JPS63228145A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sensitivity of the titled material and to suppress the generation of fogging by spectrally sensitizing a silver halide particle contd. in at least one layer of silver halide emulsion layers with a specified compd. CONSTITUTION:The silver halide particle contd. in at least one layer of the silver halide emulsion layers is spectrally sensitized with the compd. shown by formulas I, II and/or III wherein Z1-Z4 and Q1 and Q2 are each a nonmetal atomic group necessary for forming a 5 or 6 membered heterocyclic ring, W1 and W2 are each oxygen or sulfur atom., etc., R1, R3, R5 and R6 are each alkyl or a substd. alkyl group, etc., R2, R4, R7, R8 and R9 are each hydrogen atom., alkyl, a substd. alkyl, aryl, a substd. aryl or a heterocyclic ring group, etc., Y is oxygen atom. or -CONH- group, R10 is hydrogen or fluorine atom., a lower alkyl group, L1-L11 are each methine or a substd. methine group, X<-> is an acidic anion. Thus, the titled material having the sufficiently high sensitivity and with suppressed fogging is obtd.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a silver halide photographic material.

More specifically, the present invention relates to a silver halide photographic material sensitized with a new sensitizing dye and having improved photographic properties.

[Prior Art] It is generally known that when a sensitizing dye is added to a light-sensitive silver halide emulsion, the sensitive wavelength range of the silver halide emulsion is expanded and the emulsion is optically sensitized.

A large number of compounds have been known as optical sensitizing dyes used for such purposes. Cyanine dyes, merocyanine dyes, xanthine dyes, etc., which are described in pages 194 to 234 of Macmillan Publishing Co., Ltd., Threshold, Y., 2013, are known.

When these sensitizing dyes are normally applied to silver halide emulsions, they must not only simply expand the sensitive wavelength range of the silver halide emulsions, but must also satisfy the following conditions.

(1) The spectral sensitization range due to dye sensitization is appropriate.

(2) High sensitization efficiency and sufficiently high sensitivity can be obtained.

(3) There should be no adverse interaction with other additives 1, such as stabilizers, antifoggants, coating aids, color formers, etc.

(4) The occurrence of fogging can be suppressed.

(5) Sensitivity is unlikely to decrease over time.

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

The conditions (1) to (6) above have an important meaning in preparing a silver halide emulsion. That is, conventionally, as sensitizing dyes used in visible wavelength-sensitive silver halide emulsions, the above-mentioned cyanine dyes, merocyanine dyes, etc. have been considered, but many of the cyanine dyes and merocyanine dyes do not necessarily have sufficient sensitizing efficiency; Not only is it not possible to obtain the desired sensitivity, but there are many cases in which fogging occurs, and the sensitivity deteriorates over time, so that no satisfactory method has been found.

[Object of the Invention] The object of the present invention is, first, to provide a silver halide photographic material that has high sensitivity and can suppress the occurrence of fog; The third objective is to provide a silver halide photographic light-sensitive material that is difficult to use. An object of the present invention is to provide a silver halide photographic material having excellent blood stability over time.

[Structure of the Invention] As a result of various studies, the present inventors have found that the above object is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on the support layer. Halogenation characterized in that silver halide grains contained in at least 1M are spectrally sensitized with a compound represented by the following general formula [I], general formula [II] and/or general formula [ml] It has been discovered that this can be achieved using a silver photographic material.

General formula [1] General formula [II] General formula [ml In the formula, L , Zt , Z:+ and z4 each represent a group of nonmetallic atoms necessary to form a 5 to 6n heterocycle, and as the heterocycle 1 For example, thiazole nucleus (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, etc.), benzothiazole nucleus (e.g. 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-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6-methylbenzothiazole , 5,6-dimethylbenzothiazole, 5-hydroxy-tomethylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, etc.)
, naphthothiazole nucleus (if healthy, naphtho(2,l-d)
Thiazole, naphtho(1,2-d)thiazole, naphtho(2,3-d)thiazole.

