JPH06317879A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photosensitive material for laser exposure suitable for rapid development with which high-quality picture images can be obtd. CONSTITUTION:This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer sensitized to show the sensitizing max. in longer wavelength than 600nm. The emulsion layer or other hydrophilic colloid layers contain solid dispersion of at least one kind of dye expressed by general formula D-(X)y. In formula, D is a compd. having chromophore, X is a dissociative proton or a group having dissociative proton connected directly to D or connected with a bivalent connecting group, and (y) is an integer 1-7.

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 spectrally sensitized to a wavelength longer than 600 nm, and particularly to a hard-sensitive light-sensitive material suitable for helium neon laser and semiconductor laser exposure. Regarding things.

[0002]

2. Description of the Related Art Generally, in a silver halide photographic light-sensitive material, for the purpose of adjusting sensitivity, improving safety of safelight, adjusting light color temperature, preventing halation, or adjusting sensitivity balance in a multilayer color light-sensitive material. It has been conventionally practiced to incorporate a light absorbing compound into a silver halide emulsion layer or other hydrophilic colloid layer in order to absorb light having a specific wavelength.

Particularly when the colored layer is a filter layer,
Alternatively, in the case of an antihalation layer which is placed on the same side of the support as the photographic emulsion layer, it is preferable that those layers are selectively colored so that the other layers are not substantially colored. Often needed. This is because otherwise, not only the detrimental spectroscopic effect is exerted on other layers, but also the effect as a filter layer or an antihalation layer is diminished. However, when the dye-added layer and other hydrophilic colloid layers come into contact with each other in a wet state,
It often happens that some of the dye diffuses from the former to the latter. Many efforts have been made to prevent the diffusion of such dyes.

As another means for keeping a dye in a specific layer in a photographic light-sensitive material, JP-A-56-12639 (USP43).
11787), No. 55-155350, No. 55-15.
No. 5351, No. 52-92716 (USP40921)
68), 63-197943 (USP485744).
6), 63-27838 (EP201190), 64-40827 (USP48555221), JP-A-2-110453 (USP4988611), and 2-.
277045, European Patent 0015601B1
No. 0276566A1, International Application Publication 88/04
It has been proposed to have the dye present as a dispersed solid as disclosed in 794.

Further, a method of dyeing a specific layer by using metal salt fine particles having a dye adsorbed thereon is disclosed in US Pat. No. 2,719,
088, 2,496,841 and 2,496,8
No. 43, JP-A No. 60-45237 and the like.

On the other hand, one of the exposure methods for photographic light-sensitive materials is
A so-called scanner method has been widely used in which an original image is scanned and a silver halide photographic light-sensitive material is exposed based on the image signal to form a negative image or a positive image corresponding to the original image. It was He-
Ne lasers and semiconductor lasers are becoming more important as light sources. In recent years, there has been a strong demand in the printing industry for work efficiency and speedup, and there is a widespread need for speeding up scanning and shortening the processing time of photosensitive materials. The characteristics required of photosensitive materials to meet such needs are that they have sufficient sensitivity in the long wavelength region in high-illuminance exposure and have high contrast.
In addition, it is desired that it has rapid processing suitability and high safety in safelight, but there has been no silver halide photographic light-sensitive material capable of sufficiently satisfying both image quality and rapid processing suitability.

In order to shorten the development time of the photographic light-sensitive material as described above, it is effective to improve the drying property of the silver halide photographic light-sensitive material to shorten the drying time. One of the means for improving the drying property is to reduce the amount of hydrophilic colloid in silver halide photographic light-sensitive material, especially the amount of gelatin coating, but if the total amount of gelatin in the light-sensitive layer is simply reduced, the mechanical strength of the light-sensitive material decreases. However, problems such as abrasion blackening and generation of roller marks occur. On the other hand, in order to obtain a clear image and enhance the safety of the safelight, the method of using the dye in a solid dispersion state is an effective means, but it prevents halation and irradiation of long wavelength light. As a dye that can be fixed in a specific layer, a material having excellent storage stability has not been found.

[0008]

Therefore, the present invention is
Provided is a silver halide photographic light-sensitive material which solves these problems, is suitable for rapid development processing, and is suitable for long-wavelength exposure, in particular, for semiconductor laser and He-Ne laser exposure, capable of obtaining a high-quality image. Especially.

[0009]

[Wherein D represents a compound having a chromophore, X represents a dissociative proton bonded to D directly or through a divalent linking group or a group having a dissociative proton, and y is 1 to 1
Represents an integer of 7. ]

In the light-sensitive material of the present invention, the light-sensitive layer contains 60 mol% of silver chloride.
It is preferable that the total amount of gelatin contained on the side where the photosensitive layer is provided with respect to the support is 3 g / m ² or less. Further, as the dye to be used, those having good dispersibility and high covering power are particularly preferable. The specific configuration of the present invention will be described below.

First, the solid dispersion of the dye used in the present invention will be described. The dye used in the present invention is represented by the following general formula (F). General formula (F) D- (X) y [In formula, D represents the compound which has a chromophore, X has a dissociative proton couple | bonded with D directly or through the bivalent coupling group or a dissociative proton. Represents a group, and y is 1 to
Represents an integer of 7. The compound having a chromophore represented by D can be selected from many known dye compounds. Examples of these compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, anthraquinone dyes and indoaniline dyes.

