JPH06102624A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material adapted to laser beam exposure and high in safety to safelight. CONSTITUTION:This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer on a support and it is characterized by having a hydrophilic colloidal layer (a first dye layer) containing a fine crystal dispersion of at least one kind of compound formed on the outside of the photosensitive emulsion layer on the support, and another hydrophilic colloidal layer (the second dye layer) containing a fine crystal dispersion of at least one kind of compound having a maximum spectral absorption wavelength in 600-1200nm formed between the support and the photosensitive emulsion layer.

Description

Detailed Description of the Invention

[0001]

The present invention is suitable for laser exposure,
The present invention relates to a silver halide photographic light-sensitive material having high safety.

[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. When it is necessary to control the spectral composition of light to be incident on the photosensitive emulsion layer, a coloring layer is usually provided on the side farther from the support than the photosensitive emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of light-sensitive emulsion layers, the filter layer may be located between them. Light scattered during or after passing through the light-sensitive emulsion layer is reflected at the interface between the emulsion layer and the support or at the surface of the light-sensitive material on the side opposite to the emulsion layer and re-enters the light-sensitive emulsion layer. For the purpose of preventing blurring or halation of the image based on
A colored layer called an antihalation layer is provided between the photosensitive emulsion layer and the support or on the surface of the support opposite to the photosensitive emulsion layer. When there are a plurality of photosensitive emulsion layers, an antihalation layer may be placed in the middle of those layers. In order to prevent deterioration of image sharpness (this phenomenon is generally called irradiation) due to light scattering in the light-sensitive emulsion layer, the light-sensitive emulsion layer is also colored.

Such colored layers often consist of hydrophilic colloids and are therefore usually used for their coloring.
A water-soluble dye is contained in the layer. This dye is required to satisfy the following conditions. (1) It has appropriate spectral absorption according to the purpose of use. (2) Photochemically inert. That is, it should not adversely affect the performance of the silver halide photographic emulsion layer, for example, lowering of sensitivity, lowering of image density, lowering of contrast, fog or latent image regression. (3) In the course of photographic processing, it should not be decolorized or dissolved and removed to leave harmful coloring on the photographic light-sensitive material after processing. (4) Do not diffuse from the dyed layer to other layers. (5) It has excellent stability over time in a solution or in a photographic light-sensitive material, and should not discolor. In particular, when the coloring layer is a filter layer or an antihalation layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are colored. Often need to be substantially below. 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, wet contact between the dyed layer and other hydrophilic colloid layers often causes some of the dye to diffuse from the former to the latter. Many efforts have been made to prevent the diffusion of such dyes. For example, a method in which a hydrophilic polymer having a charge opposite to that of a dissociated anionic dye is allowed to coexist in a layer as a mordant and the dye is localized in a specific layer by interaction with a dye molecule is disclosed in US Pat. No. 564, No. 4,124,386, No. 3,625,694 and the like.

Further, as another means for keeping a dye in a specific layer in a photographic light-sensitive material, JP-A-56-12639 (USP).
431787), ibid. 55-155350, ibid. 55-.
No. 155351, No. 52-92716 (USP409)
2168), and 63-197943 (USP4857).
No. 63-27838 (EP20119).
0), No. 64-40827 (USP485522).
1), JP-A-2-110453 (USP498861)
1), No. 2-277045, European Patent 0015.
It has been proposed to have the dye present as a dispersed solid as disclosed in 601 B1, 0276566 A1 and WO 88/04794.

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
There is known an image forming method by a so-called scanner method in which an original image is scanned, and a silver halide photographic light-sensitive material is exposed on the basis of the image signal to form a negative image or a positive image corresponding to the image of the original image. There are various types of recording apparatuses that use the scanner-type image forming method, and conventionally, a glow lamp, a xenon lamp, a mercury lamp, a tungsten lamp, a light emitting diode, or the like has been used as a recording light source of these scanner-type recording apparatuses. However, each of these light sources has a practical drawback that the output is small and the life is short. When a coherent laser light source such as He-Ne, Ar, or He-Cd laser is used to compensate for these drawbacks, high output can be obtained, but the device becomes large. It is expensive. A modulator is needed. Since visible light is used, the safelight of the light-sensitive material is limited and the handleability is poor. On the other hand, a semiconductor laser is small and inexpensive, and can be easily modulated, and has a longer life than the above laser and emits light in the infrared region. Therefore, when a photosensitive material having photosensitivity in the infrared region is used,
Since a bright safelight can be used, there is an advantage that handling workability is improved. However, if the semiconductor laser is used as it is without shaping the laser beam, the energy distribution is broad and it is difficult to obtain a good halftone dot image or line image. Further, 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 infrared region at high illuminance exposure, high contrast, fast development progress, rapid processing suitability, and safe light safety. It is desired that the property is high.