5-methoxynaphtho(1,2-d)thiazole, 7-nitoxynaphtho(2,1-d)thiazole, 8-methoxynaphtho(2,1-d)thiazole, 5-methoxynaphtho(2,3-d)thiazole ), thiazoline nuclei (e.g. thiazoline, 4-methylthiazoline, 4-nitrothiazoline, etc.), oxazole nuclei (e.g. oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4.5 -diphenyloxazole, 4-ethyloxazole, etc.), benzoxazole nuclei (e.g. benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5 -methoxybenzoxazole,
5-nitropenzoxazole, 5-trifluoromethylbenzooxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6
-Nitrobenzoxazole, 6-medoxybenzoxazole, 6-hydroxybenzoxazole, 5.
6-dimethylbenzoxazole, 4. dimethylbenzoxazole, 5-ethoxybenzoxazole, etc.), naphthoxazole core (e.g., nut(2,1-d
)oxazole, naphtho(1,2-d)oxazole, naphtho(Z,3-d)oxazole, 5-nitronaphtho(2,1-d)oxazole, etc.), oxazoline nuclei (e.g. 4,4-dimethyloxazoline, etc.), selenazole core (e.g. 4-methylselenazole, 4-nitroselenazole, 4-phenylselenazole, etc.),
Benzoselenazole core (e.g. benzoselenazole, 5
-chlorobenzoselenazole, 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole, 5-chloronitrobenzoselenazole, etc.),
Naphthoselenazole core (e.g. naphtho(2,1-d)
selenazole, naphtho(1,2-d) selenazole, etc.), 3,3-dialkylindolenine core (e.g. 3,
3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3
．． 3-dimethyl-6-nitroindolenine, 3.3-dimethyl-5-nitroindolenine, 3.3-dimethyl-
5-methoxyindolenine, 3,3.5-)-dimethylindolenine, 3,3-dimethyl-5-chloroindolenine, etc.), imidazole core (e.g. 1-alkylimidazole, !-alkyl-4-phenylimidazole, ■ -alkylbenzimidazole, 1-alkyl-5
- p-Lobenzimidazole l-alkyl-5,6-
Dichlorobenzimidazole, l-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-trifluoromethylbenzimidazole, 1-alkylnaphtho(1,2-d)imidazole, l-allyl-5,6-dichlorobenzimidazole, l-allyl-
5-chlorobenzimidazole, 1-arylimidazole, 1-arylbenzimidazole, l-aryl-5-chlorobenzimidazole, 1-aryl-5,
6-dichlorobenzimidazole, 1-aryl-5-
Methoxybenzimidazole, l-aryl-5-cyanobenzimidazole,! -arylnaf) (1,2
-d) imidazole, etc., and the alkyl mentioned above is one having 1 to 8 carbon atoms, such as an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, or a hydroxyalkyl group (e.g. 2-hydroxyalkyl, 3-hydroxyalkyl group). -hydroxypropyl, etc.) are preferred, and methyl and ethyl groups are particularly preferred. The aforementioned aryl is
phenyl, halogen (e.g. chloro) substituted phenyl, alkyl (e.g. methyl) substituted phenyl, alkoxy (e.g. methoxy) It-substituted phenyl, etc.), pyrrolidine nucleus (e.g. 2-pyrrolidine etc.), pyridine nucleus (e.g. 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine, etc.), quinoline nucleus (e.g. 2-quinoline, 3-methyl-2-quinoline, 5-methyl-2-pyridine, etc.),
-ethyl-2-quinoline, 6-methyl-2-quinoline,
6-nitro-2-quinoline, 8-fluoro-2-quinoline, 6-medoxy-2-quinoline, 6-hydroxy-2-
Quinoline, 8-chloro-2-quinoline, 4-quinoline,
6-nitoxy-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,S-b
) Quinoxalisonucleus (l,3-tylimidazo(4,5-b
) quinoxaline, 6-chloro-1,3-diallylimidazo(4,5-b)quinoxaline, etc.), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, etc.

Q, , Qt represent a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle, and the heterocycle includes a rhodanine nucleus,
2-Thiohydantoin nucleus, 2-thioxooxasilysin-4-one nucleus, 2-pyrazolin-5-one nucleus, barbylic acid group, 2-thiobarbyl nucleus, thiazolidine-
Examples include 2,4-dione nucleus, thiazolidin-4-one nucleus, isoxacilone nucleus, hydantoin nucleus, and indandione nucleus.

W3 and W2 represent S, 0 or >NR.

