JPH02193139A - Method for spectrally sensitizing silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To spectrally sensitize a silver halide photographic emulsion in a satisfactory state and to improve stability and reciprocity law characteristics by using a cyanine dyestuff which gives J band when added to the emulsion, adding the dyestuff to the emulsion and aging this emulsion under specified conditions. CONSTITUTION:When a silver halide photographic emulsion is spectrally sensitized, a cyanine dyestuff which gives J band in the emulsion is used. The dyestuff is added to the emulsion and this emulsion is aged before coating under conditions required to obtain <=1/2, preferably <=1/3 of relative quantum yield phir of spectral sensitization obtd. by aging under the conditions of 40 deg.C and 20min. Satisfactory spectral sensitization can be carried out, the silver halide is firmly adsorbed on the dyestuff to improve the stability of a photosensitive material using the resulting emulsion and the chemical aging stage is improved to improve the performance of the photosensitive material such as the reciprocity law characteristics.

Description

[Detailed description of the invention] (Industrial application field) Regarding the improvement of

(Prior Art) In the production technology of silver halide photographic emulsions, it is desired to further increase the sensitivity of photographic emulsions.

Chemical sensitization and spectral sensitization are known as useful methods for increasing the sensitivity of silver halide photographic emulsions.

Spectral sensitization is the process of incorporating a sensitizing dye into a silver halide photographic emulsion to extend the sensitivity of the silver halide emulsion from the short wavelength range of visible light to the long wavelength range of visible light. This is a technique for increasing the sensitivity of a photographic emulsion by enlarging it, and cyanine dyes and the like are mainly used as sensitizing dyes, and many sensitizing dyes and their application methods have come to be known.

Spectral sensitizing dyes are generally added to chemically ripened emulsions before coating. US Pat. No. 4,425,426 and others disclose a method of adding it to an emulsion before or during chemical ripening. Additionally, methods of adding a spectral sensitizing dye to an emulsion before the formation of silver halide grains are completed are disclosed in US Pat. No. 2,735,766 and US Pat. No. 3,628,9.
No. 60, US Pat. No. 4,183,756 J and US Pat. No. 4,225,666.

In particular, U.S. Pat.
．． No. 666, by adding a spectral sensitizing dye to the emulsion after the formation of stable nuclei during silver halide grain formation,
It is disclosed that there are advantages such as increased photographic sensitivity and enhanced adsorption of spectral sensitizing dyes by silver halide grains.

Also, JP-A-61133941 and JP-A No. 61-1607
No. 39 discloses a method of spectral sensitization characterized by carrying out chemical sensitization in the presence of a spectral sensitizing dye.

In recent years, there have been a wide variety of methods for adding spectral sensitizing dyes, and compared to conventional methods of adding spectral sensitizing dyes, the adsorption of sensitizing dyes by silver halide grains is strengthened, chemical sensitizing centers are concentrated, etc. characteristics have been discovered.

It is well known that heterocyclic compounds having mercapto groups are useful as antifoggants in photographic emulsions; however, such compounds are also known to reduce the sensitivity of photographic emulsions. For example, co-edited by C, E, Mees and T, H, James; The Theory
of the Photographic Proc
ess (The Theory of the Photographic Process), 3rd edition, pages 344-346.

On the other hand, JP-A-51-77224 discloses that when a heterocyclic compound having a mercapto group is contained in a silver halide emulsion together with a trimethine cyanine sensitizing dye after chemical sensitization is completed, the spectral sensitization effect of the cyanine dye is disclosed to be enhanced. Furthermore, JP-A-51-36130
In this issue, a heterocyclic compound having a mercapto group is a unique compound of a silver halide emulsion in which most of the silver halide consists of either silver bromide or silver chloride, and the silver halide grains have a cubic crystal shape. It is disclosed to increase sensitivity.

The spectral sensitizing effect of a cyanine dye having a pyridine nucleus in at least one of the heterocyclic nuclei, that is, a pyridinocyanine dye (or pyridocyanine dye), can be achieved by combining a certain mercapto compound having an acidic group with the dye. The increase due to use is described in Japanese Patent Application Laid-Open No. 49-64419.
Disclosed in No.

As mentioned above, a number of spectral sensitization methods have been disclosed, such as the addition of spectral sensitizing dyes and the combination with a heterocyclic compound having a mercapto group. Many points remain to be improved from the viewpoint of improved chemical sensitization and/or higher efficiency of spectral sensitization.

It is known that some cyanine dyes form J aggregates when added to silver halide emulsions and exhibit an absorption band called a J band. The characteristics of the J band in contrast to the M band caused by dye monomers are that the maximum absorption wavelength λmax is longer and sharper (the half width is narrower) than the M band. is indispensable. Although there is no way to directly measure the size of J-aggregates, from comparison with theory, it can be estimated that the longer the wavelength of J-band λmax and the narrower the half-width, the larger the J-aggregates. , Ro
senoff, K, S, Norland ^
, E. Ames.

V, L Walworth, G, R, Bird
by Photogr.

Sci, Eng-+ Vol. 12 No. 4 Page 185 (19
68).

As a result of intensive research on the method of spectral sensitization, the present inventor found that by using a cyanine dye that gives a J band when added to a silver halide emulsion, the relative quantum yield φr of spectral sensitization was improved by adding the dye to the emulsion. The aging conditions from 40℃ to coating are 20℃.
By adding a dye to the emulsion and ripening it under conditions such that φr for the same emulsion becomes 1/2 or more preferably 1/3 or less of the value obtained when the halogen It was discovered for the first time that the stability of light-sensitive materials can be improved by strong adsorption of dyes onto silver oxide, and the performance of light-sensitive materials, such as reciprocity law properties, can be improved by improving the chemical ripening process that follows the addition of dyes.

Furthermore, it has been found that by adding a heterocyclic compound having a mercapto group to the emulsion prior to the addition of the dye under the above conditions, φr is significantly improved and a sensitive material with high sensitivity can be obtained.

(Objects of the Invention) The first object of the invention is to obtain a new method for spectrally sensitizing silver halide photographic emulsions.

A second object of the present invention is to provide a new method for spectrally sensitizing silver halide photographic emulsions, which is characterized by providing a light-sensitive material with improved stability and reciprocity properties.

A third object of the present invention is to provide a silver halide photographic emulsion that is characterized by providing a silver halide photographic material with improved stability and reciprocity law characteristics and a high relative quantum yield φr of spectral sensitization. The aim is to obtain a new method of sensitization.