[0007]

A water-soluble dye is generally used in the photographic light-sensitive material as described above, and a light-sensitive emulsion layer is used for a support using a water-soluble dye which has been conventionally used. A photographic light-sensitive material having a hydrophilic colloid layer (first dye layer) provided outside and a hydrophilic colloid layer (second dye layer) provided between the photosensitive emulsion layer and the support was prepared and used. In this case, as described above, the dye diffused to the hydrophilic colloid layer adjacent to the layer to which the dye was added, which had an unfavorable adverse effect on the photographic characteristics. The method of allowing a dye to be present as a dispersed solid in a specific layer, which has been proposed to solve such a problem, is an excellent method for preventing the diffusion of the dye. However, when a photographic light-sensitive material having a first dye layer and a second dye layer containing a previously disclosed specific dye in a dispersed and fixed manner is prepared and used, some dyes are decolorized during rapid development processing. It is observed that the speed is slow, and in some cases, the dye diffuses into the hydrophilic colloid layer adjacent to the layer to which the dye is added, which may have an unfavorable adverse effect on the photographic characteristics, or may cause decomposition in the wet heat state. I knew it was. In particular, when the spectral sensitivity of the photosensitive silver halide emulsion is in the near infrared region, that is, the spectral absorption region of the dye used in the first dye layer is in the visible region and the spectral sensitivity of the dye used in the second dye layer is in the visible region. It was remarkable when the absorption region was in the near infrared region.

(Object of the Invention) An object of the present invention is to provide a photographic light-sensitive material which has high sharpness and high sensitivity and is excellent in handling safety under a safelight.

[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 on a support and having a maximum absorption wavelength in the absorption spectrum. A hydrophilic colloid layer (first dye layer) containing a microcrystalline dispersion of at least one compound in the range of 300 to 750 nm is provided outside the photosensitive emulsion layer with respect to the support, and has an absorption spectrum. Having a hydrophilic colloid layer (second dye layer) containing a microcrystalline dispersion of at least one compound having a maximum absorption wavelength in the range of 600 to 1200 nm outside the photosensitive emulsion layer with respect to the support. This is achieved by using a silver halide photographic light-sensitive material characterized by the following.

The photographic light-sensitive material of the present invention will be described in detail below. The photographic light-sensitive material of the present invention has at least one photosensitive silver halide emulsion layer on a support, and a hydrophilic colloid layer (first dye layer) on the outside of the photosensitive emulsion layer with respect to the support. And a hydrophilic colloid layer (second dye layer) between the support and the photosensitive emulsion layer. The following,
The hydrophilic colloid layer (first dye layer), the hydrophilic colloid layer (second dye layer), and the photosensitive silver halide emulsion layer will be described in this order. The hydrophilic colloid layer (first dye layer) contains a microcrystalline dispersion of at least one compound having a maximum absorption wavelength in the absorption spectrum of 300 to 750 nm. The maximum absorption length in the absorption spectrum is more preferably 30.
It is in the range of 0 to 700 nm. Preferred compounds include microcrystalline dispersions of at least one compound selected from the group consisting of the following general formulas (I) to (V).