R2, R4, R2, R, and R are bonded to the nitrogen atom contained in these nuclei, and have a hydrogen atom, preferably 1 to 18 carbon atoms, more preferably 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms. Alkyl groups (e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.), substituted alkyl groups (e.g. aralkyl groups (e.g. benzyl, 2 -phenylethyl group, etc.), hydroxylalkyl group (e.g. 2-hydroxyethyl group, 3-hydroxypropyl group, etc.), carboxyalkyl group (e.g. 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, carboxy methyl group, etc.)
, alkoxyalkyl groups (e.g. 2-methoxyethyl group, 2-(2-methoxyethoxy)ethyl group, etc.), sulfoalkyl groups (e.g. 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group) , 2-(3-sulfopropoxy)ethyl group, 2-hydroxy-3-sulfopropyl group, cosulfoproboxyethoxyethyl group), sulfatoalkyl group (e.g. 3-sulfatopropyl group, 4-sulfatobutyl group) ), heterocyclic alkyl groups (e.g. 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 (e.g. phenyl group, 2-naphthyl group, etc.), substituted aryl group (e.g. 4-carboxyphenyl group, 4-sulfophenyl group) , 3-chlorophenyl group, 3-methylphenyl group, etc.)
, a heterocyclic group (eg, 2-pyridyl group, 2-thiazolyl group, etc.) or +CH*)tY(CHt)j(CFt)hR*. , where Y is an oxygen atom or 100NH- (however, -C
The carbon atom of ON represents +CI+2), which is bonded to the side), i is an integer from 1 to 10, and j is an integer from 0 to 4. RIG is a hydrogen atom, a lower alkyl group, or a fluorine atom. represents.

R,, R,, R5 and R6 preferably have a carbon number of 1 to
18, more preferably 1 to 7. Particularly preferably 1 to 4 alkyl groups, substituted alkyl groups (e.g. aralkyl group, hydroxylalkyl group, carboxyalkyl group, alkoxyalkyl group, sulfoalkyl group, sulfatoalkyl group, heterocyclic substituted alkyl group, 2-acetoxyethyl group) , carbomethoxymethyl group, 2-methanesulfonylaminoethyl group, etc.), or +CHz)tY(CHt)=(
Specific examples of these groups are R2,
There are the same ones listed in the description of R4, R7, Re S and R9.

Also, here Y, R,. , i, j and k have the same meanings as above.

However, at least one of R1 or R2 is +cll
t)tY(CHt)i(CF2)J+o, and R
3. At least one of R4゜Rs and R9 is +Cl1t) t Y(Clla) J (CF t
) represents J lo, Rs, R? , n, , at least one of R9 is +C1b) r Y(C1l□)J(CF2)itL
. , where Y.

RIG + 'I + J and k have the same meanings as above.

L,, L,,1,1,L,, L,, L,,L7,
La, Ls, L+o and Lll are methine groups or substituted methine groups (substituted with alkyl groups (e.g. methyl group, ethyl group etc.), aryl groups (e.g. phenyl group etc.) or halogen atoms (e.g. chloro, bromine etc.) xe represents an acid anion, specific examples include halide anion, alkyl sulfate anion, p-toluenesulfonate, etc.* nls nt, R3 and R4 represent 0 or 1, nr, lo, sentence 3, sL4 and ki represent 0.1.2 or 3, p represents 0 or 1.

General formula [engine], general formula [nl and/or general formula [m]
Specific examples of the compound represented by l are listed below, but the scope of the present invention is not limited thereto.

[Exemplary compounds] (2) Ce1ls ■ (Cut)tOcHt(CFt)J (Cut)*OCH*(CFt)tH (CH*)*C0NHCHt(CFt)tHCHICO
NI(CIll(CPri, H(CHs)aOcH*(C
Ft)sH CIIxCONIIC)It(CFJtH The above general formula [E], general formula [rl] and/or -C according to the present invention
The compound represented by formula [I11] (hereinafter referred to as the compound of the present invention) is described, for example, in Cyanine Soybean and Related Compounds (19
1964, published by Inter Science Publishers), Special Publication No. 46-549, No. 46-18105, No. 46-18106, No. 46-18108, No. 47-
No. 4085, No. 5B-52574, U.S. Patent No. 2,83
No. 9,403, No. 2,839,404, No. 3,384
, No. 486, No. 3,625,698, No. 3,48
Those skilled in the art can easily synthesize the compound according to the synthesis methods described in No. 0,439, No. 3,567.458, and the like. Furthermore, the method of introducing +GHt)iY(CIlt)j(Crt)hRto into the N-position, which is a feature of the present invention, can be easily carried out by the method described below.