(Disclosure of the Invention) The above aspects of the present invention are such that when a silver halide photographic emulsion is spectrally sensitized, a cyanine dye giving a J band is used in the emulsion, and the relative quantum yield φr of the spectral sensitization is The φr for the same emulsion is 1/2, more preferably 1/3 or less, of the value obtained when the aging condition from adding to the emulsion to coating is 40°C for 20 minutes. By adding the dye to the emulsion and ripening it under the above conditions, furthermore, in the above method, a heterocyclic compound having a mercapto group is added to the emulsion in advance of the dye in an amount and under conditions sufficient to increase φr. This was achieved by

The J band is an absorption band that occurs when cyanine dye molecules form a J aggregate. Knowledge regarding the J band of cyanine dyes is provided by T. H. James f4 “The The
ory of the Photographic P
rocess'' 4th edition, 1977 Macmjllan
Publishing Co, + Ltd, Publishing, 2
It is described on pages 18-222. In addition, the wave number of the absorption peak of cyanine dye that does not form an aggregate is ``1''.
Tadaaki Tan1+S, Ki
5tudies of the Ad
sorption of Photographic S
Ensitizing and Desensitizing
zingDyes to 5ilver Bromid
e Grains on the Ba5isof T
hair visible and infrared
5pectraBulletin of th
e 5ociety of Science
cPhotography of Japan, l
lb, 17. 1-1 1 (1967). The J-band is characterized by the absorption peak wave number "imax"
force < y max estimated from the McRae formula (that is, the wavelength of the absorption peak is long), and the absorption band is sharp (that is, the half-width is narrow). As a guideline, an absorption band whose '7jmax is 1500 cm-' or more smaller than the absorption band in ethanol and whose half-width is also small can be regarded as the J band. In addition, the J band of the cyanine dye in the emulsion is 4-hydroxy-6-methyl 1.3.3a, 7-titraazaindene (TAI).
If too much is added, it becomes weaker or smaller, so
can be easily distinguished.

The efficiency of spectral sensitization φr is J, 5pence B, H, C
arrow.

J, PhysColloidChem, 52.
1090 (1948), or by the method described in Tadaaki Tani and Hitoshi Tobe, Journal of the Photographic Society of Japan, Vol. 41, 325 (1978).

Cyanine dyes that form J-aggregates in the emulsion used in the present invention include dyes represented by the following general formula (1).

In the formula, 71 and Z2 may be the same or different, and each represents an atomic group necessary to complete a 5- or 6-membered nitrogen-containing heteroartic ring commonly used in cyanine dyes. The above-mentioned heterocyclic rings include a thiazoline ring, a pyrroline ring, an oxazole ring, a thiazole ring, a selenazole ring, an imidazole ring, a tetrazole ring, etc.; That is, this includes indolenine nucleus, benzindolenine nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, naphthothiazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, etc. . However, the heterocyclic nuclei that complete the atomic groups formed by Zl and Z2, respectively, are indolenine nuclei or benzindolenine nuclei (
Dyes that are (unsubstituted and substituted) are not used in the present invention.

These heterocyclic rings include alkyl groups or alkoxy groups having up to 4 carbon atoms, aryl groups, aralkyl groups, hydroxyalkyl groups, carboxyalkyl groups, alkoxycarbonylalkyl groups, halogen atoms, carboxy groups, sulfo groups, and trifluoromethyl groups. , alkoxycarbonyl group (
(up to 4 carbon atoms in the alkyl moiety), a cyano group, a hydroxy group, an alkylamino group, etc. may be substituted. Further, aliphatic hydrocarbon chains (eg, trimethylene chains, tetramethylene chains, etc.) may be bonded to form a condensed ring. For example, a thiazole nucleus (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 4.5-dimethylthiazole, 4.5-diphenylthiazole, etc.);
Benzothiazole core (e.g. benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole,
6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenyl Benzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-
Fluorobenzothiazole, 5-trifluoromethylhendithiazole, 56-dimethylbenzothiazole, 5
-hydroxy-6-methylbenzothiazole, tetrahydrohendithiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, etc.); naphthothiazole nucleus (e.g. naphthoC2,1-d) thiazole, nand(1,2-d) thiazole , Naphtho C2,3-d)
Thiazole, 5-methoxynaphtho(1,2-d)thiazole, 8-methoxynaphtho(2,1-d)thiazole,
5-methoxy(2,3-d]thiazole, etc.); thiazoline nucleus (e.g., thiazoline, 4-methylthiazoline, etc.); oxazole nucleus (e.g., oxazole, 4-methyloxacyl, 4-ethyloxazole, etc.); benzoxazole Nuclei (e.g. benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-
Methoxybenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6
Methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4
．． 6-dimethylbenzoxazole, 5-ethoxybenzoxazole); naphthoxazole core (e.g.
Naphtho(2,1-d)xazole, Naphtho(1,2-
d) Oxazole, naphtho(1,2-d)oxazole, naphtho[23-d]oxazole, etc.); selenazole nucleus (e.g. 4-methylselenazole, 4-phenylselenazole, etc.); benzoselenazole nucleus (e.g. benzoselenazole, etc.); selenazole, 5-chlorobenzoselenazole,
5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, etc.)
; naphthoselenazole nucleus (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-5-methoxyindolenine, 3.3-
Dimethyl-5-methylindolenine, 33-dimethyl-
5-chlorindolenine, etc.); imidazole core (e.g., 1-methylimidazole, 1-ethylimidazole, 1-methyl-4-phenylimidazole, 1-ethyl-4
-phenylimidazole, etc.); benzimidazole core (e.g. benzimidazole, -methylhenzimidazole, 1-ethylhenzimidazole, 1-methyl-
5-Chlorbenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl-56-cyclolhenzimitazole, 1-ethyl-5,6-cyclolhenzimidazole, 1-ethyl-5-methoxybenz Imidazole, 1-methyl-5-cyanohenzimidazole, 1-ethyl-5-cyanohenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-
5-fluorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5
-trifluoromethylbenzimidazole, 1-allyl-56-cyclobenzimidazole, ■-allyl 5-
Chlorbenzimidazole, ■-phenylimidazole, 1-phenylbenzimidazole, 1-phenyl-5
-Chlorbenzimidazole, 1-phenyl-5,6-
cyclobenzimidazole, 1-phenyl-5-methoxybenzimidazole, ■-phenyl-5-cyanobenzimidazole, etc.); naphthoimidazole core (e.g., 1-ethylnaphthoCL 2-d) imidazole,
■-Phenylnaphtho [1,2-d)imidazole, etc.)
; Tetrazole nucleus (e.g., 1,3-dimethyltetrazole nucleus, 1-methyl-3-ethyltetrazole nucleus, etc.)
; Ro is a hydrogen atom, an alkyl group having up to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group), hydroxyalkyl group (e.g. β-hydroxyethyl group), carboxyalkyl group (e.g. β-carboxyethyl group), cyano group , an aralkyl group (eg, phenethyl group), a phenyl group, a substituted phenyl group (eg, 0-carboxyphenyl group), etc.

