JPH01124844A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To obtain a photographic emulsion improved in dye desensitization by incorporating an ascorbic acid compd. and other specific compds. into a silver halide photographic emulsion which is spectrally sensitized by spectral sensitizing dyes. CONSTITUTION:One kind of the ascorbic acid compd. and one kind of the compd. expressed by formula I are incorporated into the silver halide photographic emulsion which is spectrally sensitized by at least one kind of the sensitizing dyes expressed by formula II and formula III. In formulas, A: a divalent arom. residue; R1-R4: an H atom, hydroxy group, etc.; Z1-Z3: a 5- or 6-membered nitrogenous heterocycle forming atom group; R7-R9: an H atom, lower alkyl group, etc.; R5, R6, R10: an alkyl group or alkenyl group; l1: 1, 2 or 3; k1, m1: 0 or 1; x1: acid anion, r1: 0 or 1, Q1: a nitrogenous 5- or 6-membered ketomethylene ring forming atom group; R12: an H atom or alkyl group, R13: an H atom or phenyl group, etc.; R11: synonymous with R10 and in addition, H atom, monocyclic aryl group which may be substd., etc.; l2: 2 or 3; k2: 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to spectrally sensitized silver halide photographic emulsions, and more particularly to improvement of desensitization caused by enhancing dyes.

(Prior art) Spectral sensitization technology is an extremely important and essential technology for producing photosensitive materials with high sensitivity and excellent color reproducibility.0 Spectral sensitizers are originally silver halide photographic emulsions. It has the function of absorbing light in a long wavelength range that is not substantially absorbed by silver halide and transmitting the light absorption energy to silver halide. Therefore, expanding the sensitive wavelength range and increasing photographic sensitivity using spectral sensitizers has become an essential technology. For this reason, attempts have been made to increase the amount of light captured by increasing the amount added to silver halide emulsions. However, if the amount of spectral sensitizer added to the silver halide emulsion exceeds the optimum amount, it will result in greater desensitization, which is generally referred to as dye desensitization.
This is a phenomenon in which desensitization occurs in the photosensitive range unique to silver halide, where there is virtually no light absorption by sensitizing dyes.If 0 dye desensitization is large, the overall sensitivity will be low even though there is a spectral sensitizing effect. In other words, as the dye desensitization decreases, the sensitivity of the light absorption region by the sensitizing dye (ie, spectral sensitization) increases accordingly. Therefore, improvement of dye desensitization is a major issue in spectral sensitization technology. In addition, dye desensitization is generally greater for exacerbating dyes whose photosensitive range is at longer wavelengths.
Op the Photograph 4-/Re-Process (The
Theory of, thePhotography
c Process)” pages 1067-1069 (Macmillan Publishing, 1942).

(Problems to be Solved by the Invention) Methods for increasing sensitivity by reducing dye desensitization include JP-A-47-28916, JP-A-49-46738, and JP-A-54-
No. 118236, U.S. Pat. No. 4,011,083 discloses acetylene silver complex salts, pyrazolone compounds, N-aminoimmonium compounds, N-imine compounds, or azaindenes. A method using complex salts is disclosed. In addition, a method of using a bisaminostilbene compound substituted with a pyrimidine derivative and a triazine derivative in combination was disclosed in Japanese Patent Publication No. 45-2
No. 2189, JP-A-54-18726, JP-A-52-
No. 4822, Japanese Patent Application Laid-Open No. 52-151026, and US Patent No. 2.945.762, and the current method is considered to be an effective method. In addition, as a method to improve dye desensitization and obtain high sensitivity by using a bisaminostilbene compound substituted with a triazine derivative in combination with an ascorbic acid compound,
For example, US Patent No. 3,695.888, British Patent No. 1.
No. 064.193 and British Patent No. 1,255.084 are known. However, the effect was not sufficient, and it was still desired to increase the frequency range of the layer.

As a result of examining various methods, the present inventors have found that the desensitization of a sensitizing dye with a certain limited chemical structure is significantly improved by using a combination of an ascorbic acid compound and a bisaminostilbene compound substituted with a triazine derivative. It has been found that an increase in spectral sensitivity can be obtained.

The first object of the present invention is to provide a silver halide photographic emulsion which is highly sensitive by improving dye desensitization. Second
An object of the present invention is to provide a silver halide photographic emulsion having excellent stability over time. The third object is to provide a silver halide photographic emulsion with little residual coloring due to sensitizing dyes.

(Means for Solving the Problems) The object of the present invention is to solve the problems by solving the general formula (It) and/or (I
At least one ascorbic acid compound and at least one compound represented by general formula (I) are added to a silver halide photographic emulsion spectrally sensitized with at least one sensitizing dye represented by [[]. This was achieved by including

General formula (I) where A represents a divalent aromatic residue eRI, R,,R
, and R4 are each a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, a troxy group, a halogen atom, a heterocyclic nucleus, an alkylthio group, a heterocyclylthio group, an arylthio group, an amino group, and a substituted or unsubstituted alkyl group. Amino group, arylamino group, aralkylamino group,
Represents an aryl group or a mercapto group. However, A, R,
, R, , R1 and R4 have a sulfo group.

General formula (n) In the formula, Z+ and Zt may be different or the same, 5
represents a group of atoms forming a nitrogen-containing or 6-membered nitrogen-containing heterocycle. R
t, Rt and R1 each independently represent a hydrogen atom, a lower alkyl group, an optionally substituted phenyl group, or an optionally substituted aralkyl group, and when l represents 2 or 3, a different R1 This indicates that R1 or R8 and R1 can be linked to form a 5- or 6-membered ring that may contain an oxygen atom, a sulfur atom, a nitrogen atom, or the like.

R3 and R1 each independently represent an optionally substituted alkyl group or an optionally substituted alkenyl group which may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain. 11 represents 1.2 or 3. k
1 s m 1 each independently represents 0 or l.

X1e represents an acid anion, and r represents O or l.

General Formula (Ill) In the formula, Z represents a nitrogen-containing 5- or 6-membered heterocycle-forming atom group, and Q represents a nitrogen-containing 5- or 6-membered ketomethylene ring-forming atom group. R1ff1 represents a hydrogen atom or an alkyl group, R11 represents a hydrogen atom, an optionally substituted phenyl group, or an optionally substituted alkyl group, and different R13 and R11 are connected to form an oxygen atom, a sulfur atom, or a nitrogen atom. May contain atoms, 5
Ro represents that it can also form a ring or a six-membered ring. represents an optionally substituted alkyl group or an optionally substituted alkenyl group which may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain.

