JPH0469893B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a spectrally sensitized silver halide photographic emulsion, and particularly to a silver halide photographic emulsion with increased spectral sensitivity in the green sensitive region. (Prior art) One of the manufacturing technologies for photographic light-sensitive materials is the technology of expanding the sensitive wavelength range to the longer wavelength side by adding a certain type of cyanine dye to a silver halide photographic emulsion, that is, spectral sensitization technology. It is well known that this applies. In this case, the sensitivity obtained by spectral sensitization, that is, the spectral sensitivity, is determined by the chemical structure of the sensitizing dye, various properties of the emulsion, such as the halogen composition of silver halide, crystal habit, crystal system, silver ion concentration, hydrogen ion concentration, etc. It is also known that it is influenced by Furthermore, the spectral sensitivity is also influenced by photographic additives such as stabilizers, antifoggants, coating aids, precipitants, color couplers, hardeners, etc. that coexist in the emulsion. Generally, in light-sensitive materials, one sensitizing dye is used to sensitize a predetermined spectral wavelength range. On the other hand, it is known that the presence of a second, specifically selected dye or other organic substance in addition to this dye significantly increases the efficiency of spectral sensitization; It is known as feeling. In general, the addition of a second dye or an organic substance often does not increase the sensitivity or even reduces the sensitivity, so supersensitization can be said to be a unique phenomenon and is used in this composition. Extremely strict selectivity is required for the organic compound used and the second sensitizing dye. Therefore, what appears to be a slight difference in chemical structure at first glance has a significant effect on this supersensitizing effect, and it is difficult to obtain a supersensitizing combination simply by predicting from the chemical structural formula. When applying supersensitization to a silver halide photographic emulsion, the sensitizing dye used is first required to provide high spectral sensitivity. It is desirable to strongly sensitize a specific narrow wavelength range.
In particular, in spectral sensitization of the green-sensitive region, broadening the spectral sensitivity to the long-wavelength side or the short-wavelength side increases the overlap with the red-sensitive and blue-sensitive regions, resulting in increased color turbidity in color photosensitive materials. In some cases, the sensitivity to safe light increases, resulting in poor handling, so it is necessary to provide higher sensitivity in a narrow wavelength range. For this purpose, a sensitizing dye that provides spectral sensitivity called the J-band is usually used, but it is desirable to further narrow the wavelength range of this spectral sensitivity without expanding it, thereby providing high green sensitivity. Furthermore, the sensitizing dye used must not have adverse interactions with color couplers other than the sensitizing dye or other photographic additives, and must also have stable photographic properties even during storage of the photosensitive material. This is what is happening. Furthermore, the sensitizing dye used is required not to leave any residual coloring caused by the sensitizing dye in the photographic material after processing. In particular, it is required that no residual coloring be left in a short-time treatment (usually several seconds to several + seconds) such as rapid treatment. Furthermore, the sensitizing dye used is required to have little fog caused by the dye. In particular, combinations of dyes that exhibit supersensitizing effects in the green sensitive region include U.S. Pat.
It is known as No. 3397060. however,
The techniques disclosed in these documents are insufficient to obtain a light-sensitive material that has high green sensitivity, has little fog, has good storage stability over time, and has little residual color after processing. It is well known that the addition of certain benzimidazolocarbocyanine dyes is extremely effective as a means of increasing the green sensitivity of silver halide. These matters are described in US Pat. No. 2,912,329,
Specification No. 2739149, British Patent No. 654690,
It is described in the specification of No. 815172. However, when conventionally known benzimidazolocarbocyanine dyes are used, there is an increase in fog at high temperatures or high temperatures and high humidity after coating the emulsion, and the stability over time after coating the emulsion is poor, resulting in a large decrease in sensitivity. Improving these disadvantages of using conventionally known benzimidazolocarbocyanine dyes, such as increased fogging at high temperatures or high temperatures and high humidity, and decreased sensitivity over time, is an important issue in photosensitive material manufacturing technology. This has become one of the most important issues. (Object of the Invention) An object of the present invention is to provide a spectrally sensitized silver halide photographic emulsion with high green sensitivity. Another object of the present invention is to provide a spectrally sensitized silver halide photographic emulsion that provides high green sensitivity without broadening the wavelength range of spectral sensitivity in the green sensitive region. Yet another object of the present invention is to provide a spectrally sensitized silver halide photographic emulsion that exhibits little change in photographic properties, ie, sensitivity, fog, etc., during storage. (Structure of the Invention) In order to achieve the above-mentioned objects of the present invention, the present inventors have made various studies and found that these objects can be achieved by at least one of the sensitizing dyes represented by the general formula () or (). It has been found that the present invention can be effectively achieved by obtaining a silver halide photographic emulsion characterized by containing a combination of 1 and at least one compound represented by the general formula (2). General formula () General formula () In general formulas () and (), a represents an integer from 1 to 8. R ₁ , R ₂ and R ₃ may be the same or different from each other and represent a -CH ₂ (CF ₂ ) _b H group or a substituted or unsubstituted alkyl group. However, at least one of R ₁ , R ₂ , and R ₃ has an acid substituent. b may be the same as or different from a, and represents an integer from 1 to 8. l is 0 or an integer from 1 to 8, m is 0 or 1
represents an integer from 8 to 8. However, l+m>0. R ₄ , R ₅ and R ₆ may be the same or different from each other and represent a -(CH ₂ ) _j (CF ₂ ) _k F group or a substituted or unsubstituted alkyl group. However, at least one of R ₄ , R ₅ and R ₆ has an acid substituent. j is 0 or an integer from 1 to 8, k is 0 or 1
represents an integer from 8 to 8. However, j+k>0. V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V ₇ and V ₈ may be the same or different from each other, and may include a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, It represents an acyl group, acyloxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, cyano group, or trifluoromethyl group. X represents an anion. n represents 1 or 2. However, when the dye forms an inner salt, n is 1. General formula () In the formula, R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxycarbonyl group, an acyloxy group, an alkoxy group, an amino group, a substituted amino group, an acylamido group, or a carbamoyl group. Y
is alkylene, arylene, aralkylene, −