The dissociative proton represented by X or the group having a dissociative proton is non-dissociated when the compound represented by the general formula (F) is added to the silver halide photographic light-sensitive material of the present invention. It has a property of making the compound of the general formula (F) substantially water-insoluble, and has a property of making the compound of the general formula (F) substantially water-soluble by dissociating in the process of developing the material. Examples of these groups include a carboxylic acid group, a sulfonamide group, an arylsulfamoyl group, a sulfonylcarbamoyl group, a carbonylsulfamoyl group, an enol group of an oxonol dye, and a phenolic hydroxyl group.

As the solid fine particle dispersion of the dye that can be used in the present invention, any dispersion can be used, but one having absorption in the near infrared region is preferable. Maximum absorption wavelength is 600 nm or more and 1200 nm or less, more preferably 65
Those in the range of 0 nm to 1000 nm are preferable. Various solid fine particle dispersions are known. For example, JP-A-2-173630 and JP-A-2-173630.
No. 230135, No. 2-277044, No. 2-282
No. 244, No. 3-7931, No. 3-13937, No. 3-206443, No. 3-208047, No. 3-1.
92157, 3-216645, 3-2740.
No. 43, No. 4-37841, No. 4-45436, No. 4-138449, etc. can be mentioned. As preferred compounds, the compounds represented by the following general formula can be given.

[0013]

[Chemical 2]

[Wherein T ¹⁰ , T ¹¹ and T ¹² are independently of each other a hydrogen atom, a halogen atom, cyano, nitro, carboxy, alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, Represents sulfamoyl, carbamoyl, amino, sulfonamide, carbonamide, ureido, sulfamide, hydroxy, vinyl or acyl, and R ¹³ and R ¹⁴ independently of each other are hydrogen atom, halogen atom, alkoxy, alkyl, alkenyl, aryloxy or aryl. And R ¹⁵ and R ^{16 each} independently represent a hydrogen atom or a group capable of substituting it, R ¹⁷ and R ¹⁸
Are, independently of one another, alkyl, aryl, vinyl, acyl, or alkyl or arylsulfonyl. However, T ¹¹ and T ¹² , R ¹³ and R ¹⁵ , R ¹⁴ and R ¹⁶ , R ¹⁷
And R ¹⁸ , R ¹⁵ and R ¹⁷ , and R ¹⁶ and R ¹⁸ may be linked to each other to form a ring. ] General formula (II)

[0015]

[Chemical 3]

[Wherein R ²¹ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ²² represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, COR ²⁴ or SO ₂ R
Represents ^24, R ₂₃ is a hydrogen atom, a cyano group, a hydroxyl group, a carboxylic acid group, an alkyl group, an aryl group, COOR ^24, OR
²⁴ , NR ²⁵ R ²⁶ , CONR ²⁵ R ²⁶ , NR ²⁵ COR ²⁴ , N
R ²⁵ SO ₂ R ²⁴ or NR ²⁵ CONR ²⁵ R ²⁶ (where R
²⁴ represents an alkyl group or an aryl group, and R ²⁵ and R ²⁶ represent a hydrogen atom, an alkyl group or an aryl group. ), L ²¹ , L ²² , and L ²³ each represent a methine group, and n ²¹
Represents 1 or 2. ] General formula (III)

[0017]

[Chemical 4]

In the formula, R ³¹ and R ³² each represent an alkyl group, an alkenyl group or an aryl group, R ³³ and R ³⁴ each represent a hydrogen atom or a monovalent group, and Z ³¹ and Z ³² each represent 5 or Represents a nonmetallic atom group necessary for forming a 6-membered nitrogen-containing heterocycle, L ³¹ represents a linking group formed by linking 5 or 7 methine groups by a conjugated double bond, and X ⁻ represents an anion. Represents an ion, and p ³¹ and p ³² each represent 0 or 1. General formula (IV)

[0019]

[Chemical 5]

[In the formula, X ⁴¹ and X ⁴² are a hydrogen atom, a hydroxyl group, a carboxy group, -COOR ⁴¹ , -COR ⁴¹ , -CO, respectively.
NH _2, -CONR ⁴¹ R ^42, an alkyl group, an aryl group or a heterocyclic group, Y ^41, Y ⁴² represent each a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, Z ^41,
Z ⁴² is a hydrogen atom, —CN, a carboxy group, or —COO.
_{^{R 43, -COR 43, -CONH 2}} , -CONR 43 R 44,
It represents —NHCOR ⁴³ , —NHSO ₂ R ⁴³ , —SO ₂ R ⁴³ , an alkyl group, an aryl group or a heterocyclic group. R ⁴¹ ,
R ⁴³ represents an alkyl group or an aryl group,
R ⁴² and R ⁴⁴ each represent a hydrogen atom, an alkyl group or an aryl group. L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ and L ⁴⁵ each represent a methine group, and m ⁴¹ and n ⁴¹ each represent an integer such that the sum thereof is 2. ] General formula (V)

[0021]

[Chemical 6]

In the formula, R ⁵¹ and R ⁵² represent an alkyl group, an alkenyl group or an aryl group, L ⁵¹ represents a connecting group formed by connecting 5 or 7 methine groups by a conjugated double bond, and Z ⁵¹ Represents an atomic group for completing the aromatic ring, and X ⁻ represents an anion. General formula (VI)

[0023]

[Chemical 7]

(In the formula, R ⁶¹ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ are each a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group or a carboxyl group. Group, a hydroxyl group, an amino group, L ⁶¹ , L ⁶² , L ⁶³ , L ⁶⁴ , and L ⁶⁵ each represent a methine group, and m ⁶¹ and n ⁶¹ each represent an integer such that the sum thereof is 2.) (VII)

[0025]

[Chemical 8]