R11 has the same meaning as R1゜, and also represents a hydrogen atom, an optionally substituted monocyclic aryl group, or a 5- or 6-membered
It also represents a monocyclic heterocyclic group whose members may be substituted.

i' represents 2 or 3, and k represents O or 1.*RIl and R1° may be linked to form a 5- or 6-membered ring.

The compounds used in the present invention will be explained in detail below.

In the general formula (I), -Am represents a divalent aromatic residue,
These may contain a -3oSM group (where M is a hydrogen atom or a cation imparting water solubility), and -A- is usefully selected from, for example, the following -A, - or -A8-. However, when Rt, Rs and R4 do not contain -SO or M groups, A is selected from the group -A1-.

A + -F, etc., where M represents a hydrogen atom or a cation imparting water solubility.

-A, -: R, , R, , R, and R4 are each a hydrogen atom, a hydroxy group, a lower alkyl group (the number of carbon atoms is preferably 1 to 8), for example, a methyl group, an ethyl group, n-propyl, n −
butyl group, etc.), alkoxy group (number of carbon atoms is 1
~8 are preferred, such as methoxy group, ethoxy group, propoxy group, butoxy group), aryloxy group (such as phenoxy group, naphthoxy group, o-)lyloxy group, p
-sulfophenoxy group, etc.), halogen atom (e.g., chlorine atom, bromine atom, etc.), heterocyclic nucleus (e.g., morpholinyl group, piperidyl group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, etc.), heterocyclylthio group (e.g., benzylthio group, etc.), thiazolylthio group, benzimidazolylthio group, phenyltetrazolylthio group, etc.), arylthio group (e.g. phenylthio group, tolylthio group),
Amino group, alkylamino group or substituted alkylamino group (e.g. methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di(β -hydroxyethyl)amino group, β-sulfoethylamino group), arylamino group (e.g. anilino group, 0-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, o-)luidino group, m-)luidino group, p-toluidino group, 〇-carboxyanilino group, m-carboxyanilino group, p-carboxyanilino L O-chloroanilino group, m-chloroanilino group, p-chloroanilino group, p-aminoanilino group, 0-anisidino group, m-anisidino group, p-anisidino group, 〇-acetaminoanilino group, hydroxyanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc.), heterocyclylamine group (e.g. 2-benzothia zolylamino group, 2-pyridyl-amino group, etc.), aralkylamino group (e.g. benzylamino group, 0-anisylamino group, m-anisylamino group, p-anisylamino group, etc.), oryl group (e.g. phenyl group, etc.) ), or @R1, Rt sR3, and R4 representing a mercapto group may be the same or different from each other, and particularly preferred substituents are a monoloxy group, a heterocyclylthio group, an arylthio group, and an arylamino group. -A- is -A! -, at least one of R2, R1, R3, and R4 must have one or more sulfo groups (which may be free acid groups or may form a salt). is necessary.

Zl or 2. The 5- or 6-membered nitrogen-containing heterocycle formed by, for example, thiazoline, thiazole, benzothiazole, naphthothiazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxazole,
benzimidazole, naphthimidazole, pyridine,
Examples of one substituent include quinoline, indolenine, imidazo(4,5-b)quinoxaline, penzotelllazole, etc., and the heterocyclic nucleus of these may be substituted, such as a lower alkyl group ( Preferably, the carbon number is 6 or less, and may be further substituted with a hydroxy group, a halogen atom, a phenyl group, a substituted phenyl group, a carboxy group, an alkoxycarbonyl group, an alkoxy group, etc.), a lower alkoxy group (preferably a carbon number of 6) below), acylamino group (preferably carbon number 8 or less), monocyclic ring group, carboxyl group, lower alkoxycarbonyl group (preferably carbon number 6 or less),
(below), a hydroxy group, a cyano group, a halogen atom, etc.

In addition, when the heterocycle represented by ZISZz contains another substitutable nitrogen atom such as benzimidazole, naphthimidazole, imidazo(4,5-b)quinoxaline, the other nitrogen atom of those heterocycles is For example, it may be substituted with an alkyl or alkenyl group having 6 or less carbon atoms (these alkyl or alkenyl groups may be further substituted with a hydroxy group, an alkoxy group, a halogen atom, a phenyl group, an alkoxycarbonyl group, etc.). .

R7, RIl and R9 each independently represent a hydrogen atom, a lower alkyl group (preferably carbon number 4 or less), an optionally substituted phenyl group, or an optionally substituted aralkyl group, and when 11 represents 2 or 3; represents that different R7 and Ry or Rs and R1 can be linked to form a 5- or 6-membered ring that may contain an oxygen atom, a sulfur atom, a nitrogen atom, etc.

R1 and R each independently represent an optionally substituted alkyl group or an optionally substituted alkenyl group having 10 or less carbon atoms which may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain, Examples of substituents include sulfo group,
Examples include carboxy group, hydroxy group, halogen atom, alkoxycarbonyl group, carbamoyl group, phenyl group, substituted phenyl group, and tetrahydrofuryl group.

11 represents l, 2 or 3, and m.

each independently represents 0 or l, Xl. represents an acid anion, r represents 0 or l, and at least one of RS and R6 is preferably a group having a sulfo group or a carboxy group.

In general formula (n), the following general formula (I
I-A) and the compound represented by the general formula (II-B).

General formula (II-A) In the formula, Z4 is an oxygen atom, a sulfur atom, a selenium atom, -CH
-CH- or >N RIl, R11k is an alkyl or alkenyl group having 6 or less carbon atoms (these alkyl or alkenyl groups are a hydroxy group, an optionally substituted phenyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, etc.) 1 (optionally)) Examples include methyl group, ethyl group, propyl group, methoxyethyl group, ethoxycarbonylmethyl group, 2-fluoroethyl group, phenethyl group, 2-hydroxyethyl group, allyl group, etc. It will be done.

(1) 1 and v4 represent hydrogen atoms.