Compounds in which Y is -CONH- are listed in "Journal of Organic Chemistry J (J, Org.

Cbc Shin, ), A, 4021 (1961), r
"Industrial and Engineering Chemistry" (Ind, & Eng, Chea,), 4
8,209 (1956) etc. using a fluorinated argylamine compound synthesized according to the method described in
It can be induced into a halogen alkylcarboxylic acid amide compound, and then synthesized by the method described in JP-A No. 61-294429 and the above-mentioned known method.

Compounds where Y is an oxygen atom are classified as “industrial and
Engineering Chemistry” (Ind, & En
g, Ches, ), 48, 445 (1956), Z
h, Vsses.

Him, o-va, 22(4), 489 (19
77), Khim, Prom-st.

Ser, Reakt, 0sobo, Chist, Ves
Synthesized according to Japanese Patent Application No. 61-68285 and the above-mentioned known method using a fluorinated alkyloxyalcohol synthesized according to the method described in J. Hchestva, 1979.55, etc., or a fluorinated alkyloxyalkylparite compound. be able to.

The compounds of the invention (sensitizing dyes) are used in amounts of 1 x 10-a mol-5 x 10-' mol, preferably 1 x 10-a mol to 2.5 x 10-' mol, particularly preferably 4 x 10-' mol, per mole of silver halide. It is contained in the silver halide emulsion in a proportion of -'mol-1x10-''mol.

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

For adding the compound of the present invention (sensitizing dye) to the emulsion, methods well known in the art can be used. For example,
These sensitizing dyes can be directly dispersed in the emulsion or dissolved in water-soluble solvents such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, fluorinated alcohols, or mixtures thereof; The sensitizing dye can be diluted or dissolved in water and added to the emulsion in the form of a solution.The sensitizing dye can be added to the emulsion at any time during the emulsion manufacturing process, but during chemical ripening. Or preferably 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 silver halide emulsions that can be optically sensitized to a desired wavelength range using a sensitizing dye are used to prevent fogging. Agents, stabilizers, etc. can be added. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other wood-philic colloid layers can be emulsion hardened, and can also contain a plasticizer and a dispersion (latex) of a water-soluble or sparingly soluble synthetic polymer. When used in color photographic materials,
A coupler is used in the emulsion layer. Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized product of a developing agent, a development inhibitor,
Development accelerator, bleach accelerator, developer, silver halide solvent,
Compounds that release photographically useful fragments such as toning agents, hardeners, fogging agents, antifogging agents, chemical sensitizers, spectral sensitizers and desensitizers can be used.

The photosensitive material includes a filter layer, an antihalation layer, an antiirradiation layer, and a protective layer. An auxiliary layer such as IN7 may be provided. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

For the photosensitive material 4), formalin scavenger, tit
Optical brighteners, matting agents, lubricants, image stabilizers, color cast inhibitors, development accelerators, development retarders and bleach accelerators can be added.

As a support, paper laminated with polyethylene, etc.
Bolier, tylene terephthalate film, baryta paper,
Cellulose triacetate etc. can be used.

Silver halide emulsions to which the compounds of the present invention can be applied include, for example, the silver halide emulsions described in the following patent publication,
That is, any of the normal crystal, twin crystal, core/shell type, and flat type (one particle) chamber with an aspect ratio of 5 or more can be applied.
B-100846, 5B-106532, 58
-107530, 58-108525, 58-
No. 108532, No. 58-113928, No. 58-1
No. 81037, No. 58-209730, No. 58-21
No. 1143, No. 58-211753, and the like.

Note that the type of silver halide is not limited either.

The photosensitive material of the present invention may be used for color or black and white negative photography, color or black and white vapor photography, X-ray photography, plate making, motion picture photography, color copying or the like.

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

[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 a double jet method, physically ripened by a conventional method, desalted, and further chemically ripened by a gold sensitization method and a sulfur sensitization method to obtain 47 mol% iodide. A silver iodobromide emulsion containing . The silver halide grains contained in this emulsion have (100) faces and an average diameter of 0.6
．． -It was.

0.60 mol of silver halide and 880 g of seratin binder are contained in 1 kg of this emulsion.

1 kg of this emulsion was weighed into a pot and heated to 40°C to dissolve it. Then, a methanol solution was added to each of the sensitizing dye according to the present invention and the comparative sensitizing dye at a dye concentration of 3 x
It was added so that the amount of silver was 10-'71 mol, and mixed and stirred.

