JPH0267542A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To obtain the novel sensitizing dye which provides high spectroscopicsensitivity by using specific compds. as the silver halide photographic emulsion. CONSTITUTION:At least one kind of the compds. expressed by the formula I are incorporated into the emulsion. In the formula I, Dye denotes a residual dye group having the chromophore expressed by the formula II; Hyd denotes a residual hydrazine group, one of the two nitrogen atoms of which is substd. with a carbonyl group, alkylidene group, etc.; L denotes a bivalent combination group which bonds Dye and Hyd. In the formula II, R, R1 denotes an alkyl group, Z, Z1 denote the atom group necessary for forming 5- to 6-membered heterocycle; Q denotes the atom group necessary for forming 5- to 6-membered carbon rings, etc.; A denotes an oxygen atom, etc.; (n), (d), (m) respectively denote 0 or 1. High spectroscopicsensitivity is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a silver halide photographic emulsion, and particularly to a silver halide photographic emulsion containing a spectral sensitizing dye having a hydrazine derivative as a substituent group. be.

(Prior art) Spectral sensitization technology in silver halide photography is known and is an important technology as a means of expanding the sensitive wavelength range of silver halide photographic emulsions from the inherent sensitivity range of silver halide to the longer wavelength side. It becomes. The sensitive wavelength range can now be adjusted almost to the infrared range by selecting the structure of the sensitizing dye according to the desired purpose.

However, there is a strong desire for silver halide photographic emulsions having higher sensitivity, and great efforts are being made day and night to improve the sensitivity of emulsions. Against this background, it is a natural consequence that there is a need for the development of new sensitizing dyes that can provide higher spectral sensitivity.

One way to develop a sensitizing dye that can provide higher spectral sensitivity is to increase the original absorption rate, and based on this idea, US Patent No. 3.
t22.317, 3゜27 Otsu, Hiroshi 23, 3. There is No. 74, 4 Hiro O. Another approach is to remove the desensitizing factor caused by sensitizing dyes. Many examples of so-called supersensitization are known based on this idea. In addition, desensitization factors include inhibition of development by sensitizing dyes, and for this, the use of a development accelerator can be considered.

However, ordinary spectral sensitizing dyes often lack coexistence with other components contained in silver halide emulsions. Therefore, even if a development accelerator is simply used in combination, the desired effect cannot necessarily be obtained.

The reason for this lack of coexistence is considered to be a competitive phenomenon between the sensitizing dye and other chemical components to occupy positions on the silver halide grain surface. Intended to avoid such a competitive phenomenon, the relationship between the nucleating agent and the sensitizing dye is as follows:
2671r, U.S. Patent No. 3,7/1,1170, Research Disclosure
The concept and compound examples are described in Section 11162, February 2007. however,
In any case, there is no description suggesting that competitive phenomena can be avoided, nor is there any description indicating that a higher spectral sensitivity than ordinary sensitizing dyes is provided.

Also, Tokukai Shout No! Tata! Although it is stated in No. 3 that higher spectral sensitivity can be obtained, it is desired to obtain even higher spectral sensitivity.

(Problem to be Solved by the Invention) That is, the first objective of the present invention is to provide a novel sensitizing dye that provides high spectral sensitivity, and the second objective is to provide a novel sensitizing dye that provides high spectral sensitivity. ) An object of the present invention is to provide a silver oxide photographic emulsion.

(Means for Solving the Problems) As a result of intensive research efforts to achieve these objects, the present inventors have discovered that a compound represented by the following general formula (1) can be used in a silver halide photographic emulsion. The inventors have discovered that the above object can be achieved, and have completed the present invention.

General formula (1) % formula %) [In the formula, Dye represents a dye residue having a chromophore represented by the following general formula (It), and Hyd represents a dye residue in which 10,000 of the λ nitrogen atoms are carbonyl groups or sulfonyl groups. , represents a hydrazine residue substituted with a sulfoxy group, a phosphoryl group, or an alkylidene group. L represents a divalent linking group that connects Dye and Hya.

General formula (n) In the formula, R and R1 may be the same or different, each represents an alkyl group, and Z and Zl may be the same or different, ! represents a group of atoms necessary to form a 6-membered heterocycle.

Q is! Indicates the atomic group necessary to form a to t-membered carbocycle or heterocycle. A represents an oxygen atom or a sulfur atom, %n%d, and m are respectively Q or 7'1jI: Table 1. ] To explain in more detail, it is formed by 2 and zl! Examples of the t-membered heterocycle include the following.