Z4 is an oxygen atom, a sulfur atom, a selenium atom, or -CI-
When representing C11-, vl and V each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethyl group, an alkylacyl group having 5 or less carbon atoms, an alkoxycarbonyl group having 5 or less carbon atoms, It represents an acylamino group having 5 or less carbon atoms, an alkyl group having 5 or less carbon atoms, an alkoxy group having 5 or less carbon atoms, an optionally substituted phenylacyl group having 8 or less carbon atoms, or phenyl. vl and■
2. V2 and V; Also, when Z4>N-R'' is represented, vyo and V represent electron-withdrawing substituents which may be the same or different, and in particular, chlorine atom, trifluoromethyl A cyano group, an alkylacyl group having 5 or less carbon atoms, or an alkylsulfonyl group having 5 or less carbon atoms are preferred.

V, , V, , V, and V each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethyl group, an alkyl group having 5 or less carbon atoms, an alkoxy group having 5 or less carbon atoms, or a carbon atom Represents an alkoxycarbonyl group of 5 or less.

Preferred examples of the heterocycle represented by Z4 include benzothiazole, 5-methylbenzothiazole,
5-ethylbenzothiazole, 5-methoxybenzothiazole, 6-methylbenzothiazole, 5-chlorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5.6-dimethylbenzothiazole, 5-phenylbenzothiazole, 5 -acetylaminobenzothiazole, 6-propionylminobenzothiazole, 5.6
-Simethoxybenzothiazole, 5,6-cyoxymethylenebenzothiazole, 5,6,7°8-tetrapyronaphtho(2,3-d)thiazole, paidioxazole,
5-methylbenzoxazole, 5-isopropylbenzoxazole, 5-methoxybenzoxazole, 5
-ethoxybenzoxazole, 5-chlorobenzoxazole, 5-chloro-6-methylbenzoxazole, 5-phenylbenzoxazole, 5-p-)lylbenzoxazole, benzoselenazole, 5-methylbenzoselenazole, 5-methoxy benzoselenazole,
6-methoxybenzoselenazole, 6-methylbenzoselenazole, 5-ethylbenzoselenazole, 5-phenylbenzoselenazole, 5-chlorobenzoselenazole, 5-chlorobenzimidazole, 5,6-cyanobenzimidazole, 5 -cyanobenzimidazole, 6
-Chloro-5-cyanobenzimidazole, 6-chloro-5-trifluorobenzimidazole, 5-butoxycarbonylbenzimidazole, 5-ethoxycarbonylbenzimidazole, 5-methylsulfonylbenzimidazole, 6-chloro-5-ethoxycarbonylbenz Imidazole, naphtho(I,2-d)thiazole, natutho[2゜1-d]thiazole, naphtho(I,2-d)
selenazole, naphtho(2,1-d) selenazole, naphtho(I,2-d)oxazole, naphtho[2°3-d
] Oxazole, nut(2,1-d)oxazole,
2-quinoline, 4-quinoline, 8-fluoro-4-quinoline, 6-methyl-2-quinoline, 6-hydroxy-2
-quinoline, 6-medoxy-2-quinoline, and many others.

R14 and RlS represent an optionally substituted alkyl group or an optionally substituted alkenyl group having 6 or less carbon atoms,
Examples of the substitution of these alkyl or alkenyl groups include an alkoxy group, a halogen atom, a carbamoyl group, a carboxy group, an alkoxycarbonyl group, a sulfo group, an optionally substituted phenyl group, and a hydroxy group. Specific examples of alkyl or alkenyl groups include methyl group, ethyl group, propyl group, pentyl group, allyl group, methoxymethyl group, ethoxyethyl group, 2.2.
2-trifluoroethyl group, 2,2.3.3tetrafluoropropyl group, carbamoylethyl group, hydroxyethyl group, carboxymethyl group, carboxyethyl group, 2
-sulfoethyl group, 3-sulfoethyl group, 3-sulfobutyl group, 4-sulfobutyl group, phenethyl group, p-sulfophenethyl group, ethoxycarbonylethyl group, 2-hydroxy-3-sulfopropyl group, and the like.

It is preferable that at least one of R'' and R+s has a sulfoalkyl group.

X2° represents an acid anion, and R2 represents O or l.

General formula (II-B) V啼Vll R1?
(Xs'L
In the s formula, Z is an oxygen atom, a sulfur atom, a selenium atom, >
Represents N-R13 or -CH mist CH-, R1 is R
It has the same meaning as 16.

Z represents an atomic group forming benzothiazole, benzoselenazole, benzoxazole, benzimidazole, quinoline, naphthothiazole, naphthoselenazole, naphthoxazole, or naphthimidazole, and the heterocyclic nucleus thereof has a substituent. You can do it, v
Examples of l or V include the substituents listed above.

R9, vl ugly vll and V + t 4;! +t
L sotL V +,■! , R3 and R4.

When Z, represents > N-R2m, vl. is a hydrogen atom,
represents a chlorine atom, and ■ represents a chlorine atom, a perfluoroalkyl group having 4 or less carbon atoms (e.g., trifluoromethyl group, 1.1.2.2-tetrafluoroethyl group, etc.)
, cyano group, alkoxycarbonyl group having 5 or less carbon atoms,
Alkylacyl group having 5 or less carbon atoms (e.g. acetyl group,
(propionyl group, methanesulfonyl group) is preferred.

Further, when Z represents an atomic group necessary to form benzimidazole, the substituent for the benzimidazole nucleus is preferably an electron-withdrawing group, and those listed as preferred examples of Vll are particularly preferred.

Preferred examples of the heterocycle represented by Z or Z include the heterocycles listed in the compound of general formula (II-A).

R1ff and R1 have the same meaning as RI4 or RIS, and R1? may be linked with Rzl to form a 5- or 6-membered ring, and it is particularly preferred that at least one of R1ff or R1'' represents a sulfoalkyl group.

Rzl represents a hydrogen atom, R20 and R1 represent a hydrogen atom, an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, and R26 and R1 or different R1
0 and R1 may be connected to form a 5- or 6-membered ring which may contain an oxygen atom, sulfur atom or nitrogen atom in the ring.

Rzl represents a hydrogen atom, an alkyl group having 5 or less carbon atoms, or an optionally substituted benzyl group having 9 or less carbon atoms.

! , represents 1 or 2, X and e represent acid anions, and m2 and R3 represent 0 or l.

-8 The compound represented by the formula (II-B) is the compound represented by the general formula (II-B).
It is more preferable than the compound represented by -A).