In the formula, m, n and P each represent an integer 0 or 1. R■ and R2 each represent an aliphatic group or an aromatic group having 1 to 8 carbon atoms. The aliphatic group has an oxygen atom in the carbon chain,
It may be interrupted by a sulfur atom or a nitrogen atom, or it may partially form a ring. Both aliphatic and aromatic groups may have substituents. For example, unsubstituted alkyl groups having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, n-propyl group, hexyl group, etc.); substituted alkyl groups (preferably alkyl radicals (moiet groups having 1 to 4 carbon atoms) , such as vinylmethyl group, aralkyl group (e.g. benzyl group,
phenethyl group), hydroxyalkyl group (e.g. 2
-Hydroxyethyl group, 3-hydroxypropyl group, 4-
hydroxybutyl group, etc.), acetoxyalkyl group (e.g. 2-acetoxyethyl group, 3-acetoxypropyl group, etc.), alkoxyalkyl group (e.g. 2-methoxyethyl group, 4-methoxybutyl group, etc.), sulfatoalkyl group (e.g. , 3-sulfatopropyl group, 4-sulfatobutyl group), alkyl groups containing carboxyl groups (e.g. 2-carboxyethyl group, 3-carboxypropyl group, 2-(2carboxyethoxy)ethyl group,
p-carboxybenzyl group, etc.), alkyl groups containing sulfo groups (e.g. 2=sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2-
Hydroxy-3-sulfopropyl group, 2-(3sulfopropoxy)ethyl group, 2-acetoxy-3-sulfopropyl group, 3-methoxy-2-(3sulfopropoxy)propyl group, 2-[2-(3sulfopropoxy) ) ethoxy]
ethyl group, 2hydroxy-3-(3'-sulfopropoxy)propyl group, p-sulfophenethyl group, p-sulfobenzyl group, etc.) or an aryl group (eg, phenyl group, p-tolyl group, etc.).

) (e represents an inorganic or organic acid anion that forms a salt with the dye, such as a chloride ion, bromide ion, iodide ion, perchlorate ion, p-toluenesulfonate ion, etc. The dye forms an inner salt. Represents time or 1.

l is Oll or 2, preferably O or 1
and more preferably 1.

Among the cyanine dyes represented by the general formula (1) used in the present invention, particularly useful dyes are expressed by the following general formula.

The dye (I[) is a dye represented by the following general formula (III) or IX).

In the formula, Y1 and Y2 represent a sulfur atom, a selenium atom, or an oxygen atom. R1+ and R21 each represent an alkyl group, a hydroxyalkyl group, a carboxyalkyl group, a sulfoalkyl group or a sulfoalkoxyalkyl group. Wl and w2 are each an alkyl group having 1 to 4 carbon atoms, a phenyl group, a fused Hensen ring, an aralkyl group,
It includes an alkoxy group having 1 to 4 carbon atoms, a hydroxy group, a halogen atom, a cyano group, a carboxy group, an alkoxycarbonyl group (up to 4 carbon atoms in the alkyl moiety), or a trifluoromethyl group. q and r each represent an integer from 0 to 4. ! , Ro, X'' and p are represented by the general formula (1
) has the same meaning as in

Among these dyes, preferred in the present invention is ×O (■) (■) In general formulas (III) to (IX), β, Ro, w,
, w2, xe, q and r do not have the same meanings as in general formula (I). Y3 and Y4 each represent a sulfur atom or a selenium atom. R3□ and R41
represents an alkyl group having up to 4 carbon atoms. R4□, R5, and R5□ represent a dissociated sulfoalkyl group or a sulfoalkoxyalkyl group (up to 4 carbon atoms). MO represents a cation such as a hydrogen ion, an alkali metal ion, or an ammonium ion. R6 may not be a methyl group or an ethyl group.

The substituents represented by R35, R3□ and R41 are preferably ethyl groups, and the substituents represented by R4□, R51 and R5° are ω-sulfoalkyl groups consisting of straight carbon chains, such as β-sulfoethyl groups, γ-sulfopropyl group and δ-sulfobutyl group are preferred. R6 is preferably an ethyl group. Sulfur atoms are preferred as Y3 and Y4.

In general formula (IX), Y represents a sulfur atom or an oxygen atom. R7 represents a hydroxyalkyl group having up to 4 carbon atoms (eg, β-hydroxyethyl group, γ-hydroxypropyl group, etc.).

Specific examples of cyanine dyes useful in the present invention are shown below.

Specific examples of dyes represented by general formula (]1): 3.31
-diethyl-9-ethyl-thiacarbocyanine iodide, 3.3'-diethyl-9-ethyl-naphthothiacarbocyanine iodide, 5.5'-dichloro-3,3'-diethyl-9ethyl-
Thiacarbocyanine iodide, 5,5'-dimethyl-3,3'-diethyl-9ethyl-
Thiacarbocyanine iodide, 55'-dimethoxy-3,3'-diethyl 9-ethyl-
Thiacarbocyanine iodide, 5.51-diphenyl-3
, 3'-diethyl 9-ethyl-thiacarbocyanine iodide, 5.5'-dichloro-3,3'-diethyl-thiacyanine iodide, 5.5I-diphenyl-3,3'-diethylthiacyanine iodide, Although 3.3''-diethyl-naphthocyanine iodide and iodide salts have been exemplified, these may also be chlorides, bromides, perchlorates, p-,)luenesulfonates, and the like.

Specific examples of dyes represented by general formula (I'/): 5.5
'-Dichloro-3-ethyl-3'-sulfopropyl-thiacyanine, 55'-diphenyl-3-ethyl-31-sulfopropyl-thiacyanine, 3-ethyl-3'-sulfopropyl-naphthothiacyanine, 5.5' -dichloro-3-ethyl-31-sulfopropyl-9-ethyl-thiacarbocyanine, 55'-dimethyl-3-ethyl-3'-sulfopropyl-9-ethyl-
Thiacarbocyanin, 5.51-dimethoxy-3-ethyl-3'-sulfopropyl-9-ethyl-thiacarbocyanine, 5.51-diphenyl-3-ethyl-3'-sulfopropyl-9-ethyl-thiacarbocyanine A specific example of a dye represented by cyanine and general formula (V) is shown below.