[0011]

[Chemical 1]

[In the formula, A and A'may be the same or different and each represents an acidic nucleus, B represents a basic nucleus,
X and Y may be the same or different and each represents an electron-withdrawing group. R represents a hydrogen atom or an alkyl group,
R ₁ and R ₂ each represent an alkyl group, an aryl group, an acyl group or a sulfonyl group, and R ₁ and R ₂ are linked to each other to form 5
Alternatively, a 6-membered ring may be formed. R ₃ and R ₆ each represent a hydrogen atom, an alkyl group, a hydroxy group, a carboxyl group, an alkoxy group or a halogen atom, and R ₄ and R ₅ each represent a hydrogen atom or R ₁ and R ₄ or R ₂ and R ₅ are linked. Represents a non-metal atom group necessary for forming a 5- or 6-membered ring. L ₁ , L ₂ and L ₃ each represent a methine group. m represents 0 or 1, n and q each represent 0, 1 or 2, p represents 0 or 1, and p is 0
In this case, R ₃ represents a hydroxy group or a carboxyl group and R ₄ and R ₅ represent a hydrogen atom. However, the compounds represented by the general formulas (I), (II), (III), (IV) and (V) have a volume ratio of water to ethanol of 1 in one molecule.
It has at least one dissociative group having a pKa in the range of 4 to 11 in the mixed solution of 1: 1. ]

Hereinafter, general formulas (I), (II), (III),
(IV) and (V) will be described in detail. A or A '
The acidic nucleus represented by is preferably 2-pyrazoline-5.
-On, rhodanin, hydantoin, thiohydantoin,
It represents 2,4-oxazolidinedione, isoxazolidinone, barbituric acid, thiobarbituric acid, indandione, pyrazolopyridine or hydroxypyridone. The basic nucleus represented by B is preferably pyridine,
Represents quinoline, indolenine, oxazole, benzoxazole, naphthoxazole or pyrrole. P in a mixed solution of water and ethanol in a volume ratio of 1: 1
A group having a dissociative proton having a Ka (acid dissociation constant) in the range of 4 to 11 makes the dye molecule substantially water-insoluble at pH 6 or pH 6 or less, and substantially water-soluble at pH 8 or pH 8 or more. There is no particular limitation on the type and the substitution position on the dye molecule as long as it is represented by the formula (1), but a carboxyl group, a sulfamoyl group, a sulfonamide group and a hydroxy group are preferable, and a carboxyl group is more preferable. The dissociative group not only substitutes directly for the dye molecule,
It may be substituted via a divalent linking group (for example, an alkylene group or a phenylene group). Examples via a divalent linking group include 4-carboxyphenyl, 2-methyl-3-carboxyphenyl, 2,4-dicarboxyphenyl,
3,5-dicarboxyphenyl, 3-carboxyphenyl, 2,5-dicarboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyphenyl, 2,4,6-trihydroxy Phenyl, 3-benzenesulfonamidophenyl,
4- (p-siamibenzenesulfonamide) phenyl,
3-hydroxyphenyl, 2-hydroxyphenyl, 4
-Hydroxyphenyl, 2-hydroxy-4-carboxyphenyl, 3-methoxy-4-carboxyphenyl,
2-methyl-4-phenylsulfamoylphenyl, 4
-Carboxybenzyl, 2-carboxybenzyl, 3-
Examples thereof include sulfamoylphenyl, 4-sulfamoylphenyl, 2,5-disulfamoylphenyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl and 8-carboxyoctyl.

The alkyl group represented by R, R ₃ or R ₆ is preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isoamyl and n-octyl groups. The alkyl group represented by R ₁ and R ₂ is preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, n-propyl, n-butyl, n-octyl, n-octadecyl, isobutyl, isopropyl) and substituted. Group [for example, halogen atom such as chlorine bromine, nitro group, cyano group, hydroxy group, carboxy group, alkoxy group (for example, methoxy, ethoxy), alkoxycarbonyl group (for example, methoxycarbonyl,
i-propoxycarbonyl), an aryloxy group (for example, a phenoxy group), a phenyl group, an amide group (for example,
Acetylamino, methanesulfonamide), a carbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl), a sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].
The aryl group represented by R ₁ or R ₂ is preferably a phenyl group or a naphthyl group, and has a substituent [as the substituent
_The groups and alkyl groups (for example, methyl and ethyl) listed as the substituents of the alkyl group represented by ₁ and R ₂ are included. ] May be included. The acyl group represented by R ₁ or R ₂ is preferably an acyl group having 2 to 10 carbon atoms, and examples thereof include groups such as acetyl, propionyl, n-octanoyl, n-decanoyl, isobutanoyl and benzoyl. Examples of the alkylsulfonyl group or arylsulfonyl group represented by R ₁ or R ₂ are groups such as methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, o-carboxybenzenesulfonyl and the like. Can be mentioned. The alkoxy group represented by R ₃ or R ₆ is preferably an alkoxy group having 1 to 10 carbon atoms, such as methoxy, ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy,
Examples thereof include groups such as isobutoxy and isopropoxy. Examples of the halogen atom represented by R ₃ or R ₆ include base, bromine and fluorine. R ₁ and R ₄
Alternatively, examples of the ring formed by connecting R ₂ and R ₅ include a julolidine ring. Examples of the 5- or 6-membered ring formed by linking R ₁ and R ₂ include a piperidine ring, a morpholine ring, and a pyrrolidine ring. The methine group represented by L ₁ , L ₂ or L ₃ is
It may have a substituent (for example, methyl, ethyl, cyano, phenyl, chlorine atom, hydroxypropyl).