The nitrogen-containing 5- or 6-membered heterocycle formed by z3 is, for example, thiazoline, thiazole, benzothiazole, naphthothiazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxazole, benz Imidazole, naphthoimidazole, pyridine, quinoline, pyrrolidine, indolenine, imidazo(4,5-b)
Examples of substituents include heterocyclic nuclei normally used for cyanine formation such as quinoxaline and penzotelllazole, and these heterocyclic nuclei may be substituted. Examples of substituents include lower alkyl groups (preferably 10 or less, and may be further substituted with a hydroxy group, a halogen atom, a phenyl group, a substituted phenyl group, a carboxy group, an alkoxycarbonyl group, an alkoxy group, etc.), a lower alkoxy group (
preferably 7 or less carbon atoms), acylamino group (preferably 8 or less carbon atoms), monocyclic aryl group, monocyclic aryloxy group, carboxy group, lower alkoxycarbonyl group (preferably 7 or less carbon atoms), hydroxy group, cyano A group or a halogen atom can be mentioned.

Q represents a nitrogen-containing 5- or 6-membered ketomethylene ring-forming atomic group. For example, rhodanine, 2-thiohydantoin,
2-Selenathiohydantoin, 2-thioxazolidine-2,4-dione, 2-selenaoxazolidine-2.
Heterocycles that can usually form merocyanine dyes such as 4-dione, 2-thioselenazolidine-2,4-dione, 2-selenothiazolidine-2,4-dione, and 2-selenaselenazolidine-2,4-dione. Examples include the group of atoms that form the nucleus.

In the heterocycle represented by Z and Q, when the heterocycle-forming atomic group contains two or more nitrogen atoms, such as benzimidazole or thiohydantoin, R+
. , the nitrogen atom to which R11 is not connected may be substituted, and the carbon atom in the alkyl chain may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom, and the nitrogen atom to which R11 is not connected may be substituted. Examples include an optionally substituted alkyl or alkenyl group having 8 or less carbon atoms, an optionally substituted monocyclic aryl ring, or a monocyclic heterocyclic group.

Rlz represents a hydrogen atom or an alkyl group having up to 4 carbon atoms, and RIm represents a hydrogen atom, an optionally substituted phenyl group (examples of substituents include an alkyl or alkoxy group having up to 4 carbon atoms, a halogen atom, a carboxy hydroxy group, etc.), or an optionally substituted alkyl group (examples of substituents include hydroxy group, carboxy group, alkoxy group, halogen atom, etc.). RIm may be linked to form a 5- or 6-membered ring that may contain an oxygen atom, sulfur atom, or nitrogen atom.

R5° represents an optionally substituted alkyl or alkenyl group having a carbon number of lθ or less which may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain; examples of the substituent include a sulfo group; Carboxy group, hydroxy group,
Examples include a halogen atom, a flukoxycarbonyl group, a carbamoyl group, a phenyl group, a substituted phenyl group, and a monosaturated heterocyclic group.

R11 has the same meaning as R1゜, and also includes a hydrogen atom, an optionally substituted monocyclic aryl group (examples of substituents include a sulfo group, a carboxy group, a hydroxy group, a halogen atom, and an alkyl group having 5 or less carbon atoms). , acylamino or alkoxy group), or a 5- or 6-membered monocyclic heterocyclic group (e.g., 2-pyridyl group, 3-pyridyl group, 4-methyl-2-pyridyl group, furyl group, etc.) also represents.

Ilt represents 2 or 3, k! represents 0 or 1.

RIm and R+o may be linked to form a 5-membered or 6R ring.

It is more preferable that at least one of R1° and Ro is a group containing a sulfo group or a carboxy group.

-a Formula (m) is more preferably the general formula <m-A
) is a compound represented by

General formula (ff[-A) Ris where, 2. represents a 5- or 6-membered heterocyclic atomic group, more preferably thiazoline, thiazole, benzothiazole, naphthothiazole, selenazoline, selenazole, benzoselenazole, naphthoselenazole, oxazole, benzoxazole, naphthoxazole, benzimidazole, This is the case when it represents an atomic group forming naphthimidazole, pyridine, quinoline or penzotelllazole. The 5- or 6-membered heterocyclic nucleus may be substituted, and examples include those listed in general formula (III), and particularly preferred substituents include, when the heterocyclic nucleus is benzimidazole, a chlorine atom, a cyano group, Examples thereof include an alkoxycarbonyl group having 5 or less carbon atoms, a perfluoroalkyl group having 4 or less carbon atoms, and an acyl group having 5 or less carbon atoms (eg, acetyl group, methanesulfonyl group, etc.). Other than benzimidazole, it has 5 or less carbon atoms (may be substituted with hydroxy group, carboxy group, halogen atom, phenyl group, alkoxycarbonyl group, alkoxy group, etc.)
Alkyl group, phenyl group (which may be substituted with hydroxy group, halogen atom, alkoxy group, acylamino group, alkylaminocarbonyl group, carboxy group, etc.) having 8 or less carbon atoms, furyl group, thienyl group, pyridyl group, carbon number Particularly preferred substituents include an alkoxy group having 5 or less carbon atoms, an alkoxycarbonyl group having 5 or less carbon atoms, a hydroxy group, a halogen atom, or a carboxy group.

Qt is an oxygen atom, a sulfur atom, a selenium atom or >NR
zt, Rxq may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain, (hydroxy group,
an alkyl group having 8 or fewer carbon atoms, or an optionally substituted monocyclic aryl or a monocyclic heterocyclic group, particularly preferably a 6-carbon group which may be substituted with a hydroxy group, an alkylaminocarbonyl group, an alkoxycarbonyl group, or a carboxy group, and which may contain an oxygen atom in the carbon chain. This is a case where it represents an alkyl group, or a phenyl or pyridyl group which may be substituted with the following alkyl group, hydroxy group, alkyl group, chloro atom, alkoxy group, etc.

Y represents a sulfur atom or a selenium atom.

R14 represents an optionally substituted alkyl or alkenyl group having 8 or less carbon atoms which may contain an oxygen atom or a sulfur atom in the carbon chain. Examples of the substituent include a sulfo group, a carboxy group, a hydroxy group, Examples include a halogen atom, an alkoxycarbonyl group, a carbamoyl group, an optionally substituted phenyl group, and a monocyclic saturated heterocycle.

R□ has the same meaning as R14, and preferred examples of substituents include a hydrogen atom, an optionally substituted monocyclic aryl group having 8 or less carbon atoms, or a 5- or 6-membered monocyclic heterocyclic group. Examples of the aryl group include an alkyl group, an alkoxy group, a chloro atom, a carboxy group, a sulfo group, and an acylamino group. Preferred examples of the aryl group include a phenyl group, and a 5- or 6-membered monocyclic heterocyclic group. Preferred examples include pyridyl, furyl or thienyl.