55'-dichloro-33'-disulfopropyl-thiacyanine, 5,5'-diphenyl-3,31-disulfopropyl-
Thiacyanin, 3.31-disulfobropyrinaphthocyanine, 5.
51-dichloro-3,3'-disulfoethyl-9-ethyl-thiacarbocyanine, 5,51-dimethyl-3,3
I-disulfopropyl-9-ethyl-thiacarbocyanine, 5,5'-dimethoxy-3,3''-disulfopropyl-9-ethyl-thiacarbocyanine, 5,51-diphenyl-3,3'-disulfoethyl -9-ethyl-thiacarbocyanine, a specific example of a dye represented by general formula (Vl): 5,5'-dichloro-3,31-diethyl-9
Ethyl-oxacarbocyanine perchlorate, 5.51-
Dichloro-3,31-diethyl-9-ethyl-oxathiacarbocyanine, 5.51-dimethyl-3,3'-diethyl-9ethyl-oxathiacarbocyanine iodide, 5.
51-dimethyl-3,31-diethyl-9ethyl-oxathiacarbocyanine iodide, 5,51-dimethoxy-
3,3″-diethyl 9-ethyl-oxacarbocyanine iodide, 5,51-dimethoxy-3,3′-diethyl 9
-Ethyl oxathiacarbocyanine iodide, 5.5'-
Diphenyl-3,3'-diethyl 9-ethyl-oxathiacarbocyanine-p-toluenesulfonate, 5.51-diphenyl-3,31-diethyl 9-ethyl-oxathiacarbocyanine-p-)toluenesulfonate , Specific examples of dyes represented by the general formula (■): 3-propyl-3'-sulfopropyl-9-ethyl-oxacarbocyanine, 3-propyl-3''-sulfopropyl-9-ethyloxathiacarbocyanine , 551-dimethyl-3-ethyl-31-sulfoethyl-
9-ethyl-oxacarbocyanine, 5,5'-dimethyl-3-3-ethyl-3'sulfoethyl-9-ethyl-
Oxathiacarbocyanine, 5.5'-dimethoxy-3-ethyl-3'-sulfoethyl-9-ethyl-oxathiacarbocyanine, 55'-dimethoxy-3-ethyl-3'-sulfoethyl-9-ethyloxathiacarbo Cyanine, 55'-diphenyl-3-ethyl-3'-sulfoethyl-9-ethyl-oxacarbocyanine, Specific examples of dyes represented by general formula (■): 5,5'-dimethyl-3,
3'-disulfoethyl-9-nityluoxacarbocyanine, 5.5'-dimethyl-3,3'-disulfoethyl-9-ethyl-oxathiacarbocyanine, 5.5'-
dimethoxy-3,31-disulfoethyl-9-ethyl-
Oxacarbocyanine, 5,5'-dimethoxy-3,3
″-disulfoethyl-9-ethyloxathiacarbocyanine, 5.5′-dimethoxy-3,31-disulfopropyl-9-ethyl-oxacarbocyanine, 5.5′-
diphenyl-3,3+-disulfoethyl-9-ethyl-
The amount of oxacarbocyanine and cyanine dye added may be sufficient to effectively spectral sensitize the silver halide photographic emulsion. This amount can vary over a wide range depending on the emulsion conditions, but is usually 1o-6 per mole of silver halide.
~10 −3 mol, particularly advantageously 5×10
-6 to lXl0-' moles.

Regarding the adsorption process of dyes to silver halide grains,
Paper by Tadaaki Tan1 “mouth uantit”
Active Determination of Cry
stal Habit of 5ilverHali
de Grains Through Its Inf
Luence on Dye 8d
, Journal of Imaging
5science, Vol. 29, No. 5, pp. 165-170 (1985). according to it,
Pigment molecules repeat adsorption and desorption, and the adsorption state of the dye changes moment by moment during the ripening process, and each dye molecule gradually settles into the most stable state, reaching an equilibrium state.

3, 3'-b is (4-sulfobutyl)-
In the case of 9-methylthiacarbocyanine, it took several hours to reach equilibrium when the ripening temperature was 40°C. The rate-determining process for the change in the adsorption state of the dye was the desorption of the dye, and the activation energy was 26 Kcal/mol.

Therefore, the change in the adsorption state of the dye increases rapidly with the aging temperature, and it takes less than a few minutes to reach the equilibrium state at 70°C. As the adsorption state of the dye changes, φ
r will change. In the present invention, when the aging conditions from the addition of the dye to the emulsion to the coating are changed, φr is 1/2 of the φr after aging at 4°C for 20 minutes.
It has been found that when the value is more preferably selected to be 1/3 or less, a photosensitive material with improved stability and reciprocity properties can be obtained.

In order to reduce φr to 1/2 or less of the aging condition of 40°C for 20 minutes, it is effective to increase the aging temperature or lengthen the aging time, but the methods are not limited to these. isn't it. As a guideline, when ripening for 20 minutes, a ripening temperature of 50°C or higher is effective, preferably 60°C or higher, more preferably 70°C or higher.
It is effective to ripen at 0°C or higher. 40 again
In the case of ripening at .degree. C., a ripening time of 1 hour or more, preferably 4 hours or more is effective.

These sensitizing dyes can also be directly dispersed in emulsions,
or dissolved in a water-soluble solvent such as pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, etc. (or a mixture of such solvents), in some cases diluted with water, and in other cases in water. dissolve,
These can be added to the emulsion in the form of a solution. Moreover, ultrasonic vibration can also be used for this melting. In addition, the dye is as described in U.S. Patent No. 3,469.987, etc.
A method of dissolving a dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion to an emulsion, as described in Japanese Patent Publication No. 46-24185, etc., dissolves a water-insoluble dye. Alternatively, a method may be used in which the compound is dispersed in a water-soluble solvent and this dispersion is added to the emulsion. The dye can also be added to the emulsion in the form of a dispersion by an acid dissolution and dispersion method. Other additions to emulsions include U.S. Patent No. 2,912.
No. 345, No. 3,342,605, No. 2゜996.2
The methods described in No. 87, No. 3,425,835, etc. can also be used.