In the formula, L ⁷¹ is a nitrogen atom, or 3 or 7
Represents a group formed by linking optionally substituted methine groups with a conjugated double bond, and E is O, S, NR ⁷⁹
R ⁷⁰ and R ^{79 each} independently represent a hydrogen atom, an alkyl group,
Alkenyl group, alkynyl group, aryl group, heterocyclic group,
Represents an amino group, a hydrazino group, or a diazenyl group;
R ⁷¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, or a heterocyclic group; R ⁷² represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group,
Carboxyl group, alkyl group, aryl group, alkenyl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, acyloxy group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, Represents an alkylsulfonyl group, an arylsulfonyl group, or an alkynyl group; R ⁷⁰ and R ⁷⁹ may ^combine with each other to form a ring; R ⁷³ and R ⁷⁴ independently of each other, a hydrogen atom, a halogen atom, an alkoxy group A group, an alkyl group, an alkenyl group, an aryloxy group or an aryl group, R ⁷⁵ ,
R ⁷⁶ independently represents a hydrogen atom or a group capable of substituting it, and R ⁷⁷ and R ⁷⁸ independently represent an alkyl group, an aryl group, a vinyl group, an acyl group, or an alkyl or arylsulfonyl group. However, R ⁷³ and R ⁷⁵ , R ⁷⁴
And R ⁷⁶ , R ⁷⁷ and R ⁷⁸ , R ⁷⁵ and R ⁷⁷ , and R ⁷⁶ and R ⁷⁸ may combine with each other to form a ring. General formula (VIII)

[0027]

[Chemical 9]

[Wherein L ⁸¹ represents a nitrogen atom, or a group formed by linking 3 or 7 optionally substituted methine groups with a conjugated double bond, and X ⁸¹ represents a hydrogen atom, a hydroxyl group, COOR ⁸⁷ , CONR ⁸⁷ R ⁸⁸ , an alkyl group, an aryl group, Y represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, NR ⁸⁷ R ⁸⁸ , Z ⁸¹ represents a hydrogen atom,
Alkyl group, aryl group, cyano group, COOR ⁸⁹ , CO
NR ⁸⁷ R ⁸⁸ , COR ⁸⁹ , SO ₂ R ⁸⁹ , NR ⁸⁸ COR ⁸⁹ ,
Represents a nitro group and a pyridine group, R ⁸¹ , R ⁸² , R ⁸³ , R
⁸⁴ is a hydrogen atom, an alkyl group, OR ⁸⁹ , NR ⁸⁹ COR
⁸⁷ , COOR ⁸⁹ , CONR ⁸⁷ R ⁸⁸ , and a halogen atom, R ⁸⁵ and R ⁸⁶ each represent a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group, and R ⁸⁷ , R ⁸⁸ , and R ⁸⁹ each represent a hydrogen atom. Represents an alkyl group, an aryl group, or a heterocyclic group, provided that R ⁸¹ and R ⁸² , R ⁸⁵ and R ⁸⁶ , R ⁸² and R ⁸⁵ , R ⁸³ and R ⁸⁶ , R ⁸⁷ and R ⁸⁸ are each independently linked. To form a 5- or 6-membered ring. ] General formula (IX)

[0029]

[Chemical 10]

[0030] ^{(wherein, R 91, R 92, R} 93 represents a hydrogen atom, an alkyl group or an aryl group,, Q ₁ is .L ⁹¹ that represents an atomic group necessary for forming a basic heterocycle, L ⁹² ,
L ⁹³ , L ⁹⁴ , L ⁹⁵ and L ⁹⁶ each represent a methine group. p ⁹¹ ,
m ⁹¹ and n ⁹¹ represent 0 or 1, and p ⁹¹ + m ⁹¹ + n ⁹¹ is an integer of 2 or more. However, the compound represented by the general formula (IX) has at least one carboxyl group, sulfonic acid arylamide group, or phenolic hydroxyl group in the molecule. The dye represented by formula (Fa) described in European Patent No. 0524598A1 is also a preferable compound because it has good dispersibility and high covering power.

[0031]

[Chemical 11]

Examples of specific compounds capable of forming the preferred solid fine particle dispersion are given below, but the present invention is not limited thereto.

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

[0036]

[Chemical 15]

[0037]

[Chemical 16]

[0038]

[Chemical 17]

[0039]

[Chemical 18]

[0040]

[Chemical 19]

[0041]

[Chemical 20]

[0042]

[Chemical 21]

[0043]

[Chemical formula 22]

[0044]

[Chemical formula 23]

[0045]

[Chemical formula 24]

[0046]

[Chemical 25]

[0047]

[Chemical formula 26]

[0048]

[Chemical 27]

[0049]

[Chemical 28]

[0050]

[Chemical 29]

[0051]

[Chemical 30]

[0052]

[Chemical 31]

[0053]

[Chemical 32]

[0054]

[Chemical 33]

[0055]

[Chemical 34]

[0056]

[Chemical 35]

Regarding the synthesis of these compounds, the above-mentioned published patent publications (JP-A-2-173630 and JP-A-2-23630).
No. 0135, No. 2-277044, No. 2-28224
No. 4, No. 3-7931, No. 3-13937, No. 3-
206443, 3-208047, 3-192
No. 157, No. 3-216645, No. 3-274043.
No. 4, No. 4-37841, No. 4-45436, No. 4-
(No. 138449, etc.) for easy synthesis.