Represents COO−, −COO−Y ₁ −OCO−. however
Y ₁ represents alkylene, arylene, or aralkylene having 1 to 18 carbon atoms. X ₁ represents an anion. m ₁ and m ₂ each represent an integer from 1 to 19. In general formula () or (), the following substituents are preferably used. That is, R ₁ , R ₂ , and R ₃ may be the same or different from each other, and -CH ₂ (CF ₂ ) _b H group (b may be the same or different from a, and an integer from 1 to 8) ) An unsubstituted alkyl group having 6 or less carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, pentyl group, vinylmethyl group, cyclohexyl group, etc.), substituted alkyl group {as a substituent, carboxyl group, Sulfo group, cyano group, halogen atom (fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxycarbonyl group having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group) groups), alkoxy groups having 8 or less carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), carbocyclic aryloxy groups having 10 or less carbon atoms (e.g. phenoxy group, p-tolyloxy group, etc.), Acyloxy groups having 3 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), acyl groups having 8 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl groups (for example, carbamoyl group,
N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,
N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), aryl groups having 10 or less carbon atoms, (e.g. phenyl group, p
- an alkyl group having 6 or less carbon atoms, such as a hydroxyphenyl group, p-chlorophenyl group, p-carboxyphenyl group, p-sulfophenyl group, p-methylphenyl group, α-naphthyl group}
represents. R ₄ , R ₅ , R ₆ may be the same or different from each other, -(CH ₂ ) _j (CF ₂ ) _k F group (j and k may be the same or different from each other, 0 or 1 represents an integer from 8 to 8 (provided that j+k>0) or has the same meaning as R ₁ , R ₂ , and R ₃ shown in the general formula (). However, at least one of R ₁ , R ₂ , R ₃ and at least one of R ₄ , R ₅ , R ₆ is an alkyl group having 6 or less carbon atoms or having a sulfo group or a carboxyl group. Up to 10 substituted alkyl groups. V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V ₇ and V ₈ may be the same or different from each other, and may be hydrogen atoms, halogen atoms (e.g. fluorine atoms, chlorine atoms, bromine atoms). ), alkyl groups having 6 or less carbon atoms (e.g. methyl group, ethyl group, vinylmethyl group, cyclohexyl group, etc.), acyl groups having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), Acyloxy group having 3 or less carbon atoms (e.g. acetoxy group), alkoxycarbonyl group having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), carbamoyl group having 8 or less carbon atoms (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group), sulfamoyl group having 8 or less carbon atoms (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group) etc.), a cyano group, a trifluoromethyl group, and a hydroxyl group are preferable. In general formula (), the following substituents are preferably used. That is, R ₅ is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.),
Alkyl groups (1 to 18 carbon atoms, e.g. methyl, ethyl, propyl, etc.), alkoxycarbonyl groups (2 to 18 carbon atoms, e.g. methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, benzyloxycarbonyl) groups), acyloxy groups (having 1 to 18 carbon atoms, such as acetyloxy groups, propionyloxy groups,
benzoyloxy group, cyclohexylcarbonyloxy group, etc.), alkoxy group (carbon atoms 1 to
18, such as methoxy group, ethoxy group, propoxy group, butoxy group), amino group, substituted amino group (such as methylamino group, ethylamino group, propylamino group, dimethylamino group, dodecylamino group, cyclohexylamino group, β -hydroxyethylamino group, anilino group, p-anisylamino group, o-toluidino group, 2-benzothiazolyl amino group, etc.), acylamide group (e.g. acetylamide, propionylamide, benzoylamide, methanesulfonylamide, etc.), carbamoyl groups (eg, carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.). Y is alkylene having 1 to 18 carbon atoms, arylene having 6 to 18 carbon atoms, and 7 to 18 carbon atoms.
Aralkylene, -CO・O- -COO-Y ₁ -
OCO−. Here, Y ₁ is alkylene having 1 to 18 carbon atoms, arylene having 6 to 18 carbon atoms, or aralkylene having 7 to 18 carbon atoms. In the general formulas () and () of the sensitizing dye used in the present invention, the following substituents are particularly preferably used as each substituent. That is, R ₁ , R ₂ , R ₃
may be the same or different, −CH ₂
(CF ₂ ) _b H group (here, b may be the same as or different from a and represents an integer from 1 to 8), an unsubstituted alkyl group having 6 or less carbon atoms (e.g. methyl group, ethyl group) , propyl group, butyl group, pentyl group, vinylmethyl group, cyclohexyl group, etc.) or a substituted alkyl group having 12 or less carbon atoms {substituents such as carboxy group, sulfo group, cyano group, halogen atom (fluorine atom, chlorine atom, etc.) , bromine atom),
Hydroxy group, alkoxycarbonyl group with 6 or less carbon atoms, alkoxy group with 6 or less carbon atoms, 10 carbon atoms
An alkyl group having 6 or less carbon atoms substituted with the following monocyclic aryloxy group, acyloxy group having 3 or less carbon atoms, acyl group having 8 or less carbon atoms, sulfamoyl group, aryl group having 10 or less carbon atoms} Particularly preferred. R ₄ , R ₅ , R ₆ may be the same or different from each other, -(CH ₂ ) _j (CF ₂ ) _k F group (where j and k may be the same or different from each other, 0 or represents an integer from 1 to 8 (provided that 8≧j+k>0) or has the same meaning as R ₁ , R ₂ , and R ₃ shown in the general formula (). However, at least one of R ₁ , R ₂ , R ₃ and
At least one of R ₄ , R ₅ and R ₆ has a carboxyl group or a sulfo group as a substituent. V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V ₇ and V ₈ may be the same or different, and each may be a hydrogen atom, a halogen atom (such as a chlorine atom),
Alkyl groups having 4 or less carbon atoms (e.g. methyl group, ethyl group, vinylmethyl group, etc.), acyl groups having 7 or less carbon atoms (e.g. acetyl group, propionyl group,
benzoyl group, etc.), alkoxycarbonyl group having 8 or less carbon atoms, carbamoyl group having 6 or less carbon atoms (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbamoyl group, etc.),
Sulfamoyl group having 6 or less carbon atoms (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morphonylsulfonyl group, piperidinosulfonyl group, etc.), cyano group, trifluoromethyl group,
Hydroxy groups are particularly preferred. Examples of compounds represented by the general formulas (), (), and () are shown below. However, the present invention is not limited thereto. Compounds of the general formulas () and () of the present invention are described in J.Org.Chem., 26 , 4021 (1961); J.Amer.
Chem.Soc., 77 , 3149 (1955); J.Amer.Chem.
Soc., 78 , 4999 (1956) etc. using fluorinated alkyl esters of sulfonic acids, fluorinated alkyl amines, fluorinated alkyl iodides, etc. It can be easily synthesized based on the description in the literature. That is, U.S. Pat. No. 2,912,329, U.S. Pat. No. 2,739,149, British Pat.
and related compounds−”chapter V,
pages 116-147, by FM Hamer, John. Wiley &
Published by Sons (New York, London) in 1964,
“Heterocyclic Compounds−Special topics in
heterocyclic chemistry−”chapter, sec.
pages 482-515, by DMSturmer, John Wiley &
Published by Sons (New York, London) in 1977. Further, the compound represented by the general formula () is a known compound, and can be easily synthesized by referring to the method described in JP-A-53-44025. The sensitizing dye represented by the general formula () or () used in the present invention is preferably 1 x 10 ^-6 mol to 5 x 10 ^-3 mol, respectively, per 1 mol of silver halide.