The photographic emulsion sensitized using the present invention may contain sensitizing dyes other than the dyes represented by formula (I) or (II) or supersensitizing agents to the extent that the effects of the present invention are not impaired. Known substantially colorless compounds may also be included. For example, U.S. Patent No. 2,933°390, U.S. Pat.
No. 3,615.613, No. 3,615.632, No. 3615.641, etc., compounds having a pyrimidinylamino group or a triazinylamino group, British Patent No. 1,137,580 The aromatic organic acid-formaldehyde condensate, azaindenes, or cadmium salts described in .

The heterocyclic compound having a mercapto group used in the present invention has at least one nitrogen atom, preferably at least two nitrogen atoms in the heterocyclic ring, and has a thionamide group having the following tautomerism. have. In addition to the nitrogen atom, the heterocycle may have a heteroatom such as an oxygen atom NH-C-N→-N=C 3SH , a sulfur atom, or a selenium atom. Preferred compounds are monocyclic heterocycles having at least two 5- or 6-membered aza nitrogen atoms, or bicyclic compounds consisting of two or three fused heterocycles having at least one aza nitrogen atom. or a tricyclic heterocyclic compound in which a mercapto group is substituted on the carbon atom adjacent to the aza nitrogen.

In the nitrogen-containing heterocyclic compound having a mercapto group used in the present invention, the heterocycle includes a pyrazole ring, pyrimidine ring, 1.2.4-) lyazole ring, L 2.3-1
- Riazole ring, 1,3.4 thiadiazole ring, 1,2
．． 3-thiadiazole ring, 1.2.4-thiadiazole ring, 1.2.5-thiadiazole ring, 1,2,3.4-tetrazole ring, pyridazine ring, 1,2.3-triazine ring, 1.2. , 1-triazine ring, 1,3.5-1-riazine ring, rings in which 2 to 3 of these rings are bonded, such as triazolotriazole ring, diazaindene ring, triazaindene ring, tetrazaindene ring, pentazaindene ring Rings etc. can be applied. Heterocycles in which a monocyclic heterocycle and an aromatic ring are condensed, such as a phthalazine ring, a henzimidazole ring, an indazole ring, and a hendithiazole ring, are also applicable.

Preferred among these rings are 1,2.4-triazole ring, 1.3.4-thiadiazole ring, and 1.2,3.4-triazole ring.
-tetrazole ring, l, 2.4 triazine ring, triazolotriazole ring and tetraazaindene ring.

Although the mercapto group may be substituted on any carbon atom of these rings, the following bond is preferably formed.

a) -N-N=C H H H The heterocycle may have a substituent other than a mercapto group. Examples of substituents include alkyl groups having 8 or less carbon atoms (for example, methyl group, ethyl group, cyclohexyl group, cyclohexylmethyl group, etc.), substituted alkyl groups (for example, hydroxymethyl group, etc.), alkoxy groups having 8 or less carbon atoms (for example, methoxy group, ethoxy group), alkylthio group having 8 or less carbon atoms (methylthio group, butylthio group, etc.), hydroxy group, amino group, hydroxyamino group, alkylamino group having 8 or less carbon atoms (for example, methylamino group, butylamino group) ), dialkylamino groups having 8 or less carbon atoms (e.g. dimethylamino group, diisopropylamino group), arylamino groups (e.g. anilino group, etc.), halogen atoms (e.g. chlorine atom, bromine atom, etc.)
, a cyano group, a sulfone group, a sulfoalkyl group having 8 or less carbon atoms, a carboxyl group, a carboxyalkyl group having 8 or less carbon atoms, etc. can be applied.

Specific examples of the compound having a mercapto group used in the present invention are listed below. (However, it is not limited to these only.) Compound (Il) N\/ゞCompound (III) Compound (■) Compound (II/) Compound (IX) Compound (V) Compound (X) Compound (VI ) Sl+ Compound (XI) Compound (■) Compound (X■) Compound (Xlll> Compound (XIV) The amount and conditions for addition of the heterocyclic compound having a mercapto group may be an amount sufficient to increase φr. Addition The amount and conditions vary over a wide range depending on the type of compound, the properties of the silver halide emulsion, etc., but the amount of the heterocyclic compound having a mercapto group added is 0.1 molar ratio to the amount of the sensitizing dye added. ~100 times more effective, preferably 1
~10 times, more preferably 2 to 5 times, is particularly effective. It is effective to add the heterocyclic compound having a mercapto group prior to the addition of the sensitizing dye, and it may be added during or after the formation of silver halide grains, before, during or after chemical ripening. . Preferably, it is added after silver halide grains are formed, and the aging temperature before adding the dye is 50°C or higher, preferably 60°C or higher, more preferably 70°C or higher, and the aging time is 3 minutes or higher. , preferably 10 minutes or more, more preferably 30 minutes or more.

Preferred amounts of mercapto compound and dye of general formula (1) range from 40/1 to 1/10, particularly preferably from 5/1 to 115.

The feature of the present invention is that the aging conditions from the addition of the spectral sensitizing dye to the coating are set so that the value of φ4 is 1/2 or less of φr when the same emulsion is aged at 40°C for 20 minutes after addition of the dye. In determining the ripening conditions, it is necessary to ensure that no heterocyclic compound having a mercapto group is present in the emulsion.

In an emulsion in which a heterocyclic compound having a mercapto group is not present, the ripening condition is 1/2 or less of φr when the ripening condition is 40° C. for 20 minutes.

It is decided that

After determining the aging conditions in this way, the effect of the present invention is most noticeable by adding a heterocyclic compound having a mercapto group prior to adding the dye, further adding the dye, and aging under the determined aging conditions. can be played.

The photographic emulsion sensitized using the present invention may contain sensitizing dyes other than the dyes represented by general formula (1) or known to have supersensitizing action, within a range that does not impair the effects of the present invention. Substantially colorless compounds may also be included. For example, US Patent 2,
933.390, 3.511664, 3.61
No. 5,613, No. 3,615.632, No. 3,615
, 641, aromatic organic acid-formaldehyde condensates, azaindenes, or cadmium salts as described in British Patent No. 1,137,580. May include.

A light-sensitive material formed using a photographic emulsion sensitized by the method of the present invention may also have a spectrally sensitized emulsion layer or a non-spectrally sensitized emulsion layer other than the present invention, and the light-sensitive material thereof Various positional relationships can be selected as required.

The silver halide in the photographic emulsion used in the method of the present invention may be, for example, any one of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like. Particularly advantageous is silver bromide or silver iodobromide.

