol to 5 × 10 ^-2 mol, preferably 1 mol, per mol of silver halide.
× 10 ^-5 mol to 2.5 × 10 ^-3 mol, particularly preferably 4 × 10 ^-5
It is contained in the silver halide emulsion in a proportion of 1 mol to 1 × 10 ^-3 mol.

The compounds of the present invention may be used alone or in combination of two or more. Furthermore, if necessary, a sensitizing dye other than the present invention may be used in combination.

A method well known in the art can be used to add the compound (sensitizing dye) of the present invention to the emulsion. For example, these sensitizing dyes can be dispersed directly in the emulsion, or can be dissolved in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, fluorinated alcohol, or a mixture thereof, or Dilute with water or dissolve in water,
These solutions can be added to the emulsion, and the sensitizing dye may be added to the emulsion at any time during the emulsion production process, but preferably during or after chemical ripening.

The silver halide emulsion used in the light-sensitive material of the present invention can be chemically sensitized by a conventional method, and a silver halide emulsion that can be optically sensitized to a desired wavelength region by using a sensitizing dye is
Antifoggants, stabilizers and the like can be added. It is advantageous to use gelatin as the binder of the emulsion. The emulsion layer and other hydrophilic colloid layers may be emulsion hardened and may contain a plasticizer and a dispersion (latex) of a water-soluble or sparingly soluble synthetic polymer. When the compound of the present invention is used in a color photographic light-sensitive material, a coupler is used in its emulsion layer. Further, a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a hardener, a color coupler, a competing coupler, and an oxidant of a developing agent, which have an effect of color correction, are coupled to each other. Compounds that release photographically useful fragments such as film agents, fog agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

The photosensitive material includes a filter layer, an antihalation layer,
An auxiliary layer such as an irradiation prevention layer or a protective layer can be provided. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development process may be contained.

Formalin scavengers, fluorescent whitening agents, matting agents, lubricants, image stabilizers, antifoggants, development accelerators, development retarders and bleaching accelerators can be added to the light-sensitive material.

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

The silver halide emulsion to which the compound of the present invention can be applied includes, for example, silver halide emulsions described in the following patent publications, that is, normal crystal, twin crystal, core / shell type, and flat type having an aspect ratio of 5 or more ( T particles) or the like can be applied. For example, JP-A-58-95337 and 58-1
00846, 58-106532, 58-107530, 58-108
525, 58-108532, 58-113928, 58-18103
No. 7, No. 58-209730, No. 58-211143, No. 58-211753
And the like. The type of silver halide is not limited, either.

The light-sensitive material of the present invention is for color or black and white negative photography, for color or black and white paper, for X-ray, for plate making, for movies,
It may be for color copying or the like.

In order to obtain an image using the light-sensitive material of the present invention, a commonly known black-and-white photographic process or color photographic process can be carried out after exposure.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Silver halide grains were precipitated by the double jet method, physically ripened by a usual method, desalted, and further chemically ripened by a gold sensitizing method and a sulfur sensitizing method to obtain 7 mol of silver iodide. % Silver iodobromide emulsion was obtained. The silver halide grains contained in this emulsion have a (100) face and an average diameter of 0.6 μm.
Met. 1 Kg of this emulsion contains 0.60 mol of silver halide and 880 g of gelatin binder.

Each 1 Kg of this emulsion was weighed into a pot and heated to 40 ° C. to dissolve. Then, a methanol solution was added to each of the sensitizing dye of the present invention and the comparative sensitizing dye so that the dye concentration became 3 × 10 ⁻⁴ / 1 mol silver, and the mixture was stirred.

Further, 20 ml of a 1.0% by weight aqueous solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and 10 ml of a 1.0% by weight aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt was added. Was further added, and 10 ml of a 1.0% by weight aqueous solution of dodecylbenzenesulfonic acid sodium salt was added and stirred. This finished emulsion was coated on a cellulose triacetate film base so as to have a dry film thickness of 5 μm and dried to obtain a sample of a light-sensitive material. This sample was cut into strips and divided into two parts. One part was subjected to optical wedge exposure with a yellow filter attached to the light source using a sensitometer having a light source with a color temperature of 5400 ° K immediately after preparation of the sample (condition a). After exposure, development was carried out for 1 minute at 20 ° C. using a developer having the following composition, then stopped, fixed, washed with water and dried to obtain strips having a predetermined black and white image. The density of each treated sample was measured using an optical densitometer, and the sensitivity and fog were measured. The reference point of the optical density for which the sensitivity was determined was the point of fog +0.20.