Further, 20 mJL of a 1.0% by weight aqueous solution of 4-hydroxy-tomethyl-1,3,3a,7-chitrazaindene was added.

105M of a 1.0% by weight aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt was added, and then 105M of a 1.0% by weight aqueous solution of dodecylbenzenesulfonic acid sodium salt was added and stirred. This finished emulsion was applied to a cellulose triacetate film base with a dry film thickness of 5.
A sample of the photosensitive material was obtained by coating and drying so as to give a uniform pattern.

This sample was cut into strips and divided into two parts. 1m
Immediately after the sample was prepared (condition a), a photosensitive needle with a light source with a color temperature of 5400 @ was used, and a yellow filter was attached to the light source, and post-lateral exposure was performed. 20℃ using the developer with the following composition.
Developing was carried out for 1 minute, stopped, fixed, washed with water, and dried to obtain strips with a prescribed black and white image. The density of each processed sample was measured using an optical densitometer, and the sensitivity and fog were measured. The optical density reference point for determining the sensitivity was the fog +0.20 point.

Developer composition Metol 2g anhydrous sodium sulfite 4.0g hydroquinone
4g sodium carbonate/l hydrate
28g potassium bromide
Add 1g water to make 1fL.

The other part was left for one day at a temperature of 60° C. and a relative humidity of 70% (condition b), and then exposed and developed in the same manner as above, and the sensitivity and fog were measured.

The results are shown in Table 1.

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

Example 2 Cubic monodispersed silver chloroiodobromide emulsion (composition ^gc
l:AgBr:Agl=69=30:1
) was prepared according to a conventional method and subjected to gold-sulfur sensitization. This emulsion was divided, a sensitizing dye was added to each emulsion as shown in Table 2, and 2-methyl-4-hydroxy- 1,
3゜3a,7-chitrazaindene (3 g/silver 1 mol),
1-phenyl-5-mercaptotetrazole (10 g
/silver 1 mol), 3% saponin as a coating aid, polyethyl acrylate as a softening agent, the following polyalkylene oxide compound (600 g/m 1 mol) as a halftone dot improver, and an amount of gelatin attached to the emulsion layer 2 g/mole. gelatin was added so that the amount of silver deposited was 3.5 g/rn'', and the mixture was coated on a polyester base with a thickness of mm* at the same time as the following protective layer solution and dried.The above protective layer solution was gelatin, and the coating aid was It consists of octyl octyl ester, 4ILm silica as a matting agent, and mucochloric acid as a hardening agent.
It was simultaneously coated on the emulsion layer so that the amount of gelatin attached was 2 g/rn' and dried.

The coating sample obtained as described above was heated at a relative humidity of 80%.
This sample was left for 5 days at a temperature of 50°C, and this sample and the above sample, which had been stored for 5 days at a relative humidity of 40% and a temperature of 23°C, were exposed to a green light filter (Wratten-C) using a plate-making camera. Wedge exposure was performed through 58). After exposure, development was performed at 38° C. for 20 seconds using a developer having the following composition, and fixing was performed using Sakura Fixer Type 821.

(Developer-1) Hydroquinone 25g4.4
-Dimethyl-3-pyrazolidone 0.5g Potassium sulfite 100g Potassium bromide 3g Triethylene glycol 30g Polyethylene glycol (average molecular weight 150G) 3g5
-Nitroindazole 0.1 g 1R potassium acid 30 g Sodium ethylenediaminetetraacetate 2 g 5-Methylbenzotriazole 042 g The solution was brought to 11 with water and the pH was adjusted to 10.7 with caustic potassium.

The obtained results are shown in Table 2 below. In the table, sensitivity was evaluated based on the point showing a concentration of 3.0 on the characteristic curve.
The green sensitivity when stored at 23° C. and 40% RH of No. 1 is set as 100, and the relative sensitivity is displayed.

Also, the fog is displayed including the base concentration.

Furthermore, the gradation is expressed by the slope of the straight line on the characteristic curve. Furthermore, the numbers of the sensitizing dyes in the table are indicated by the numbers of the exemplified compounds.