It is contained in the silver halide photographic emulsion in a proportion of 1 x 10 ^-5 mol to 2.5 x 10 ^-3 mol, particularly preferably 4 x 10 ^-5 mol to 1 x 10 ^-3 mol. The sensitizing dye used in the present invention can be directly dispersed into the emulsion. Alternatively, these may be first dissolved in a suitable solvent, such as methyl alcohol, ethyl alcohol, n-propanol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution. can. Ultrasonic waves can also be used for dissolution. In addition, the method of adding this sensitizing dye is as described in US Pat. 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. A method in which the pigment is dispersed in a water-soluble solvent and the resulting dispersion is added to an emulsion; A method in which a dye is dissolved in a surfactant and the solution is added to an emulsion as described in US-3822135. ; A method of dissolving a red-shifting compound using a red-shifting compound as described in JP-A No. 51-74,624, and adding the solution into an emulsion; A method is used in which the compound is dissolved in acid-free acid and the solution is added to the emulsion. Other additions to emulsions include U.S. Patent No.
The methods described in No. 2912343, No. 3342605, No. 2996287, No. 3429835, etc. can also be used. The sensitizing dye may also be uniformly dispersed in the silver halide emulsion before being coated on a suitable support;
Of course, it can also be dispersed during the process of preparing silver halide emulsions. The compound represented by the general formula () used in the present invention is about 0.01 mol per mol of silver halide in the emulsion.
Amounts of from gram to 5 grams are advantageously used, particularly preferably from 0.2 to 2.5 grams. The ratio (weight ratio) of the sensitizing dye represented by the general formula () or () to the compound represented by the general formula () is the dye represented by the general formula () or ()/the compound represented by the general formula (). Compound =
A range from 100/1 to 1/100 is advantageously used, particularly a range from 40/1 to 1/40. The compound represented by the general formula () used in the present invention can be directly dispersed into the emulsion,
It can also be added to the emulsion after being dissolved in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. 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. They can also be dispersed and added into the emulsion by the method described in JP-A-50-80119. The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, US Patent No.
3703377, U.S. Patent No. 2688545, U.S. Patent No.
3397060, U.S. Patent No. 3615635, U.S. Patent No.
3628964, UK Patent No. 1242588, UK Patent No.
No. 1293862, Special Publication No. 43-4936, Special Publication No. 14030-1973
No., Special Publication No. 43-10773, U.S. Patent No. 3416927,
Sensitizing dyes described in Japanese Patent Publication No. 43-4930, US Pat. No. 3,615,613, US Pat. No. 3,615,632, US Pat. No. 3,617,295, US Pat. No. 3,635,721, etc. can be used. In particular, a sensitizing dye represented by the following general formula () or () may be used in combination. General formula () In the formula, Y ₁₁ represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₄ . Z ₁ and Z ₂ may be the same or different, and each represents an atomic group necessary to form an unsubstituted or substituted benzene ring or naphthalene ring. R ₁₁ , R ₁₂ and R ₁₄ represent unsubstituted or substituted alkyl groups. However, at least one of R ₁₁ , R ₁₂ and R ₁₄ has an acid substituent. R ₁₃ represents a hydrogen atom, an alkyl group or an aralkyl group. X ₁₁ represents an anion. n ₁ is expressed as 1 or 2, and is 1 when the dye forms one intramolecular salt. General formula () In the formula, Y ₁₂ represents a sulfur atom, a selenium atom, or NR ₁₈ . Z ₃ and Z ₄ may be the same or different, and each represents an atomic group necessary to form an unsubstituted or substituted benzene ring or naphthalene ring. R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ represent unsubstituted or substituted alkyl groups. However, _R15 , _R16 , _R17 , _R18
At least one of them has an acid substituent. X ₁₂ represents an anion. n ₂ represents 1 or 2, and is 1 when the dye forms an inner salt. In the general formula () of the dye, the following are preferably used as Y ₁₁ , Z ₁ , Z ₂ and R ₁₁ to R ₁₃ . Y ₁₁ is an oxygen atom, a sulfur atom, a selenium atom or NR ₁₄ , and an oxygen atom is particularly preferred. Z ₁ and Z ₂ may be the same or different, and are atomic groups necessary to form an unsubstituted or substituted benzene ring or naphthalene ring. Substituents on the benzene ring or naphthalene ring include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups having 6 or less carbon atoms (e.g. methyl group, ethyl group, propyl group, vinylmethyl group, 2 -methylpropyl group, butyl group,
hexyl group, etc.), alkoxy groups having up to 8 carbon atoms (e.g., methoxy group, ethoxy group, butyloxy group, benzyloxy group, phenethyloxy group, etc.), aryl groups having up to 8 carbon atoms (e.g., phenyl group, 4-methylphenyl group, -chlorophenyl group, etc.), an aryloxy group having 8 or less carbon atoms (e.g., phenoxy group, 4-methylphenoxy group,
(4-chlorophenoxy group, etc.), an acyl group having 8 or less carbon atoms (such as an acetyl group, a propionyl group,
benzoyl group, mesyl group, etc.), alkoxycarbonyl groups having 8 or less carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group, butyloxycarbonyl group, benzyloxycarbonyl group, etc.),
Preferred are acyloxy groups having 3 or less carbon atoms (for example, acetyloxy groups, propionyloxy groups, etc.), cyano groups, trifluoromethyl groups, carboxyl groups, and hydroxy groups. In particular, for Z ₁ and Z ₂ , the 5th position of the benzene ring is a phenyl group, a chlorine atom,
Or those substituted with a methoxy group are preferred. R ₁₁ , R ₁₂ , and R ₁₄ include an alkyl group having 8 or less carbon atoms (e.g., methyl group, ethyl group, propyl group, vinylmethyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc.); and substituents such as hydroxy group, carboxy group, sulfo group, cyano group, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkoxycarbonyl group having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy groups having 8 or less carbon atoms (e.g. methoxy group, ethoxy group, butyloxy group, benzyloxy group, phenethyloxy group, etc.), aryloxy groups having 8 or less carbon atoms (e.g. phenoxy group, p-tolyloxy group) ), acyloxy groups having 3 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), acyl groups having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, 4-fluorobenzoyl group, etc.), carbon Carbamoyl groups of up to 6 carbon atoms (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl groups of up to 6 carbon atoms (e.g. sulfamoyl group, N,N-dimethylsulfur group) moyl group, morpholinosulfonyl group, piperidinosulfonyl group), aryl group having 10 or less carbon atoms (e.g. phenyl group, p-fluorophenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p- An alkyl group having 6 or less carbon atoms substituted with a sulfophenyl group, etc. is preferred.