Ro is a hydrogen atom, an optionally substituted phenyl group having 8 or less carbon atoms (examples of substituents include an alkyl group, an alkoxy group, a chloro atom, a carboxy group, a hydroxy group, etc.), or a substituted represents an alkyl group having 6 or less carbon atoms (examples of substituents include hydroxy group, carboxy group, alkoxy group, fluorine atom or chlorine atom).

Rlm represents a hydrogen atom, as well as Ro and Ro or R2,
and Ro may be linked to form a 5- or 6-membered heterocycle which may contain an oxygen atom or a nitrogen atom in the ring.

Rzt represents a hydrogen atom or an alkyl group having 4 or less carbon atoms.

k represents 0 or 1, and 14 represents 1 or 2.

Next, specific examples of compounds used in the present invention are shown below.
However, the compounds used in the present invention are not limited to these.

Specific examples of ascorbic acid compounds include the following.

(A-1) L-ascorbic acid (A-2) Sodium L-ascorbate (A-
3) Potassium L-ascorbate (A-4) D
L-ascorbic acid (A-5) Sodium D-ascorbate (A-6
) L-ascorbine a-6-acetate (A-7)
L-ascorbic acid-6-palmitate (A-8) L-ascorbic acid-6-pentzate (A-,9) L-ascorbic acid-6-diacetate (A-10) L-ascorbic acid-5,6- Specific examples of the compound represented by o-isopropylidene-a formula (I) include the following.

Among these specific examples, (I-1), (I-4),
(I-5), (I-7>, and (I-8)) are preferred.

Specific examples of the sensitizing dye represented by the general formula (II) include the following.

GHzCOOHI0 (II-3) (n -4) (If -5) CJ5 (+;1
lt) 5SUs-(I[-6) C, II SC! H5 (n −9) (CHz) ashs.

(IF-10) (II-11) (CHz) ash, l” (C
Ht) as03Na(II-12) (II-13) C! H5CzHs Ie (II-15) (CHz)! SO3-(CHi) CzH to xSOs
s CJs C1
20ae(II-18) (CHz) 5sOs. (CHi) zsOJa(II
-19) (■-20) Specific examples of the sensitizing dye represented by the general formula (I[I) include the following.

(I[l-2) (C1,) asOsNa CzHs(I
[l-3) (III-4) C,H.

(III-5) ans CJs CHiCOONa(I[
[-7) (III-8) czos ■ CtH, CIl□C00H (III-9) (III-11) (Ill-12) How to incorporate the above ascorbic acid compound into the silver halide emulsion of the present invention , they may be directly dispersed in the emulsion, or they may be added to the emulsion after being dissolved in a solvent such as water, methanol, ethanol, etc., alone or in a mixed solvent. It can be present and used in any process. Moreover, it does not matter whether or not the sensitizing dye is added.

The ascorbic acid compound used in the present invention has a concentration of 1X10-'' mol to 5×10-” mol, preferably 1X10-' mol-2×1, 6×10-
"Contained in molar proportions in silver halide photographic emulsions.

The compound represented by the general formula (I) is
Those skilled in the art can easily synthesize compounds that are known in Japanese Patent Publication No. 41, etc. and are not described in the aforementioned Japanese Patent Publication No. 32741 by referring to the synthesis example described in Japanese Patent Publication No. 45-32741.

The compound represented by the general formula (I) used in the present invention can be directly dispersed in an emulsion, or it can be dispersed in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It can also be dissolved in and added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes. Also, Japanese Patent Application Publication No. 1973-
It can also be dispersed and added into the emulsion by the method described in Japanese Patent No. 80119.

Usage ratio (molar ratio) of the sensitizing dye represented by general formula (n) or (I[I) and the compound represented by general formula (I)
is a dye represented by general formula (II) or (]II)/
- Compound represented by general formula 1) = 1/1-1/3 0
A range of 0 is advantageously used, especially 1/2 to 1/100
A range of is preferred.

The sensitizing dye used in the present invention represented by the general formula (II) or (I[[) is a known compound. For example, the general formula (
Compounds represented by I[) and general formula ([11)] are disclosed in JP-A-51-126140, JP-A-51-139323, JP-A-51-14313, and JP-A-55-35386.
No., JP-A-52-109925, JP-A-53-135
No. 322, West German Open Patent Application (OLS) 2,158,553
No., Special Publication No. 52-2614, Japanese Patent Publication No. 47-28916
Specifications such as No.F. M. ) Iamer+ The
Chemistry of Hetero-cycle
c Coa+pounds, Vol. 18, Th
e Cyanine Dyesand Re1ated
Compounds, A., Weissbarger
ed.

Interscience+ Nes York+
1964, D. M. Sturmer.

The Chemistry of 1 (etsroc
yclic compounds, Vat.

30, ^, Weissberger and E,C
, Taylor ed, , John Wiley,
New York+ 1977 + p, 441,
etc., and can be synthesized by referring to them.

In order to incorporate the compounds represented by the above general formulas (n) and (III) into the silver halide emulsion of the present invention, they may be directly dispersed in the emulsion, or they may be dispersed in water, methanol, ethanol, propane. tools, methyl cellosolve,
2.2, 3.3-Tetrafluoropropanol may be added to the emulsion by dissolving it in a single or mixed solvent such as a solvent such as 2.2, 3.3-tetrafluoropropanol.
No. 7555, Japanese Patent Publication No. 57-22089, etc., an aqueous solution is prepared by coexisting an acid or a base, or US Pat.
, 822,135, U.S. Pat. No. 4,006.025, etc., an aqueous solution or colloidal dispersion may be added to the emulsion in the presence of a surfactant. After dissolving in a water-immiscible solvent, a hydrophilic colloid may be added to the emulsion by dispersing it in water or a hydrophilic colloid, as described in JP-A-53-102733 and JP-A-58-105141. It may also be directly dispersed in a sex colloid and the dispersion added to the emulsion.

The sensitizing dye used in the present invention is U.S. Patent No. 3,485.6
In addition to the method of dissolving or dispersing the aggravating dye of the present invention using ultrasonic vibration as described in U.S. Patent No. 34, US Pat.
2.981, 3゜585.195, 3,469
, No. 987, No. 3.425.835, No. 3,342,
605, British Patent No. 1,271,329, British Patent No. 1,03
The methods described in US Pat. No. 8,029, US Pat. No. 1,121,174, US Pat.