Developer composition Metol 2g Anhydrous sodium sulfite 40g Hydroquinone 4g Sodium carbonate monohydrate 28g Potassium bromide 1g Add water to make 1.

The other part is 1 at a temperature of 60 ° C and a relative humidity of 70%.
After leaving for one day (condition b), the same exposure and development processing as above were carried out, and the sensitivity and fogging were measured.

 Table 1 shows the results.

[Comparative sensitizing dye] From Table 1, it was clearly recognized that the sensitizing dye according to the present invention showed little change in sensitivity when stored under high temperature and high humidity conditions and little increase in fog.

Example 2 0.2 μm cubic monodisperse silver chloroiodobromide emulsion (composition AgCl: Ag
Br: AgI = 69: 30: 1) is prepared according to a conventional method and subjected to gold-sulfur sensitization. This emulsion was divided, and a sensitizing dye was added to each emulsion as shown in Table 2, and further 2-methyl-4- was added to each emulsion.
Hydroxy-1,3,3a, 7-tetrazaindene (3 g / silver 1 mol), 1-phenyl-5-mercaptotetrazole (10 mg
/ Silver 1 mol), 3% saponin as a coating aid, polyethyl acrylate as a softener, the following polyalkylene oxide compound (600 mg / silver 1 mol) as a dot improving agent, and the amount of gelatin in the emulsion layer 2 g / m ^2. Gelatin was added so that the amount of silver attached would be 3.5 g / m ^2, and the polyester base was coated simultaneously with the following protective layer solution and dried. The above-mentioned protective layer liquid is composed of gelatin, octyl succinate as a coating aid, silica of 4 μm as a matting agent, and mucochloric acid as a hardening agent. The amount of gelatin attached is 2 g.
The emulsion layer was coated at the same time so as to be / m ² and dried.

The coated sample obtained as described above, the relative humidity 80%,
Let stand for 5 days at a temperature of 50 ° C, and compare this sample with the relative humidity.
The above samples, which had been stored at 40% and a temperature of 23 ° C. for 5 days, were subjected to wedge exposure together with a plate making camera through a green light filter (Ratten-58). After exposure, development was performed for 20 seconds at 38 ° C. using a developing solution having the following composition, and fixing processing was performed using Sakura fixing solution type 821.

(Developer-1) Hydroquinone 25 g 4,4-Dimethyl-3-pyrazolidone 0.5 g Potassium sulfite 100 g Potassium bromide 3 g Triethylene glycol 30 g Polyethylene glycol (average molecular weight 1500) 3 g 5-Nitroindazole 0.1 g Potassium carbonate 30 g Sodium ethylenediaminetetraacetate 2 g 5-Methylbenzotriazole 0.2 g Water was adjusted to 1 and pH was adjusted to 10.7 with potassium hydroxide.

The obtained results are shown in Table 2 below. In the table, the sensitivity was evaluated at the point where the concentration on the characteristic curve was 3.0, and the results of Sample No. 61, 23.
The relative sensitivity is displayed with the green sensitivity when stored at 40 ° C and 40% RH as 100. The fogging is displayed including the base density. Further, the gradation is displayed by the inclination of the straight line portion on the characteristic curve. Further, the numbers of the sensitizing dyes in the table are indicated by the numbers of the exemplified compounds.

Halftone improver Halftone improver [Comparative sensitizing dye] From the above results, the sample spectrally sensitized by using the dye according to the present invention, compared with the comparative sample similarly spectrally sensitized by using the comparative sensitizing dye, also during storage under high temperature and high humidity. It can be seen that the sensitivity is extremely low, and there is almost no increase in fog or gradation, and it is extremely stable.