Gelatin is usually used as a binder in the silver halide emulsion used in the present invention.
gum arabic, alginic acid, etc., or polyvinyl alcohol, polyvinylpyrrolidone, acrylic acid copolymer,
It may be replaced with a hydrophilic resin such as polyacrylamide or a substance that does not have a harmful effect on the photosensitive silver halide, such as a cellulose derivative.

The silver halide emulsion used in the present invention may be coarse grains, fine grains, or a mixture thereof, and these silver halide grains may be prepared by known methods such as single jet method,
Formed by double jet method or controlled double jet method.

Furthermore, even if the crystal structure of silver halide grains is similar to the inside, there are also those where the inside and outside have a layered structure that is different from each other.
The so-called conversion type described in No. 2,318 may also be used. Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. These photographic emulsions are by Mees r Th
eTheory of Photography
Process J (published by MacMtllan), G
rPhotographic by lafkid @ s
ChemistryJ (Fountain Press
It can be adjusted using various generally accepted methods such as the ammonia method, neutral method, and acid method.

The average diameter of the silver halide grains used (for example, measured by the projected area method or number average) is not particularly limited, but is preferably from about 0.04 μm to about 2 μm. The particle size distribution (particle size indicates the meaning as described above) may be narrow or wide.

The silver halide emulsion may or may not be physically ripened.

Silver halide emulsions that are not chemically sensitized (so-called unripened emulsions) can be used, but they may also be chemically sensitized. As a method of chemical sensitization, the above-mentioned Mees, Glafk
It is possible to use the method described in the book written by J.I.D.S. or Frleser (ed.), and various other known methods. That is, compounds containing sulfur that can react with silver ions, such as 1,000 sulfates, or U.S. Pat.
, No. 410.689, No. 3,189,458, No. 3.
501. No. 313, French Patent No. 2,059,24
Sulfur sensitization method using compounds described in No. 5 or activated gelatin; Gold sensitization method using gold complex salts or gold osulfate complexes described in U.S. Patent No. 2,399,083 - U.S. Patent 2 , No. 448,060, No. 2,540
, No. 086, 2. 566, No. 245, 2,566
．． The sensitization method using salts of noble metals such as platinum, palladium, iridium, rhodium, and ruthenium described in No. 263 can be used alone or in combination. The selenium sensitization method described in US Pat. No. 3,297.446 may also be used in place of or in conjunction with the sulfur sensitization method.

In the photographic emulsion sensitized according to the present invention, fog is prevented during the manufacturing process, during storage of the light-sensitive material, or during development processing.
Alternatively, various compounds may be included for the purpose of stabilizing photographic performance. For example, azaindene compounds, such as tetraazaindenes, such as U.S. Pat.
4.605, 2,444,606, 2,450
．． No. 397, Special Publication No. 39-10166, No. 42-10
Compounds described in No. 516, etc.; pentaazaindenes,
For example, U.S. Patent No. 2,713,541,
Compounds such as those described in No. 13495 can be added. Furthermore, benzenesulfinic acid described in US Pat. No. 2,394,198, henzenesulfinic acid amide described in Japanese Patent Publication No. 43/41'36, etc. can be added. In addition, various chelating agents described in U.S. Patent No. 2,691.588, British Patent No. 623.488, Japanese Patent Publication No. 43-4941, and Japanese Patent Publication No. 43-13496 may be added to prevent fogging caused by metal ions. can.

Photographic emulsions sensitized according to the invention may be used to increase speed, contrast, or accelerate development, such as polyalkylene oxides as described in U.S. Pat. No. 2,44L 389, Ethers, esters and amides of alkylene oxides, British Patent No. 1,145゜186, Japanese Patent Publication No. 1989-10989
No. 4515188, No. 46-43435, No. 4
Other polyalkylene oxide derivatives described in No. 78106 and No. 47-8742; U.S. Patent No. 3°772.0
Quaternary ammonium compound described in No. 21; Japanese Patent Publication No. 1973-
Pyrrolidine etc. described in No. 27037; Japanese Patent Publication No. 40-23
Urethane or urea g conductor described in Japanese Patent Publication No. 465; imidazur derivatives described in Japanese Patent Publication No. 47-45541; polymers described in Japanese Patent Publication No. 4526471;
3-pyrazolidones described in No. 27670 may also be included.

An inorganic or organic mercury compound may be added to the photographic emulsion of the present invention for the purpose of sensitization or fog prevention. For example, mercury complex salts described in U.S. Pat. No. 2,728.664, benzothiazole mercury salts described in U.S. Pat. No. 2,728.667, U.S. Pat.
, 302, U.S. Patent No. 2.
728. Organic mercury compounds described in No. 665 and No. 3,420,668 can be used.

The photographic emulsion of the present invention includes a hardening agent, a coating aid, a plasticizer,
It can contain additives with various functions for improving the quality of photographic materials, such as emulsion polymerization latex, antistatic agents, ultraviolet absorbers, and antioxidants.

The photographic emulsion sensitized according to the present invention can be hardened by adding a commonly used hardening agent. As a hardening agent,
For example, compounds with reactive halogens, such as the 2,4-dichloro-
6-Hydroxy-1°3.5-triazine, mucohalogenic acid, such as mucochloric acid, mucobromic acid, described in U.S. Pat. Bis(methanesulfonate esters) as described in US Pat. No. 726,162; sulfonyl compounds such as bis(benzenesulfonyl chloride)nidivinyl sulfones as described in US Pat. No. 2,725,295, as described in US Pat. No. 2,579,871 compounds with reactive olefinic bonds, such as divinyl ketone, such as the compound described in German Patent No. 872.153; inorganic hardeners, such as chromium alum, chromium acetate, alone or in a variety of Can be used in combination.

The photographic emulsion sensitized according to the present invention may contain additives as coating aids, antistatic properties, improved slipperiness, and other purposes.
Various known surfactants can be added. For example, saponin, polyethylene glycol, US patent 3,
294,540, a polyethylene glycol-polypropylene glycol condensate, as described in U.S. Patent No. 2,240.
Nonionic surfactants such as polyalkylene glycol ethers, polyalkylene glycol esters, and polyalkylene glycolamides described in No. 472 and No. 2,831.766; for example, alkyl carboxylates, alkyl sulfonates, alkyl Henzensulfonate, alkylnaphthalene sulfonate, alkyl sulfate, N-acylated-N-alkylclarine described in U.S. Pat. No. 2,739,891, U.S. Pat.
No. 59.980, No. 2,409,930, No. 2447
．． Maleopimarate described in US Pat. No. 750, US Pat.
823.123; anionic surfactants such as the compounds described in British Patent No. 3,415.649;
, No. 159,825, Japanese Patent Publication No. 40-378, Japanese Patent Publication No. 4
Amphoteric surfactants such as the compounds described in No. 8-43924 and US Pat. No. 3,726,683 can be used.

