JP3430386B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material or a light-sensitive material) which is spectrally sensitized with a novel light-sensitive dye and has improved photographic characteristics. Also referred to as).

[0002]

2. Description of the Related Art When a certain dye is added to a light-sensitive silver halide emulsion (hereinafter, also referred to as a silver halide emulsion or simply an emulsion), the light-sensing wavelength range of the silver halide emulsion is expanded and the light is increased optically. It is well known that it is felt.

A large number of compounds have been conventionally known as dyes used for this purpose, and for example, "H. Theory of the Photographic Process", 4th Edition (1977, Macmillan) by TJ James. Company, N.
Y. ) P. 194-234, Francis M. Harmer, "The Cyanine Soybean and Related Compounds" (1964, John Willy &.
Sands, N.N. Y. ), D. M. Starmer, "The Chemistry of Heterocyclic Compounds, Vol. 30," p. Various dyes such as styryl dyes, hemicyanine dyes, cyanine dyes, merocyanine dyes, and xanthene dyes described in 441 to (1977, John Willy and Sons, NY) are known, and various dyes are known. By selecting and combining the heterocyclic nucleus or aromatic ring, the length of the conjugated chain, and the substituent, a dye having an arbitrary maximum absorption wavelength from the near ultraviolet region to the near infrared region is derived.

These spectral sensitizing dyes must not only expand the photosensitive wavelength range of the silver halide emulsion, but must also satisfy the following conditions.

1) Appropriate spectral sensitization range 2) High spectral sensitization efficiency 3) Between other additives such as stabilizers, antifoggants, coating aids, high boiling point solvents, etc. 4) No adverse effect on the characteristic curve such as fogging or gamma change 5) When a silver halide photographic light-sensitive material containing a sensitizing dye is aged (especially at high temperature / high temperature). Do not change the photographic performance such as fog when stored under moist conditions) 6) The added photosensitive dye should not diffuse into layers of different photosensitive wavelength range to cause color turbidity 7) Develop / fix After washing with water However, the spectral sensitizing dyes disclosed hitherto have not yet reached the level of sufficiently satisfying all of these conditions.

In recent years, the processing time of the light-sensitive material has been shortened, and a processing solution recycling system and an anhydrous washing processing system have been introduced to avoid environmental pollution. When these treatments are carried out, there arises a problem that the coloring material remains in the light-sensitive material without being completely removed, thereby lowering the commercial value.

By the way, among various dyes, many of the dyes photographically useful have a substituent on the methine chain.
There are various types of substituents on the methine chain, such as an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group and a halogen atom.

Examples of substituting a halogen atom on the methine chain include, for example, British Patent 1,187,411, US Patents 3,501,309, 4,959,294, and German Patent 2,116, No. 253, European Patent 22,753
Issue, Russian Chemical Review
s 52 (10), 993-1009 (1983) and the like.

Among these known halogen atom-substituted dyes, the dyes in which chlorine atom, bromine atom, and iodine atom are substituted have a low spectral sensitizing ability of the negative working silver halide emulsion, and are rather strong as a desensitizing dye. On the other hand, a dye in which a fluorine atom is substituted exhibits spectral sensitization property, but when a light-sensitive material prepared by coating a support with a spectrally sensitized silver halide emulsion and drying the product is used, When the silver emulsion was stagnant for a long time, the sensitivity was lowered and stable performance could not be obtained. Further, when a dye in an amount capable of spectral sensitization was used, coloring (hereinafter, referred to as residual color contamination) after development, fixing and washing with water remained strongly, resulting in insufficient performance that cannot be used.

[0010]

Therefore, a first object of the present invention is to provide a silver halide photographic light-sensitive material having improved photographic characteristics with a sensitizing dye having a small sensitivity variation during storage and a reduced residual color contamination. The second object is to provide a silver halide photographic light-sensitive material having a silver halide emulsion layer spectrally sensitized by a new light-sensitive dye and having improved photographic characteristics.

[0011]

The above objects of the present invention can be achieved by the following constitutions.

(1) At least three aliphatic groups having at least one fluorine atom on the methine chain and having at least one water-soluble group on the nitrogen atom forming the azole ring. A silver halide photographic light-sensitive material having a silver halide emulsion layer spectrally sensitized with a polymethine dye bound by a methine group.

(2) The polymethine dye is represented by the following general formula [I] or [II] (1)
The described silver halide photographic light-sensitive material.

[0014]

[Chemical 3]

[In the formula, Z ¹ and Z ² represent a group of non-metal atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group.
J ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ¹ represents an aliphatic group having 1 to 10 carbon atoms. V ¹ is an acidic group, -T ^{1-
_{CH 2 - (T 2) n1}} -G 1 or -T ¹ -NH- (T ²⁾ _n1
Represents -G ¹ , T ¹ and T ² each represent a sulfonyl group or a carbonyl group, and G ¹ represents a hydrogen atom, an alkyl group, an amino group, a hydroxy group, an alkoxy group or an alkylthio group. L ^{1 to} L ⁹ each represent a methine group. However, a fluorine atom is substituted for at least one group of the methine group forming the cyanine dye. l ¹ , l ² , m ¹ , m ² , m ³ ,
m ⁴ and n 1 are each an integer of 0 or 1, and m ¹ and m
² , m ³ and m ⁴ represent numbers that do not become 0 at the same time. M ₁ represents an ion necessary for canceling the total charge of the molecule, and k ¹ represents a number necessary for neutralizing the charge in the molecule. ]

[0016]

[Chemical 4]

[Wherein Z ¹¹ represents a non-metal atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group, and Q ¹¹ represents a 5- or 6-membered acidic ring group. Represents the necessary non-metallic atomic group. J ¹¹ represents an alkylene group having 1 to 6 carbon atoms, V ¹¹ is an acidic group, —T ¹¹ —CH ₂ — (T ¹² ) _n ¹¹ —G ¹¹
Or an _{^{-T 11 -NH- (T 12) n11}} -G 11, T 11
And T ¹² each represent a sulfonyl group or a carbonyl group, and G ¹¹ represents a hydrogen atom, an alkyl group, an amino group, a hydroxy group, an alkoxy group or an alkylthio group. L ¹¹
To L ¹⁶ each represent a methine group. However, at least one of the methine groups forming the merocyanine dye is substituted with a fluorine atom. l ¹¹ , m ¹¹ , m ¹² and n ¹¹ are each 0
Alternatively, it is an integer of 1 and represents a number in which m ¹¹ and m ¹² are not 0 at the same time. The present invention will be described in detail below.

The novel polymethine dye (photosensitive dye) of the present invention will be described.

In the polymethine dye of the present invention described above,
As the water-soluble group, for example, a sulfo group, a carboxy group, a phosphono group, a sulfate group, a hydroxy group, a sulfino group, a sulfonylaminocarbonyl group (for example,
Methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.), acylaminosulfonyl group (eg, acetamidosulfonyl group, methoxyacetamidosulfonyl group, etc.), acylaminocarbonyl group (eg, acetamidocarbonyl group, methoxyacetamidocarbonyl group, etc.), Examples thereof include sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl group, ethanesulfinylaminocarbonyl group, etc.), sulfoamino group, sulfamoyl group, and the like. Specific examples of the aliphatic group substituted with these water-soluble groups include carboxymethyl group. , Carboxyethyl group, sulfoethyl group,
Sulfopropyl group, 4-sulfobutyl group, ω-sulfopentyl group, 3-sulfobutyl group, 6-sulfo-3-oxahexyl group, 8-sulfo-3,6-dioxaoctyl group, ω-sulfopropoxycarbonylmethyl group , Ω-sulfopropylaminocarbonylmethyl group, 3-sulfinobutyl group, 3-phosphonopropyl group, hydroxyethyl group, N-methanesulfonylcarbamoylmethyl group,
4-sulfo-3-butenyl group, 2-carboxy-2-propenyl group, 2-sulfamoylethyl group, 3-sulfoaminopropyl group, 2-morpholinosulfonylethyl group, o-sulfobenzyl group, p-sulfo Phenethyl group,
Examples thereof include p-carboxybenzyl group.