However, at least one of R ₁₁ , R ₁₂ and R ₁₄ has an acid substituent. R ₁₃ is a hydrogen atom, an alkyl group having 4 or less carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.) or an aralkyl group having 10 or less carbon atoms (e.g. benzyl group, phenethyl group, 3-phenylpropyl group) groups) are preferred. In the general formula () of the dye used in the present invention, the following are preferable as Y ₁₂ , Z ₃ , Z ₄ and R ₁₅ to R ₁₇ . That is, Y ₁₂ is a sulfur atom,
A selenium atom or N-R ₁₈ is preferred, and Z ₃ and Z ₄ may be the same or different, and an atomic group necessary to form an unsubstituted or substituted benzene ring or naphthalene ring is preferred. As a substituent on the benzene ring or naphthalene ring, a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group having 6 or less carbon atoms (e.g. methyl group, ethyl group, propyl group, vinylmethyl group, 2- Methylpropyl group, butyl group,
hexyl group, etc.), alkoxy groups having up to 8 carbon atoms (e.g., methoxy group, ethoxy group, butyloxy group, benzyloxy group, phenethyloxy group, etc.), aryl groups having up to 8 carbon atoms (e.g., phenyl group, 4-methylphenyl group, -chlorophenyl group, etc.), an aryloxy group having 8 or less carbon atoms (e.g., phenoxy group, 4-methylphenoxy group,
4-chlorophenoxy group, etc.), an acyl group having 8 or less carbon atoms (such as an acetyl group, a propionyl group,
benzoyl group, mesyl group, etc.), alkoxycarbonyl groups having 8 or less carbon atoms (e.g., methoxycarbonyl group, ethoxycarbonyl group, butyloxycarbonyl group, benzyloxycarbonyl group, etc.),
Preferred are acyloxy groups having 3 or less carbon atoms (for example, acetyloxy groups, propionyloxy groups, etc.), cyano groups, trifluoromethyl groups, carboxyl groups, and hydroxy groups. R ₁₅ , R ₁₆ , R ₁₇ , and R ₁₈ are alkyl groups having 8 or less carbon atoms (for example, methyl group, ethyl group, propyl group, vinylmethyl group, butyl group, pentyl group,
hexyl group, heptyl group, octyl group, etc.), or as a substituent hydroxy group, carboxyl group, sulfo group, cyano group, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkoxycarbonyl having 8 or less carbon atoms groups (e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy groups having 8 or less carbon atoms (e.g. methoxy group, ethoxy group, butyloxy group, benzyloxy group, phenethyloxy group, etc.), 8 or less carbon atoms Aryloxy group (e.g. phenoxy group, 4-methylphenoxy group,
4-chlorophenoxy group, etc.), an acyloxy group having 3 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.), an acyl group having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, 4-fluorobenzoyl group, etc.) ), a carbamoyl group having 6 or less carbon atoms (e.g. carbamoyl group, N,N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.),
Sulfamoyl groups having up to 6 carbon atoms (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.), aryl groups having up to 10 carbon atoms (e.g. phenyl group, p-fluorophyl group) An alkyl group having 6 or less carbon atoms substituted with an enyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, etc.) is preferable. however,
At least one of R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ has an acid substituent. Next, specific examples of dyes represented by general formula () and general formula () will be illustrated. The sensitizing dyes represented by the general formula () or () are known, for example “Heterocyclic
compounds−Cyanine dyes and related
compounds−”chapter, pages 116-147, F.
M. Hamer, John. Wiley & Sons (New York,
London), 1964, “Heterocyclic
Compounds−Special topics in heterocyclic
chemistry−”chapter, sec. page482〜
515, by DMSturmer, John Wiley & Sons (New
It can be easily synthesized based on the description in 1977, published by Co., Ltd. (York, London). The sensitizing dye represented by the general formula () or () is usually used in a molar ratio of 1/100 to 100 to the sensitizing dye represented by the general formula () or (). Further, these sensitizing dyes can be added in the same manner as the sensitizing dyes of general formula () or (). Furthermore, it is generally known that when a silver halide photographic emulsion is spectrally sensitized, iodine ions are also added when a spectral sensitizing dye is added to the photographic emulsion. In other words, most of the cyanine dyes that are commonly used as spectral sensitizing dyes are cationic dyes, but when dyes have iodine ions as counterions, the iodine ions are unintentionally added to the photographic emulsion along with the dye cations, resulting in halogen May be adsorbed to silver oxide particles. However, the amount of iodine ions added unintentionally in this way is equimolar to the amount of dye, and the amount of iodine ions cannot be changed. Furthermore, when anionic cyanine dyes are used, it is not possible to unintentionally add iodine ions. Japanese Patent Application No. 57-175198 discloses a silver halide color photosensitive emulsion in which color sensitization sensitivity is increased by adsorbing iodide ions to the grain surface when spectrally sensitizing a silver halide photographic emulsion. Although the invention related to materials is described, this method can also be applied to the present invention. In this method, if a large amount of iodide ions is added (for example, 1 mol % per 1 mol of silver halide), the inherent desensitization of silver halide grains increases,
There may also be disadvantages in that color sensitization is reduced, and the development speed of silver halide grains is slowed down. Furthermore, if the amount of iodide ions added is too small, adsorption of the sensitizing dye may not be sufficiently promoted, making it difficult to obtain the desired high spectral sensitivity.
Therefore, it is preferable to select the amount of iodide ions added within a range in which the above-mentioned drawbacks are unlikely to occur. Due to these drawbacks, the amount of iodine ions to be adsorbed per mole of silver halide is 10 ^-6 to _{10 -3} ^.
The amount is more preferably 10 ⁻⁶ to 10 ^{−4 mol, and even more preferably 10 −6 to 10 −4} mol. In the present invention, there is no particular limitation on the order of addition of the sensitizing dye represented by the general formula () or () and the compound represented by () and iodide ions,
Although they may be added at the same time, it is preferable to add the iodide ion before the sensitizing dye represented by the general formula () or () and the compound represented by (). Alternatively, an iodide ion compound and a bromide ion compound may be mixed to form an aqueous solution, and this may be added to the sol-form silver iodobromide emulsion. The silver halide used in the present invention may be, for example, any one of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and the like. In the present invention, among the above-mentioned silver halides, silver chlorobromide and silver iodobromide are particularly preferred. These emulsions may be coarse grains, fine grains, or mixed grains thereof, and these silver halide grains are prepared by known methods such as single jet method,
It is formed by a double jet method or a controlled double jet method. Furthermore, even if the crystal structure of silver halide grains is uniform throughout the interior, there are also those with a layered structure with different interior and exterior structures, as described in British Patent No. 635,841 and U.S. Patent No. 3,622,318. It may also be of a so-called conversion type. 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 based on Mees' The Theory of
Photographic Process” published by Mac Millan,
"Photographic Chemistry" by Grafikides
It is also written in books published by Fountain Press, etc.
It can be adjusted by various methods such as the generally accepted ammonia method, neutral method, and acid method. After forming such silver halide grains, they are washed with water to remove by-product water-soluble salts (for example, potassium nitrate when silver bromide is made using silver nitrate and potassium bromide) from the system, and then heat treated. is carried out in the presence of a chemical sensitizer to increase sensitivity without coarsening the particles. It is also possible to carry out the process without removing by-product water-soluble salts. These general laws are set out above. The average diameter of the silver halide grains (e.g. measured by the projected area method, number average) is approximately
0.04μ to 4μ is preferred. In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (e.g., U.S. Pat.