Here, the sensitizing dye can be used in any step of the manufacturing process of the photographic emulsion, or can be present in any stage after manufacturing until immediately before coating. Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process.
It may be added during particle formation as described in No. 89.

The sensitizing dyes of the general formulas (I1) and ([) used in the present invention are 5X10-' moles per mole of silver halide.
0-"mol, preferably 5X10-"mol to 2X10-"mol
'mol, particularly preferably lXl0-'mol-lXl0-
It is contained in silver halide photographic emulsions in molar proportions.

In the photographic emulsion of the present invention, any of silver bromide, silver iodobromide, silver chloroiobromide, silver chlorobromide, and silver chloride may be used as the silver halide. Preferred silver halides include silver bromide, silver chlorobromide,
Silver chloroiodobromide or silver chloride.

Regardless of the crystal phase of the silver halide grains, they are spectrally sensitized. However, in order to obtain higher spectral sensitivity (I00
) planes are preferred, and more specifically, the area ratio of the (I00) planes to the total surface area of all grains is preferably 50%, more preferably 80% or more.

To determine the crystal phase of silver halide grains, that is, the ratio of the area of the (I00) plane to the total surface area of all grains, see Tadaaki Tani's book, ``Crystal phase determination of fine II halide grains in photographic emulsions using dye adsorption phenomenon. Identification” Journal of the Chemical Society of Japan, 1984, (61P-
942-947.

The silver halide emulsion used in the present invention has a thickness of 0.5 microns or less, preferably 0.3 microns or less, a diameter of preferably 0.6 microns or more, and grains with an average aspect ratio of 5 or more have a total projection. They may be tabular grains that occupy 50% or more of the area.

Alternatively, the emulsion may be a monodisperse emulsion in which 95% of the grains have a grain size within ±40% of the average grain diameter.

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 P. gelafchides (
"Chimie et Phy Photography" by P. Glafkides
siquePhoto(raphique) J (
Published by Pau1Monte1, 1967
), The F Duffin CG, F, Duffin
) Author: Photographic Emulsion Chemistry
+wistry) J (Focal Breath Foca
Press, 1966), V.L. Zelikman et al.
, ), “Making and Coating Photographic Emulsion (Making and Coating Photographic Emulsion)”
Coating Photographic
[! +5olsion) J (Focal Press Foc
Al Press, 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 the 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, halogenated illumination agents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574,628 No. 3,704,130, No. 4
, No. 297,439, No. 4,276.374, etc.),
Thione compounds (e.g., JP-A-53-144319, JP-A-53-82408, JP-A-55-77737, etc.), amine compounds (e.g., JP-A-54-100717, etc.)
It can be used for etc.

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. 3,761,27
No. 6, and 3.935. Examples include emulsions containing different metals as described in No. 014 and the like.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H Freezer (
H, Fr1eser) ``Die Grundlagend Photography
erPhotographischen Prozas
Silberhalogsniden)
J (Akademische Verlag)
cheVerlagsgesellschafL 19
The method described in 1968, pp. 675-734 can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, reduction sensitization using noble metal compounds (e.g., total complex salts,
A noble metal aggravation method using complex salts of metals of group 1 of the periodic table such as pt, Ph, Ir, and Pd can be used alone or in combination.

More specific chemical aggravating agents include sulfur sensitizers such as allylthiocarbamide, thiourea, sodium thiosulfate and cystine; noble metal sensitizers such as bottasium chloroaurate, aurous thiosulfate and bottasium chloroparadate; Sensitizer: May contain reduction sensitizers such as tin chloride, phenylhydrazine, and reductone. Sensitizers such as polyoxyethylene compounds, polyoxypropylene compounds, and compounds having quaternary ammonium groups may also be included.

The photographic emulsion of the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. 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 (
Especially 1-phenyl-5-mercaptotetrazole, 1-
(3-N'-methylureidophenyl)-5-mercaptotetrazole, 1-(3-sulfophenyl)-5-mercaptotetrazole), mercaptopyrimidines; Terocyclic mercapto compounds; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindene! W (particularly 4-hydroxy substituted (I, 3,
Many compounds known as antifoggants or stabilizers can be added, such as (3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; etc.

The silver halide emulsion of the present invention is disclosed in U.S. Patent No. 3,411.9.
No. 11, No. 3,411.912, No. 3゜142.56
No. 8, No. 3,325.286, No. 3.547,650
Polymer latex consisting of homo- or copolymers of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc., described in Japanese Patent Publication No. 45-5331, etc., is used to improve the dimensional 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, U.S. Pat. ,294,53
No. 7, Specification No. 3,294゜540, French Patent No. 1,
No. 491,805, specification No. 1,596,673, specification of Japanese Patent Publication No. 40-23466, Japanese Patent Application Publication No. 1564-1977
No. 23, No. 54-18726, No. 56-151933
Such compounds can be used as described in the patent specification. 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 of water, aliphatic alcohol, aromatic alcohol, fatty acid, organic amine, hexitol derivative, etc. It includes condensates with individual compounds, block polymers of two or more types of polyalkylene oxides, and the like. That is, examples of polyalkylene oxide compounds include polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol alkylaryl ethers, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, and polyalkylene glycols. Amines, polyalkylene glycol 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 15,00.
0. Preferably it is 600 to 8,000. The amount of these polyalkylene oxide compounds added is preferably 10 to 3 g per mole of silver halide, and the time of addition 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, it may contain a compound that can develop color by oxidative coupling with an aromatic primary amine developer (eg, phenylene diamine derivative, aminophenol derivative, etc.) in color development treatment.

For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides). , etc., and cyan couplers include naphthol couplers, phenol couplers, etc. 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 may contain various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). But that's fine.

Nonionic surfactants such as saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol), polyethylene glycol alkyl ethers, glycidol derivatives, fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylic acids Anionic surfactants such as salts, alkyl sulfonates, alkylbenzene sulfonates, alkyl sulfates; heterocyclic quaternary surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium, etc. Cationic surfactants such as grade ammonium salts can be used. Also,
When used as an antistatic agent, fluorine-containing surfactants are 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 antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

The photographic emulsion of the present invention may contain inorganic or organic hardeners, such as chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), activated vinyl compounds (
I,3,5-)lyacryloyl-hexahydro-3-triazine, 1゜3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6
-hydroxy-5-) riazine, 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 addition to gelatin as a protective colloid, the silver halide photographic emulsion of the present invention contains acylated gelatin such as phthalated gelatin and malonated gelatin, cellulose compounds such as hydroxyethyl cellulose and carboxymethyl cellulose; and soluble starch such as dextrin. ; hydrophilic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and polystyrene sulfonic acid, plasticizers for dimensional stabilization, latex polymers and matting agents may be added. The finished emulsion is coated onto a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.