The polymethine dye of the present invention is preferably in the form of a cyanine dye and a merocyanine dye having two heterocyclic nuclei bonded through at least two methine groups, as well as a hemicyanine dye, a styryl dye, an azacyanine dye and an aza dye. It can take the form of a merocyanine dye or a holopolar dye, and is preferably represented by the above general formula [I] or [II].

In the above general formula [I] or [II], the 5- or 6-membered nitrogen-containing heterocyclic group formed by Z ¹ , Z ² and Z ¹¹ is a saturated carbocycle, a benzene ring or a naphtho group. The ring may form a condensed ring. Specific examples of these azole rings include, for example, pyridine (2-, 4
-), Quinoline (2-, 4-), isoquinoline, oxazolidine, oxazoline, oxazole, 4,5-trimethylene oxazole, 4,5,6,7-tetrahydrobenzoxazole, benzoxazole, naphtho [1,2-d ] Oxazole, naphtho [2,3-d] oxazole, thiazolidine, thiazoline, thiadiazole, thiazole, 4,5-trimethylenethiazole,
4,5,6,7-Tetrahydrobenzothiazole, benzothiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, selenazole, selenazoline, benzoselenazole, naphtho [1,2-d] ] Selenazole, imidazole, benzimidazole, naphthimidazole, indole, indolenine, benzoterrazole, thieno [1,2-d] thiazole, thieno [2,1-d] thiazole and the like can be mentioned.

These azole rings may have a substituent at any position, for example, an alkyl group (for example, methyl, ethyl, n-propyl, t-pentyl, isobutyl, benzyl, etc.), Alkynyl groups (eg 1-
Groups such as propynyl), halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), trifluoromethyl group,
Alkoxy groups (eg, groups such as methoxy, ethoxy, butoxy, 2-methoxyethoxy, benzyloxy, etc.), alkylmercapto groups (eg, groups such as methylmercapto, ethylmercapto, etc.), hydroxy groups, cyano groups, aryloxy groups (For example, substituted or unsubstituted groups such as phenoxy or tolyloxy), or aryl group (for example, substituted or unsubstituted groups such as phenyl or p-chlorophenyl), styryl group, heterocyclic group (for example, furyl, Each group such as thienyl, pyrrolyl and imidazolyl), carbamoyl group (for example, each group such as carbamoyl and N-ethylcarbamoyl), sulfamoyl group (for example, each group such as sulfamoyl and N, N-dimethylsulfamoyl), acylamino Groups (eg acetylamino, propionylamino, benzoylua) No.), acyl group (eg, acetyl, benzoyl, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl, etc.), sulfonamide group (eg, methanesulfonylamide, benzenesulfonamide, etc.) Group), a sulfonyl group (eg, methanesulfonyl, butanesulfonyl, p
-Each group such as toluenesulfonyl) and any group such as a carboxy group can be substituted.

Specific examples of the 5- or 6-membered cyclic acidic ring group formed by Q ¹¹ include the following.

[0024]

[Chemical 5]

[0025]

[Chemical 6]

In the formula, R ^a , R ^b and R ^c are each independently a hydrogen atom or a monovalent substituent, and a substituted or unsubstituted alkyl group (eg, methyl, ethyl, octyl, sec
-Octyl, carboxymethyl, hydroxyethyl, o
-Each group such as sulfobenzyl), an allyl group (for example, an allyl group), an aryl group (for example, phenyl, p-tolyl,
Each group such as p-methanesulfonylaminophenyl) or a heterocyclic group (for example, each group such as thienyl, furyl, pyridyl, thiazolyl, triazolyl, pyrazolyl). Further, R ^a , R ^b, and R ^{c in the} case of substituting on a carbon atom are halogen atom, (fluorine atom, chlorine atom, etc.), trifluoromethyl group, alkoxy group (eg, methoxy, ethoxy, etc.). Each group), hydroxy group, cyano group, aryloxy group (eg, substituted or unsubstituted group such as phenoxy), styryl group, carbamoyl group (eg, carbamoyl group), sulfamoyl group (eg, sulfamoyl group) , An acylamino group (eg, acetylamino group), an acyl group (eg, acetyl group), an alkoxycarbonyl group (eg, ethoxycarbonyl group), a sulfonamide group (eg, methanesulfonylamide group), a sulfonyl group ( For example, methanesulfonyl group, etc., carboxy group, substituted / unsubstituted amino group (eg, N, N-dimethyl) Groups such as amino groups).

The carbon number represented by J ¹ and J ¹¹ is 1 to 6
The alkylene group of may contain an oxygen atom or a sulfur atom therebetween, and specific examples thereof include methylene, ethylene, propylene, 3-methylpropylene, pentylene,
Examples thereof include groups such as 3-oxapentylene, 3-thiapentylene and 4-oxahexylene.

The aliphatic group having 1 to 10 carbon atoms represented by R ¹ is, for example, a branched or straight chain alkyl group (eg, methyl, ethyl, propyl, iso-pentyl, 2
-Ethylhexyl or the like), an alkenyl group (for example,
2-propenyl, 3-butenyl, each group such as 1-methyl-3-propenyl), an aralkyl group (for example, benzyl,
Each group such as phenethyl).

The groups represented by J ¹ , J ¹¹ and R ¹ further include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkoxy group (eg, methoxy group, ethoxy group, etc.). An aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), cyano group, carbamoyl group, hydroxy group, sulfamoyl group, methanesulfonyl group, alkoxycarbonyl group (eg, methoxycarbonyl group, hydroxyethoxycarbonyl group, etc.), Acyl group (eg, acetyl group, benzoyl group, etc.), aryl group (eg, phenyl group, carboxyphenyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), halo-substituted alkyl (eg, trifluoro group) Methyl group, difluoromethyl group, etc.), sulfonamide group (example For example, methanesulfonylamide group, butanesulfonylamide group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.), acylamino Sulfonyl group (eg, acetamidosulfonyl group, methoxyacetamidosulfonyl group, etc.), sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl group, ethanesulfinylaminocarbonyl group, etc.), sulfoamino group, sulfo group, carboxy group, heterocyclic group ( For example, it may be substituted with a substituent such as a furanyl group, a pyridyl group, a thiazolyl group or a pyrimidyl group).

Examples of the acidic group represented by V ¹ and V ¹¹ include a sulfo group, a carboxy group, a sulfate group,
Phosphoric acid groups are included and may form the free acid form or counter salt.

The alkyl group represented by G ¹ and G ¹¹ has the same meaning as R ¹ described above, and the amino group may be substituted, for example, methylamino group, dimethylamino group, morpholino group, pyrrolyl group. Examples of the alkoxy group include a methoxy group and a methoxyethoxy group, and examples of the alkylthio group include a methylthio group, an ethylthio group and a hydroxyethylthio group.