Thiazole nucleus (e.g., thiazole, Hiro-methylthiazole, gouphenylthiazole, Hiro,!-dimethylthiazole, Hiro,!-diphenylthiazole), benzothiazole nucleus (e.g., benzothiazole, ≠-chloropenzothiazole, !-ria lobenzothiazole, 6-
Chlorobenzthiazole! -nitrobenzothiazole, ≠-methylbenzothiazole, termethylbenzothiazole, t-methylbenzothiazole,! -Glomobenzothiazole, 6-bromobenzothiazole, j-iodobenzothiazole, j-phenylbenzothiazole,
! -methoxybenzothiazole, t-methoxybenzothiazole,! -Ethoxybenzothiazole, j-ethoxycarbonylbenzothiazole, j-carboxybenzothiazole, j-7enethylbenzothiazole,! -fluorobenzothiazole, 1-chloro-6-methylbenzothiazole,! 96-Simethoxybenzothiazole,
j, G-dioxymethylenebenzothiazole,! -acetylaminobenzothiazole, j, i<-dimethylbenzothiazole,! -Hydroxy-t-methylbenzothiazole, tetrahydrobenzothiazole, hiro-phenylbenzothiazole, etc., f7 tothiazole nucleus (e.g., Na7) (J, /-d) thiazole, nut [1, no d] thiazole, naphtho [ 2,3-dJ thiazole,!
-methoxy7f(/,nod)thiazole,7-nitoxynut[co,/-d)thiazole,r-methoxyf
7 [λ, /-dnotiazole,! -Metki 7 Naft [
Co, J-dJ thiazole, r, y-dihydronat (/
, λ-d]thiazole, etc.), thiazoline core (e.g.,
thiazoline, ≠-methylthiazoline, Hiro-nitrothiazoline, etc.), oxazole core (e.g., oxazole,
goomethyloxazole, Hiro-nitrooxazo-A/,
j-methyloxazole, 4t-phenyloxazole, Hiroshi! - diphenyloxazole, goomethyloxazole, etc.), benzoxazole nucleus < benzoxazole,! -Chlorobenzoxazole,! -Methylbenzoxazole, z-yamobenzoxazole,! −
Fluorobenzoxazole, j-phenylbenzoxazole, j-methoxybenzoxazole, j-nitrobenzoxazole, jl”lifluoromethylbenzoxazole, !-hydroxybenzoxazole, !
- Ruboxybenzoxazole, A-methylbenzothiazole, a-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, j, J-dimethylbenzoxazole, ≠, 6- Methylbenzoxazole! -ethoxybenzoxazole nato), naphthoxazole nucleus (e.g. f7to[ko, 1-dJ oxazole, nut(/,, 2-dJ oxazole, natu[ko, j-d)oxazole, !-nido of''7to [
λ, /-d]oxazole, etc.), oxazoline nucleus (e.g., Hiro, Hiro-dimethyloxazoline, etc.), selenazole nucleus (e.g., Hiro-methylselenazole, ≠-nitroselenazole, ≠-phenylcelecazole, etc.), Penzocelecazole core (e.g. benzoselenazole, !-
Chlorobenzoselenazole! -Nitrobenzocelecazole,! -Methoki7 benzocelecazole,! -hydroxybenzocelecazole, 6-nidrobenzocelecazole, j-chloro-bu-nitropensoceleosole, etc.λ,
Force 7 Toselenazole nucleus (e.g. naphtho[λ,/-d)
selenazole, nut (/, J-d) selenazole, etc.), 3°3-dialkylindolenine nucleus (e.g., 3.
3-dimethylindolenine, i,i-diethylindolenine, 3,3-dimethyl-yo-cyanoindolenine, 3
．． 3-dimethyl-t-nitroindolenine, J, J
-Dimethyl-yo-nitroindolenine, 3,3-dimethyl-! -Methoxyindolenine, J, 3. j-) Limethylindolenine, 3゜3-dimethyl-! - cloa indolenine 71Zl, imidazole nucleus (e.g. l-alkylimidazole, l-alkyl-pi-phenylimidazole, /-furkylbenzimidazole, l-alkyl-r-chlorobenzimidazole, l-alkyl-!,
t-dichlorobenzimidazole, l-alkyl-
Methoxybenzimidazole, /-alkyl-! -cyanobenzimidazole, /-alkyl-! -fluorobenzimidazole, l-alkyl-y-trifluoromethylbenzimidazole, l-alkyl-t-chloro-
1-77 nobenzimidazole, l-alkyl-4-p
acoch-trifluoromethylbenzimidazole,
l-alkylcapto(/,λ-d]imidazole, l-
Allyl! , t-dichlorobenzimidazole, l-allyl-! -chlorobenzimitazole, l-arylimidazole, l-arylbenzimidazole, /-aryl-y-chlorobenzimidazole, l-aryl-jlt-dichlorobenzimidazole, l-aryl-y-methoxybenzimidazole, l- Ariel!
-cyanobenzimidazole, l-aryl f″7(
/.

2-d] imidazole, the alkyl group mentioned above is a carbon atom/
-r such as methyl, ethyl, propyl,
Unsubstituted alkyl groups such as isopropyl and butyl, hydroxyalkyl groups (flJ, t#:I', no-hydroxyethyl, 3-hydroxypropyl, etc.) are preferred. Particularly preferred are methyl group and ethyl group. The aforementioned aryl represents phenyl, halogen (e.g. chloro) substituted phenyl, alkyl (e.g. methyl) substituted phenyl, alkoxy (e.g. methoxy) substituted phenyl, and the like. ), pyridine nucleus (e.g. 2-pyridine, ≠-pyridine, !-
J, quinoline nuclei such as methyl-no-pyridine, 3-methyl-no-pyridine, etc. -fluoronoquinoline, t-methoxy-λ-quinoline, t
-Hydroxyalquinoline, t-chloro-Hiro-quinoline, Hiro-quinoline, -ethoxy-≠-quinoline, -dito-a-μm quinoline, t-chloro-Hiro-quinoline, r-
fluoro-hiro-quinoline, t-methyl-hiro-quinoline,
r-methoxy-≠-quinoline, isoquinoline, t-nitro-7-in quinoline, 3. p-cihytrol-inoquinoline, 6-nitro-3-isoquinoline, etc.], imidazo (#, j-b) quinoxaline core (e.g., 1,3-diethylimidazo [μ, j-b) quinoxaline, t-chloro-/ , J-diallylimidazo [μ, t-b) quinoxaline, etc.], oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, and piri gin nucleus.