Halftone dot improver Halftone improver [ff=30] [Comparative sensitizing dye] From the above results, the samples spectral sensitized using the dye according to the present invention are the same as those using the comparative sensitizing dye. Compared to comparative samples that were similarly spectrally sensitized, there was very little decrease in sensitivity even when stored under high temperature and high humidity, and there was also almost no increase in fog or decrease in gradation, indicating that it is extremely stable. Recognize.

Example 3 Polyethylene-coated photographic paper support containing 11% by weight of titanium oxide in anatase form (basis weight 170 g/m''
) was subjected to corona discharge machining, and on top of this, after adjusting the coating liquid, 2
Over time, the following seven photographic constituent threads were sequentially coated in layers to produce a color photographic material for printing. Furthermore, after 100 hours had elapsed after the preparation of the coating solution, another sample was prepared in the same manner as above.

Incidentally, unless otherwise specified, the amount of each substance added is expressed as the amount used per one substance, and the amount of silver halide is expressed in terms of silver.

Layer 1... (145 g of blue-sensitive silver chlorobromide emulsion (average grain size 0.70 #L, containing #198 mol% chloride, cubic crystal),
1.47 g of gelatin, and 0.8 g of yellow coupler (YC knee 1) dissolved in 0.4 g of di-Z-ethylhexyl phthalate (hereinafter abbreviated as DOP) and 0.
A blue-sensitive emulsion layer containing a color stain inhibitor ()IQ-1> of DISg.

Layer 2...1.03g of Ze, Latin, 0.03g of D
0.015 g of color stain inhibitor (HQ-1) dissolved in OP
＞A first intermediate layer containing ＞.

Layer 3... 0.40g of green-sensitive silver chlorobromide emulsion (average grain size 0.45JL, containing 97 mol% silver chloride, cubic crystal),
Green sensitive emulsion layer containing 1.85 g gelatin and 0.63 g magenta coupler (MC-1) and 0.015 g color antifouling agent (HQ-1) dissolved in 0.35 g DOP.

Layer 4...1.45g gelatin, 0.22g oop
0.2 g of ultraviolet absorber (UV-1) dissolved in 0.2 g of ultraviolet absorber (UV-1), 0.
3g (7) ultraviolet absorber (UV-2) and 0.05g (
7) Second intermediate layer containing color stain inhibitor (HQ-1).

Layer 5... 0.30 g red-sensitive silver chlorobromide emulsion (average grain size 0.40 JAII, containing 98 mol% silver chloride, cubic), 1.6 g gelatin, and 0.3 g DOP dissolved in 0, 42g of cyan coupler (CC-t) and 0
．． Red-sensitive emulsion layer containing 0.005g of color stain inhibitor (HQ-1).

Layer 6...1.45g gelatin, 0.22g DO
0.2 g of ultraviolet absorber (UV-I) dissolved in P, 0
．． Third intermediate layer containing 3g CD ultraviolet absorber (UV-2) and 0-05g color stain inhibitor (IQ-1).

Layer 7: Protective layer containing 1.8 g of gelatin.

(YC-1) 0g (HQ-1) CJ,? (t) (UV-1) H (UV-2) H (CC-1) R Surfactant A C=Ils C,H,CHCHt-OCOCH-3OsNaCJII
S At least one of the photographic constituent layers contains, as a hardening agent,
Bis(vinylsulfonylmethyl)ether and saponin were included as coating aids.

Photographic additive dispersion (yellow coupler dispersion) Yellow coupler (YC-1) 20g, color stain prevention agent (
HQ-1) 0.375g was dissolved in 20g of a high boiling point organic solvent and 40g of ethyl acetate. 1.3g of the obtained liquid
The mixture was mixed into 250 g of a 10% aqueous gelatin solution containing surfactant A with stirring, and then dispersed for 20 minutes using an ultrasonic disperser to obtain a dispersion.

Below, similar to the yellow coupler, other oil-soluble photographic additives (other couplers, ultraviolet absorbers) are listed below.

Dispersions were also produced using high-boiling point organic solvents (color stain inhibitors, etc.).

In addition, the blue-sensitive silver halide emulsion (layer 1), the green-sensitive silver halide emulsion (calendar 3), and the red-sensitive silver halide emulsion (layer 7)
iJ5) is IX1 per mole of silver halide emulsion.
Add 0-' mol of sodium thiosulfate, perform chemical ripening, and chemical iy! Five minutes after the completion of I formation, l! is added as a sensitizing dye for each emulsion layer. 11 and layer 5 contained the sensitizing dye of the present invention or a comparative sensitizing dye, and layer 3 contained the following sensitizing dye (D-1).
)3. OxlO-' moles were added as a 0.1% solution. 4-Hydroxy-tomethyl-1,3,3a as a stabilizer at the end of the chemical ripening.

