JPH0572661A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to reduce changes of sensitivity and fog during storage of the photosensitive material by incorporating a pentamethine or nonamethine type cyanine dye having naphthoazole ring substituted by an alkylthio group. CONSTITUTION:This photosensitive material contains the compound represented by formula I in which each of L1-L9 is methine; Z1 is an atomic group necessary to form a naphtho-(thia-, oxa, or selena-)zole, or naphthimidazole ring, substituted such as -SR3 an atomic group necessary to form a 5-or 6-membered hetero ring; each of R1 and R2 is, independently, alkyl or aryl; R3 is 1-18 C alkyl; m1 is an integer of 1-6; each of n1 and n2 is 0 or 1; an X is a counter ion.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having improved sensitivity and stability, and more particularly to a silver halide photographic light-sensitive material spectrally sensitized in the infrared region.

[0002]

2. Description of the Related Art As one of the exposure methods for a photographic light-sensitive material, an original image is scanned, and a silver halide photographic light-sensitive material is exposed on the basis of the image signal, and a negative image or a positive image corresponding to the image of the original image An image forming method using a so-called scanner method for forming an image is known. There are various types of recording apparatuses that use the image forming method by the scanner method, and conventionally, glow lamps, xenon lamps, mercury lamps, tungsten lamps, light emitting diodes, and the like have been used as the light sources for recording in these scanner type recording apparatuses. However, each of these light sources has a practical drawback that the output is weak and the life is short. To compensate for these drawbacks,
There is a scanner that uses a coherent laser light source such as a Ne-He laser, an argon laser, and a He-Cd laser as a light source of a scanner system. These are capable of obtaining high output, but are large in size, expensive, require a modulator, and use visible light, which limits safelight of the photosensitive material, resulting in poor handling. There are drawbacks such as. On the other hand, a semiconductor laser is small and inexpensive, easy to modulate, has a longer life than the above laser, and emits light in the infrared region. Since it can be used, it has an advantage that handling workability is improved.

However, since the output of the semiconductor laser which can be used at present is not necessarily high, the sensitivity of the conventional photosensitive material for scanners is insufficient for performing scanning exposure of a large screen in a short time. Therefore, a photosensitive material having improved sensitivity in the infrared region has been demanded. It is known to increase the size of silver halide grains or to add various chemical sensitizers as a method for increasing the sensitivity of photographs, but these methods are often used to improve the graininess of silver images. There were unfavorable side effects such as deterioration and the appearance of fog, and it was not suitable as a light-sensitive material for scanners which requires particularly sharp image quality.
U.S. Pat. No. 4,975,362 discloses sensitizing dyes allegedly effective in improving infrared sensitivity, but these dyes are not sufficiently high for light sources of various wavelengths. It did not give sensitivity.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material having high contrast and photographic characteristics with sufficiently high sensitivity to infrared light.

[0005]

The above object has been achieved by a silver halide photographic light-sensitive material containing a compound represented by the following general formula (I). General formula (I)

[0006]

[Chemical 2]

Where L ₁ , L ₂ , L ₃ , L ₄ , L ₅ ,
_{L 6, L 7, L 8} , L 9 each represents a good methine group which may have a substituent; Z ₁ is substituted with -SR _3, which may further have other substituents naphthothiazole , Naphthoxazole, naphthimidazole, or a group of atoms for completing the naphthoselenazole nucleus; Z ₂
Represents an atomic group for completing a 5- or 6-membered heterocyclic ring which may have a substituent; R ₁ and R ₂ each represent an optionally substituted alkyl or aryl group; R ₃ represents an optionally substituted alkyl group having 1 to 18 carbon atoms; m ₁ represents an integer of 1 to 6; n ₁ and n ₂ each represent 0 or 1;
X represents a counter ion.

In the general formula (I), the atom group represented by Z ₁ may have a known substituent in addition to —SR ₃ . Examples of this substituent include halogen (eg F, C
l, Br), alkoxy (eg methoxy, ethoxy,
Known substituents include 2-methoxyethoxy), alkyl (eg methyl, ethyl, isobutyl, cyclohexyl), aryl (eg phenyl), aralkyl (eg benzyl), sulphonato. Z ₂
The heterocyclic ring completed by the atomic group represented by