Example 3 A polyethylene-coated photographic paper support containing 11% by weight of anatase-type titanium oxide (basis weight 170 g / m ² ) was subjected to corona discharge machining, and 2 hours after adjustment of the coating solution, , The following seven photographic constituent layers are sequentially applied in multiple layers,
A color photographic light-sensitive material for printing was prepared. Further, 10 hours after the preparation of the coating solution, another sample was prepared in the same manner as above.

Unless otherwise specified, the addition amount of each substance means that it was used in an amount per 1 m ² , and the silver halide is shown in terms of silver.

Layer 1 ... 0.45 g of blue-sensitive silver chlorobromide emulsion (average grain size 0.7
0 μm, containing 98 mol% of silver chloride, cubic), 1.47 g of gelatin, and 0.8 g of yellow coupler (YC-1) and 0.015 dissolved in 0.4 g of di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP). A blue sensitive emulsion layer containing g of a color stain inhibitor (HQ-1).

Layer 2 ... dissolved in 1.03 g gelatin, 0.03 g DOP
A first intermediate layer containing 0.015 g of a color stain inhibitor (HQ-1).

Layer 3 ... 0.40 g of green-sensitive silver chlorobromide emulsion (average grain size 0.4
5 μm, containing 97 mol% of silver chloride, cubic), 1.85 g of gelatin, and 0.63 g of magenta coupler (MC-1) dissolved in 0.35 g of DOP and 0.015 g of color stain inhibitor (HQ-1). Contains a green-sensitive emulsion layer.

Layer 4--dissolved in 1.45 g gelatin, 0.22 g DOP
The 2nd intermediate | middle layer containing 0.2-g ultraviolet absorber (UV-1), 0.3-g ultraviolet absorber (UV-2), and 0.05-g color stain inhibitor (HQ-1).

Layer 5: 0.30 g of red-sensitive silver chlorobromide emulsion (average grain size 0.4
0 μm, containing 98 mol% of silver chloride, cubic), 1.6 g of gelatin, and 0.42 g of cyan coupler (CC-1) and 0.005 g of color stain inhibitor (HQ-1) dissolved in 0.3 g of DOP. Red-sensitive emulsion layer containing.

Layer 6 ... dissolved in 1.45 g gelatin, 0.22 g DOP
The 3rd intermediate | middle layer containing 0.2 g of ultraviolet absorbers (UV-1), 0.3 g of ultraviolet absorbers (UV-2), and 0.05 g of color stain inhibitors (HQ-1).

 Layer 7 ... A protective layer containing 1.8 g of gelatin.

At least one of the photographic constituent layers contained bis (vinylsulfonylmethyl) ether as a hardener and saponin as a coating aid.

Photographic additive dispersion (Yellow coupler dispersion) Yellow coupler (YC-1) 20g, Color stain inhibitor (HQ
-1) 0.375 g was dissolved in 20 g of a high boiling organic solvent and 40 g of ethyl acetate. The obtained liquid contains 1.3 g of the surfactant A 10
% Gelatin aqueous solution while stirring, and then dispersed for 20 minutes using an ultrasonic disperser to obtain a dispersion.

Similarly to the yellow coupler, other oil-soluble photographic additives (other couplers, ultraviolet absorbers, color stain inhibitors, etc.) were also used to prepare a dispersion using a high-boiling organic solvent.

The blue-sensitive silver halide emulsion (layer 1), the green-sensitive silver halide emulsion (layer 3) and the red-sensitive silver halide emulsion (layer 5) are 1 × 10 ⁻⁵ mol per mol of silver halide emulsion. Sodium thiosulfate is added to perform chemical ripening, and 5 minutes before the completion of the chemical ripening, the sensitizing dye of the present invention or the comparative sensitizing dye is added to Layers 1 and 5 as a sensitizing dye for each emulsion layer. To
In Layer 3, the following sensitizing dye (D-1) 3.0 × 10 ^-4 mol
% Solution. After 5 minutes, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer was added as a 0.5% aqueous solution at the end of the chemical ripening. Then 1
A 0% gelatin aqueous solution was added, and the mixture was stirred and then cooled to manufacture.