Formed by Q! Examples of the t-membered ring include the following. For example, rhodanine nucleus, corchiohydantoin nucleus, corchioxooxazolidine-one nucleus, novirazolin-j-one nucleus, barbital acid group, λ-thiobarbital acid group, thiazolidine-co, ko-dione nucleus,
These include thiazolidine-≠-one nucleus, inoxacillone nucleus, hydantoin nucleus, and indandione nucleus.

Formed by Z and zl! The t-membered heterocycle is preferably a thiazole nucleus, and particularly preferably at least one of the rings is a nat[l, nord]thiazole nucleus. The 57'l:t-membered ring formed by Q is particularly preferably a barbyl acid group.

Examples of the alkyl group represented by R1 include carbon atoms/~it, preferably 7 to 7, particularly preferably l-alkyl groups (unsubstituted alkyl groups (e.g., methyl, ethyl, propyl, isopropyl) , Gutil,
methyl, hexyl, octyl, dodecyl, octadecyl, etc., substituted alkyl groups, such as aralkyl groups (eg benzyl, -phenylethyl, p-sulfo-!
-7enethyl, etc.), human myxylargyl groups (e.g., eva, λ-hydroxy7ethyl, 3-hydroquinepropyl, etc.), carboxyalkyl groups (e.g., λ-carboxyethyl, 3-carboxypropyl, d-carboxygether, Carboxymethyl etc.J.

Alkoxyalkyl groups (e.g., nomethoxyethyl,
λ-(nomethoxyethoxy]ethyl, etc.), sulfoalkyl groups (e.g., nosulfoethyl, 3-sulfopropyl, 3-sulfobutyl, μm sulfobutyl, 2-(J
-sulfopropoxy]ethyl, -monohydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, etc., sulfatoalkyl group (91e, 3-sulfatopropyl, gasul7atobutyl, etc.), heterocyclic substituted alkyl M ( flJ, such as λ-(pyrrolidin-on-/-yl)ethyl, tetrahydrofurfuryl, etc.),
(lambda-acetoxyethyl, carbomethoxymethyl, lambda-memensulfonylaminoethyl, allyl group, etc.).

The hydrazine residue represented by Hyd is preferably a 7-enylhydrazine residue, in which 10,000 of the λ nitrogen atoms are formyl groups, and the number of carbon atoms is ! Those substituted by lfi with the following alkylcarbonyl or benzoyl groups are preferred. Particularly preferred is the case where Holval is substituted. Therefore, heformylphenylhydrazine residues are most preferred.

Examples of the divalent linking group represented by L include the following.

-O--CH2--NH--CON)i-5O2NH
-1- to H3O2--N)icN)l -Of the above,
-CONHl-8O2 to H--NHCNH- is preferred.

Examples of the compound represented by the general formula (1) of the present invention are shown below, but the scope of the present invention is not limited thereto.

-t For the synthesis of the compound group represented by the general formula (1), the general formula (I
It can be synthesized using either of the following methods: a method in which the dye moiety represented by I) is synthesized and then linked to the hydrazine moiety through an amide bond, etc., or a method in which the hydrazine moiety is linked at the intermediate stage and then dyed. It is possible. The formation of these bonds is described, for example, in [Organic Functional Group Preparations J (OrganicFu
nctional Group Preparati
ons), S, R, Sandra (5andler); W
, Karo (written by KaroJ, published by Academic Publishing (h6v)
York.

This can be easily done by referring to the annual publication of London)/ftr. The synthesis of the hydrazine derivative moiety is described, for example, in JP-A No. 3-2092/, JP-A No. 13-202-2, J.
"J-46732, 13-203/r description, or Research Disclosure (RESERC) II
It can be easily synthesized by referring to the literature cited in DISCLO8 [JRE] magazine (February 2013 issue, No. 3 μt page - 3, page 3), y1623110.

The compound represented by general formula (It), which is the dye moiety of the compound represented by general formula (I) of the present invention, is manufactured by F.M. Bermer (F,M).

Hamar) IF r Heterocyclic Compound Zucyanine Gui and Related:,
7. +! Unzu (Heterocyclic Comp
ounds-Cyanine dies andre
rated compounds-)JChapter 1J-Chapter 64CJ~t4csx<John Wiley & Sons John Wiley & Sons Company-2! −
It can be synthesized based on the description of ``York, London, 1996''.

Next, synthesis examples of representative compounds among the compounds represented by the general formula (N) will be described.