For example, thiazole nucleus [eg benzothiazole, 5-methylthiobenzothiazole, 5,6-bismethylthiobenzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-
Methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole,
5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy -6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, 8-methylthionaphtho [1,2-d] thiazole, Naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,2]
1-d] thiazole, 5-methoxynaphtho [2,3-
d] thiazole], selenazole nucleus [for example, benzoselenazole, 5-chlorobenzoselenazole, 5-methylthiobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho] 2,1-d] selenazole, naphtho [1,2-d] selenazole], oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-methylthiobenzoxazole,
5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-
Trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole,
6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5
-Ethoxybenzoxazole, naphtho [2,1-d]
Oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, imidazole nucleus (for example, 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1 -Ethyl-5-chlorobenzimidazole,
1-ethyl-5-methylthiobenzimidazole, 1-
Methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-methoxybenzimidazole, 1-methyl-5
-Cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1- Allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1
-Phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho [1,2-d] imidazole ), A pyridine nucleus (eg, pyridine, 5-methyl-2-pyridine, 3-methyl-4-).
Pyridine). Of these, a thiazole nucleus and an oxazole nucleus are preferably used advantageously. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used.

The alkyl group represented by R ₁ and R ₂ is preferably a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, which may further have a substituent. Examples of the substituent include a carboxyl group, a sulfo group,
Cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxyl group, alkoxycarbonyl group (preferably having 8 or less carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.), alkoxy group (preferably) Has 7 carbon atoms
Hereinafter, for example, methoxy, ethoxy, propoxy, butoxy, benzyloxy), an alkylthio group (for example, methylthio, 2-methylthioethylthio), an aryloxy group (for example, phenoxy, p-tolyloxy, α-naphthoxy), an acyloxy group (preferably carbon). 3 or less atoms,
For example, acetyloxy, propionyloxy), an acyl group (preferably having 8 or less carbon atoms, for example, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (for example, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl). , A sulfamoyl group (eg, sulfamoyl, N,
N-dimethylsulfamoyl, morpholinosulfonyl), an alkyl group substituted with an aryl group (eg, phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl) (preferably carbon of the alkyl moiety). The number of atoms is 6 or less). However, two or more of these substituents may be combined and substituted with an alkyl group.

The alkyl group represented by R ₃ preferably has 1 to 12 carbon atoms and has halogen (eg F, Cl, Br), alkoxy (eg methoxy, ethoxy), aryloxy (eg phenoxy), alkylthio ( For example, it may have a known substituent such as methylthio, ethylthio), aryl (eg phenyl, 2-pyridyl), sulfonate, hydroxy, carboxy and the like. Particularly preferred is a lower alkyl group having 1 to 6 carbon atoms, and preferred substituents are F, methoxy, ethoxy, methylthio, sulfonato, carboxy and hydroxy.

The methine group represented by L ₁ to L ₉ may have a substituent, and examples of the substituent include alkyl (preferably having 1 to 6 carbon atoms), aryl (eg phenyl), Aralkyl (eg benzyl),
Alkoxy (eg methoxy, ethoxy), alkylthio (eg methylthio, ethylthio) and the like can be mentioned. These groups may further have a substituent. When L ₂ and L ₄ , L ₃ and L ₅ , and n ₁ is 1, L ₄ and L ₆ , and when both n ₁ and n ₂ are 1, L ₆ and L ₈ are connected to each other to form a ring. It may be formed. This ring is 5 or 6
It is preferably a membered carbocycle. More specifically, the skeleton shown in the following (a), (b), (c) and (d) may further have a substituent.

[0013]

[Chemical 3]

M ₁ is preferably 1, 2 or 3.
The counterion represented by X is a cation or anion selected such that the total charge of the compound represented by the general formula (I) is 0, and X is Z ₁ , Z ₂ , R ₁ , R _2, etc. An internal salt may be formed as a substituent of Examples of cations are Na ⁺ , K ⁺ , NH ₄ ⁺ , (n-C ₄ H ₉ ) ₄ N.
⁺ , And so on. Examples of anions include acid anions (eg chloride, bromide, iodide, tetrafluoroborate, hexafluorophosphate, methylsulfate, ethylsulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfone). Nato, 4-nitrobenzene sulfonate, trifluoromethane sulfonate, perchlorate and the like).

Among the compounds represented by the general formula (I), preferred compounds are those represented by the following general formula (II).

[0016]

[Chemical 4]

Where L ₁ to L ₇ , Z ₁ , R ₁ , R ₃ ,
m ₁ , X ₁ and n ₁ have the same meanings as defined in the general formula (I), and Z ₃ represents a benzothiazole nucleus, a naphthothiazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzoselenazole nucleus and a naphthoselenazole nucleus. represents an atomic group for completing, R ₄ is independently of R _1, represents a group selected from the group R ₁ as defined, R ₅ is selected from groups of R ₃ as defined independently of R ₃ Represents a group, and m ₂ represents an integer of 1 to 6.