The methine groups represented by L ^{1 to} L ⁹ and L ^{11 to} L ¹⁶ are each independently a substituted or unsubstituted methine carbon, which is a combination of L ^{1 to} L ⁹ and L ^{11 to} L ^16. At least one methine carbon is replaced by a fluorine atom. The groups substituted on these methine carbons include
For example, lower alkyl groups (eg, groups such as methyl, ethyl, trifluoromethyl, benzyl, etc.), alkoxy groups (eg, groups such as methoxy, ethoxy, etc.), alkylthio groups (eg, groups such as methylthio, ethylthio, etc.) , Acyl group (eg, acetyl group), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, aryl group (eg, phenyl, carboxyphenyl, etc.), heterocyclic group (For example, 2-thienyl,
2-furyl, 1,3-bis (2-methoxyethyl) -6
Groups such as -hydroxy-2,4-dioxo-1,2,3,4-tetrahydro-5-pyrimidyl and 5-hydroxy-3-methyl-1-phenyl-4-pyrazolyl). Also, the methine carbon is the adjacent methine carbon,
Alternatively, they can be bonded to methine carbons separated from each other through an alkylene group to form a 5- or 6-membered carbon ring, and a substitution on a nitrogen atom forming an azole ring bonded to a methine chain. It is also possible to combine with a group to form a 5- or 6-membered nitrogen-containing heterocycle. The following are specific examples.

[0033]

[Chemical 7]

In the formula, Z ⁴ is the above-mentioned general formula [I], [II]
Synonymous with Z ¹ , Z ² and Z ¹¹ therein. R ^A and R ^B are
Each represents a hydrogen atom, an alkyl group, an aralkyl group, a heterocyclic group or an aryl group, and R ^C represents a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkylthio group,
It represents an aryl group, an amino group, a heterocyclic group or a halogen atom, and t is an integer of 3 or 4. R ^A , R ^B and R
Examples of the alkyl group represented by ^C include lower groups such as methyl, ethyl, propyl and isopropyl, and cyclic groups such as cyclopropyl and cyclopentyl, and examples of the aryl group include phenyl and p-tolyl. Examples of the alkoxy group include groups such as methoxy and ethoxy, examples of the alkylthio group include groups such as methylthio, and examples of the aralkyl group include benzyl, phenethyl, and m-bromo. Examples of the heterocyclic group include benzyl and the like, and examples of the heterocyclic group include morpholino, piperidino, pyrrolidino, imidazolyl,
Each group such as pyrrolyl can be mentioned. Examples of the amino group represented by R ^C include N, N-dimethylamino, N, N-
Examples of each group include diethylamino and the like. Examples of the halogen atom include atoms such as fluorine and chlorine.

M ₁ represents a cation or an acid anion, and specific examples of the cation include a proton, an organic ammonium ion (eg, each ion of triethylammonium, triethanolammonium, etc.), an inorganic cation (eg, lithium, sodium, Each cation such as potassium), and specific examples of the acid anion include, for example, a halogen ion (eg, chlorine ion, bromine ion, iodine ion, etc.), p-toluenesulfonate ion,
Examples thereof include perchlorate ion, boron tetrafluoride ion, and sulfate ion. k ¹ is 0 when an intramolecular salt is formed and the charge is neutralized.

Specific examples of the polymethine dye of the present invention are shown below, but the polymethine dye used in the present invention (hereinafter, also referred to as the photosensitive dye of the present invention) is not limited to these compounds.

[0037]

[Chemical 8]

[0038]

[Chemical 9]

[0039]

[Chemical 10]

[0040]

[Chemical 11]

[0041]

[Chemical 12]

[0042]

[Chemical 13]

[0043]

[Chemical 14]

[0044]

[Chemical 15]

[0045]

[Chemical 16]

[0046]

[Chemical 17]

[0047]

[Chemical 18]

[0048]

[Chemical 19]

[0049]

[Chemical 20]

[0050]

[Chemical 21]

[0051]

[Chemical formula 22]

[0052]

[Chemical formula 23]

[0053]

[Chemical formula 24]

[0054]

[Chemical 25]

[0055]

[Chemical formula 26]

[0056]

[Chemical 27]

The above compounds are described, for example, in Zh. Obshc
h. Khim. 31, 3955 (1961), 37,
2470 (1967), 38, 1732 (196)
8), Zh. Org. Khim. 8, 2182 (197)
2), the same 8,2447 (1972), the same 10,1321
(1974), 11, 11, 880 (1975), 11,
2163 (1975) and 11,116 (197)
5), 13, 1992 (1977), 13, 199.
6 (1977), JP-A-57-15067, a method of introducing a fluororesin onto the methine chain of a polymethine dye, and a fluorine-containing atom intermediate compound can be used for synthesis.

The synthesis examples of the compound of the present invention are shown below.

Synthesis Example 1 (Synthesis of Compound 25)

[0060]

[Chemical 28]

Synthesis of [1-A] To 80 ml of a chloroform solution of 16 g of 2-mercapto-5-chloroaniline was added N, N-diethyl-N- (1,
15 ml of a chloroform solution of 24.5 g of 1,2,3,3,3-hexafluoropropyl) amine was added dropwise under ice cooling, and the reaction was performed while keeping the internal temperature at 20 ° C or lower. 3 at room temperature
After stirring for an hour, the chloroform phase was washed with water and dried over anhydrous sodium sulfate. Distill off the chloroform solvent,
The remaining oily substance was subjected to reduced pressure upstream to obtain 17.8 g of a fraction having a bp _{5 of} 84 to 88 ° C.

Synthesis of [1-B] 14.2 g of the ring-closure product [1-A] was dissolved in 70 ml of methanol, and a 3-fold molar equivalent amount of 28 w / v% sodium methoxide methanol solution was added dropwise at room temperature. Stir for hours. Methanol was distilled off, water was added to the residue, the mixture was extracted with an ethyl acetate solution, washed with saturated saline and dried over anhydrous sodium sulfate. 40 ml of methanol and 40 ml of 2N hydrochloric acid were added to the brown oily substance remaining after distilling off the ethyl acetate solvent.
Was added and the mixture was heated under reflux for 3.5 hours, and then the reaction solution was poured into ice water to cause precipitation. The crude crystals obtained by filtration and washing with water were recrystallized from methanol to obtain 7.0 g of pale yellow needle crystals.

Synthesis of [1-C] 5 g of the benzothiazole derivative [1-B] was mixed with 6.1 g of 1,3-propane and the mixture was heated and stirred at an internal temperature of 120 ° C. for 1 hour. Acetone was added to the solidified product to form a dispersion, which was collected by filtration and washed with methanol to obtain 5.1 g of [1-C].

[Synthesis of Compound 25] Quaternary Salt [1-C]
1.6 g and 1.7 g of 5-chloro-2- [2-ethylthio-2-propenyl] -3-ethylbenzothiazolium chloro salt were added to 30 ml of an acetonitrile solution at 60 ° C.
The mixture was heated and suspended with stirring. Add 1 g of triethylamine and add 3
The reaction was carried out for 0 minutes and the mixture was allowed to cool.

The precipitate was collected by filtration and washed with an acetonitrile solvent to obtain crude crystals. The target compound 25, which is a blue-violet crystal, is obtained by recrystallization from a mixed solvent of methanol and chloroform.
Was obtained. Absorption maximum wavelength is 5 in methanol solution
It showed 76 nm.

Synthesis Example 2 [Synthesis of Compound 10]

[0067]

[Chemical 29]

Synthesis of [2-A] N, N-diethyl-N- (1,1,2,3,3,3) was added to 25 ml of a solution of 9.5 g of N-methyl-orthophenylenediamine in tetrahydrofuran (hereinafter referred to as THF). 3-hexafluoropropyl) amine 12.3 g of THF1
The 2.5 ml solution was added dropwise while cooling with ice while keeping the internal temperature at 25 ° C or lower. After heating under reflux for 1 hour, the solvent was distilled off and the solution was neutralized with a sodium hydrogen carbonate solution. It was extracted with a solvent of ethyl acetate, washed with a dilute aqueous alkali solution, and dried over anhydrous sodium sulfate. The black liquid remaining after distilling off the solvent was separated and purified by column chromatography (silica gel) using a hexane solvent, and recrystallized from a hexane solvent to give [2-A] as 1
1.3 g was obtained.