7-Chitrazaindene was added as a 0.5% aqueous solution. Thereafter, a 10% gelatin aqueous solution was added, stirred, and then cooled to produce the mixture.

The obtained coating sample was divided into two parts, and one part was used with a photosensitive needle (manufactured by Konishiroku Photo Industry Co., Ltd., KS) to examine the stability of the coating solution over time.
Post-transverse exposure was carried out using a camera (type -7), and processing was performed according to the following processing steps. The sample sensitivity ratio (%) after 2 hours of application and 10 hours was determined and used as an index of the stability of the coating solution over time.

In addition, in order to examine the degree of color staining caused by the sensitizing dye after the development process, the other part was subjected to the same process as above without being exposed to light, and residual color was visually observed. Regarding residual color, it was expressed in 4 grades from the one with the least color staining, and is shown in Table 3.

Degree of color contamination 1: Very clean with only base concentration 2: Very slight color contamination 3: Weak coloring 4: Coloring processing process (32, 8°C) Processing time: Developing residual colors: 50 seconds Bleach-fixing: 50 seconds: Washing with water: 90 seconds (Color developing solution composition): Toethyl-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 10.0
-Imperial Polyethylene Glycol 3-OmJ
l (average degree of polymerization 400) Add water to make 11, and use potassium hydroxide to make pl+
10. [Adjust to l.

(Bleach-fix solution composition) Ethylenediaminetetraacetic acid iron sodium salt 60.0g Ammonium thiosulfate 100.0g Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Add water and IJ
1 and adjust the pH to 6.5 using sulfuric acid.

Redox potential -70■V Sensitizing dye D-1 From Table 3, the sensitizing dye according to the present invention has less color staining and less color staining than the comparison.
The coating liquid has excellent stability over time. This means that +CIl*)+Y((:1lJJ(CPt)h
R+.

It is shown that the sensitivity of the coated emulsion is maintained at a high level by introducing the above, and the obtained image is also shown to be a good image without color staining.

Claims (1)

[Scope of Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide grains contained in at least one of the silver halide emulsion layers are as follows: A silver halide photographic material characterized by being spectrally sensitized with a compound represented by the general formula [I], the general formula [II] and/or the general formula [III]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z_1, Z_2, Z_3 and Z_4 and Q_
1 and Q_2 each represent a nonmetallic atomic group necessary to form a 5- to 6-membered heterocycle, W_1 and W_2 represent an oxygen atom, a sulfur atom, or >N-R_9. R_1
, R_3, R_5 and R_6 are an alkyl group, a substituted alkyl group, or -(CH_2)_iY(CH_2)_j
(CF_2)_kR_1_0 is represented. R_2, R_4, R_7, R_8 and R_9 are bonded to nitrogen atoms contained in these nuclei, and are hydrogen atoms, alkyl groups, substituted alkyl groups, aryl groups, substituted aryl groups, heterocyclic groups, or -(CH_2) _iY(CH_2)_j(CF_2)_
Represents kR_1_0. However, at least one of R_1 or R_2 is −(C
H_2)_iY(CH_2)_j(CF_2)_kR_
1_0, and at least one of R_3, R_4, R_5, and R_9 is −(CH_2)_iY(CH_2)_j(CF_2)_
kR_1_0, R_5, R_7, R_8, R_9
At least one of them is -(CH_2)_iY(CH_2)_j(CF_2)-
It is R_1_0. Y is an oxygen atom or -CONH-(
However, the carbon atom of -CONH- is bonded to the -(CH_2)_i side), i is an integer of 1 to 10, j is an integer of 0 to 4, and k is an integer of 1 to 10. be. R_
1_0 represents a hydrogen atom, a lower alkyl group, or a fluorine atom. L_1, L_2, L_3, L_4, L_5, L_6, L
_7, L_8, L_9, L_1_0, and L_1_1 represent a methine group or a substituted methine group. X^e represents an acid anion. n_1, n_2, n_3 and n_4 represent 0 or 1. l_1, l_2, l_
3, l_4 and l_5 represent 0, 1, 2 or 3. p represents 0 or 1.