Among the compounds represented by the general formula (I), particularly preferred are the compounds represented by the following general formula (III).

[0019]

[Chemical 5]

In the formula, L ₁ to L ₇ , X and n ₁ represent groups having the same meanings as defined in the general formula (I), and R ₆ and R ₇
Represents a lower alkyl group having 1 to 6 carbon atoms, R
R ₈ and R ₉ are lower alkyl groups having 1 to 6 carbon atoms and may have a substituent selected from the groups enumerated as the substituents of R ₁ and R _{2 in} the general formula (I). Good. Particularly preferred substituents are F, carboxy, hydroxy,
Sulfonato, lower alkoxy (eg methoxy, ethoxy), aryloxy (eg 1-naphthoxy, 2-naphthoxy) and the like can be mentioned.

Specific examples of the compounds represented by formula (I) of the present invention are shown below, but the scope of the present invention is not limited to these.

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical formula 12]

[0029]

[Chemical 13]

The compound represented by formula (I) of the present invention can be synthesized by referring to a known synthesis method. For example, U.S. Pat. No. 4,975,362 discloses a method for synthesizing a tricarbocyanine having a benzothiazole nucleus having a methylthio group, Research Disclosure No. 173.
63, 173, September 1978, a method for synthesizing a carbocyanine having a methylthio group and a dicarbocyanine is disclosed. Next, the method for synthesizing the compound represented by formula (I) of the present invention will be described with reference to specific examples. Synthesis Example Synthesis of compound I-2 1-aminonaphthalene 7 g, sodium thiocyanate 2
0 g and 250 ml of methanol were mixed, and 6.5 g of bromine was added dropwise over 15 minutes while stirring with ice cooling. Then, after stirring at room temperature for 1 hour, the resulting precipitate was collected by filtration,
Wash with methanol, water, and then methanol for 12.4
g of 2-amino-8-thiocyano-naphtho [1,2-
d] thiazole was obtained. Water 10.3 g of this compound
5 ml, ethanol 150 ml, 50% aqueous sodium hydroxide solution 46 ml and sodium tetrahydroborate 1.8
5 g was added, and the mixture was heated under reflux under a nitrogen stream for 10 hours. After cooling to room temperature, 14 g of methyl iodide was added and stirred for 30 minutes. The reaction solution was extracted with chloroform, and the tar-like substance obtained by distilling the solvent was dissolved by adding anhydrous acid and heating on a steam bath for 15 minutes to solidify. 100 ml of ethyl acetate was added to this, and the precipitate was collected by filtration and washed with ethyl acetate to obtain 4.8 g of gray needle crystals of 1-acetamide-.
2,4-bismethylthionaphthalene was obtained. To 4 g of this compound, 4 ml of acetonitrile and 10 ml of phosphorus oxychloride were added, and the mixture was heated and stirred on a steam bath for 1 hour. After adding 50 ml of acetone, the precipitate was collected by filtration and 100 ml of methanol
And 8.5 ml of triethylamine were added and dissolved. The mixture was concentrated under reduced pressure, 150 ml of water was added, and the resulting crystals were collected by filtration and dried to obtain 2.6 g of 2-methyl-8-methylthionaphtho [1,2-d] thiazole as off-white needle crystals. 2.45 g of this crystal was mixed with ethyl paratoluenesulfonate 2.
4g was added and it stirred at 150 degreeC for 3 hours. Acetone 100
The resulting crystals were collected by filtration to obtain 2.15 g of 3-ethyl-2-methyl-8-methylthionaphtho [1,2-d] thiazolium paratoluenesulfonate. To 0.9 g of this crystal was added 7.7 ml of 1,1,3,3-tetraethoxy-2-methylpropane, 13 ml of acetic anhydride, and 2.8 ml of acetic acid, and the mixture was heated on a steam bath for 15 minutes and then cooled with ice. After adding 75 ml of ethyl acetate, the resulting crystals were collected by filtration and 0.46 g of 2- (4-ethoxy-3-methyl-).
1,3-Butadiene-1-yl) -3-ethyl-8-methylthionaphtho [1,2-d] thiazolium paratoluenesulfonate was obtained. Add 20 ml of ethanol to this.
37 g of 3-ethyl-2-methyl-8-methylthionaphtho [1,2-d] thiazolium paratoluenesulfonate and 0.13 ml of triethylamine were added, and the mixture was heated and stirred on a steam bath for 15 minutes. The precipitated green precipitate was collected by filtration, dissolved by heating in 300 ml of chloroform and 300 ml of ethanol, and the solvent was distilled off under reduced pressure to precipitate crystals again. The crystals were collected by filtration and washed with ethanol to obtain 50 mg of compound I-2 crystals. Melting point 198-200 [deg.] C. λmax (CH ₃ OH) = 704nm