Synthesis of [2-B] 9 g of the benzimidazole derivative [2-A] was dissolved in 40 ml of methanol, and a 3-fold molar equivalent of sodium methoxide 28 w / v% methanol solution was gradually added dropwise, followed by heating for 5 hours. Reflux was performed. Distill off the methanol solvent,
Water was added to the residue and the mixture was extracted with ethyl acetate solvent, washed with saturated brine, and dried over anhydrous sodium sulfate. 6 ml of 10N sulfuric acid was added to the residue obtained by distilling off the solvent, and the mixture was heated under reflux in an oil bath for 3 hours. The acidic reaction solution was neutralized with a 10% aqueous sodium carbonate solution, and the precipitated crystals were collected by filtration. The crude crystals were recrystallized from 80 ml of n-hexane containing a small amount of ethanol to obtain 5.5 g of colorless needle crystals.

Synthesis of [2-C] 2.3 g of the benzimidazole derivative [2-B] was mixed with 2.3 g of p-toluenesulfonic acid ethyl ester, and 1
The reaction was carried out by heating and stirring at 10 ± 10 ° C. for 4 hours. Acetone was added to the solidified product to form a dispersion, which was collected by filtration and washed with acetone.
3.2 g of crude crystals were obtained.

[Synthesis of Compound 10] Quaternary Salt [2-C]
1.9 g and 3- [2- [2- [N-acetylanilinovinyl]]-1-methyl-5-trifluoromethyl-3-
1.9 g of benzimidazolio] propane sulfonate was added to 10 ml of dimethyl sulfoxide, and the mixture was heated to 80 to 90 ° C., 0.5 g of diazabicycloundecene was added and reacted for 5 minutes. The reaction solution was cooled, and water was added to form a dispersion, which was allowed to stand. The supernatant was removed by decantation, ethanol was added to the residue for crystallization, and then the crystals were collected by filtration. The obtained crude crystals were recrystallized twice from ethanol to obtain 1.1 g of the objective dye, Compound 10. The maximum absorption wavelength in the methanol solution was 505.6 nm, and the molar absorption number was 11.3 × 10 ⁴ .

The above-mentioned intermediates and target compounds are NM
The structure was confirmed by R spectrum and mass spectrum.

Other compounds of the invention can be similarly synthesized.

The addition amount of the light-sensitive dye of the present invention varies greatly depending on the conditions used and the type of emulsion, but is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻³ mol per mol of silver halide, More preferably, it is in the range of 2 × 10 ⁻⁶ to 2 × 10 ⁻³ mol.

The photosensitive dye of the present invention can be added to a silver halide emulsion by a conventionally known method. For example, the protonated dissolution addition method described in JP-A-50-80826 and JP-A-50-80827, U.S. Pat. No. 3,822,1
No. 35, JP-A No. 50-11419, a method of dispersing and adding together with a surfactant, US Pat. No. 3,67.
No. 6,147, No. 3,469,987, No. 4,24
7,627, JP-A-51-59942, 5
No. 3-16624, No. 53-102732, No. 53-
102733 and 53-137131, a method of dispersing and adding to a hydrophilic substrate, East German Patent 143,
No. 324, a method of adding it as a solid solution, or a water-soluble solvent capable of dissolving a dye typified by Research Disclosure 21,802, JP-B-50-40659 and JP-A-59-148053 (for example, water,
Low boiling point solvents such as methanol, ethanol, propyl alcohol, acetone, fluorinated alcohols, high boiling point solvents such as dimethylformamide, methylcellosolve, phenylcellosolve, etc.) alone or dissolved in a mixed solvent thereof and added. It is optionally used and added to the emulsion.

The photosensitive dye of the present invention may be added at any stage in the emulsion production process from physical ripening to coating after chemical ripening, but it is added between physical ripening and completion of chemical ripening. It is preferable.

Addition of the compound of the present invention during physical ripening or prior to addition of the chemical sensitizer in the chemical ripening step or immediately after addition of the chemical sensitizer has the effect of obtaining higher spectral sensitivity. And is preferably used.

The photosensitive dye of the present invention can also be used in combination with other photosensitive dyes.

These plural photosensitive dyes may be added to the emulsion at the same time or separately at different times, and the order and time interval at that time may be arbitrarily determined depending on the purpose.

Further spectral sensitivity can be obtained by using the photosensitive dye of the present invention in combination with another compound which exerts a supersensitizing effect. Examples of such a compound having a supersensitizing effect include, for example, US Pat. No. 2,933,390,
No. 3,416,927, No. 3,511,664, No. 3,615,613, No. 3,615,632, No. 3,635,721, and the like, JP-A-3-15042.
Compounds having a pyrimidinylamino group or a triazinylamino group described in JP-A Nos. 3-110545, 4-2555841 and the like, British Patent No. 1,137,580, JP-A-61-169833. Aromatic organic formaldehyde condensate described in JP-A-4-18433
No. 2, a calixarene derivative, a halogenated benzotriazole derivative described in US Pat. No. 4,030,927, and JP-A-59-142541 and JP-A-59-142541.
No. 9-188641, a bispyridinium compound, an aromatic heterocyclic quaternary salt compound described in JP-A-59-191032, an electron-donating compound described in JP-A-60-79348, and U.S. Pat. No. 4,307. No. 183, a polymer containing an aminoallylidene malononitrile unit, a hydroxytetrazaindene derivative described in JP-A-4-149937, and US Pat. No. 3,615,633.
1,3-oxadiazole derivatives described in U.S. Pat. No. 4,780,404, amino-1,
2,3,4-thiatriazole derivative and the like can be mentioned.
The timing of addition of these supersensitizers is not particularly limited, and they can be optionally added according to the timing of addition of the light-sensitive dye in the previous period. The addition amount is selected in the range of 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver halide, and the addition amount is 1/10 to 10/1 with the photosensitive dye.

The silver halide used in the silver halide emulsion of the light-sensitive material of the present invention includes silver iodobromide, silver bromide, silver chlorobromide, silver chloroiodobromide, silver chloride and silver chloroiodide. It is arbitrarily selected. The silver halide grains may be any of cubic crystal, octahedral crystal, tetradecahedral crystal, spherical crystal, or tabular crystal having an aspect ratio of 5 or more, and [(standard deviation of particle diameter) / (particle diameter) Average value) × 100], the monodisperse particles having a coefficient of variation of 15% or less are preferable. The average grain size of the silver halide grains is not particularly limited, but is 0.05 to 2.0 μm, preferably 0.1 to 1.2 μm.

Examples of the hydrophilic protective colloid used for preparing the silver halide photographic light-sensitive material of the present invention include gelatin used in ordinary silver halide emulsions and gelatin derivatives such as acetylated gelatin and phthalated gelatin. , Water-soluble cellulose derivatives and other synthetic or natural hydrophilic polymers.