The dyes represented by the general formulas (I) to (IX) are
Methods known to those skilled in the art, such as the condensation reaction of the corresponding ketomethylene compound and the 3-formylmalin compound in the presence of an acid or base (in some cases in the presence of an acid and a base), "The Cyanine Dyes and Related Compound
s ", F. Hamer, Interscience Publishers, 1964
(The cyanine soybean and rewound compounds, F, Harmer, Interscience Publishers, 1964) can be used for the synthesis. The solid fine particle dispersion of the dye according to the present invention can be used in any of the emulsion layer and other hydrophilic colloid layers, and may be used in a single layer or a plurality of layers.

The solid fine particle dispersion of the dye according to the present invention comprises
Known grinding methods in the presence of a dispersant (for example, ball mill, vibrating ball mill, planetary ball mill, sand mill,
It can be formed by a colloid mill, a jet mill, or a roller mill, and in that case, a solvent (for example, water or alcohol) may coexist. Further, after dissolving the dye of the present invention in a suitable solvent, a poor solvent for the dye of the present invention may be added to precipitate a fine crystal powder, in which case a surfactant for dispersion is used. Good. Alternatively, it may be dissolved by controlling the pH, and then the pH may be changed to perform microcrystallization. The microcrystalline particles of the dye of the present invention in the dispersion have an average particle size of 10 μm or less, preferably 1 μm or less, more preferably 0.5 μm or less,
In some cases, it is preferably 0.1 μm or less.

The solid fine particle dispersion of the dye of the present invention, when added to the light-sensitive emulsion layer, is 0.5 mg / m ^{2 to} 100 mg /
m ^2, preferably when the ^{1mg / m 2 ~50mg / m 2} , is added to the other ^{layers, 1mg / m 2 ~500mg / m} 2, is preferably from 5mg / m ² ~300mg / m ² .

The silver halide photographic emulsion according to the present invention may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide and silver iodobromide as the silver halide. Among them, those having a silver chloride content of 70 mol% are preferable. The silver iodide content is 5
It is preferably not more than 2 mol%, more preferably not more than 2 mol%. The shape of silver halide grains is cubic, tetradecahedral, octahedral,
Either an irregular shape or a plate shape may be used, but a cubic or plate shape is preferable. The average grain size of the silver halide grains is 0.01 μm
1 μm is preferable, but 0.4 μm or less is more preferable, and {(standard variation of particle size) / (average particle size)} × 100.
The coefficient of variation represented by 15% or less, more preferably 1
A narrow particle size distribution of 0% or less is preferable. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have different phases.

The photographic emulsion used in the present invention is P. Glafki.
des by Chimie et Physique Photographique (Paul Mont
e Company, 1967), Photographic by GF Duffin
Emulsion Chemistry (The Focal Press, 1966
,) By VL Zelikman et al Making and Coating Ph
otographic Emulsion (Published by The Focal Press, 1964
, Etc.) and the like. That is, any of the acidic method, the neutral method, the ammonia method, etc. may be used, and as the formation of reacting the soluble silver salt and the soluble halogen salt, any one-side mixing method, simultaneous mixing method, a combination thereof, etc. may be used. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. A method of keeping pAg constant in a liquid phase in which silver halide is produced, as one form of the simultaneous mixing method,
That is, the so-called controlled double jet method can also 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 order to make the particle size uniform,
British Patent 1,535,016, Japanese Patent Publication No. 48-3689
As described in No. 0 and No. 52-16364,
A method of changing the addition rate of silver nitrate or an alkali halide according to the grain growth rate, and British Patent 4,242,44
As described in JP-A-55-158124 and JP-A-55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow it quickly within a range not exceeding the critical saturation. The grain formation of the silver halide emulsion of the present invention is preferably carried out in the presence of a silver halide solvent such as a tetra-substituted thiourea or an organic thioether compound. A preferred tetra-substituted thiourea silver halide solvent used in the present invention is disclosed in JP-A-5-58.
3-82408, 55-77737 and the like.

The organic thioether silver halide solvent preferably used in the present invention is, for example, JP-B-47-11386.
No. (U.S. Pat. No. 3,574,628) compounds comprising at least one of the recited oxygen atom and a sulfur atom groups optionally separated by ethylene (e.g. -O-CH ₂ CH ₂ -S-) in such, JP JP-A-54-155828 (U.S. Pat. No. 4,276,374) describes that both ends have an alkyl group (each alkyl group is at least 2 selected from hydroxy, amino, carboxy, amido or sulfone).
It is a chain thioether compound having one substituent).

The amount of the silver halide solvent added varies depending on the kind of the compound used, the intended grain size, the halogen composition, etc., but is 10 ^-5 to 1 mol per mol of the silver halide.
10 ^-2 mol is preferred. If the grain size becomes larger than intended by using a silver halide solvent, the temperature during grain formation,
A desired particle size can be obtained by changing the addition time of the silver salt solution or the halogen salt solution.

The silver halide used in the present invention preferably contains 10 ⁻⁵ mol or less of an iridium compound per mol of silver halide. As the iridium compound used in the present invention, a water-soluble iridium compound can be used. For example, an iridium (III) halide compound,
Also, iridium (IV) halide compounds, or iridium complex salts having halogens, amines, oxalates, etc. as ligands, such as hexachloroiridium (III) or (IV) complex salts, hexaammineiridium (III) or (IV) Complex salts, trioxalatoiridium (III) or (IV) complex salts and the like can be mentioned. In the present invention, any of these compounds may be used in any combination of a trivalent compound and a trivalent compound. These iridium compounds are used by dissolving them in water or a suitable solvent, and a method commonly used for stabilizing the solution of the iridium compound, that is, an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) , Or alkali halide (eg KCl, NaCl, KBr, NaBr, etc.)
Can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide grain. The total addition amount of the iridium compound according to the present invention is appropriately 1 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, and preferably 5 × 10 ⁻⁸ to 1 per 1 mol of finally formed silver halide. × 10 ⁻⁶ mol. The addition of these compounds can be appropriately carried out at the time of producing the silver halide emulsion and at each stage before coating the emulsion, but in particular, it can be added at the time of grain formation and incorporated into the silver halide grains. preferable. Specific compounds include iridium (III) chloride, first bromide
Iridium (III), secondary iridium chloride (IV), sodium hexachloroiridium (III), hexachloroiridium (III) salt, hexaammineiridium (IV)
Preference is given to halogen amines such as salts, trioxalatoiridium (III) salts, trioxalatoiridium (IV) salts, and oxalato complex salts.