The silver halide emulsion that can be used in the present invention is
It may contain any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. The silver halide grain may have a regular crystal such as a cube, an octahedron, a tetrahedron, and a rhodohedron, or an irregular crystal such as a sphere or a plate. It may have a shape or a composite of these crystal shapes. It may consist of a mixture of particles of various crystal forms.
The plate-like particles have a thickness of 0.5 μm or less,
The diameter is preferably 0.3 micron or less, and the diameter is preferably 0.
Tabular grains having a grain size of 6 microns or more and having an average aspect ratio of 5 or more occupy 50% or more of the total projected area are preferable. The silver halide grains may have different phases in the inside and the surface layer, or may be composed of a uniform phase. Further, it may be a grain in which a latent image is mainly formed on the surface (for example, a negative emulsion) or a grain in which a latent image is mainly formed inside the grain (for example, an internal latent image type emulsion).
Core / shell types are also used. The preferred silver halide emulsions in the present invention are described in detail below. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate.
Those having a regular) crystal form, or those having a composite form thereof can be used. It may also be a mixture of those having various crystal forms.
The silver chlorobromide emulsion used in the present invention is a Chimie by P. Glafkides.
et Phisique Photographique (published by Paul Montel, 19
67), by GF Duffin Photographic Emulsion Chemi
stry (Focal Press, 1966), VL Zelikman e
t al Making and Coating Photographic Emulsion (Foc
al Press, 1964) and the like. That is, any method such as an acidic method, a neutral method, or ammonia may be used, and as a method of reacting the soluble silver salt and the soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof is used. May be. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or Group VIII elements iron, ruthenium,
Examples thereof include salts or complex salts of rhodium, palladium, osmium, iridium, platinum and the like. Particularly, the above Group VIII elements can be preferably used. The addition amount of these compounds is wide depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol with respect to the silver halide. The silver halide emulsion used in the present invention is usually chemically and spectrally sensitized. Regarding the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. To the silver halide emulsion used in the present invention, various compounds or precursors thereof are added for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. be able to. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of 15272 Publication are preferably used.

The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface. When a semiconductor laser is used as a light source for digital exposure in the present invention, it is necessary to efficiently spectrally sensitize the infrared region. Since infrared sensitization uses sensitization of the sensitizing dye in the M band, the spectral sensitivity distribution is generally broader than that in the J band. Therefore, it is preferable to provide a coloring layer containing a dye in the colloid layer on the photosensitive surface side of the predetermined photosensitive layer to correct the spectral sensitivity distribution. This colored layer is effective in preventing color mixing due to the filter effect. To incorporate the spectral sensitizing dyes in the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methylcellosolve, 2,2,3,3-. It may be added to the emulsion by dissolving it in a solvent such as tetrafluoropropanol alone or in a mixed solvent. In addition, Japanese Examined Patent Publication No. 44-23389,
As described in JP-B-44-27555 and JP-B-57-22089, an acid or a base is allowed to coexist to form an aqueous solution, or US Pat. No. 3,822,135 and US Pat.
As described in No. 25, etc., an aqueous solution or colloidal dispersion in which a surfactant coexists may be added to the emulsion. Alternatively, the emulsion may be dissolved in a solvent which is substantially immiscible with water such as phenoxyethanol and then dispersed in water or a hydrophilic colloid to add to the emulsion. JP-A-53-1
No. 02733 and JP-A No. 58-105141, the dispersion may be directly dispersed in a hydrophilic colloid and the dispersion may be added to the emulsion. The timing of addition to the emulsion is
It may be at any stage in the preparation of emulsions heretofore known to be useful. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before the application, but is described in US Pat. No. 3,628,896.
JP-A-58-113928 discloses that the distribution sensitization is performed at the same time as the chemical sensitizer by adding the chemical sensitizer at the same time as described in JP-A No. 9225/1992 and No. 4225666. As described above, the chemical sensitization can be carried out prior to the chemical sensitization, and the spectral sensitization can be started by adding the silver halide grains before the completion of precipitation. Furthermore, US Patent No. 4
It is also possible to add the spectral sensitizing dyes separately as taught in US Pat. No. 225,666, ie to add some prior to chemical sensitization and the rest after chemical sensitization. It can be at any time during the formation of the silver halide grains, including the method taught in Japanese Patent No. 4183756. Of these, it is particularly preferable to add a sensitizing dye before the emulsion washing step or before chemical sensitization. The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 × 10 ⁻⁶ mol to 1.0 × per mol of silver halide.
A range of 10 ^-2 mol is preferred. More preferably, 1.0
It is in the range of × 10 ^-6 mol to 5.0 × 10 ^-3 mol. Compounds described in JP-A-2-157749, page 13, lower right column, line 3 to page 22, lower right column, lower line 3 from red to infrared sensitization in the present invention are particularly useful for M-band type sensitization. Supersensitization by is effective.