Synthesis Example 1> l-Gutyl-3-ethoxy7carbonylmethylurea In a 500 yd Mirofask equipped with a stirrer, a thermometer, a dropping funnel, and an air condenser, 7 kJ of glycine ethyl hydrochloride≠, 2i<o, 25 mol 2 and acetonitrile solution were mixed together and stirred in an ice-salt bath. Subsequently, triethylamine oil was added. Internal temperature is o'C
n-butyl isocyanate 2!19 (
0,2! λ mole) is the internal temperature! It was added dropwise at 0C or lower. After the dropwise addition, the mixture was similarly stirred for 2 hours. Filter out the precipitated salt,
The reaction solution was concentrated under reduced pressure in a water bath of 4 tr'c or less. 200ml of water 7j# was added to the concentrated residue and extracted with 200Kl of chloroform. The extract was dried by adding magnesium sulfate. The solvent was distilled off under reduced pressure to obtain urea derivative (I) in the amount of jPg. Yield Quantitative White waxy <JilJ2>/-
Glythyl-3-ethoxycarbonylmethylbarbylic acid A stirrer, thermometer, dropping funnel, and cooling tube were installed/
Urea derivative (N70.99 (0,
2! mole) and acetonitrile 3ooy and 'Ik7yl]
The mixture was then stirred in an aqueous salt bath. Malonic acid dichloride J r, ig (0, 2
g mol) was added dropwise to 1:r oC or less. After the dropwise addition, the mixture was stirred for 2 hours in the same manner.Then, the internal temperature was returned to room temperature,
The mixture was further heated and stirred for 3θ minutes at an internal temperature of jO°C. 7 of the reaction solution
．． 2 in ice water. Extracted with 100ml of chloroform and dried over magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 63.2 g of barbylic acid derivative (ill
Obtained. Yield: 4g% Brown oil <Synthesis Example 3>/-Gutyl-3-carboxymethylbarbital acid Thermometer and reflux condenser? In a 100 ml Mirofask attached, 3.2 g of barbylic acid derivative (11) A and concentrated hydrochloric acid / 00rnl and 'a-7JD were added, and the internal temperature in the oil bath was ≦
The mixture was heated and stirred at OoC for 30 minutes. Subsequently, the oil temperature was raised and the mixture was stirred and refluxed. Add 20 ml of hydrochloric acid in half an hour,
Refluxing was continued for an additional 3 hours. After cooling, add 20% to the reaction mixture.
Add 0 ml of water and extract with 200 ml of chloroform. After washing the extract with water seven times, it was dried over magnesium sulfate. The solvent was distilled off under reduced pressure to hydrolyze the ester of (II) (ill) Yg2.7. ! i! Obtained. Yield 7 grams! H Brown oil (Synthesis example≠) l-butyl-3-carboxymethyl-4-(/-(J-ethyl-J(j)I
J-naphtho (/, no d) thiazolinylidene J-propyl-2-ylidenecobarbituric acid (11) in a /l Mirofask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser.

<HBo, io mol J and 3-ethyl-2-methyl-β-
7 Tothiazolium tosylate 3! , 2g (0,02 mol) and orthoacetic acid ethyl ester, Z7.jp (0,
/rmok)-pyridyjtOyl was added, and the mixture was heated and stirred on a hot water bath. Internal temperature! θ~! ! After setting it to 0C, triethylamine≠! d was added dropwise. Soma 1! After stirring with heat for λ hour, the reaction solution was added to 1 liter of ice water. Next, while stirring well, gradually add hydrochloric acid, and adjust the pH of the liquid.
Adjusted to 3 to Hiroshi. While stirring for an additional hour at room temperature, most of the dye crystallized. The crude crystals of the dye were collected by filtration and washed with water.

Rinse the crude crystals with acetonitrile (00 rsl) and water with Od/triethylamine 2λ,! Salt production @22. ! td was added and purified by acid precipitation.

Dimetine merocyanine (IV) t'λ7. /i got it.

Yield 4/% orange-red crystal mp, 2jJ~Jj Hiro'Cλm
ax(MeOH)44P Onmku Synthesis Example j＞/-Butyl-j-(/-(J-ethyl-2(!H)-su7t(
/,,2-dJ thiazolinyritene J2'a virukoilytene)-3-(1'l-(Hiro-(noformylhydrazino)7enyl)carbamidomethyl)barbylic acid Stirrer and air with chloride calclum tube material at the tip Dimethine merocyanine (■)!, 79 (o, o// 1 mol) and l-formylluco-(≠-aminophenyl)-hydrazi 7/, ri 2/ were placed in a 100xl three-loaf flask equipped with a condenser.
l (0.0/2r% l) and 200 nl of pyridine in 7J
D got it. Furthermore, N,N'-dicyclohexyl flare! ,
rg (0,0/7 μmol)? In addition, the mixture was stirred at room temperature for 4 tr hours.

Subsequently, 20 al of acetonitrile was added to the contents to disperse them, and the crude crystals were collected by filtration. The crude crystals were concentrated and recrystallized twice using a mixed solvent of methanol and chloroform. Dimethine merocyanine amide conjugate (V)w7ro19 was obtained. Yield 1% Orange-red crystal mpJj7-240'C
λmax(MenH) data Onm Synthesis example t>i-butyl-j-(((J-ethyl-2(
3H)-naphtho(/, nod]thiazolinylidene] methyl J-NJ-methyl-2(3H)-f7to(/, ?-
d]Thiazolinylidenemethyl]methylidene)-J-(
N-(≠-(no-formylated dorazino)phenyl]-carbamidomethyl)barbylic acid (Compound Example I-/) (V)rxomy(t) in a 100 ml Mirofask equipped with a stirrer, thermometer and reflux condenser.