3271157, 3574628, 3704130, 4297439, 4276374, etc.), thione compounds (e.g. JP-A-53-144319, JP-A-53-82408)
No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) can be used. Silver halide photographic emulsions can be prepared using commonly used chemical sensitization methods, such as gold sensitization (US Pat. No. 2,540,085).
No. 2597876, No. 2597915, No. 2597915, No. 2597876, No. 2597915, No.
No. 2399083), sensitization with group metal ions (US Pat. No. 2448060, US Pat. No. 2540086, US Pat. No. 2566245)
2566263, 2598079, etc.) Sulfur sensitization (U.S. Patent Nos. 1574944, 2278947,
No. 2440206, No. 2410689, No. 3189458, No. 3415649, etc.), reduction sensitization (U.S. Patent No.
2518698, 2419974, 2983610, etc.), sensitization with thioether compounds (for example, U.S. Pat.
3038805, 3046129, 3046132, 3046133, 3046134, 3046135,
Same No. 3057724, Same No. 3062646, Same No. 3165552,
Same No. 3189458, Same No. 3192046, Same No. 3506443,
Same No. 3671260, Same No. 3574709, Same No. 3625697,
No. 3635717, No. 4198240, etc.), or various sensitization methods combining them are applicable. More specific chemical sensitizers include Allyl thiocarbamide, thiourea,
Sulfur sensitizers such as sodium thiosulfate and cystine; noble metal sensitizers such as potassium chlorooleate, aurous thiosulfate and Potassium Chloro Palladate; reduction sensitizers such as tin chloride, phenylhydrazine and reductones. Examples include agents. Other polyoxyethylene derivatives (British Patent No. 981470, Japanese Patent Publication No. 31-6475, U.S. Patent No.
2716062 etc.), polyoxypropylene derivatives,
It may also contain a sensitizer such as a derivative having a quaternary ammonium group. Various compounds can be added to the photographic emulsion of the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material.
These compounds include nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, 3-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole, and many others. A large number of compounds have been known for a long time, including heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. An example of a compound that can be used is K.
“The Theory of the Photographic” by Mees
Other compounds listed with original references on pages 344 to 349 of "Process" (3rd edition, 1966) include:
For example, thiazolium salts described in US Pat. No. 2,131,038 and US Pat. No. 2,694,716;
Azaindenes described in No. 2886437 and No. 2444605; urazoles described in U.S. Patent No. 3287135; U.S. Patent No. 3236652
Sulfocatechols described in British Patent No. 623448, etc.; Oximes described in British Patent No. 2403927, British Patent No. 3266897, British Patent No.
Mercaptotetrazoles and nitrones described in No. 3397987, etc.; nitroindazoles;
Polyvalent metal salts described in U.S. Patent No. 2839405 and others;
Thiuronium salts described in U.S. Patent No. 3220839, etc.; palladium described in U.S. Pat.
Examples include platinum and gold salts. Silver halide photographic emulsions contain developing agents such as hydroquinones; catechols; aminophenols; 3-pyrazolidones; ascorbic acid and its derivatives; reductones or phenylenediamines, or a combination of developing agents. can be done. The developing agent may be incorporated into the silver halide emulsion layer and/or other photographic layers (eg, protective layers, interlayers, filter layers, antihalation layers, back layers, etc.). The developing agent may be dissolved in a suitable solvent, or as described in US Pat. No. 2,592,368,
It can be added in the form of a dispersion as described in FR 1505778. Hardening of the emulsion can be carried out according to conventional methods. Examples of curing agents include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis(2-chloroethylurea), and 2-hydroxy-4,6-dichloro-1,3. , 5-triazine, and other U.S. Patent No. 3288775, U.S. Patent No. 2732303,
Compounds containing reactive halogens as shown in British Patent No. 974723 and British Patent No. 1167207, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and other U.S. patents. No. 3635718, No. 3232763
Compounds with reactive olefins such as those shown in U.S. Patent No. 994869, N-hydroxymethylphthalimide, and other N-methylol compounds such as those shown in U.S. Patent Nos. 2732316 and 2586168. , Isocyanates as shown in US Pat. No. 3,103,437, etc., Aziridine compounds as shown in US Pat. No. 3,017,280, US Pat. No. 2,983,611, etc., US Pat.
No. 2,725,295, etc., carbodiimide compounds as shown in U.S. Pat. No. 3,100,704, and U.S. patents.
Epoxy compounds as shown in US Pat. No. 3,091,537, isoxazole compounds as shown in US Pat. No. 3,321,313 and US Pat. and other dioxane derivatives, and inorganic hardeners such as chloralum and zirconium sulfate. In place of the above-mentioned compounds, compounds in the form of precursors such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic nitroalcohols, etc. may be used. Surfactants may be added alone or in combination to the photographic emulsion of the present invention. Although they are used as coating aids, they are sometimes used for other purposes, such as emulsification, dispersion,
It is also applied to improve sensitized photographic properties, prevent static electricity, and prevent adhesion. These surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide type, glycerin type, and glycidol type, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles,
Cationic surfactants such as phosphonium or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfate ester groups, phosphoric ester groups, amino acids, aminosulfonic acids, and sulfuric or phosphoric acids of amino alcohols. It is divided into amphoteric active agents such as esters. Some examples of surfactant compounds that can be used include U.S. Pat.
Same No. 2739891, No. 3068101, No. 3158484, Same No.
No. 3201253, No. 3210191, No. 3294540, No.
No. 3415649, No. 3441413, No. 3442654, No. 3441413, No. 3442654, No.
No. 3475174, No. 3545974, German patent application
1942665, British Patent Nos. 1077317 and 1198450, Ryohei Oda et al., "Synthesis of Surfactants and Their Applications" (Maki Shoten 1964 edition), and A. W. Perry, "Surface Active Agents" (Interscience Publications). Incorporated
1958 edition), JP Sisley, “Encyclopedia of Surf S Active Agents Volume 2” (Chemical Publishing Company 1964)
It is written in books such as 2011 edition). In addition to gelatin as a protective colloid, the silver halide photographic emulsion used in the present invention contains acylated gelatin such as phthalated gelatin and malonated gelatin, and cellulose compounds such as hydroxyethyl cellulose and carboxymethyl cellulose;
Soluble starches such as dextrins; hydrophilic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and polystyrene sulfonic acid, plasticizers for dimensional stabilization, latex polymers and matting agents may be added. Silver halide photographic emulsions may also contain antistatic agents, plasticizers, fluorescent brighteners, development accelerators, air fog inhibitors, toning agents, and the like. in particular,
RESERCH DISCLOSURE vol.176RD−17643
(1978.12) can be used. The silver halide photographic emulsions of this invention can contain color couplers such as cyan couplers, magenta couplers, yellow couplers, and compounds that disperse the couplers. 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 and have a hydrophobic group called a ballast group in the molecule. The coupler is 4 for silver ions.