In the light-sensitive material according to the present invention, a hydrophilic colloid layer is used for the purpose of improving the sharpness of an image and the like, and it is described in EP No. 0,337,490A2, Nos. 27-37.
A dye that can be decolorized by treatment (among others, an oxonol dye) described on page 76 is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, and a water-resistant resin for a support is added. 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a dihydric or tetrahydric alcohol (eg, trimethylolethane) in the layer
It is preferably contained.

Colloidal silver and dyes are used in the light-sensitive material of the present invention for preventing irradiation and halation, particularly for separating the spectral sensitivity distribution of each light-sensitive layer and ensuring safety against safe light.

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler. Further, the light-sensitive material according to the present invention contains a fungicide such as that described in JP-A-63-271247 in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferable to add it. The support used in the light-sensitive material according to the present invention may be a white polyester-based support for a display or a support provided with a layer containing a white pigment on the support having a silver halide emulsion layer. You may use. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light. The exposed light-sensitive material may be subjected to conventional black-and-white or color development processing, but in the case of a color light-sensitive material, it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering.
Further, as the cyan coupler, in addition to the diphenylimidazole type cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine type cyan coupler described in European Patent EP 0,333,085A2 Described in JP-A-64-32260, and a 4-equivalent coupler of the coupler (42) enumerated above as a 4-equivalent coupler having a chlorine-releasing group to make it 2-equivalent, and couplers (6) and (9) are particularly preferable). It is also preferable to use cyclic active methylene cyan couplers (among others, coupler examples 3, 8, and 34 listed as specific examples are particularly preferable). The processing temperature of the color developer applicable to the present invention is 2
The temperature is 0 to 50 ° C, preferably 30 to 45 ° C. The processing time is preferably substantially 20 seconds or less. It is preferable that the replenishment amount is small, but ^{20 to} 600 per 1 m ^{2 of} light-sensitive material
ml is suitable, preferably 50 to 300 ml. More preferably 60-200 ml, most preferably 60-15
It is 0 ml. In the present invention, the development time is preferably substantially 20 seconds or less, but the term "substantially 20" as used herein.
"Second" refers to the time from when the photosensitive material enters the developer tank until the photosensitive material enters the next tank, and it also includes the transit time in the air from the developer tank to the next tank. .. The pH of the washing step or the stabilizing step is preferably 4 to 10, more preferably 5 to 8. Although the temperature can be set variously depending on the use and characteristics of the light-sensitive material, it is generally 30 to 45 ° C, preferably 35 to 42 ° C. The time can be set arbitrarily,
Shorter is preferable from the viewpoint of reduction of processing time. It is preferably 10 to 45 seconds, more preferably 10 to 40 seconds.
The smaller the replenishment amount, the lower the running cost and the emission amount.
It is preferable from the viewpoint of handleability. A specific preferable amount of replenishment is 0.5 to 50 times, preferably 2 to 15 times the amount carried from the prebath per unit area of the light-sensitive material. Alternatively, it is 300 ml or less, preferably 150 ml or less per 1 m ^{2 of the} light-sensitive material. The replenishment may be performed continuously or intermittently. The liquid used in the washing and / or stabilizing step can be further used in the previous step. An example of this is that the overflow of washing water reduced by the multi-stage countercurrent method is caused to flow into the bleach-fixing bath of the preceding bath, and the bleach-fixing bath is replenished with a concentrated liquid to reduce the amount of waste liquid. Next, the drying process that can be used in the present invention will be described. A drying time of 20 to 40 seconds is desired in order to complete an image by the ultra-rapid processing of the present invention. As a means for shortening the drying time, as a means on the side of the light-sensitive material, it is possible to improve by reducing the amount of water taken into the film by reducing the amount of a hydrophilic binder such as gelatin. Further, from the viewpoint of reducing the carry-in amount, it is also possible to accelerate the drying by absorbing the water with a squeeze roller or a cloth immediately after leaving the washing bath. As a means of improvement from the dryer, as a matter of course, it is possible to accelerate the drying by increasing the temperature or increasing the drying air. Further, the drying can be accelerated by adjusting the blowing angle of the drying air to the light-sensitive material or by removing the exhausted air.