3/mmol), 3-methyl-metherthio β-nandothiazolium doolet OOη (31 mmol), and some dimethylacetamide were added and stirred on a water bath. Subsequently, after adjusting the internal temperature to 70 to 7z 0c, triethylamine o and bRt were added. After heating and stirring for 2 hours, the reaction solution was added to Oyd of ethyl acetate. The precipitated crystals were collected by filtration, and concentrated and recrystallized twice using a mixed solvent of methanol and chloroform. Target compound 4! I got lO■. Yield 3r% Dark green crystal m p
213~,2jj'Cλmax-trnmIn order to incorporate the compounds represented by the above general formulas (I) and (n) into the silver halide emulsion of the present invention, they may be directly dispersed in the emulsion. or water, methanol, ethanol, polyol, methyl cellosolve, 2,2,3
．． It may be added to the emulsion after being dissolved in a solvent such as 3-tetrafluoropropatol, N,N-dimethylformamide, etc. alone or in a mixed solvent. Also, special public Showa 4L Hiro-λsi
rri issue, special public showa 4c guichi 27! ! ! As described in Japanese Patent Publication No. Shoj7-CocoOr, etc., an aqueous solution is prepared by coexisting an acid or a base, or as described in US Patent I, rλλ, 13! No., U.S. Patent Office, oot, oco! A water bath solution or a colloidal dispersion may be added to the emulsion in the presence of a surfactant as described in No. 1, etc. Alternatively, after being dissolved in a substantially water-immiscible solvent such as phenoxyethanol, a dispersion in water or a hydrophilic colloid may be added to the emulsion. JP-A-Sho pi-io No. 2733, JP-A-Sho RR-10! //I
As described in No. 1, it may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion.

The sensitizing dye used in the present invention is described in US Patent No. 3. ≠rz,t
Melting may also be carried out using ultrasonic vibrations as described in No. i4A. Other methods for adding the sensitizing dye of the present invention by dissolving or dispersing it into an emulsion include US Patent No. 3. Hiro 12. 1/No. 3, No. 111.191, s.
aty, ri lr No. 7, ri lr No. 3, 'l-21, 13j,
Same 3.3 Hiro 2.60! No., British Patent/ , , z7/ ,
No. 329, same/, 03! .

No. 02, same/, /21. /74L, US Patent 3゜t
The methods described in to, ioi, i, try, and zμ can be used.

Here, the sensitizing dye can be present in any step of the photographic emulsion manufacturing process, or can be present at any stage at 1° C. after manufacturing and immediately before coating. An example of the former is 1. These include a silver halide grain formation process, a physical ripening process, a chemical ripening process, and the like. An example would be Tokukai Akihito! -2tz
It may be added to r2car2tzr during particle formation.

The sensitizing dye of general formula (1) used in the present invention has a ratio of X/Q % A/~2×10−3 mol, preferably /X10 mol to 1×10−3 mol, per mol of silver halide.
It is particularly preferably contained in the silver halide photographic emulsion in an amount of /X/0-5 mol-/X10 mol.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide in the photographic emulsion of the present invention.

The silver halide grains may have any crystal phase.1 The silver halide emulsion used in the present invention has a thickness of 0.5 microns or less, preferably 40.3 microns or less, and a diameter of preferably 0.6 microns or more. It may also be a tabular grain in which grains with an average aspect ratio of 5 or more occupy 50% or more of the total projected area.

The emulsion may be a monodisperse emulsion in which particles having a particle size within ±40% of the average particle diameter account for 95% or more of the number of particles.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

It may also be a grain in which a latent image is mainly formed on the surface (for example, a negative emulsion), or a grain in which a latent image is mainly formed inside the grain (for example, an internal latent image emulsion, a pre-fogged direct reversal emulsion). It may be.

The photographic emulsion used in the present invention is B. gelafchides (
"Chimie et Phy Photography" by P. Glafkides
photographique) J (Paul Montel, 1967)
), G.F.

Duffin) “Photographic Emulsion”
Chemistry (Photographic E+5ul
sion Chemistry) J (Focal Press, 1966), V, L, Zelikman et al.
Making and Coating Photographic Emulsions (Making and Coating Photographic Emulsions)
CoatingPhotographic Emul
sion) J (Focal Pre
It can be prepared using the method described in, for example, Published by S.S. Co., Ltd., 1964).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (for example, U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574, U.S. Pat. No. 628, No. 3,704,130.

No. 4,297,439, No. 4,276.374
etc.), thione compounds (e.g. JP-A-53-14431
No. 9, No. 53-82408, No. 55-77737
), amine compounds (e.g. JP-A-1007-1987), amine compounds (e.g.
No. 17, etc.) can be used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, zinc salt, thallium salt, iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

In addition, examples of internal latent image type emulsions used in the present invention include, for example, U.S. Pat.
No. 13, No. 3,447,927, No. 3,761. ．． 2
Examples include emulsions incorporating different metals as described in No. 76, No. 3,935.014, No. 1, and the like.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H Freeza () 1
．． Fr1esar) ed.
erPhotographischen Prozes
se mit Silver-halogenidan
)J (Akademische Verlag) Akadem
ischaVerlagsgesellschaft
, 1968), pages 675-734, can be used.