Either equivalence or 2-equivalence may be used. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product may contain a colorless DIR coupling compound that is colorless and releases a development inhibitor. Further, among the color couplers, a magenta coupler may be particularly included, and may be a 4-equivalent magenta coupler or a 2-equivalent magenta coupler.
Preferably, it is a 2-equivalent magenta coupler. A specific example of a magenta coloring coupler is a U.S. patent
No. 2600788, No. 2983608, No. 3062653, No.
No. 3127269, No. 3311476, No. 3419391, No. 3127269, No. 3311476, No. 3419391, No.
No. 3519429, No. 3558319, No. 3582322, No.
No. 3615506, No. 3725067, No. 3770447, No. 3770447, No. 3725067, No. 3770447, No.
No. 3834908, No. 3891445, British Patent No. 1047612,
West German Patent No. 1810464, West German Patent Application (OLS)
No. 2408665, No. 2417945, No. 2418959, No.
No. 2424467, Japanese Patent Publication No. 1973-6031, Japanese Patent Publication No. 1973-20826
No. 52-58922, No. 49-129538, No. 49-
No. 74027, No. 50-159336, No. 52-42121, No. 49
-74028, 50-60233, 51-26541, same
No. 53-55122, Patent Application No. 121689, No. 54-
No. 136497, No. 54-163167, No. 54-163168, No.
No. 55-31320, No. 58-23434, Fuji Photo Film
Co., Ltd., dated March 17, 1988, in the specification of the patent application (A) (title of the invention: "Color image forming method"). Further, as the cyan coupler, it is preferable to use a cyan coupler having a ureido group that improves the fading property of the dye because it has good light and heat fastness. Examples of these are U.S. Pat. No. 3,446,622, U.S. Pat.
No. 3758308, No. 3880661, Specification of JP-A-56-65134, Specification of Patent Application No. 196-19676, No. 57-1620
No. 57-72202, etc. Two or more types of the above-mentioned couplers and the like can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, and the same compound can of course be added to two or more different layers. The above-mentioned couplers include couplers having a water-soluble group such as a carboxyl group, a hydroxyl group, or a sulfo group, and hydrophobic couplers. be introduced. In the case of hydrophobic couplers, the couplers are mixed with high boiling point organic solvents such as phthalate esters, trimellitic acid esters, phosphoric esters, fatty oils and waxes that are liquid at room temperature.
Dispersion with the aid of anionic surfactants, such as those described in U.S. Pat. For example, US Pat. No. 2,801,170,
2801171, 2949360, etc., the coupler itself has a sufficiently low melting point (preferably
below 75℃), couplers to be used alone or in combination with others, such as colored couplers, DIR−
A method of dispersing in combination with a coupler or other couplers, such as the method described in German Patent No. 1143707, is applicable. The water-soluble coupler can be added as an alkaline solution or together with the hydrophobic coupler as an aid for dispersing the hydrophobic coupler (as an anionic surfactant). In addition, a color image can also be formed by developing with a color developer containing a diffusible coupler. In addition, as an anti-irradiation dye that may be contained depending on the purpose, for example, Japanese Patent Publication No. 41-20389
No. 43-3504, U.S. Patent No. 13168, U.S. Patent No. 2697037, U.S. Patent No. 3423207,
2865752, British Patent No. 1030392, British Patent No. 1100546
The one listed in the number etc. is used. The present invention can be applied to the sensitization of silver halide emulsions used in various color light-sensitive materials in addition to black-and-white photographic emulsions. Such an emulsion is
Color positive emulsions, color paper emulsions, color negative emulsions, color reversal emulsions (which may or may not contain couplers), color diffusion transfer processes (U.S. Pat. No. 3,087,817;
No. 3185567, No. 2983606, No. 3253915, No. 3227550, No. 3227551, No. 3227552,
Emulsions used in dye transfer processes (described in U.S. Patent No. 3415644, U.S. Patent No. 3415645, U.S. Patent No. 3415646, etc.), emulsions used in die transfer processes (described in U.S. Patent No. 2882156, etc.), silver pigments Bleaching method {Friedman, History of Color
Photography”American Photographic
Publishers Co.1944, especially Chapter 24, “British
Journal of Photography” vol.111, P308～
309Apr.7 (1964) etc.). Exposure to obtain a photographic image may be carried out using a conventional method. That is, any of a variety of known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon mark lamps, xenon flash lamps, cathode ray tube flying spots, etc., and the exposure time is In addition to exposure times of 1/1000 seconds to 1 second, which are normally used with cameras, exposure times shorter than 1/1000 seconds, such as 1/10 ⁴ ~ using xenon flash lamps and cathode ray tubes.
Exposures of 1/10 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 beams, X-rays, γ-rays, α
Exposure may be by light emitted from a phosphor excited by a line or the like. The layer structure of the multilayer color light-sensitive material applicable to the present invention is not particularly limited, but for example, from the side closest to the support, a blue-sensitive layer (B), a green-sensitive layer (G), a red-sensitive layer (R). It may be applied in this order, or it may be applied in the order of (R), (G), and (B). Alternatively, (B), (R), and (G) may be applied in this order. In the case of (R), (G), (B), (G) and
It is desirable to use a yellow filter during (B). The silver halide photographic emulsion is coated on a support together with other photographic layers if necessary. Namely, dip coat, air knife coat, curtain coat,
Alternatively, it can be applied by various coating methods including extrusion coating using a hopper as described in US Pat. No. 2,681,294. U.S. Patent No. 2761791 and U.S. Pat.
It is also possible to apply two or more layers simultaneously by the methods described in Japanese Patent No. 3508947, Japanese Patent No. 2941898, Japanese Patent No. 3526528, and the like. The finished emulsion is coated on a suitable support. The support includes a planar material that does not undergo significant dimensional changes during processing, such as a hard support such as glass, metal, or ceramic, or a flexible support depending on the purpose. Typical flexible supports include cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film, and polycarbonate, which are commonly used in photographic materials. Films, other laminates of these, thin glass films,
There are paper, etc. Baryta or α-olefin polymers, especially polyethylene, polypropylene, ethylene-butene copolymers, etc. with 2 to 10 carbon atoms
Paper coated or laminated with olefin polymer, plastic whose surface has been roughened to improve adhesion to other polymeric substances and improve printability as shown in Japanese Patent Publication No. 47-19068. Supports such as films also give good results. These supports are selected to be transparent or opaque depending on the purpose of the photosensitive material. In addition, when it is transparent, it is not only colorless and transparent, but also dyes and pigments can be added to make it colored and transparent. Any known method can be used for the photographic processing of the light-sensitive material of the present invention. A known treatment liquid can be used. Processing temperature is usually 18
The temperature is selected between 18°C and 50°C, but the temperature may be lower than 18°C or above 50°C. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied. The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), 1-phenyl-3- pyrazolines,
Ascorbic acid and heterocyclic compounds such as those described in US Pat. No. 4,067,872 in which a 1,2,3,4-tetrahydroquinoline ring and an indolene ring are condensed can be used alone or in combination. The developing solution generally contains other known preservatives, alkaline agents, PH buffers, antifoggants, etc., and further contains solubilizers, color toning agents, development accelerators, etc. as necessary.