Exposure to obtain a photographic image may be carried out using a conventional method. i.e. natural light (sunlight), tungsten electric light,
Any of a variety of known light sources can be used, such as a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, a laser, and an LED%CRT. The exposure time is not only the 1/1000 second to 1 second exposure time normally used in cameras, but also the exposure time shorter than 1/1000 second,
For example, 1/10' to 1/10 using a xenon flash lamp
Exposures of 6 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 using a color filter.

Laser light can also be used for exposure. Also, electron beam,
Exposure may be performed using light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

The silver halide emulsion of the present invention is used in various color and black-and-white light-sensitive materials, such as color positive emulsions, color paper emulsions, color negative emulsions, and color reversal emulsions (which may or may not contain couplers). ),
Emulsions for photosensitive materials for plate making (e.g. lithium film, etc.), emulsions for use in photosensitive materials for cathode ray tube displays,
Emulsions used in silver salt diffusion transfer processes, emulsions used in color diffusion transfer processes, Gui transfer
process (imbitio transfer pro
cess) (as described in U.S. Pat. No. 2,882,156, etc.); emulsions for use in silver dye bleaching methods; Direct Pr1nt
i+wage) photosensitive materials (e.g., U.S. Pat. No. 3,033)
These include emulsions used in color photosensitive materials for heat development, etc.

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.

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

(Example) Next, specific examples used in the present invention will be shown, but the present invention is not limited to these specific examples.

Example-1 A silver halide emulsion (hereinafter referred to as Emulsion-A) consisting of pure silver bromide and having a cubic crystal shape (the area ratio of the (I00) plane to the total grain surface area was 89%) ) and has an octahedral crystal shape ((I11) relative to the total surface area of the particle
Silver halide emulsion (hereinafter referred to as
Emulsion-B) was prepared. The silver halide emulsion described above was subjected to sulfur sensitization treatment. The average diameter of silver halide grains contained in these emulsions is 0.7 μm, and 1 kg of emulsions
It contained 0.55 mol of silver halide.

Weigh out 1 kg of each of the two types of emulsions mentioned above into a pot,
As shown in Tables 1-1 to 1-11, a sensitizing dye was added, followed by an ascorbic acid compound and a bisaminostilbene compound, followed by mixing and stirring at 40°C. Furthermore, 0.1 g/1 kg of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene and 0.1 g/1 kg of 2,4-dichloro-6-hydroxy-1,3,5-)riazine soda were added. After sequentially adding 1 m of emulsion and 0.1 g of sodium dodecylbenzenesulfonate/1 kg of emulsion,
A photographic material was obtained by coating on a polyethylene terephthalate film base.

Each of these samples was exposed to tungsten light (2854
”K) for 5 seconds.

After exposure, development was performed at 20° C. for 4 minutes 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 (S
R), blue filter sensitivity (SB), and capri were determined. The optical density reference point that determined the sensitivity was [fog +0.
2].

Composition of developer water 700-
Metol 3.1g Anhydrous Sodium Sulfite 45g Hydroquinone
12g sodium carbonate (-water salt)
79g potassium bromide 1.9
g Add water to make 1 g When using, add 2 volumes of water to make a working solution.

1-1 to 1-11 using the obtained results as relative values.
Shown in the table.

It will be understood from the results of Example 1 that the present invention brings about an improvement in dye desensitization and an even greater sensitizing effect. That is, it can be seen that it is more advantageous to use the alkorbic acid compound or the bisaminostilbene compound represented by the general formula (I) in combination with the dye than to use each alone in combination with the dye.

Comparative dye X-1 used in Table 1-3 is a dye included in the general formula of the dye disclosed in U.S. Patent No. 3,695,888, but it has a sensitizing effect and the sensitivity actually obtained. It can be seen that the dyes of the invention are advantageous.

Furthermore, if we compare the results in Tables 1-10 and 1-11 using Emulsion-B with Tables 1-4 and 1-8 using Emulsion-A, we find that the halogenated It can be seen that silver emulsions are significantly advantageous when their silver halide grains consist of (I00) planes.

Chemical structure of dye X-1 used for comparison (CHi)
aSOs-(CHz)SOsHN(CtH's) sExample-2 Photographic materials for the present invention and for comparison were obtained by the same method as in Example-1 using the same silver halide photographic emulsion-A. Some of these photographic materials were processed on the fifth day after coating under the same exposure and development conditions as in Example-1. The remaining samples were stored for 6 months at a temperature of 25°C and a relative humidity of 60% and then developed under the processing conditions described above. As is clear from Table 2, which shows the obtained results as relative values, it can be seen that the sample according to the present invention shows less decrease in sensitivity and less increase in fog compared to the comparative sample.

Example-3 A silver halide emulsion was prepared as follows.

(1 liquid) H, 01000cc Na C15.5g Gelatin 32g (2 liquids) Sulfuric acid (IN) 24cc (3
Liquid) The following halogenated l! Solvent (I%) 3 ccH
3 H3 (4 liquids) KBr 15.66gNa C
j! 3. Add 30g H2O to 200 cc (5 liquids) A g N Os
Add 32 g HtO and 200 c
c (6 liquid) KBr 62.72g
Na Cj 13.
22gK! I r CL, (0,001%)
Add 4.54ccHxO
600cc (7 liquids) Add 128gH2o of AgN03 and heat 600cc (liquid I) to 56℃
(Liquid 2) and (Liquid 3) were added. after that,(
Liquids 4) and 5 were added simultaneously over a period of 30 minutes. After a further 10 minutes, (Liquid 6) and (Liquid 7) were added simultaneously over a period of 20 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Water and dispersed gelatin were added to adjust the pH to 6.2 to obtain a monodisperse cubic silver chlorobromide emulsion with an average grain size of 0.458 ml and 70 mol % of silver bromide. This emulsion contains 1.0 x 10-4
Optimal chemical sensitization was performed by adding 1 mol Ag of chloroauric acid and further sodium thiosulfate.