That is, sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas).

mercapto compounds, rhodanines); reduction sensitization using reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g. , total complex salts, as well as pt, ph.

A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as Ir and Pd can be used alone or in combination.

More specific chemical sensitizers include sulfur sensitizers such as allylthiocarbamide, thiourea, sodium thiosulfate and cystine; noble metals such as bottasium chloroaurate, aurous thiosulfate and bottasium chlorovaladate. Sensitizers: may include reduction sensitizers such as tin chloride, phenylhydrazine, and reductone, and may also include sensitizers such as polyoxyethylene compounds, polyoxypropylene compounds, and compounds having quaternary ammonium groups.

The photographic emulsion used in the present invention is used for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance.

Various compounds can be included. Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercapto. Benzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (special number 1-phenyl-5)
-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfo group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3
Many compounds known as antifoggants or stabilizers can be added, such as (13a, 7) tetraazaindenes); benzenethiosulfonic acids: benzenesulfinic acid;

The silver halide emulsion of the present invention is disclosed in U.S. Pat.
No. 11, No. 3,411,912, No. 3,142,56
No. 8, No. 3,325゜286, No. 3,547,650
Polymer latexes made of homo- or copolymers of alkyl acrylates, alkyl methacrylates, acrylic acids, glycidyl acrylates, etc., described in Japanese Patent Publication No. 45-5331, etc., are used to improve the stability of photographic materials and improve film properties. It can be included for purposes such as improvement.

When the silver halide emulsion of the present invention is used as a lithium-type photosensitive material for printing, a polyalkylene oxide compound that enhances the contagious development effect can be used. For example, US Pat. .294,53
No. 7, Specification No. 3,294,540, French Patent No. 1
, No. 491,805, Specification of No. 1,596,673, Specification of Japanese Patent Publication No. 40-23466, Japanese Unexamined Patent Application Publication No. 50-15
No. 6423, No. 54-18726, No. 56-1519
Compounds such as those described in No. 33 can be used. Preferred examples are alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2
- oxide, butylene-1,2-oxide, etc., preferably a polyalkylene oxide consisting of at least 10 units of ethylene oxide, and at least one active hydrogen atom such as water, aliphatic alcohol, aromatic alcohol, fatty acid, organic amine, hexitol derivative, etc. It includes a condensation product with a compound having a polyalkylene oxide, a block polymer of two or more types of polyalkylene oxide, and the like. That is, specific examples of polyalkylene oxide compounds include polyalkylene gelyl alkyl ethers, polyalkylene gelicol aryl ethers, polyalkylene glycol alkyl aryl ethers, polyalkylene glycol esters, and polyalkylene glycol fatty acid amides.

Polyalkylene glycol amines, polyalkylene gellicol block copolymers, polyalkylene glycol graft polymers, and the like can be used. The polyalkylene oxide compound that can be used has a molecular weight of 300 to 15,
000. Preferably 600-g, oo.

The amount of these polyalkylene oxide compounds added is preferably 10.about.3 g per mole of silver halide, and the addition time can be selected at any time during the manufacturing process.

The silver halide photographic emulsion of the present invention can contain color pigments such as cyan coupler, magenta coupler, yellow coupler, etc.
It can include a coupler and a compound that disperses the coupler.

That is, in color development processing, aromatic primary amine developers (for example, phenylenediamine derivatives, etc.) are used.

It may also contain a compound that can develop a color by oxidative coupling with an aminophenol derivative (such as an aminophenol derivative).

For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetyl coumaron couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetonitrile couplers.
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive ones that have a hydrophobic group called a ballast group in the molecule.Couplers can be either 4-equivalent or 2-equivalent to silver ions, and colored couplers that have a color correction effect are preferred. Alternatively, it may be a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to the DIR coupler, the coupling reaction product may include a colorless DIR coupling compound which is colorless and releases a development inhibitor.

The silver halide photographic emulsion of the present invention may contain water-soluble dyes (eg, oxonol dyes, hemioxonol dyes, and merocyanine dyes) as filter dyes or for various purposes such as preventing irradiation.

The photographic emulsion of the present invention contains various surfactants for various purposes such as coating aid, antistatic, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). May include.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol), polyethylene glycol alkyl ethers, glycidol v
Nonionic surfactants such as I conductors, fatty acid esters of polyhydric alcohols, alkyl esters of sugars; anionic interfaces such as alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfate esters, etc. Activator: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium,
Heterocyclic 4R ammonium salts such as imidazolium,
Cationic surfactants such as can be used. Further, when used as an antistatic agent, a fluorine-containing surfactant is preferred.

In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include hydrokenols and the like.

The photographic emulsions of the invention may contain inorganic or organic hardeners, such as chromium salts (chromium alum).

chromium acetate, etc.), aldehydes (formaldehyde,
glyoxal, geltaraldehyde, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2
- propatool, etc.), active halogen compounds (2,4-
dichloro-6-hydroxy-5-triazine, etc.), etc. can be used alone or in combination.

The photosensitive material produced using the present invention contains hydroquinone derivatives, aminophenol derivatives,
It may also contain gallic acid derivatives, etc.