Photographic emulsions sensitized according to the present invention may contain plasticizers such as glycerin, diols described in U.S. Pat. No. 2,960.404, trihydric aliphatic alcohols as described in U.S. Pat. May include.

The photographic emulsion sensitized according to the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for purposes such as improving dimensional stability.

In addition, examples of anti-irradiation dyes that may be contained depending on the purpose include JP-B No. 41-20389, JP-B No. 3504-1983, JP-B No. 4313168, U.S. Pat. No. 2,697,037, U.S. Pat. Those described in British Patent No. 423.207, British Patent No. 2,865.752, British Patent No. 1,030.392, British Patent No. 1,100.546, etc. are used.

Photographic emulsions sensitized according to the invention may also contain conventional non-diffusible color image-forming couplers. A color image-forming coupler is a compound that reacts with an oxidation product of an aromatic amine developing agent to form a dye during photographic development (hereinafter abbreviated as coupler). The coupler may be either 4-equivalent or 2-equivalent, and may be a colored coupler for color correction or a coupler that releases a development inhibitor. Useful examples of yellow-forming couplers include open-chain ketomethylene compounds such as acylaminoacetamide-based couplers, pyrazolone-based or cyanoacetyl-based compounds as magenta-forming couplers, and naphthol-based or phenol-based compounds as cyan-forming couplers. The coupler can be introduced into the photographic emulsion layer using a method commonly used for multicolor light-sensitive materials.

Such couplers include 4-equivalent type or 2-equivalent type diketomethylene yellow couplers, such as U.S. Pat.
, 277.157, 3,415.652, 3,
No. 447.928, No. 3311.476, No. 3,40
Compounds described in US Pat. No. 8,194, etc., U.S. Pat.
．． No. 875057, No. 3,265.506, No. 3,4
No. 09.439, No. 3,551,155, No. 3551
．． No. 156, West German Patent Application (OLS) 1.956.
Compounds described in No. 281, No. 2,162,899, etc., or JP-A-47-26133, No. 4B-66
Compounds described in U.S. Pat. No. 759,
Same No. 3,062,653, Same No. 3,214゜437,
3,253.924, 3,419.391, 3,419,808, 3476.560, 3,
Compounds described in U.S. Pat. 698.
No. 794, No. 3.034, 892, No. 3.214.4
No. 37, No. 3,253,924, No. 3.311.47
No. 6, No. 3,458.315, No. 3,59L 38
No. 3, Special Publication No. 42-11304, No. 14-32461
Compounds described in No. 1, etc. are used. In addition, U.S. Patent Nos. 3,227.554 and 3,148.06
No. 2, No. 3.297.445, No. 3,253.924
No. 3,311.416, No. 3,379,529, No. 3,516.831, No. 3. 617. 291
No. 3,705.801, No. 3. 632°345
DIR couplers or DIR compounds, such as those described in German Patent Application No. 2,163.811, can also be used. Couplers, etc. are disclosed in U.S. Patent No. 2,800.
It can be dispersed by the method described in, for example, No. 1,171.

The photographic emulsion of the present invention can be coated on a support alone or together with other parent colloid layers by various known coating methods.

Application methods include dip application method, air knife application method,
Roller coating methods, curtain coating methods, and extrusion coating methods are included. The method described in US Pat. No. 2,681,294 is one advantageous method. Also, U.S. Patent No. 2,76
More than one layer may be applied simultaneously using methods such as those described in US Pat. No. 1,791 and US Pat.

Any known method can be used for the photographic processing of the photographic emulsion of the present invention. A known treatment liquid can be used, and the treatment temperature is lower than 18°C, 18°C.
The temperature can be anywhere from 50°C to 50°C and above 50°C.

Depending on the purpose, the light-sensitive material of the present invention can be subjected to either a development process for forming a silver image (black and white photographic process) or a color photographic process consisting of a development process for forming a dye image. The present invention will be explained in more detail below with reference to Examples.

Preferred embodiments of the present invention are as follows: 1) A spectral sensitization method characterized by adding a cyanine dye giving a J band and then ripening at a temperature of 60°C or higher.

2) The method of 1) above, which involves aging at 70°C or higher.

3) The method of 1) or 2) above, in which a heterocyclic compound having a mercapto group is added prior to adding the cyanine dye.

4) After the formation of silver halide grains, a heterocyclic compound having a mercapto group is added, and the mixture is aged at 50°C or higher for 3 minutes or more, and then a cyanine dye that gives a J band is added.
A spectral sensitization method characterized by aging at a temperature of 0°C or higher.

(Example 1) Ordinary CDJ method (chondral double jet method)
Based on this, an IN AgNO3 aqueous solution and an IN KBr aqueous solution were simultaneously added to a gelatin aqueous solution containing 1.25 g/n of NH3, and the silver potential during the reaction was maintained at -40 mV.
An emulsion consisting of octahedral A g B r grains having a grain size (circle equivalent diameter of projected area) of 0.87 μm was prepared. Emulsion 11 contains 0. Contains 77 moles of AgB,
The pH was 6.35 and the pAg was 8.94.

Separate 95 cc of each from the above emulsion, add 5 cc of a 0.16 wt% methanol solution of dye (1) having the following structure to each, and heat one at 40°C for 20 minutes and the other at 70°C. After aging for 20 minutes, it was coated on a TAC film base and φ.

was measured.

Pigment (1) The measurement results are shown in Table 1.

It can be seen that the sample of Experiment 2 in Table 1 has a longer absorption maximum wavelength of the J band of the dye than that of Experiment 1, and the J aggregate has grown to a large extent. In Experiment 2, although ψ1 decreased compared to Experiment 1, dye adsorption was enhanced and an emulsion that was extremely stable over time was obtained.

(Example 2) The octahedral AgBr emulsion prepared in Example 1 was separated into 95 cc portions, kept at 70°C and stirred well, and the following mercapto compounds xm, XrV, ■, ■, ■, and ■10-
A known amount of methanol solution in mol/It was added.

After stirring the above emulsion at 70'C for 20 minutes,
5cc of 0.16% by weight methanol solution of dye (1)
After stirring at 70°C for 20 minutes, TAC
It was applied onto a film base and φr was measured by a conventional method. The measurement results are shown in Table 3.