Various techniques and additives known in the art can be used in the silver halide photographic light-sensitive material of the present invention, if necessary. For example, auxiliary layers such as a protective layer, a filter layer, an antihalation layer, a crossover light cut layer, and a backing layer can be provided in addition to the light-sensitive silver halide emulsion layer. Sensitizers, noble metal sensitizers, couplers, high boiling point solvents, antifoggants, stabilizers, development inhibitors, bleaching accelerators, fixing accelerators, color mixing inhibitors, formalin scavengers, color toning agents, hardeners, surfactants Agents, thickeners, plasticizers, slip agents, ultraviolet absorbers, anti-irradiation dyes, filter light absorbing dyes, polymer latex, heavy metals, antistatic agents, matting agents and the like can be incorporated by various methods.

As the support which can be used in the silver halide photographic light-sensitive material of the present invention, cellulose triacetate, cellulose nitrate, polyethylene terephthalate, polyester such as polyethylene-2,6-naphthalate, polyolefin such as polyethylene, Examples thereof include polystyrene, baryta paper, paper laminated with polyethylene and the like, glass, metal and the like.

These supports may be used, if necessary, for example,
Substrate processing such as corona discharge treatment and installation of an undercoat polymer adhesive layer is performed.

The above-mentioned additives are described in more detail in Research Disclosure, Vol. 176, Item.
/ 17643 (Dec. 1978), vol. 184, Ite
m / 18431 (August 1979) and Vol. 187 It.
em / 18716 (November 1979).

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.W. H. James The Theory of the Photographic Process No. 4
Edition (The Theory of the Photo
graphic Process, fourth Ed
291) to 334 and the Journal of the American Chemical Society (Journ)
al of theAmerican Chemica
l Society) Vol. 73, p. 3,100 (195
The developer as described in 1) can be effectively used.

[0088]

EXAMPLES Next, the present invention will be explained based on examples.
Embodiments of the present invention are not limited to these.

Example 1 Polyethylene containing titanium oxide was formed on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side and each layer having the constitution shown in Tables 1 and 2 below. By coating on the layer side, a multilayer silver halide color photographic light-sensitive material sample I-1 was prepared. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (EY-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (S
T-2) 6.67 g, stain inhibitor (HQ-1) 0.
To 67 g and 6.67 g of a high boiling organic solvent (DNP), 60 ml of ethyl acetate was added and dissolved, and this solution was mixed with 220 ml of a 10% gelatin aqueous solution containing 7 ml of a 20% aqueous solution of a surfactant (SU-2) and an ultrasonic homogenizer. It was emulsified and dispersed to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver chlorobromide emulsion (containing 8.67 g of silver) shown below, and an anti-irradiation dye (AIY-1) was further added to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Also, as a hardener, the second layer and the fourth layer
(HH-1) was added to the layer and (HH-2) was added to the seventh layer. As the coating aid, surfactants (SU-1), (S
U-3) was added to adjust the surface tension.

[0093]

[Table 1]

[0094]

[Table 2]

The structural formulas of the compounds used in the above layers are shown below.

[0096]

[Chemical 30]

[0097]

[Chemical 31]

[0098]

[Chemical 32]

[0099]

[Chemical 33]

[0100]

[Chemical 34]

[0101]

[Chemical 35]

Blue-Sensitive Silver Chlorobromide Emulsion (Em-B) Monodisperse Cubic Emulsion with Average Grain Size 0.85 μm, Coefficient of Variation = 0.07, Silver Chloride Content 99.5 mol% Sodium Thiosulfate 0.8 mg / Mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ^{− 4} mol / mol AgX Green-sensitive silver chlorobromide emulsion (Em-G) Monodisperse cubic emulsion with average particle size 0.43 μm, coefficient of variation = 0.08, silver chloride content 99.5 mol% Sodium thiosulfate 1. 5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX red-sensitive silver chlorobromide emulsion ( Em-R) Average particle size 0.50 μm, fluctuation coefficient Number = 0.08, monodisperse cubic emulsion with silver chloride content 99.5 mol% sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 x 10 ^-4 mol / Molar AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX The coefficient of variation is calculated by the following formula 1.

[0103]

[Equation 1]

Here, ri represents the particle size of each particle, and ni represents the number thereof. The grain size means the diameter of a spherical silver halide grain, and the diameter of a cubic image or a grain having a shape other than spherical when the projected image is converted into a circular image having the same area.

The structural formulas of the compounds used in each monodisperse cubic emulsion are shown below.

[0106]

[Chemical 36]

Next, the photosensitive dye (sensitizing dye) RS-1 of the red-sensitive silver chloride emulsion (Em-R) of the fifth layer of Sample I-1 was used in an equimolar amount of the photosensitive dye of the present invention (sensitizing dye). Samples I-2 to I-13 were prepared in the same manner as Sample I-1, except that the components were replaced as shown in Table 3 below.

In order to investigate the change in sensitivity when the coating solution for these photosensitive materials was stagnant, after preparing the fifth layer coating solution, 40 ° C.
The sample which was applied for 10 hours at room temperature and then applied,
After preparing the layer coating solution for 30 minutes at 40 ° C., each sample coated with the coating solution was exposed to an optical wedge through a red filter and subjected to color development processing according to the processing steps shown below.

<< Evaluation of Photographic Performance >> The reflection density of the processed sample was measured, and the sensitivity was calculated as the reciprocal of the exposure amount required to give a density of fog density + 0.5. Sensitivity S _{A of} the sample applied with the 5-layer coating solution after aging at 40 ° C. for 30 minutes and the sample S applied with the 5-layer coating solution after aging at 40 ° C. for 10 hours and then the application solution
The ratio of _B was expressed as ΔS = S _B / S _A. The sensitivity variation is smaller as ΔS is closer to 1.0.

Color development processing Treatment process temperature time Color development 35.0 ± 0.3 ℃ 45 seconds Bleach-fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-34 ° C 90 seconds Dry 60-80 ℃ 60 seconds The composition of each treatment liquid is shown below.

The replenishing amount of each processing solution is 80 ml per 1 m ^{2 of} silver halide color photographic light-sensitive material.

Color developing solution Tank solution Replenishing solution Pure water 800 ml 800 ml Triethanolamine 10 g 18 g N, N-diethylhydroxylamine 5 g 9 g Potassium chloride 2.4 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g 1.8 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4 g 8.2 g Optical brightener (4,4′-diaminostilbene sulfonic acid derivative) 1.0 g 1. 8 g potassium carbonate 27 g 27 g Water was added to make the total volume 1 liter, and p was added to the tank liquid.
H = 10.10, pH in replenisher is 10.60
Adjust to.

Bleach-fix solution (tank solution and replenisher are the same) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water In addition, the total amount is adjusted to 1 liter, and the pH is adjusted to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing solution (tank solution and replenisher are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 0.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4′-diaminostilbene sulfonic acid derivative) 1.5 g Water was added to make the total volume 1 liter, and sulfuric acid or Adjust the pH to 7.0 with potassium hydroxide.

The results are shown in Table 3.

[0116]

[Table 3]

[0117]

[Chemical 37]

As is apparent from Table 3, Sample I using a comparative dye which has a fluorine atom substituted on the methine chain, which is outside the scope of the present invention, is used.
-2 to I-5 have large desensitization after aging of the coating solution. It can be seen that the photosensitive dyes (sensitizing dyes) of the present invention have improved desensitization after aging of the coating solution (I-6 to I-10) and have smaller sensitivity changes than the control dyes (I-11 to I-10). I-13). Further, in the sample of the present invention, clear coloring was not observed in the white background portion, and residual color contamination was excellent.

Example 2 The addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. The silver halide and colloidal silver are shown in terms of silver, and the photosensitive dye is shown in the number of moles per mole of silver halide in the same layer.