In the silver halide photographic emulsion used in the present invention, in addition to gelatin, protective colloids include acylated gelatin such as phthalated gelatin and malonated gelatin, cellulose compounds such as hydroxyethyl cellulose and carboxymethyl cellulose; Soluble starch; polyvinyl alcohol, polyvinylpyrrolidone, hydrophilic polymers such as polyacrylamide and polystyrene sulfonic acid, plasticizers for dimensional stabilization, latex polymers and matting agents may be added. Completion (finis)
hed) The emulsion is coated onto a suitable support, such as baryta paper, resin-coated paper, synthetic paper, triacetate-1-film, polyethylene terephthalate film, other plastic bases or glass plates.

Exposure to obtain a photographic image may be carried out using conventional methods: natural light (sunlight), tungsten electric lamps,
Fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, lasers, LEDs, (, RT
Any of a variety of known light sources can be used. Exposure times include not only exposure times of 1/1000 seconds to 1 second, which are normally used in cameras, but also exposure times shorter than 1/1000 seconds, such as 1/10' to 1 seconds using a xenon flash lamp.
Exposures of /10" seconds can be used, or exposures longer than 1 second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted with color filters. Laser light can be used for exposure. Alternatively, exposure may be performed with light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like.

The spectral sensitizing dye of the present invention is used for sensitizing silver halide photographic emulsions for various color and black and white light-sensitive materials. Emulsions used include, for example, color positive emulsions, color paper emulsions, color negative emulsions, color reversal emulsions (which may or may not contain couplers), and photosensitive materials for plate making (such as lithographic film). Emulsions used in light-sensitive materials for cathode ray tube displays, emulsions used in silver salt diffusion transfer processes, emulsions used in color diffusion transfer processes, imbitio transfer processes
s) (described in U.S. Pat. No. 2,882,156, etc.), emulsions used in silver dye bleaching methods, materials for recording printout images (e.g., U.S. Pat. No. 2,3
69,449 etc.), the emulsion used in the photo-developable printing process Direct Pr1nt im
age) photosensitive materials (e.g., U.S. Pat. No. 3,033,68
2), and emulsions used in color photosensitive materials for heat development.

Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure)
Disclosure) No. 176, pages 28-30 (R
D-17643), any of the known methods and known treatment liquids can be applied.

This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. The processing temperature is usually chosen between 18°C and 50°C, but 18°C
Lower temperatures or temperatures above 50°C may also be used.

(Examples) In order to explain the content of the present invention more elegantly, Examples will be described below, but the present invention is not limited to these Examples.

Example-1 In a reaction vessel, add 1 ml of water/000 ν, deionized bone gelatin λ19.10% NH4 aqueous solution 1 ml, and add H3 aqueous solution 7. 710116 of AgNO3 aqueous solution.
and/N-KBr aqueous solution was added over 50 minutes to saturate the silver potential during the reaction and permanently maintain it at +jOmV with respect to the electrode.

The obtained silver bromide particles were cubic, with side lengths of 0.7r±o,
It was otμm. The above emulsion is desalted and deionized bone gelatinta! After adjusting g and Mizuhiro 30ml and adjusting p) i = j, j, and pAg = r, 3 with zooc,
Add sodium thiosulfate for optimal sensitivity! j0
It was aged for 50 minutes at C. This emulsion IKP contained 0.7 hmol of silver bromide.

Each log of this emulsion was sampled, and sensitizing dyes were added as shown in Table 1, and Hiro-hydroxy-4-methyl-/
,! , 3a,7-chitrazaindene f10■, 10% gel of deionized gelatin/! g.Water! −rmJ,'
? 7JO was coated on a polyethylene terephthalate film base as follows. For comparison, samples using sensitizing dyes (S-/), (S-23, and (S-3)), which will be described later, were also tested.

The amount of silver in the coating solution is λ, ! , j9/m2, gelatin 3.1177 m, and sodium dodecylbenzenesulfonate 0.2 in the upper layer to give gelatin 11/,0, jil/m2.
2 g/l, p-sulfostyrene catrium homopolymer o, r.

El/1. Co, 4'-dichloro-6-hydroxy-
/.

3,! - Sodium triazine J, /9/l, gelatin! An aqueous solution containing the 09/lY product was simultaneously applied.

Each of these samples was exposed to tungsten light through a continuous wedge using a blue filter (a bandpass filter that transmits light with wavelengths longer than 600 nm) and a red filter (a filter that transmits light with wavelengths longer than 600 nm). (21rrILt'K) for 1 second.

After exposure, it was developed for a period of time at 20C'C using a developer having the composition shown below. The density of the developed film was measured using a densitometer manufactured by Fuji Photo Film Co., Ltd., and the red filter sensitivity (
SR), blue film quality (SB), and fog were determined. The reference point for the optical density that determined the sensitivity was [Cub IJ +
0,. It was a point of 2 J. In addition, SR and SBf
"1100 (reference) Displayed as relative sensitivity to VC.

[Developer composition J water 700
rnlmetol 3. /ji Anhydrous sulfite power thorium! ltr/j Hydroquinone /, 2g Zitorium carbonate (-water salt) 7 Liy Potassium bromide
/, RiI MizugaT, Ete
When using 1 liter, add twice the amount of water to prepare a working solution.

The results obtained are shown in Table 1 as relative values.

[Compound for comparison]

(S-/) (S-3 From Table 1, it can be seen that the novel holopolar dye of the present invention exhibits high red sensitivity. This compound is described and included in US Pat. No. 41,324,023 and US Pat.