The silver halide used in the present invention may contain an iron compound, a rhenium compound, a ruthenium compound and an osmium compound. The iron compound is a divalent or trivalent iron ion-containing compound, and is preferably an iron salt or iron complex salt having water solubility in the concentration range used in the present invention. Specifically, ferrous arsenate ferrous bromide ferrous carbonate ferrous chloride ferrous citrate ferrous fluoride ferrous formate ferrous gluconate ferrous hydroxide iodide ferrate Ferrous emulsion Ferrous ferrous ferrous oxalate ferrous succinate ferrous sulphate ferrous sulphate ferrous thiocyanate ferrous nitrate ammonium ferrous nitrate basic ferric acetate ferric albumate Ferric acetate ammonium ferric bromide ferric chloride ferric chloride ferric citrate ferric fluoride ferric formate glycerophosphate ferric hydroxide ferric hydroxide acidic phosphate ferric Ferric nitrate ferric nitrate ferric phosphate ferric pyrophosphate sodium ferric pyrophosphate ferric thiocyanate ferric sulfate ferric ammonium sulfate ferric sulfate guanidine ferric ammonium citrate hexane cyanoferrate (II) Potassium bentacyanoammine ferrous potassium Chirenjinitoriro tetraacetate sodium ferric potassium hexacyanoferrate (III) chloride tris (dipyridyl) ferric preventor cyano nitrosyl ferric potassium chloride Hekisarea ferric particularly hexacyanoferrate (II), hexacyanoferrate (III)
Acid salts, ferrous thiocyanate and ferric thiocyanate show remarkable effects.

The rhenium, ruthenium and osmium compounds used in the present invention are European Published Patent (EP) 0
336689A, 0336427A1, 033
The hexadentate coordination complexes described in Nos. 6425A1 and 0336426A1 are preferable, and those containing at least 4 or more cyanide ligands are particularly preferable. In a preferred embodiment, these compounds can be represented by the formula: [M (Cn) _6-y L _y ] ⁿ Here, M is rhenium, ruthenium or osmium, L is a bridging ligand, and y is an integer 0, 1, or 2
And n is -2, -3 or -4. Specific examples include [Re (CN) ₅ ] ^-4 [Ru (CN)
₅ ] ^-4 [Os (CN) ₅ ] ^-4 [ReF (C
N) ₅ ] ^-4 [RuF (CN) ₅ ] ^-4 [OsF (C
N) ₅ ] ^-4 [ReCl (CN) ₅ ] ^-4 [RuCl (C
N) ₅ ] ^-4 [OsCl (CN) ₅ ] ^-4 [ReBr (C
N) ₅ ] ^-4 [RuBr (CN) ₅ ] ^-4 [OsBr (C
N) ₅ ] ^-4 [ReI (CN) ₅ ] ^-4 [RuI (C
N) ₅ ] ^-4 [OsI (CN) ₅ ] ^-4 [ReF ₂ (C
N) ₄ ] ^-4 [RuF ₂ (CN) ₅ ] ^-4 [OsF ₂ (C
N) ₅ ] ^-4 [ReCl ₂ (CN) ₄ ] ^-4 [RuCl
₂ (CN) ₄ ] ^-4 [OsCl ₂ (CN) ₄ ] ^-4 [RuBr
₂ (CN) ₄ ] ^-4 [OsBr ₂ (CN) ₄ ] ^-4 [ReBr
₂ (CN) ₄ ] ^-4 [RuI ₂ (CN) ₄ ] ^-4 [OsI ₂ (C
N) ₅ ] ^-4 [Ru (CN) ₅ (OCN)] ^-4 [Os (CN)
₅ (OCN)] ^-4 [Ru (CN) ₅ (SCN)] ^-4 [Os (CN)
₅ (SCN)] ^-4 [Ru (CN) ₅ (N ₃ )] ^-4 [Os (CN)
₅ (N ₃ )] ^-4 [Ru (CN) ₅ (H ₂ O)] ^-3 [Os (CN)
₅ (H ₃ O)] ^-3 .

The above iron, rhenium, ruthenium and osmium compounds are preferably added during the formation of silver halide grains. The addition position may be evenly distributed in the particles, or may be localized in the early, middle, and late stages of particle formation.
It is preferred to add after 0%, more preferably 80% is formed. The addition amount is 10 ^-3 mol or less per 1 mol of silver, and preferably 10 ^-6 to 10 ^-4 mol. In the present invention, other metals contained in Group VIII, that is, cobalt, nickel, rhodium, palladium, platinum and the like may be used in combination. In particular, the combined use with a rhodium salt such as rhodium chloride or ammonium hexachlorodium (III) is advantageous because a high contrast emulsion can be obtained.