Aggravating dye (III-6) was added to this emulsion at 1.2X 10-
1 mol AgX was added, followed by 1 mol L-ascorbic acid (A-1). OX 10-'' mol 1 mol AgX and bisaminostilbene compound (I-5) and 4XlO-4 mol 1 mol AgX were added and mixed and stirred.

After this emulsion was kept at 40° C. for 30 minutes, the couplers shown in Table 3 were added, mixed and stirred to prepare a coating sample. For comparison, samples not containing (A-1) and (I-5) were also prepared. This sample was applied to a paper support laminated on both sides with polyethylene as follows.

The amount of coating liquid is 0.35'g of silver and 1.5'g of gelatin.
Set to 5g/rd, and add 1.5g/rd of gelatin to the upper layer.
A protective layer of 5 g/rd was provided. In addition, the gelatin hardening agent is 2,4-dichloro-6-hydroxy-1°3.5
-) Two types of coating samples were prepared using riazine sodium salt and 1,3-bis(vinylsulfonyl)-2-propanol separately.

The sample was exposed to tungsten light (3200°K) for 0.5 seconds using the same red filter used in Example 1. Thereafter, it was processed using a color developing solution as shown below.

Composition of color developer Water 800-diethylenetriaminepentaacetic acid, pentasodium 2.0g Benzyl alcohol 15-diethylene glycol
10- Nat Sow
2. OgKBr 1.
0g Hydroxylamine sulfate 3.0g 4-amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido)ethyl)-p-phenylenediamine sulfate 5.0gN a z
CO3 (I water salt) 30.0g Fluorescent brightener (Stilbene type) 1.0g Add water for a total of 1000mf (pH 10,2) (Bleach-fix solution formulation) Ammonium thiosulfate (54@t%) 150MINa
zSO= tsgNHa (
Fe(Ill)(EDTA)) 55 g
EDTA2Na 4g glacial acetic acid
Add 8.61g water to make the total amount
1000d (pH 5,4) (Rinse liquid formulation) EDTA・2Na-2HtOO, 4g water was added to make the total amount 1000-(pH 7,0) The treatment conditions are shown below.

(Processing process) (Temperature) (Time) Development 33℃ 3 minutes 30 seconds Bleach fixing
33℃ 1 minute 30 seconds 28℃～
35°C 1 minute 30 seconds Photographic evaluation: L-ascorbic acid (A-1) and bisaminostilbene compound (I-5)
Relative sensitivity is expressed, with samples not containing 100 being taken as 100.

The optical density reference point that determined the sensitivity was [Capri+0.5]
This is the point.

Table 3 Table 3 shows samples using 1,3-bis(vinylsulfonyl)-2-propanol as a gelatin hardening agent. 2,4-dichloro-6-hydroxy-1,3,
5-) Almost the same results were obtained from the sample using riazine sodium salt. As is clear from the above table, sensitivity can be increased by using ascorbic acid and a bisaminostilbene compound substituted with a triazine derivative. It can also be seen that the same effect can be obtained even if the coupler is changed.

Chemical structure of the coupler used (C-1) (C-3) (C-4) (C-5) C1! (C-6) (C-7) H (C-8) Preferred embodiments of the present invention are listed below.

1. In the claims, R5 and R1 of general formula (I)
, R3 and R are an aryloxy group, a heterocyclylthio group, an arylthio group, or an arylamino group.

2. In Embodiment 1, when the aggravating dye used is represented by the general formula (n-B).

3. The sensitizing dye used in Embodiment 1 has the general formula (
Jll-A).

4. When the silver halide emulsion used in the claims has an area ratio of the (I00) plane to the total surface area of all grains of 50% or more.

5. When the silver halide emulsion used in Embodiment 2 has an area ratio of the (I00) plane to the total surface area of all grains of 50% or more.

6. When the silver halide emulsion used in Embodiment 3 has an area ratio of the (I00) plane to the total surface area of all grains of 50% or more.

Patent applicant: Fuji Film Co., Ltd. Procedural amendment February 4, 1963

Claims (1)

[Scope of Claims] At least one ascorbic acid compound and the general formula (
I ) and at least one compound represented by the general formula (
A silver halide photographic emulsion comprising at least one sensitizing dye represented by II) and/or general formula (III). General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A represents a divalent aromatic residue. R_1, R_2
, R_3 and R_4 are each a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, an alkylthio group, a heterocyclylthio group, an arylthio group, an amino group, and a substituted or unsubstituted alkylamino group , represents an arylamino group, an aralkylamino group, an aryl group or a mercapto group. However, at least one of A, R_1, R_2, R_3 and R_4 has a sulfo group. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z_1 and Z_2 may be different or the same5
represents a group of atoms forming a nitrogen-containing or 6-membered nitrogen-containing heterocycle. R
_7, R_8 and R_9 each independently represent a hydrogen atom, a lower alkyl group, an optionally substituted phenyl group, or an aralkyl group, and when l_1 represents 2 or 3, different R_7 and R_7 or R_8 Indicates that R_8 can be linked to form a 5- or 6-membered ring that may contain an oxygen atom, sulfur atom, or nitrogen atom. R_5 and R_6 each independently contain an oxygen atom in the carbon chain,
Represents an alkyl group or alkenyl group that may contain a sulfur atom or a nitrogen atom, or may be substituted. l_1 represents 1, 2 or 3. k_
1 and m_1 each independently represent 0 or 1. X_1
^■ represents an acid anion, and r_1 represents 0 or 1. General formula (III) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, Z_3 represents a nitrogen-containing 5- or 6-membered heterocyclic ring-forming atom group. Q_1 represents a nitrogen-containing 5- or 6-membered ketomethylene ring-forming atomic group. R_1_2 represents a hydrogen atom or an alkyl group, and R_1_3 represents a hydrogen atom or an optionally substituted phenyl group or an alkyl group, and different R_1_3 and R_1_3 may be linked to contain an oxygen atom, a sulfur atom, or a nitrogen atom. This indicates that a 5- or 6-membered ring can also be formed. R_1_0
represents an alkyl group or alkenyl group which may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain and may be substituted. R_1_1 has the same meaning as R_1_0, and also represents a hydrogen atom, an optionally substituted monocyclic aryl group, or a 5- or 6-membered monocyclic heterocyclic group. l_2 represents 2 or 3, and k_2 represents 0 or 1. R_1_2 and R_1_0 may be connected to form a 5- or 6-membered ring.