The obtained coating sample was divided into 2 parts, and 1 part was used to examine the stability of the coating solution over time, and a sensitometer (Konishi Roku Photo Co., Ltd., KS
-7 type) was used for optical wedge exposure, and treatment was performed according to the following treatment steps. The sample sensitivity ratio (%) after coating for 2 hours and for 10 hours was determined and used as an index of stability of the coating solution over time.

The other part was subjected to the same treatment as above with unexposed light and visually observed the residual color in order to examine the degree of color contamination by the sensitizing dye after the development treatment. The residual color is shown in Table 3 in four stages from the one with less color contamination.

Degree of color contamination 1 ... Very clean and with only base concentration 2 ... Very slight color contamination 3 ... Weak coloration 4 ... Coloration treatment process (32.8 ℃) Treatment time Color development Development 50 seconds Bleaching fixing 50 seconds Washing with water 90 seconds (color developer composition) N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 4.0g N, N-diethylhydroxylamine 10.0g Potassium carbonate 25.0g Sodium chloride 2.0g Anhydrous sodium sulfite 0.1g Diethylene glycol 10.0ml Polyethylene glycol 3.0ml (Average degree of polymerization 400) Add water 1 and pH 10.0 using potassium hydroxide
Adjust to.

(Composition of bleach-fix solution) Ethylenediaminetetraacetic acid iron sodium salt 60.0 g Ammonium thiosulfate 100.0 g Sodium bisulfite 20.0 g Sodium metabisulfite 5.0 g Water is added to adjust to pH 6.5 with sulfuric acid.

Redox potential -70 mV Sensitizing dye From Table 3, the sensitizing dye according to the present invention is superior in color contamination and stability over time of the coating solution as compared with the comparison. This shows that the sensitivity of the coating emulsion was maintained high by introducing CH ₂ ) _i Y (CH ₂ ) _j (CF ₂ ) _k R ₁₀ at the N position of the sensitizing dye and was obtained. The image shown is a good image with no color contamination.

Claims (1)

(57) [Claims] 1. A silver halide having at least one layer on a support
In a silver halide photographic light-sensitive material having an emulsion layer,
Contained in at least one of the silver halide emulsion layers
Are represented by the following general formula [I] and general formula [II]
And / or a compound represented by the general formula [III]
Photosensitization of silver halide characterized by being photosensitized
Light material. General formula [I]General formula [II]General formula [III]Where Z₁, Z₂, Z₃And Z_FourAnd Q₁And Q₂Are each
The non-metallic atomic groups necessary to form a 5- or 6-membered heterocycle
Represent W₁And W₂Is an oxygen atom, a sulfur atom or) N-R₉
Represents R₁, R₃, R_FiveAnd R₆Is an alkyl group, substituted alk
Group or CH₂)_iY (CH₂)_j(CF₂)_kR_TenRepresents R
₂, R_Four, R₇, R₈And R₉Is the source of nitrogen contained in these nuclei
Bound to the child, hydrogen atom, alkyl group, substituted alkyl
Group, aryl group, substituted aryl group, heterocyclic group, or
CH₂)_iY (CH₂)_j(CF₂)_kR_TenRepresents However, R₁Or R₂At least one of them is CH₂)_iY (C
H₂)_j(CF₂)_kR_TenAnd R₃, R_Four, R_Five, R₉Less of
At least one is CH₂)_iY (CH₂)_j(CF₂)_kR_TenAnd R
₆, R₇, R₈, R₉At least one is CH₂)_iY (C
H₂)_j(CF₂)_kR_TenIs. Y is an oxygen atom or -CONH
-(However, the carbon atom of -CONH- is CH₂)_iConnect to the side
, I is an integer from 1 to 10, and j is an integer from 0 to 4.
Is a number, and k is an integer of 1 to 10. R_TenIs a hydrogen atom,
It represents a lower alkyl group or a fluorine atom. L₁, L₂, L₃, L_Four, L_Five, L₆, L₇, L₈, L₉, L_Ten, And L₁₁Is
Represents a methine group or a substituted methine group. X Is an acid anion
Represents n₁, N₂, N₃And n_FourRepresents 0 or 1. l₁,
l₂, L₃, L_FourAnd l_FiveRepresents 0, 1, 2 or 3. p is
Represents 0 or 1.