The photosensitive silver halide emulsion of the present invention is spectrally sensitized with a sensitizing dye to red light or infrared light having a sensitization maximum of 600 nm or more. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holoholer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used. Useful sensitizing dyes used in the present invention are, for example, RES
EARCH DISCLOSURE Item 17643 IV-A (197)
December 8 p. 23) Item 1831X of the same item (1979)
August p. 437) or cited therein. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. In particular, L spectrally sensitized to 750 to 850 nm
When used as a light-sensitive material for an ED or a semiconductor laser, a light source for an LED light source is Japanese Patent Publication No.
51-9609, 55-39818, and JP-A-6-6
JP-A-59-191 discloses thiacarbocyanines and semiconductor laser light sources described in JP-A-2-284343.
No. 032, the tricarbocyanines described in JP-A-60-80841, and the dicarbocyanines containing a 4-quinoline nucleus described in JP-A-59-192242 are advantageously selected. The amount used is not particularly limited, but good spectral sensitization is achieved in the range of 1 mg to 100 mg per mol of silver halide.

There are no particular restrictions on the various additives and the like used in the photographic light-sensitive material of the present invention, and for example, those described in the following relevant parts can be used.

Item This section 1) Silver halide emulsion and JP-A-2-68539, page 8, lower right column, bottom 6 from its manufacturing line to page 10, upper right column, line 12, 3 No. 24537, page 2, lower right column, line 10 to page 6, upper right column, line 1; page 10, upper left column, line 16 to page 11 lower left column, line 19; Japanese Patent Application No. 2-225637. JP-A-2-97937, page 20, lower right column, line 12 to page 21, lower left column, line 14 and JP-A 2-1 2236, page 7, upper right column, line 19 to page 8, lower left column 12th line, Japanese Patent Application No. 3-116573, Japanese Patent Application No. 3-103318, page 6, line 10 to page 31. 2) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. The selenium sensitization method described in Japanese Patent Application No. 3-189532. 3) Antifoggants and Stabilizers JP-A-2-68539, page 10, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column . JP-A-2-103526, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5; and JP-A-1-237538. Thiosulfinic acid compounds. 4) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, left lower column, line 20; JP-A-3-94 249, page 6, lower left column, line 15 to Page 11, right upper column, line 19

5) Spectral sensitizing dye JP-B-46-10473, page 1, right column, line 18 to page 2, left column, line 24, page 2 right column, line 23 to page 6, left column, line 22. U.S. Pat. No. 3,482,978, column 2, line 22 to column 4, line 59. U.S. Pat. No. 3,623,881, second column, line 35 to seventh column, line 53. JP-A-59-191032, page 3, upper right column, line 8 to page 3, lower left column, line 9. From page 12, lower right column, line 12 to page 7, upper column, last line. JP-A-60-80841, page 4, lower right column, line 18 to page 12, lower right column, line 6. JP-A-1-97947, page 4, upper left column, line 1 to page 4, upper right column, line 11. Page 4, lower right column, line 11 to page 8, upper right column, line 6 From page 10, lower left column, line 9 to page 11, lower left column, line 2. 6) Supersensitizer JP-A-59-192242, page 10, lower left column, line 19 to page 12, lower left column, line 15. JP-A-60-80841, page 13, upper right column, line 10 to page 16, upper left column, line 1 7) Surfactant JP-A-2-68539, page 11, upper left column, line 14 Antistatic agent to page 12, upper left column, line 9 JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 to page 4, lower right column, line 18 . 8) Matting agent, slipping agent JP-A-2-68539, page 12, upper left column, line 10 to upper right column, line 10; page 14, lower left column, line 10 to lower right column, line 1. JP-A-2-103526, page 19, upper left column, line 15 to page 19, upper right column, line 15 9) Hydrophilic colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 10) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 JP-A-2-103526, page 18, upper right column, line 5 to line 17.

11) Dyes JP-A-63-49752, page 18, lower left column, line 4 to page 19, upper left column, line 2 12) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 13) Polyhydroxy JP-A-3-39948, page 11, upper left column to the same benzenes, page 12, lower left column, EP Patent No. 452772A. JP-A-2-55349, page 11, upper left column, line 9 to lower right column, line 17 thereof. 14) Polymer latex JP-A-2-103526, page 18, lower left column, lines 12 to 20. 15) Compounds having an acid group JP-A-2-103526, page 18, lower right column, line 6 to page 19, upper left column, line 1 and JP-A-2-55349, page 8, lower right column, line 13 From the same page, page 11, left upper column, line 8.

16) Hydrazine Nucleating Agent JP-A-2-12236, page 2, upper right column, line 19 to page 7, upper right column, line 3, line 3-1741 43, page 20, lower right column Compounds of general formula (II) and compound examples II-1 to II-54, from line 1 to page 27, right upper column, line 20. 17) Nucleation accelerators JP-A-2-103526, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formulas (II-m) to (II-p) and compound examples II- 1 to II-22, compounds described in JP-A-1-179939.