(Preparation of Silver Halide Photographic Emulsion) <Preparation of Seed Emulsion-1> Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 100 g potassium bromide 2.05 g with water 11.5 l B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml water with 2.6 l C1 ossein gelatin 75 g Potassium bromide 950 g Potassium iodide 27 g Water 3.0 l D1 Silver nitrate 95 g Water 2.7 l E1 Silver nitrate 1410 g Water 3.2 l To the solution A1 kept at 60 ° C in the reaction vessel, the solutions B1 and D1 are control double The jet method was used for 30 minutes, and then the C1 and E1 solutions were added by the control double jet method for 105 minutes. Stirring is 50
It was performed at 0 rpm.

The flow rate was such that new nuclei did not occur with the growth of particles, and so-called Ostwald ripening occurred, and the particle size distribution did not broaden. At the time of adding the silver ionic liquid and the halide ionic liquid, pAg was adjusted to 8.3 ± 0.05 using an aqueous potassium bromide solution, and pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the addition was completed, the pH was adjusted to 6.0, and then, in order to remove excess salts, JP-B-35-1608 was used.
Desalting treatment was performed by the method described in No. 6.

When the seed emulsion was observed with an electron microscope, it was a cubic tetradecahedral monodisperse emulsion having an average grain size of 0.27 μm and 17% of the grain size distribution with a slight lack of corners.

<Preparation of Em-C> A monodisperse core / shell type emulsion was prepared using seed emulsion-1 and the following seven kinds of solutions.

A2 Ocein gelatin 10 g Ammonia water (28%) 28 ml Glacial acetic acid 3 ml Seed emulsion-1 0.119 mol equivalent Water 11.5 l B2 ossein gelatin 0.8 g Potassium bromide 5 g Potassium iodide 3 g Water 110 ml C2 ossein gelatin 2.0 g Potassium bromide 90 g Water 240 ml D2 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Water 110 ml E2 Silver nitrate 130 g Ammonia water (28%) 100 ml Water 240 ml F2 Potassium bromide 94 g Water 165 ml G2 silver nitrate 9.9 g ammonia water (28%) 7.0 ml 110 ml A2 solution was kept warm at 40 ° C. with water and stirred at 800 rpm with a stirrer. The pH of solution A2 was adjusted to 9.90 with acetic acid, seed emulsion-1 was collected and dispersed and suspended, and then solution G2 was added at a constant rate over 7 minutes to adjust the pAg to 7.3. Further, solution B2 and solution D2 were simultaneously added over 20 minutes. At this time, pAg was kept constant at 7.3. Further, pH = 8.8 using potassium bromide aqueous solution and acetic acid over 10 minutes.
3. After adjusting to pAg = 9.0, the C2 solution and the E2 solution were simultaneously added over 30 minutes.

At this time, the flow rate ratio at the start of addition and the end of addition was 1:10, and the flow velocity was increased with time.
Also, the pH was lowered from 8.83 to 8.00 in proportion to the flow rate ratio. Further, when the C2 liquid and the E2 liquid were added by ⅔ of the total amount, the F2 liquid was additionally injected and added at a constant rate over 8 minutes. At this time, pAg was 9.0 to 11.
It rose to zero. Further, acetic acid was added to adjust the pH to 6.0.

After the addition was completed, in order to remove excess salts, precipitation desalting was carried out using an aqueous solution of demole (manufactured by Kao Atlas Co.) and an aqueous solution of magnesium sulfate to obtain pAg8.
An emulsion having an average silver iodide content of pH 5.85 at 5, 40 ° C. of about 2.0 mol% was obtained.

Observation of the obtained emulsion with an electron microscope revealed that the average grain size was 0.55 μm and the grain size distribution was 14%.
Was a rounded tetradecahedral monodisperse core / shell type emulsion.

<Preparation of Seed Emulsion-2> Seed emulsion-2 was prepared as follows.

A3 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate Na salt (10% aqueous ethanol solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B3 2.5N silver nitrate aqueous solution 2825 ml C3 bromide Potassium 824 g Potassium iodide 23.5 g Water 2825 l D3 1.75 N Potassium bromide aqueous solution The following silver potential control amount 35 ° C. Japanese Patent Publication Nos. 58-58288 and 58-5828.
Using the mixing stirrer shown in No. 9, 464.3 ml of each of solution B3 and solution C3 was added to solution A3 by the double mixing method over 2 minutes to perform nucleation.

After stopping the addition of solution B3 and solution C3, it took 60 minutes to raise the temperature of solution A3 to 60 ° C., adjust the pH to 5.0 with a 3% KOH aqueous solution, and then again. Solution B3 and solution C3 were added by the simultaneous mixing method at a flow rate of 55.4 ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 35 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B3 and C3 was +8 mv using the solution D3. And +16 mv.

After the addition was completed, p was added by a 3% KOH aqueous solution.
H was adjusted to 6 and immediately desalted and washed with water.

In this seed emulsion, 90% or more of the total projected area of silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of hexagonal tabular grains was 0.06.
It was confirmed with an electron microscope that the average particle size (in terms of salt diameter) was 0.59 μm.

<Preparation of Em-D> A tabular emulsion was prepared using seed emulsion-2 and the following three solutions.

A4 ossein gelatin 5.26 g polypropyleneoxy-polyethyleneoxy-disuccinate Na salt (10% ethanol aqueous solution) 1.4 ml seed emulsion-2 equivalent to 0.094 mol Water 569 ml B4 ossein gelatin 15.5 g potassium bromide 114 g Potassium iodide 3.19 g Water 658 ml C4 Silver nitrate 166 g Water 889 ml A4 liquid stirred vigorously at 60 ° C. was mixed with liquid B4 and liquid C4 10 times.
It was added by the double jet method in 7 minutes. During this time, the pH was kept at 5.8 and the pAg was kept at 8.7 throughout. B4 liquid and C4
The addition rate of the solution was linearly increased so as to be 6.4 times the initial and final rates.

After the addition, in order to remove excess salts, precipitation desalting was carried out using an aqueous solution of demole (manufactured by Kao Atlas Co.) and an aqueous solution of magnesium sulfate to obtain pAg8.
An emulsion having an average silver iodide content of pH 5.85 at 5, 40 ° C. of about 2.0 mol% was obtained.

Observation of the resulting emulsion with an electron microscope revealed that 82% of the projected area had a mean grain size of 0.98 μm, a broad grain size distribution of 15%, and a tabular halogenated form with an average aspect ratio of 4.5. It was a silver particle. Further, the average of the ratio (t / l) between the distance between twin planes (l) and the thickness of the tabular grains (t) is 11
Met. The crystal planes were composed of (111) planes and (100) planes, the main planes were all (111) planes, and the ratio of (111) planes to (100) planes in the edge plane was 78:22.

These emulsions were subsequently adjusted to pH 5.8 and pAg 7.0 with citric acid and sodium chloride, and then
After adding several kinds of dyes shown in Table 2 and performing optimum chemical aging at 60 ° C. using ammonium thiocyanate, sodium thiosulfate pentahydrate and chloroauric acid, 4-hydroxy-
Ripening was stopped by adding 1.0 g of 6-methyl-1,3,3a, 7-tetrazaindene per mol of silver.

(Preparation of silver halide photographic light-sensitive material) One side (surface) of a triacetyl cellulose film support is subjected to undercoating, and then the support is sandwiched between the surface opposite to the surface subjected to the undercoating. A layer having the following composition was sequentially formed on the (back surface) from the support side.