[0036]

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited to these. Example 1 Preparation of Emulsion Emulsion A: 0.13 M silver nitrate aqueous solution and a halogen salt aqueous solution containing 0.04 M potassium bromide and 0.09 M sodium chloride were added to sodium chloride and 1,8-dihydroxy-3,6. Nucleation by adding to a gelatin aqueous solution containing dithiaoctane by stirring with a double jet method at 45 ° C. for 12 minutes to obtain silver chlorobromide grains having an average grain size of 0.15 μm and a silver chloride content of 70 mol%. Was done. Then, similarly, an aqueous solution of a halogen salt containing 0.87M silver nitrate aqueous solution, 0.26M potassium bromide and 0.65M sodium chloride is similarly prepared by the double jet method.
Added over 20 minutes. After that, it was washed with water by the flocculation method according to a conventional method, 40 g of gelatin was added, and
Adjust to H6.5 and pAg7.5, and add 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per 1 mol of silver,
The mixture was heated at 0 ° C. for 75 minutes for chemical sensitization, and 150 mg of 1,3,3a, 7-tetrazaindene was added as a stabilizer. The obtained particles have an average particle size of 0.28 μm,
It was a silver chlorobromide cubic grain having a silver chloride content of 70 mol%.
(Variation coefficient 10%). Emulsion B: Sodium chloride and 1,8
An average grain size of 0.28 μm, silver chloride was prepared in the same manner as in Emulsion A except that 10 mg of the compound a contained in the general formula [II-a] was further added to an aqueous gelatin solution containing -dihydroxy-3,6-dithiaoctane. Cubic silver chlorobromide grains having a content of 70 mol% were obtained. (Variation coefficient 10%)

Preparation of Coated Sample To 1 kg of the above emulsion, 60 ml of a 0.05% solution of the sensitizing dye shown in Table 1 was added to perform sensitization in the infrared region. In order to supersensitize and stabilize this emulsion, 4,4'-bis- (4,4
70 ml of a 0.5% methanol solution of 6-dinaphthoxy-pyrimidin-2-ylamino) -stilbene disulfonic acid disodium salt and 90 ml of a 0.5% methanol solution of 2,5-dimethyl-3-allyl-benzothiazole iodo salt.
Was added. Further hydroquinone 100 mg / m ^2, silver 3 polyethyl acrylate latex as a plasticizer gelatin binder ratio of 25% of 2-bis (vinylsulfonyl acetamide) ethane as a hardening agent 86.2 mg / m ² were added on a polyester support It was applied so as to be 0.7 g / m ² . The gelatin was 2.5 g / m ² . 0.6 g / m ² of gelatin, 60 mg / m ^{2 of} polymethylmethacrylate having a particle size of 3 to 4 μ as a matting agent, a particle size of 10 to 20 mμ
70 mg / m ² of colloidal silica, silicone oil 10
mg / m ² was added, and dodecylbenzene sulfonic acid sodium salt as a coating aid and a fluorine-containing surfactant having the following structural formula were added to the protective layer upper layer and gelatin 0.7 g /
m ² , polyethyl acrylate latex 225 mg / m ² ,
20 mg / m ² of the dye represented by
0 mg / m ² and the lower layer of the protective layer to which sodium dodecylbenzene sulfonate was added as a coating aid were simultaneously coated,
A sample was prepared.

[0038]

[Chemical 14]

[0039]

[Chemical 15]

[0040]

[Chemical 16]

The base used in this example has a back layer and a back protective layer having the following compositions. (Back layer,
Has a swelling ratio of 110%. ) (Back layer) Gelatin 3.0 g / m ² Sodium dodecylbenzene sulfonate 80 mg Dye a 80 mg 〃 b 30 mg 〃 c 100 mg 1,3-divinylsulfonyl-2-propanol 60 mg / m ² Polyvinyl-benzenesulfonate 30 g / m ² (back protective layer) gelatin 0.75 g / m ² polymethyl methacrylate (particle size 4.7μ) 30mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² fluorine-based surfactant (the compound) 2 mg / m ² silicone Oil 100mg / m ²

[0042]

[Chemical 17]

[0043]