It may also contain a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, and the like. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. When forming a dye image, conventional methods can be applied. Negative-positive method (for example, “Journal of the
Society of Motion Picture and Television
Engineers, Vol. 61 (1953), pp. 667-701), developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other suitable Performs fog treatment,
The color reversal method, in which a dye-positive image is obtained by subsequent color development, and the silver dye bleaching method, in which a photographic emulsion layer containing a dye is exposed, developed and created to create a silver image, and this is used as a bleaching catalyst to bleach the dye, etc. It will be done. The silver halide photographic material of the present invention can be color-developed using an aromatic primary amine compound such as a derivative of p-phenylenediamine.
Representative examples of color developing agents include N,N-diethyl-p
-phenylenediamine, 2-amino-5-diethylaminotoluene, 2-amino-5-(N-ethyl-N-laurylamino)toluene, 4-[N-
Ethyl-N-(β-hydroxyethyl)amino]
Inorganic acid salts such as aniline, 3-methyl-4-amino-N-ethyl-N-(β-hydroxyethyl)aniline, 4-amino-3-methyl-N-ethyl-N-( β-Methanesulfoamide ethyl)aniline sesquisulfate monohydrate, N-(2-amino-5-diethylaminophenylethyl)methanesulfoamide sulfate, N,N-dimethyl-p-phenylate as described in U.S. Pat. No. 2,592,364 Nylene diamine hydrochloride, JP-A-Sho
3-Methyl-4-amino-N- described in 48-64933
Examples include ethyl-N-methoxyethylaniline. For more information on these color developing agents, please visit LFA
Written by Mason, Photographic Processing
Chemistry (Focal Press-London 1966)
It is described on pages 226-229. It is also possible to use it in combination with 3-pyrazolidones. Various additives are added to the color developing solution as necessary. Main examples of developer additives include alkali agents (e.g. large oxides of alkali metals and ammonium,
carbonates, phosphates), PH adjusting or buffering agents (e.g., weak acids and bases such as acetic acid, boric acid, and their salts), development accelerators (e.g., U.S. Pat. No. 2,648,604)
Various pyridinium compounds and cationic compounds described in No. 3671247, potassium nitrate and sodium nitrate, U.S. Patent No. 2533990,
Nonionic compounds such as polyethylene glycol condensates and their derivatives as described in British Patent No. 2577127 and British Patent No. 2950970, and polythioethers as represented by the compounds described in British Patent No. 1020033 and British Patent No. 1020032. compounds, polymer compounds with sulfite esters such as the compound described in U.S. Patent No. 3,068,097, other pyridine,
ethanolamine, organic amines, benzyl alcohol, hydrazines, etc.), antifoggants (e.g. alkali bromides, alkali iodides, nitrobenzimidazoles described in U.S. Pat. Nos. 2,496,940 and 2,656,271, and mercapto Benzimidazole, 5-methylbenztriazole,
1-Phenyl-5-mercaptotetrazole, U.S. Patent Nos. 3113864, 3342596, U.S. Patent No.
Compounds for rapid processing liquids described in No. 3295976, No. 3615522, No. 3597199, etc., British Patent No.
Thiosulfonyl compounds described in No. 972211, phenazine N oxides as described in Japanese Patent Publication No. 46-41675, and other "Science Photography Handbook"
Fogging suppressants described on pages 29 to 47 of Volume 2), as well as U.S. Patent No. 3161513 and U.S. Patent No.
3161514, British Patent No. 1030442, British Patent No. 1144481
No. 1,251,558, as well as multilayer effect accelerators and preservatives (e.g., sulfites, acid sulfites, hydroxylamine hydrochloride, formsulfite, alkanolamine sulfite adducts, etc.). After development, the silver halide photographic emulsion is fixed according to a conventional method, but in some cases it is bleached.
Bleaching can be done simultaneously with fixing or separately. When bleaching and fixing are carried out simultaneously, a bleach-fixing bath may be prepared by adding a bleaching agent and a fixing agent. Many compounds are used in bleaching agents, among them ferricyanates, dichromates, water-soluble cobalt salts, water-soluble copper salts, water-soluble quinones,
Nitrosophenols, iron (), cobalt (),
polyvalent metal compounds such as copper (), in particular complex salts of these polyvalent metal cations with organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, malon Acids, metal complex salts such as tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, and peracids such as 2,6-dipicolinate copper complex salts, such as alkyl peracids, persulfates, permanganates, hydrogen peroxide. Hypochlorite salts such as chlorine, bromine, sardine powder, etc. are commonly used alone or in appropriate combinations. Bleaching and fixing, or bleach-fixing, is described in US Pat. No. 3,582,322 and others. This treatment solution also includes U.S. Patent No. 3042520;
Various additives can also be added, including the bleach accelerators described in Japanese Patent Publication No. 3241966, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 45-8836, and the like. (Example) Next, specific examples used in the present invention will be shown. However, the invention is not limited to these specific examples. Example 1 Silver halide grains were precipitated by the double jet method, and after physical ripening and desalting treatment, they were chemically sensitized with gold and sulfur to form a silver iodobromide emulsion (average grain size 1.0 μm).
m, iodine content 4 mol%, silver amount 80g/Kg emulsion,
A gelatin amount of 60g/Kg emulsion) was prepared. Spectral sensitization was carried out by adding a predetermined amount of a methanol solution of the sensitizing dye of the present invention represented by the general formula () or () and a methanol solution of the compound of the present invention represented by the general formula () to the obtained emulsion. I went. This emulsion was mixed with magenta coupler 1-(2,4,
6-trichlorophenyl)-3-{3-(2,4-
Coated on a cellulose triacetate film with an emulsion of di-t-aminophenoxyacetamide) benzamide}-5-pyrazolone (coated silver amount
1.1 g/m ² ) and dried. The resulting sample was exposed to white light through a neutral gray sensitometry wedge using a sensitometer with a light source with a color temperature of 4800. After exposure, the following reversal process was performed to obtain a magenta color image. The treatment steps and treatment liquid used here are as follows.