Backside first layer Alumina sol AS-100 (aluminum oxide) (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g Backside second layer diacetyl cellulose 100 mg Stearic acid 10 mg Silica fine particles (average particle size 0.2 μm) 50 mg Undercoating Color photographic light-sensitive materials (Samples II-1 to II-34) were prepared by sequentially forming layers having the compositions shown below from the support side on the surface of the triacetyl cellulose film support.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Dye (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer: Intermediate layer (IL-1) Gelatin 1.3 g Third layer: Silver halide photosensitive layer Silver halide emulsions C and D 0.9 g Photosensitive Dye (described in Tables 4 and 5) 3.4 × 10 ⁻⁴ mol / mol AgX Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-1) 0.004 g High boiling point solvent (Oil2) 0.35 g Gelatin 1.0 g Fourth layer: first protective layer (Pro-1) Fine grain silver iodobromide emulsion (average grain size 0.08 μm) 0. 3g UV absorber (UV-1) 0.07g UV absorber (UV-2) 0.10g Additive 1 (HS-1) 0.2g Additive 2 (HS-2) 0.1g High boiling solvent (Oil -1) 0.07 g High boiling point solvent (Oil-3) 0.07 g Gelatin 0.8 g Fifth layer: second protective layer (Pro-2) Additive 3 (HS-3) 0.04 g Additive 4 (HS -4) 0.004 g polymethyl methacrylate (average particle size 3 μm) 0.02 g methyl methacrylate: ethyl methacrylate: methacrylic acid copolymer (3: 3: 4 weight ratio) (average particle size 3 μm) 0.13 g gelatin 0.1. 5 g In addition, the above-mentioned coated sample was further added with activators SA-2 and SA-.
3, viscosity modifier, hardener H-1, H-2, stabilizer ST-
3, ST-4, ST-5 (weight average molecular weight 10,000
And those of 1,100,000) Dyes F-4, F
Containing -5 and additives ^{HS-5 (9.4mg / m 2} ).

[0143]

[Chemical 38]

[0144]

[Chemical Formula 39]

[0145]

[Chemical 40]

[0146]

[Chemical 41]

Each of the prepared samples was divided into 2 minutes, one of them was left as it was, and the other was evaluated for stability at high temperature. Therefore, the sample was allowed to stand for 3 days in an atmosphere of 80% RH and 40 ° C. Deteriorated.

<< Evaluation of Photographic Performance >> Each of the obtained samples was subjected to wedge exposure with white light for 1/100 second, and then developed, bleached and fixed according to the processing steps shown below. The processed sample was subjected to density measurement using an optical densitometer (PDA-65 manufactured by Konica), and the sensitivity was determined by the reciprocal of the exposure amount at the fog density + 0.03 in the usual manner.

As a substitute test evaluation of the performance fluctuation that appears when the photographic material is stored for a long period of time,
Increase in fog (ΔFo
g) was determined.

Further, the sensitivity change (ΔS) was obtained by dividing the sensitivity of the sample that was forcibly deteriorated by the sensitivity of the sample that was aged at room temperature.

(Processing step) Step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleach 45 seconds 38 ± 2.0 ° C. 150 ml fixation 1 minute 30 seconds 38 ± 2.0 C 830 ml Stability 60 sec 38 ± 5.0 ° C. 830 ml Dry 60 sec 55 ± 5.0 ° C .- * Replenishment amount is a value per 1 m ² of the light-sensitive material.

<Preparation of Processing Agent> (Developer composition) Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g 4 -Amino-3-methyl-N-ethyl N- (β-hydroxyethyl) aniline sulphate 4.5 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make 1.0 l and hydroxylated. Potassium or 20
Adjust to pH 10.06 with% sulfuric acid.

(Development Replenisher Composition) Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl N -(Β-Hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make 1.0 l, potassium hydroxide or 20
Adjust to pH 10.18 with% sulfuric acid.

(Bleaching Solution Composition) Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1.0 l, and ammonia water was added. Alternatively, the pH is adjusted to 4.4 using glacial acetic acid.

(Bleaching Replenisher Composition) Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g Water was added to make 1.0 l, and ammonia was added. Adjust to pH 4.0 with water or glacial acetic acid.

(Fixer Formulation) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water is added to make 1.0 l, and the pH is adjusted to 6.2 with aqueous ammonia or glacial acetic acid.

(Fixing Replenisher Solution Formulation) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Water is added to make 1.0 l, and the pH is adjusted to 6.5 with aqueous ammonia or glacial acetic acid.

(Stabilizer and stable replenisher formulation) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Water is added to finish to 1.0 l, ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

The results are shown in Tables 4 and 5.

[0160]

[Table 4]

[0161]

[Table 5]

[0162]

[Chemical 42]

The silver halide photographic light-sensitive material of the present invention provided good photographic performance in which fogging and sensitivity fluctuation over time (substitute thermo) were suppressed as compared with the comparative sample. It was also excellent in comparison of residual color stainability.

Example 3 (Preparation of silver halide photographic emulsion A) Silver chloroiodobromide (62 mol% silver chloride, 0.5 mol% silver iodide per 1 mol of silver, etc.) was brominated by the simultaneous mixing method. A silver) emulsion was prepared.

During the mixing process from the formation of 5% of the final reached average particle size to the final reached average particle size, K ₂ IrC
l ₆ was added per mol of silver 8 × 10 ^-7 mol. After desalting by a flocculation method using a modified gelatin treated with phenyl isocyanate, the salt is dispersed in gelatin, and a mixture of the following compounds [A], [B] and [C] is added as an antifungal agent. An emulsion consisting of cubic monodisperse grains (variation coefficient 10%) having an average grain size of 0.3 μm was obtained.

To this emulsion was added p-citric acid and sodium chloride.
After adjusting H to 5.8 and pAg to 7.0, it was optimally chemically aged at 60 ° C. with sodium thiosulfate pentahydrate and chloroauric acid, and then with 1-phenyl-5-mercaptotetrazole. 4-hydroxy-6-methyl-1,3,3
a, 7-tetrazaindene, 60m per 1 mol of silver
The aging was stopped by adding g and 600 mg.

Next, the additives SA-1 and NU shown below are added.
An appropriate amount of -1, NA-1, LX-1 and HD-1 was added to prepare an emulsion coating solution.

(Preparation of silver halide photographic emulsion B) Silver chloroiodobromide (62 mol% of silver chloride, 0.5 mol% of silver iodide and others of silver bromide per mol of silver) emulsion prepared by the simultaneous mixing method. Was prepared.

Denatured gelatin treated with phenyl isocyanate was desalted by the flocculation method and then dispersed in gelatin to obtain the compound [A] described below as an antifungal agent.
The mixture of [B] and [C] is added, and the average particle size is 0.3 μm.
An emulsion consisting of cubic monodisperse grains (10% variation coefficient) was obtained. After adjusting the pH of this emulsion to 5.8 and pAg to 7.0 with citric acid and sodium chloride, it was optimally chemically ripened at 60 ° C. with sodium thiosulfate pentahydrate and chloroauric acid. 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene, 60 mg and 6 per mol silver, respectively
Aging was stopped by adding 00 mg.

The emulsion thus obtained was chemically sensitized in the same manner as in the above emulsion A, and the same additives were added to prepare an emulsion coating solution.

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate film having 0.1 μm-thick undercoat layer (see Example 1 of JP-A-59-19941) on both sides. On the undercoat layer, a silver halide emulsion layer of the following formula (1) with a gelatin amount of 2.0 g
/ M ² and silver amount of 3.2 g / m ^2, and an emulsion protective layer of the following formulation (2) on which the amount of gelatin is 1.0
by coating so as to be g / m ^2, also on the opposite side of the other subbing layer, a backing layer was coated as the amount of gelatin is 2.4 g / m ² according to the following formulation (3) Further, a backing protective layer having the following formulation (4) was further applied thereon so that the amount of gelatin would be 1.0 g / m ² , and samples III-1 to III-
I got 22.