Example 2 Silver halide emulsions used in Examples of the present invention were prepared as follows.

(1 liquid) H2O10ooca NaC1j, jll Gelatin 3211 (coliquid J Sulfuric acid (/N) λ≠CC (3 liquids) Silver halide solvent below (1%) icCCH3 (Add aCt H2O to Hongliun Br (! Liquid) gNO3 Add 710 H2O (liquid) KBr &2.729NaCI
/ J, 22jiK21rC
16 (o, oot%] 000C ir, A6g 3.309 λ oocc Add H2O (7 liquid gNO3 ≠ , ! ≠ CC tooca 121g H2O?: In addition tooca (l liquid)
was heated to rsuc, and (liquid 2) and (liquid 3) were added.

After that, (≠solution j and (liquid After that, the temperature was lowered and desalted.Water and dispersed gelatin were added to adjust the pH to 4.2 to obtain a monodisperse cubic silver chlorobromide emulsion with an average grain size of o, erμm and 70 mol of silver bromide. .In this emulsion/-
Optimal chemical sensitization was performed by adding OX/Omol/molAg of chloroauric acid and further thorium thiosulfate.

This emulsion? The mixture was divided into portions, and the sensitizing dyes shown in Table 2 were added to each portion at 00C, followed by mixing and stirring for 1j minutes.

Then, per mole of silver halide, sodium dodecylbenzenesulfonate i,og,p-sodium sulfocinnamate homopolymer 4! ,og%ll-hi)”.

xy-6-methyl-/eJ*Ja and 7-chitrasaindene/, 09 were added, and then an emulsion of the coupler shown in Table 2 was added, mixed and stirred, and then placed on a paper support laminated on both sides with polyethylene. It was applied as follows.

The amount of coating liquid is 0,3 J-17! m2, gelatin fi/, jg/m K, and the upper layer contains gelatin fi/, r9/m/, 2-bis(noethylhexyloxycarbonyl) sodium ethanesulfonate 0,0/Oi/m dodecyl. Sodium benzenesulfonate O0Qλ01!/m2p-Sodium sulfocinnamate homopolymer〇, O//, lit/m
, 2.4t-dichloroa-4-hydroxy-i,i
, j-triazine hexathorium o, otOi/m
A gelatin aqueous solution containing these as main components was simultaneously applied as a protective layer to prepare a coated sample.

The sample was exposed to tungsten light (32000K) for 0.1 seconds using the same red filter used in Example 1. Thereafter, processing was performed using a color developing solution as shown below.

(Composition of color developer) Water r00r
nl diethylenetriaminepentaacetic acid・! Sodium benzyl alcohol diethylene glycol to a2sO3 Br Hydroxylamine sulfate ≠ -amino-3-methyl-h-ethyl-~-[β-(methanesulfonamido)ethyl"-1)-Phenylenediamine sulfate Na2C03 (/7j (salt) Firefly Optical brightener (stilbene thread) Add water and dilute with water (Bleach-fix solution formulation Ammonium thiosulfate (!≠wt%) Na 2803 2.01! / !Gol O-waste Co, 09 i, og J , Og r, og io, og /, 0ji iooo punishment pH10, λn/rOytl zg NH4CFe<TH) (EDTA)) rjl
lEDTA-, 2Na
Add glacial acetic acid r, tllll water to make the total amount / 000 g(pi(j
,≠λ (Rinse thoroughly) EDTA-λNa-λ820 o, aj
i Add water and make a total of 1000d (pH 7)
, 07 The processing conditions are shown below.

(Processing process) (Temperature) (Time) Current fw
! 336C 3 minutes 30 seconds bleach fixing 31'C 7 minutes 30 seconds rinsing, 2Ir0C~3j0C 1 minute 30 seconds
Shown in the table. Photographic properties were evaluated based on the relative sensitivity between samples containing the same foggler, and samples containing the comparative compound (S-/) were each expressed as 100. At the reference point of the optical density that determined the sensitivity [fog 10,! This is the point j.

In the present invention, as in the case of Example-1 Even if the silver oxide emulsion changes and color development is used, Sensitivity was obtained.

Chemical structure of the coupler used halogen high spectroscopy -x hmm t

[Brief explanation of the drawing]

1 and 1 show spectral sensitivity curves obtained in Example 1. Figure 1 shows test 16/-J,
FIG. 1 corresponds to test /16/-/,2.

Claims (1)

[Scope of Claims] A silver halide photographic emulsion containing at least one compound represented by the following general formula (I). General formula (I) Dye-L-Hyd [In the formula, Dye represents a dye residue having a chromophore represented by the following general formula (II), and Hyd represents a dye residue in which one of the two nitrogen atoms is a carbonyl group or a sulfonyl group. , represents a hydrazine residue substituted with a sulfoxy group, a phosphoryl group, or an alkylidene group. L represents a divalent linking group that connects Dye and Hyd. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R and R_1 may be the same or different, and represent an alkyl group, and Z and Z_1 may be the same or different, respectively. It often represents a group of atoms necessary to form a 5- or 6-membered heterocycle. Q represents an atomic group necessary to form a 5- to 6-membered carbon ring or heterocycle. A represents an oxygen atom or a sulfur atom, and n, d, and m each represent 0 or 1. ]