[Chemical 18]

[0044]

[Chemical 19]

Developer formulation water 720 ml ethylenediaminetetraacetic acid disodium salt 4 g sodium hydroxide 44 g sodium sulfite 45 g 2-methylimidazole 2 g sodium carbonate 26.4 g boric acid 1.6 g potassium bromide 1 g hydroquinone 20 g diethylene glycol 39 g 5-methyl-benzo Triazole 0.2 g Pyrazone 0.7 g Water added 1 liter Fixer formulation Ammonium thiosulfate 170 g Sodium sulfite (anhydrous) 15 g Nitric acid 7 g Glacial acetic acid 15 ml Potassium alum 20 g Ethylenediaminetetraacetic acid 0.1 g Tartaric acid 3.5 g Water added 1 liter

Evaluation of Photographic Performance The obtained sample was subjected to an emission time of 1 through an interference filter having a peak at 750 nm or 830 nm and a continuous wedge.
0 ^-6 exposed with a xenon flash light of sec using a developer and fixer having the following composition, manufactured by Fuji Photo Film Co., Ltd. automatic developing machine FG-360F (washing tank capacity 6l) at 38 ° C. 2
0 ″ development, fixing, washing with water, drying, and sensitometry were performed. Sensitivity was defined as the reciprocal of the exposure dose giving a density of 3.0.
The relative sensitivity is shown in Table 1. The characteristic curve shows a concentration of 0.1
Similarly, the gradient of the straight line connecting the points
Shown in the table. Each sample is placed in a pressurized atmosphere of 50 kg / m ² at 50 ° C.
After leaving it to stand for 7 days, the same photographic property evaluation as above was carried out. The results are shown in Table 1. As is clear from Table 1,
It can be seen that the sample containing the compound represented by the general formula (I) of the present invention has higher sensitivity and less fluctuation in sensitivity during storage than the sample containing the compound of similar structure known in the related art. ..

[0047]

[Table 1]

[0048]

[Chemical 20]

[0049]

[Chemical 21]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 13, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

[0029]

[Chemical 13]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

The compound represented by formula (I) of the present invention can be synthesized by referring to a known synthesis method. For example, U.S. Pat. No. 4,975,362 discloses a method for synthesizing tricarbocyanine having a benzothiazole nucleus having a methylthio group, which is disclosed in Research Disclosure.
ure) magazine No. 17363, Volume 173, September 1978 discloses a method for synthesizing a carbocyanine having a methylthio group and dicarbocyanine. Next, the method for synthesizing the compound represented by formula (I) of the present invention will be described with reference to specific examples. Synthesis Example Synthesis of compound I-2 1-aminonaphthalene 7 g, sodium thiocyanate 2
0 g and 250 ml of methanol were mixed, and 6.5 g of bromine was added dropwise over 15 minutes while stirring with ice cooling.
Then, after stirring at room temperature for 1 hour, the resulting precipitate was collected by filtration, washed with methanol, water, and then with methanol,
2.4 g of 2-amino-8-thiocyano-naphtho [1,
2-d] thiazole was obtained. 55 ml of water, 150 ml of ethanol, 46 ml of 50% aqueous sodium hydroxide solution and 1.85 g of sodium tetrahydroborate were added to 10.3 g of this compound, and the mixture was heated under reflux for 10 hours under a nitrogen stream. After cooling to room temperature, 14 g of methyl iodide was added and stirred for 30 minutes. The reaction solution was extracted with chloroform, and the tar-like substance obtained by distilling the solvent off was dissolved by adding anhydrous acid and was heated on a steam bath for 15 minutes to solidify. 100 ml of ethyl acetate was added to this, and the precipitate was collected by filtration.
It was washed with ethyl acetate to obtain 1-acetamido-2,4-bismethylthionaphthalene as gray needle crystals of 4.8 g. To 4 g of this compound, 4 ml of acetonitrile and 10 ml of phosphorus oxychloride were added, and the mixture was heated and stirred on a steam bath for 1 hour. After adding 50 ml of acetone, the precipitate was collected by filtration, 100 ml of methanol and 8.5 m of triethylamine.
1 was added and dissolved. The mixture was concentrated under reduced pressure, 150 ml of water was added, and the resulting crystals were collected by filtration and dried to give 2.6 g of 2-methyl-8-methylthionaphtho [1,2] as off-white needle crystals.
-D] thiazole was obtained. To 2.45 g of this crystal was added 2.4 g of ethyl paratoluenesulfonate, and the mixture was mixed at 150 ° C. for 3 days.
Stir for hours. Acetone (100 ml) was added and the resulting crystals were collected by filtration to obtain 2.15 g of 3-ethyl-2-methyl-8-methylthionaphtho [1,2-d] thiazolium paratoluenesulfonate. 0.9g of this crystal has 1,1,
3,3-Tetraethoxy-2-methylpropane 7.7m
1, 13 ml of acetic anhydride, and 2.8 ml of acetic acid were added, and the mixture was heated on a steam bath for 15 minutes and then ice-cooled. After adding 75 ml of ethyl acetate, the resulting crystals were collected by filtration to give 0.46
g of 2- (4-ethoxy-3-methyl-1,3-butadiene-1-yl) -3-ethyl-8-methylthionaphtho [1,2-d] thiazolium paratoluenesulfonate was obtained. Add 20 ml of ethanol and 0.37 g of 3-
Ethyl-2-methyl-8-methylthionaphtho [1,2-
d] Add thiazolium paratoluene sulfonate and 0.13 ml of triethylamine, and add 1 on a steam bath.
The mixture was heated and stirred for 5 minutes. The precipitated green precipitate was collected by filtration, dissolved by heating in 300 ml of chloroform and 300 ml of ethanol, and the solvent was distilled off under reduced pressure to precipitate crystals again. The crystals were collected by filtration, washed with ethanol and then 50 mg of compound I-
Two crystals were obtained. Melting point 198-200 [deg.] C. λmax (CH ₃ OH) =
704 nm