18) Black Potting Agent Compounds described in US Pat. No. 4,956,257 and JP-A-1-118832. 19) Redox compounds Compounds represented by the general formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), and compounds described in JP-A No. 3-174143, pages 3 to 20 Formulas (R-1), (R-2), (R-3), Compound Examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 20) Monomethine compound Compounds of the general formula (II) described in JP-A-2-287532 (compound examples II-1 to II-26). 21) Layer structure JP-A-3-198041. 22) Development processing method JP-A-2-103037, page 16, upper right column, line 7 to page 19, lower left column, line 15 and JP-A-2-115837, page 3, lower right column, line 5 Page 6, upper right column, line 10 JP-A-2-55349, page 13, lower right column, line 1 to page 16, upper left column, line 10

[0077]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto. Example 1 (Preparation of emulsion A) A 0.13 M silver nitrate aqueous solution and 0.0
(NH ₄ ) ₃ RhCl ₆ and K ₃ IrCl ₆ were added to an aqueous solution of a halogen salt containing 33M potassium bromide and 0.11M sodium chloride to contain sodium chloride and 1,3-dimethylimidazolidine-2-thione. Nucleation was carried out by adding to the gelatin aqueous solution described above with stirring by a double jet method at 43 ° C. for 12 minutes to obtain silver chlorobromide grains having an average grain size of 0.15 μm and a silver chloride content of 75 mol%. Subsequently, similarly, a 0.87 M silver nitrate aqueous solution, a halogen salt aqueous solution containing 0.22 M potassium bromide and 0.69 M sodium chloride were added over 20 minutes by the double jet method. After that, it was washed with water by the flocculation method according to a conventional method, 40 g of gelatin was added, and the pH was 6.5, pAg.
Adjusted to 7.5, and further added 19 mg of sodium benzenethiosulfonate, 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per 1 mol of silver, heated at 60 ° C. for 75 minutes, chemically sensitized, and added as a stabilizer. -Hydroxy-6-
Methyl-1,3,3a, 7-tetraazaindene 150
mg was added. The particles obtained have an average size of 0.25μ.
m, 75 mol% silver chloride content, per mol of silver Rh compound 1 × 10 ^-7 mol, Ir compound 5 × 10 ^-7 mol to obtain the content to silver chlorobromide cubic grains (coefficient of variation 10%).

Preparation of Dye Dispersion 2.5 g of dye, surfactant (trade name: Demol SNB,
Kao Corporation's 10% aqueous solution 4.4 g and water 56.
4g is mixed by stirring beforehand and the diameter is 0.8mm-1.2mm
Was placed in an Eiger motor mill (M-50, manufactured by Eiger Japan) containing 40 cc of zirconia beads, and dispersed at a rotation speed of 4500 rpm to obtain a fine crystal dispersion of a dye having a particle size of 1 μm or less. 50 g of the obtained crystal dispersion of dye, 1.8 g of gelatin and 13.3 g of water were added to 4
The mixture was stirred and mixed at 0 ° C. and used for preparation of the photographic light-sensitive material of the present invention.

(Preparation of photographic light-sensitive materials 1 to 7) Emulsion layer coating solution To emulsion A, a 0.2% methanol solution of sensitizing dye-1 shown below was added at 80 mg per mol of silver. Further, for supersensitization and stabilization, 4,4-bis (4,6-dinaphthoxypyrimidin-2-ylamino) -stilbene disulfonic acid disodium salt and 2,5-dimethyl-3-allylbenzothiazole are used. Iodine salt is 10 for each mole of silver.
0 mg and 150 mg were added.

[0080]

[Chemical 36]

Dye layer Gelatin 0.5 g / m ² Dye type and amount are listed in Table 1 Sodium dodecylbenzene sulfonate 20 mg / m ² Sodium polystyrene sulfonate 46 mg / m ² 2-Bis (vinylsulfonylacetamide) ethane 34 mg / m ²

Emulsion layer Gelatin 1.6 g / m ² Coating amount of silver 3.4 g / m ² Hydroquinone 0.1 g / m ² Polyethylene acrylate latex 0.5 g / m ² 2-Bis (vinylsulfonylacetamide) ethane 86 mg / m ²

Protective layer Gelatin 0.7 g / m ² Polymethylmethacrylate having a particle size of 2.5 μm 60 mg / m ² Colloidal silica having a particle size of 10 μm 75 mg / m ² Sodium dodecylbenzene sulfonate 40 mg / m ²

Photosensitive materials 1 to 7 were prepared by simultaneously coating multiple layers in the order of the dye layer, the emulsion layer and the protective layer (from the side of the support) on the support in the above coating amount.

The base used in this example has a back layer and a back protective layer having the following compositions. [Back layer] Gelatin 2.1 g / m ² Sodium dodecylbenzene sulfonate 80 mg / m ² 1,3-divinylsulfone-2-propanol 60 mg / m ² [Back protective layer] Gelatin 0.5 g / m ² Particle size 4. 7 μm polymethylmethacrylate 30 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² fluorine-containing surfactant 3 mg / m ² silicone oil 90 mg / m ²

For comparison, a sample was prepared in which the following water-soluble dyes were added to the dye layer in the amounts shown in Table 1 in place of the solid dispersion of the dye of the present invention. (Comparison 1-a to 1-b)

[0087]

[Chemical 37]

Further, a sample having the following constitution was prepared. (Sample 1-c) Dye layer: gelatin 0.8 g / m ² other than Example 1 same as sample 1 Emulsion layer: same as example 1 Protective layer: gelatin 0.8 g / m ² except example 1 same as sample 1

Evaluation of Photographic Performance The obtained sample was exposed to xenon flash light having an emission time of 10 ⁻⁶ sec through an interference filter having a peak at 633 nm and a continuous wedge, and was exposed to light from Fuji Photo Film Co., Ltd.
Using an automatic processor FG-710NH manufactured by KK, sensitometry was performed at the temperature and time shown below.