Table 3 (70° C. for 20 minutes) As a result, a spectrally sensitized emulsion with enhanced dye adsorption, high stability over time, and high φr was obtained.

(Example 3) 95 cc of the octahedral AgBr emulsion prepared in Example 1 was collected, kept at 70°C, 5 cc of a 0.16% by weight methanol solution of dye (1) was added, and the mixture was stirred for 5 minutes. , 1 cc of a 0.01% by weight aqueous solution of sodium thiosulfate was added for sulfur sensitization, and after further stirring for 15 minutes, T
It was coated on an AC film base, and φr was measured by a conventional method. In addition, in the above experiment, 2 of the addition of dye (1)
10-2 mol of mercapto compound (I[) before 0 min.
The φr of a sample prepared by adding 3 cc of a methanol solution of /It, was also measured. The measurement results are shown in Table 3.

A comparison with Table 3 shows that the addition of a mercapto compound does not significantly change the maximum absorption wavelength λfnaX of the J-aggregate,
It can be seen that φr was significantly increased. From a comparison between Experiments 1 and 9, the emulsion sensitized with sulfur at 70° C. had a decreased φr, but had enhanced dye adsorption and excellent stability over time.

Furthermore, in Experiment 10, by adding compound ■ before the dye, the adsorption of the dye was strengthened, and the stability over time was excellent.
φ.

It was possible to obtain an emulsion with high spectral sensitization and sulfur sensitization.

(Example 4) When preparing an emulsion in the same manner as in Example 1, by keeping the silver potential during the reaction at +60 mV, the grain size was reduced to 0.
82μm cubic Ag8. An emulsion consisting of grains was prepared.

Cubic AgB, emulsion and octahedral Ag of Example 1
B. Separate 95 cc of each emulsion, add 5 cc of a 0.16 wt% methanol solution of dye (2) having the following structure to each, and heat at 40°C, 60°C and 70°C, respectively.
After aging at 0° C. for 20 minutes, it was coated on a TAC film base, and φr was measured by a conventional method.

to 7 (Dye 2) C2H5C2H5 The measurement results are shown in Table 4.

Table 4 It can be seen that the samples of the present invention had longer absorption maximum wavelengths in the J band of the dyes than the comparative examples, indicating that the J aggregates had grown to a large extent. In the present invention, φ compared to the comparative example.

However, dye adsorption was enhanced and an emulsion that was extremely stable over time was obtained.

(Example 5) 95 cc of the cubic AJBr emulsion prepared in Example 4 was taken, kept at 70°C, 2.5 cc of a 0.16% by weight methanol solution of dye (2) was added, and the mixture was stirred for 5 minutes. death,
0.01% by weight of sodium thiosulfate for sulfur sensitization
After adding an optimum amount of an aqueous solution of and stirring for an additional 15 minutes, the mixture was coated on a TAC film base, and φr was measured by a conventional method. In the above experiment, φr was also measured for a sample prepared by adding 3 cc of a 10 −2 mol/1 methanol solution of Compound (1) 20 minutes before adding dye (2).

The measurement results are shown in Table 5.

From the comparison of Experiments 11 and 17 in Table 5, the φr of the emulsion sensitized with sulfur at 70°C decreased, but the effect of improving dye adsorption was greater as the aging time after addition of Compound C became longer. Ta.

Table 6 (Example 7) Take 95 cc of the octahedral AgB emulsion prepared in Example 1, add a known amount of a 10-2 mol/It methanol solution of compound (X), and incubate at 70°C for 20 cc. Aged for minutes. 5 cc of a 0.16% by weight methanol solution of Dye 2 was then added with stirring at 70°C, and after 5 minutes a known amount of a 0.01% by weight aqueous solution of sodium thiosulfate was added for sulfur sensitization. After aging for another 15 minutes, TAC
It was coated on a film base and φr was measured by a conventional method. The measurement results were improved and the stability over time was excellent. Furthermore, in Experiment 18, by adding compound Ⅰ prior to the dye, the adsorption of the dye was strengthened, the stability over time was excellent, and φr
It was also possible to obtain an emulsion with high spectral sensitization and sulfur sensitization.

(Example 6) The octahedral AgBt emulsion prepared in Example 1 was separated into 95 cc portions, and a 0.16% by weight methanol solution of Dye 2 was added to
After adding cc and aging at 70° C. for 20 minutes, the mixture was coated on a TAC film base, and φr was measured by a conventional method.

In the above experiment, 3 min, 10 min prior to the addition of dye 2.
min, and 30 min before compound ■ l O-2 mol /
3 cc of methanol solution of A was added to prepare a sample, and φr was measured. The measurement results are shown in Table 6.

From the comparison of Experiments 11 and 19, the emulsion aged at 70°C has φ
Although r decreased, dye adsorption was enhanced and stability over time was excellent. Furthermore, in Experiments 20, 21 and 22, φr could be improved by adding Compound (2) prior to the dye. It is shown in Table 7 of φr.

From a comparison of Experiments 11 and 23 in Table 7, the emulsion aged at 70° C. and sulfur-sensitized had a decreased φr, but had enhanced dye adsorption and excellent stability over time. Further experiments 24.25 and 2
By adding compound X prior to the dye in step 6, φr
was also able to be improved.

(Example 8) A similar experiment was conducted in Example 7 using Compound XI instead of Compound X. The measured values are shown in Table 6.

Table 8 Case description Patent application No. 13377 of 1999 Name of the invention Method for spectral sensitization of silver halide photographic emulsions Comparison of Experiments 11, 27, and 28 reveals that aging at 70°C and sulfur enhancement Although the φr of the emulsion was reduced, the dye adsorption was strong and the stability over time was excellent. Furthermore, in Experiments 29-32, φr could also be improved by adding Compound XI prior to the dye.

Relationship with the incident

Claims (2)

[Claims] (1) In a method of spectrally sensitizing a silver halide photographic emulsion, a cyanine dye that gives a J band when added to a silver halide emulsion is used, and the relative quantum yield φ_r of spectral sensitization is The dye is added to the emulsion under conditions such that the value of φ_r for the same emulsion is 1/2 or less of the value obtained when the aging condition from the time of application to the time of coating is 40°C for 20 minutes, A method for spectrally sensitizing a silver halide emulsion, which is characterized by ripening. (2) The silver halide according to claim 1, wherein the heterocyclic compound having a mercapto group is added to the emulsion prior to the dye in an amount and under conditions sufficient to increase φ_r. A method of spectrally sensitizing emulsions.