[Table] <First developing bath> Water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl 4-methyl 4-hydroxymethyl-3-pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water to 1000ml <Reversal bath> Water 700ml Nitrilo-N-N-N-trimethylenephosphonic acid 6Na salt 3g Stannous chloride ( Dihydrate) 1g p-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Add water to 1000ml <Color developing bath> Water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 7g Sodium tertiary phosphate (12 hydrate) 36g Odor Potassium chloride 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazic acid 1.5g N-ethyl-N-(β-sulfamidoethyl)-
3-Methylaminoaniline sulfate 11g Ethylenediamine 3g Add water to 1000ml <Adjustment bath> Water 700ml Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water to 1000ml <Bleaching bath> Water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Ammonium ethylenediaminetetraacetate iron (dihydrate) 120.0g Potassium bromide 100.0g Add water 1.0 <Fixing bath> Water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0 g Sodium bisulfite 5.0g Add water 1.0 <Stabilization bath> Water 800ml Formalin (37% by weight) 5.0ml Fuji Drywell 5.0ml Add water 1.0 Measure the optical density of the magenta color image of the obtained sample The sensitivity was determined from the reciprocal of the exposure amount required to obtain a magenta density of a constant density (D=0.5). The results obtained are shown in Table 1.

[Table] From Table 1, it can be seen that the sensitivity of the sample using the sensitizing dye of the present invention in combination with the compound was significantly higher than that of the sample in which only the sensitizing dye of the present invention was added to the emulsion. Moreover, when the amount of the compound of the present invention added is increased,
It can be seen that within the tested range of added amounts, all samples show an increase in sensitivity depending on the added amount of the compound. These results indicate that supersensitization occurs when the compound of the present invention represented by the general formula () and the sensitizing dye of the present invention represented by the general formula () or () are used together. ing. Example 2 Into the same silver iodobromide emulsion as in Example 1, sensitizing dye (-3) and dye (-1) or dye (
-3) was added in combination to perform spectral sensitization. Emulsions were also prepared by adding the compound of the present invention represented by the general formula () to these emulsions. The emulsions spectrally sensitized as described above were applied and dried in the same manner as in Example 1. The obtained sample was exposed and developed in the same manner as in Example 1, and the sensitivity was measured. The results obtained are shown in Table 2.

【table】

[Table] From Table 2, dye (-1) or dye (-
3) was added to the emulsion (Test No. 1,
12), the sample to which the sensitizing dye (-3) of the present invention was added in combination with these dyes (test No. 2,
13) is found to have high sensitivity. Furthermore, as shown in the present invention, it can be seen that the sensitivity is further increased in a sample using a compound represented by the general formula () in combination. These results demonstrate that if the compound represented by the general formula () of the present invention is further used in combination with the supersensitized system of the sensitizing dye () or () and () or () of the present invention, supersensitization can be achieved. This shows that the effect is even greater. Example 3 Tests No. 2 and No. 2 of Example 2 were used, except that before spectrally sensitizing the same silver iodobromide emulsion as in Example 1, an aqueous solution of potassium iodide in the amount shown in Table 3 was added. 6
A coated sample was prepared in the same manner as in 8. The obtained sample was exposed and developed in the same manner as in Example 1, and the sensitivity was measured. The results obtained are shown in Table 3.

[Table] From Table 3, the samples to which potassium iodide was added before spectral sensitization (Tests No. 2 and 4) were compared to the samples to which potassium iodide was not added (Tests No. 1 and 3). It can be seen that the sensitivity is high. This shows that potassium iodide has the effect of promoting spectral sensitization, but even in such a system, the samples to which the compound (-2) of the present invention was added (test No. 5 to
It can be seen that 7) is even more sensitive. Example 4 A dye (-
1), the sensitizing dye of the present invention shown in Table 4, and the compound (-2) of the present invention were added to perform spectral sensitization. In addition, in order to compare with the sensitizing dye of the present invention,
A spectrally sensitized emulsion was also prepared by adding dye (-15) in place of the sensitizing dye of the present invention. Each of these emulsions was coated and dried in the same manner as in Example 1. The obtained samples were left for 3 days under the relative humidity and temperature shown in Table 4, and then exposed and developed in the same manner as in Example 1, and the change in maximum density obtained was measured. The results obtained are shown in Table 4.

[Table] From the results in Table 4, the samples using the sensitizing dyes of the present invention (Test Nos. 1 to 8) were more effective at high temperatures (55 °C, 30
%, 3 days), but under high temperature and high humidity (60℃, 60%, 3 days).
It can be seen that the decrease in the maximum concentration is small even in the case of Example 5 The same sample used in Example 4 was exposed to light in the same manner as in Example 1, and then left for 3 days under the relative humidity and temperature shown in Table 5. Table 5 shows the change in sensitivity of the highlight area (density 0.2) obtained by developing this sample in the same manner as in Example 1.

[Table] From the results in Table 5, the samples using the sensitizing dyes of the present invention (Test Nos. 1 to 8) were more effective at high temperatures than the samples using the comparative dyes (Test No. 9). 50℃, 30
%, 3 days) but under high temperature and high humidity (45℃, 808, 3 days)
However, it can be seen that the decrease in sensitivity in highlight areas is small.

Claims (1)

[Scope of Claims] 1 At least one sensitizing dye represented by the following general formula () or (), and the following general formula ()
A silver halide photographic emulsion comprising at least one of the compounds represented by the following formula. General formula () General formula () (In the general formulas () and (), a represents an integer from 1 to 8. R ₁ , R ₂ and R ₃ may be the same or different from each other, -CH ₂ (CF ₂ ) _b H group, Represents a substituted or unsubstituted alkyl group.However, at least one of R ₁ , R ₂ , and R ₃ has an acid substituent. b is an integer from 1 to 8, which may be the same as or different from a. l is 0 or an integer from 1 to 8, m is 0 or 1
represents an integer from 8 to 8. However, l+m>0. R ₄ , R ₅ and R ₆ may be the same or different from each other and represent a -(CH ₂ ) _j (CF ₂ ) _k F group or a substituted or unsubstituted alkyl group. However, at least one of R ₄ , R ₅ and R ₆ has an acid substituent. j is 0 or an integer from 1 to 8, k is 0 or 1
represents an integer from 8 to 8. However, j+k>0. V ₁ , V ₂ , V ₃ , V ₄ , V ₅ , V ₆ , V ₇ and V ₈ may be the same or different from each other, and may include a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, It represents an acyl group, acyloxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, cyano group, or trifluoromethyl group. X represents an anion. n represents 1 or 2. However, when the dye forms an inner salt, n is 1. ) General formula () (In the formula, R ₇ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxycarbonyl group, an acyloxy group, an alkoxy group, an amino group, a substituted amino group, an acylamido group, or a carbamoyl group.Y
is alkylene, arylene, aralkylene, −
Represents COO−, −COO−Y ₁ −OCO−. however
Y ₁ represents alkylene, arylene, or aralkylene having 1 to 18 carbon atoms. X ₁ represents an anion. m ₁ and m ₂ each represent an integer from 1 to 19. )