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

The silver halide emulsion that can be used in the present invention is
It may contain any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. The silver halide grain may have a regular crystal such as a cube, an octahedron, a tetrahedron, and a rhombohedron, and may have an irregular shape such as a sphere or a plate.
Lar) crystal form or a composite form of these crystal forms. It may consist of a mixture of particles of various crystal forms. The plate-like grains have a thickness of 0.5 μm or less, preferably 0.3 μm or less, and a circle-equivalent diameter of preferably 0.6 μm or more, and have an aspect ratio (circle-equivalent diameter of silver halide grains). A tabular grain in which grains having a thickness of 5 or more occupy 50% (area) or more of all silver halide grains is preferable. The silver halide grains may have different phases in the inside and the surface layer, or may be composed of a uniform phase. Further, it may be a grain in which a latent image is mainly formed on the surface (for example, a negative emulsion) or a grain in which a latent image is mainly formed inside the grain (for example, an internal latent image type emulsion). Core / shell types are also used. The preferred silver halide emulsions in the present invention are described in detail below. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate.
It is possible to use those having a (gular) crystal form or those having a composite form thereof. It may also be a mixture of those having various crystal forms. The silver chlorobromide emulsion used in the present invention is described in P. Glafki
des by Chimieet Phisique P
photographique (Paul Montel
Publisher, 1967), G.I. F. By Duffin Pho
tographic Emulsion Chemis
try (Focal Press, 1966),
V. L. Zelikman et a1 Makin
g and Coating Photographic
Emulsion (FocalPress, 19
64) and the like. That is, any method such as an acidic method, a neutral method, or ammonia may be used, and as a method of reacting the soluble silver salt and the soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof is used. May be. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or
Examples thereof include salts or complex salts of Group III elements such as iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. In particular, the above Group VIII element can be preferably used. The addition amount of these compounds varies over a wide range depending on the purpose, but is preferably 10 ⁻⁹ to 10 ⁻² mol with respect to the silver halide. The silver halide emulsion used in the present invention is usually chemically and spectrally sensitized. Regarding the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. To the silver halide emulsion used in the present invention, various compounds or precursors thereof are added for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. be able to. Specific examples of these compounds are described in the above-mentioned JP-A-62-21527.
Those described on pages 39 to 72 of the specification of Japanese Patent Publication No. 2 are preferably used.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing a compound represented by the following general formula (I). General formula (I): In the formula, L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L ₇ ,
L ₈ and L ₉ each represent a methine group; Z ₁ is —S
Naphthothiazole, naphthoxazole, naphthimidazole, which may be substituted with R _{3, and} which may further have other substituents, represents an atomic group for completing a naphthoselenazole nucleus; Z ₂ is 5- or 6-membered of represents a group of atoms to complete a heterocyclic ring; R _1, R _2, independently of one another, represent an alkyl or aryl group; R ₃ represents an alkyl group having 1 to 18 carbon atoms; m ₁ is 1 Represents an integer of ₁ to 6; n ₁ and n ₂ are 0 or 1 respectively.
X represents a counter ion.