Formulation (1) [Silver halide emulsion layer composition] Gelatin 2.0 g / m ² Silver halide emulsion: Emulsion A or B 3.2 g / m ² Photosensitive dye: Compound of the present invention or comparative compound (Table 6) Description) 2 × 10 ⁻⁴ mol / mol silver Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: adenine 10 mg / m ² : 1-phenyl -5-Mercaptotetrazole 5 mg / m ² Surfactant: Saponin 0.1 g / m ² : SA-1 8 mg / m ² Hydrazine derivative: NU-1 35 mg / m ² Nucleation accelerator: NA-1 70 mg / m ² Latex polymer: Lx-1 1.0 g / m ² polyethylene glycol (molecular weight 4000) 0.1 g / m ² Hardener: HD-1 60 mg / m ² Coloring dye F-1 60 mg / m ²

[0173]

[Chemical 43]

[0174]

[Chemical 44]

Formulation (2) [Emulsion protective layer composition] Gelatin 0.9 g / m ² Surfactant: SA-2 10 mg / m ² : SA-3 10 mg / m ² Matting agent: Single particle having an average particle size of 3.5 μm Dispersed silica 3 mg / m ² Hardener: 1,3-vinylsulfonyl-2-propanol 40 mg / m ² Formulation (3) [Backing layer composition] Gelatin 2.4 g / m ² Surfactant: Saponin 0.1 g / m ² : SA-1 6 mg / m ² colloidal silica 100 mg / m ² Coloring dye: F-2 30 mg / m ² : F-3 60 mg / m ² : F-4 20 mg / m ² : F-5 30 mg / m ²

[0176]

[Chemical formula 45]

Formulation (4) [Backing protective layer composition] Gelatin 1.0 g / m ² Surfactant: SA-2 10 mg / m ² Matting agent: Monodispersed polymethylmethacrylate having an average particle size of 5.0 μm 50 mg / m ² Hardener: Glyoxal 35 mg / m ² Each of the obtained samples was divided into 2 minutes, one of them was left as it was, and the other was subjected to 20% R to evaluate stability under high temperature.
It was left in an environment of H and 50 ° C. for 3 days for forced deterioration.

<< Evaluation of Photographic Performance >> A wedge was attached to the obtained sample, and the Ratten filter No. 1 through 21
It was exposed for 0 to ⁵ seconds, and processed under the following conditions with an automatic processor GR-26S (manufactured by Konica Corp.) for rapid processing in which a developing solution and a fixing solution having the compositions shown below were added.

The obtained sample was used as an optical densitometer PDA-65.
Density was measured with Konica Corp., and the sensitivity was measured by the reciprocal of the exposure amount at fog density +0.3 in the usual way.
It was shown as a relative value with the sensitivity of the sample immediately after coating and drying of -1 taken as 100.

[Developer composition] Potassium sulfite 60.0 g Hydroquinone 15.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.0 g Ethylenediaminetetraacetic acid disodium salt 0.5 g Potassium carbonate 50.0 g Potassium bromide 5.0 g 2-mercaptobenzimidazole 0.25 g 5-methylbenzotriazole 0.4 g Water was added to make 1 liter, and the pH was adjusted to 10.5 with potassium hydroxide.

[Fixing Solution Formulation] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17.0 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulfate (Al ₂ O ₃ conversion content is 8.1% W / V aqueous solution) 8. When using 5 g of fixer, the above composition A and composition B are added to 500 ml of water.
Were melted in this order and finished to 1 l for use. P of this fixer
H was adjusted to 4.8 with acetic acid.

[Development processing conditions] (Process) (Temperature) (Time) Development 38 ℃ 20 seconds Fixing 35 ℃ 20 seconds Washing with water 30 ℃ 15 seconds Drying 50 ℃ 15 seconds The obtained results are shown in Table 6.

[0183]

[Table 6]

[0184]

[Chemical formula 46]

As is clear from Table 6, the silver halide photographic light-sensitive material of the present invention shows good photographic performance in the evaluation of unthermo treatment, and it shows fog and sensitivity over time as compared with the comparative sample. Fluctuation is suppressed. This effect was remarkably observed in a silver halide photographic emulsion containing an iridium compound and having a high silver chloride composition concentration.

[0186]

According to the present invention, firstly, there is provided a silver halide photographic light-sensitive material in which photographic characteristics are improved by a light-sensitive dye having a small sensitivity fluctuation during storage and a reduced residual color contamination. Secondly, it was possible to provide a silver halide photographic light-sensitive material having a silver halide emulsion layer which was spectrally sensitized by a new light-sensitive dye and had improved photographic characteristics.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chen ▲ zu ▼ Flow Konica Co., Ltd. 1 Sakura-cho, Hino-shi, Tokyo (56) References JP-A-7-253630 (JP, A) JP-A-8- 184934 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 1/12 G03C 1/16 G03C 1/18 G03C 1/20 G03C 1/22

Claims (2)

(57) [Claims] 1. An aliphatic group substituting at least one fluorine atom on a methine chain and substituting on a nitrogen atom forming an azole ring has at least three water-soluble groups. A silver halide photographic light-sensitive material having a silver halide emulsion layer spectrally sensitized by a polymethine dye bonded with a methine group. 2. The polymethine dye is represented by the following general formula [I]:
Or a silver halide photographic light-sensitive material according to claim 1, which is represented by [II]. [Chemical 1] [In the formula, Z ¹ and Z ² represent a non-metal atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group. J ¹ represents an alkylene group having 1 to 6 carbon atoms, and R ¹ has 1 to 1 carbon atoms.
Represents an aliphatic group of 0. V ¹ is an acidic group, -T ¹ -CH _2-
(T ²⁾ _n1 -G ¹ or -T ¹ -NH- (T ²⁾ represents _n1 -G ^1, T ¹ and T ² each represents a sulfonyl group or a carbonyl group, G ¹ represents a hydrogen atom, an alkyl group , Amino group,
It represents a hydroxy group, an alkoxy group or an alkylthio group. L ^{1 to} L ⁹ each represent a methine group. However, a fluorine atom is substituted for at least one group of the methine group forming the cyanine dye. l ¹ , l ² , m ¹ , m ² , m ³ , m ⁴ and n
1 is an integer of 0 or 1 and represents a number in which m ¹ , m ² , m ³ and m ⁴ do not become 0 at the same time. M ₁ represents an ion necessary for canceling the total charge of the molecule, and k ¹ represents a number necessary for neutralizing the charge in the molecule. ] [Chemical 2] [In the formula, Z ¹¹ represents a non-metal atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group, and Q ¹¹ represents 5- or 6-membered.
Represents a non-metal atomic group necessary for forming a member acidic ring group.
J ¹¹ represents an alkylene group having 1 to 6 carbon atoms, V ¹¹ is an acidic group, —T ¹¹ —CH ₂ — (T ¹² ) _n ¹¹ —G ¹¹ or —T ¹¹
-NH- (T ¹²⁾ represents _n11 -G ^11, T ¹¹ and T ¹² each represents a sulfonyl group or a carbonyl group, G ¹¹ is hydrogen atom, an alkyl group, an amino group, hydroxy group, alkoxy group or alkylthio group Represents L ^{11 to} L ¹⁶ each represent a methine group. However, at least one of the methine groups forming the merocyanine dye is substituted with a fluorine atom. l ¹¹ , m ¹¹ , m ¹² and n ¹¹ are each an integer of 0 or 1, and represent numbers such that m ¹¹ and m ¹² do not become 0 at the same time. ]