Current image 38 ° C. 14 sec 9 sec Settling 37 ° C. 9.7 sec 6.2 sec Water wash 26 ° C. 9 sec 5.8 sec Squeeze 2.4 sec 1.5 sec Dry 55 ° C. 8.3 sec 5.3 seconds Total 43.4 seconds 27.8 seconds The composition of the developing solution and fixing solution used is as follows. [Developer formulation] Hydroquinone 25.0 g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.5 g potassium sulfite 90.0 g ethylenediaminetetraacetic acid disodium 2.0 g potassium bromide 5.0 g 5-methyl Benzotriazole 0.2 g 2-Mercaptobenzimidazole-5-sulfonic acid 0.3 g Sodium carbonate 20 g Water added 1 liter (Add sodium hydroxide to adjust pH = 10.6) [Fixer formulation] Ammonium thiosulfate 210 g Sodium sulfite (anhydrous) 20 g Ethylenediaminetetraacetic acid disodium 0.1 g Glacial acetic acid 15 g Water was added to 1 liter (adjusted to pH = 4.8 with ammonia water).

The logarithm of the exposure dose giving a density of 1.5 is taken as the sensitivity, and the relative sensitivity is shown in Table 1.

Safelight Safety evaluation The surface of the photographic photosensitive material is shielded from light by half and the filter No. 4LD is used.
Through a (manufactured by Fuji Photo Film Co., Ltd.) exposure was carried out for 1 minute with a tungsten lamp light of 10 W from a distance of 66 cm from the emulsion surface of the light-sensitive material, and development and fixing were carried out by the same method as in evaluation of photographic performance. The case where there was no difference in density between the unexposed portion and the exposed portion of the obtained sample was judged to have good safelight safety, and is shown by "O" in Table 1. When there was a difference in density between the unexposed portion and the exposed portion, it was judged that the safety of safelight was poor, and it was shown as "x" in Table 1.

[Evaluation of Dryability] In an atmosphere of 25 ° C. and 55% RH, using an FG-460A automatic processor (manufactured by Fuji Photo Film Co., Ltd.) at a drying temperature of 50 ° C., the line speed was changed. Samples of large size (50 cm × 61 cm) were subjected to development processing by changing the drying time, and the shortest drying time at which the sample immediately after the processing was completely dried was determined.

[Evaluation of Wet Film Strength] After immersing the sample in distilled water at 25 ° C. for 5 minutes, the sample film surface was pressed with a sapphire needle having a radius of 0.4 mm and moved at a speed of 10 mm / sec. While the load of the needle was continuously changed, the load (g) when the film was broken was measured. The measurement was performed twice, and the average value was used as the wet film strength value.

[0095]

[Table 1]

From the above results, Samples 1 to 7 of the present invention
And 1-c have high sensitivity to long-wavelength exposure and are excellent in safelight safety.
Shows that a silver halide photographic light-sensitive material having a high drying speed and a high mechanical strength can be obtained.

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[Procedure amendment]

[Submission date] August 24, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

[0009]

The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer which has been sensitized at a maximum wavelength of 600 nm. Achieved by using a silver halide photographic light-sensitive material characterized in that the emulsion layer or other hydrophilic colloid layer contains a solid dispersion of at least one dye represented by formula (F). Was done. (F) D- (X) y [In the formula, D represents a compound having a chromophore, and X represents a dissociative proton bonded to D directly or via a divalent linking group or a group having a dissociative proton. Where y is 1 to
Represents an integer of 7. In the light-sensitive material of the present invention, the light-sensitive layer contains 70 mol% of silver chloride.
It is preferable that the total amount of gelatin contained on the side where the photosensitive layer is provided with respect to the support is 3 g / m ² or less. Further, as the dye to be used, those having good dispersibility and high covering power are particularly preferable. The specific configuration of the present invention will be described below.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction content]

Current image 38 ° C. 14 sec 9 sec Settling 37 ° C. 9.7 sec 6.2 sec Water wash 26 ° C. 9 sec 5.8 sec Squeeze 2.4 sec 1.5 sec Dry 55 ° C. 8.3 sec 5.3 seconds Total 43.4 seconds 27.8 seconds The composition of the developing solution and fixing solution used is as follows. [Developer formulation] Hydroquinone 25.0 g 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.5 g potassium sulfite 90.0 g diethylenetriaminepentaacetic acid 2.0 g potassium bromide 5.0 g 5-methylbenzotriazole 0.2 g 2-Mercaptobenzimidazole-5-sulfonic acid 0.3 g Sodium carbonate 20 g Water added 1 liter (Add sodium hydroxide to adjust pH = 10.6) [Fixer formulation] Ammonium thiosulfate 210 g Sodium sulfite (Anhydrous) 20 g Diethylenetriaminepentaacetic acid 0.1 g Glacial acetic acid 15 g Water was added to 1 liter (adjusted to pH = 4.8 with ammonia water)

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0095

[Correction method] Change

[Correction content]

[0095]

[Table 1]

Claims (3)

[Claims] 1. A photosensitive silver halide emulsion layer having at least one sensitization maximum wavelength-sensitized to a wavelength longer than 600 nm, wherein the emulsion layer or another hydrophilic colloid layer has the general formula (F). A silver halide photographic light-sensitive material comprising a solid dispersion of at least one dye represented by (F) D- (X) y [In the formula, D represents a compound having a chromophore, and X represents a dissociative proton bonded to D directly or via a divalent linking group or a group having a dissociative proton. Where y is 1 to
Represents an integer of 7. ] 2. The emulsion layer contains 70 mol% or more of silver chloride, and the total amount of gelatin on the side where the emulsion layer is provided with respect to the support is 3 g / m ² or less. 1. The silver halide photographic light-sensitive material described in 1. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the dye is represented by the following general formula (Fa). [Chemical 1]