The electron withdrawing groups represented by X or Y may be the same or different, and are a cyano group, a carboxy group, an alkylcarbonyl group (an optionally substituted alkylcarbonyl group, for example, acetyl, propionyl, heptanoyl). , Dodecanoyl, hexadecanoyl, 1-oxo-
7-chloroheptyl group, etc., an arylcarbonyl group (an optionally substituted arylcarbonyl group, for example, benzoyl, 4-ethoxycarbonylbenzoyl,
3-chlorobenzoyl group and the like, alkoxycarbonyl group (alkoxycarbonyl group which may be substituted, for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyl. Oxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2-
(2-chloroethoxy) ethoxycarbonyl, 2- [2
-(2-chloroethoxy) ethoxy] ethoxycarbonyl group, etc., an aryloxycarbonyl group (an optionally substituted aryloxycarbonyl group, for example, phenoxycarbonyl, 3-ethylphenoxycarbonyl,
4-ethylphenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4
-Methoxyphenoxycarbonyl, 2,4-di- (t-
Amyl) phenoxycarbonyl group, etc.), carbamoyl group (which may be substituted, for example, carbamoyl group, ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl). , 4-ethoxycarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-
Methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4-di- (t-amyl) phenylcarbamoyl, 2-chloro-3- (dodecyloxycarbonyl) phenylcarbamoyl, 3- (hexyloxycarbonyl) phenylcarbamoyl group, etc. ), A sulfonyl group (eg, methylsulfonyl, phenylsulfonyl group, etc.), and a sulfamoyl group (which may be substituted, such as sulfamoyl and methylsulfamoyl group).

The microcrystalline dispersion of the compound in the present invention cannot be present in a molecular state in the intended hydrophilic colloid layer because the solubility of the compound itself is insufficient, and the compound substantially does not exist in the layer. It means the state of existence as a solid of a size that cannot diffuse. Regarding the preparation method, international publication (WO) 88/04794 and European patent publication (E)
P) 0276566A1, JP-A-63-197943, etc., but it is generally stabilized by a surfactant and gelatin. The preparation method in the present invention was based on the method described in JP-A-63-197943.

The particle size of the fine crystal dispersion of the compound used in the present invention is preferably 1.0 μm or less, more preferably 0.5 μm.
m or less is preferable. The amount of the compound used is 5 mg / m ^{2 to} 500 mg / m ² , particularly 10 per hydrophilic colloid layer.
is preferably ^{mg / m 2 ~250mg / m 2} . Next, gelatin is a typical hydrophilic colloid, but any of those conventionally known as those usable for photography can be used. When gelatin is used as the hydrophilic colloid in the hydrophilic colloid layer,
The amount used is preferably 3.0 g / m ² or less per hydrophilic colloid layer, more preferably 0.2 g / m ^{2 to} 1.5.
It is in the range of g / m ² .

The hydrophilic colloid layer (second dye layer) contains a microcrystalline dispersion of at least one compound having a maximum absorption wavelength in the absorption spectrum of 600 to 1200 nm. Preferred compounds include the following general formula (VI)
A microcrystalline dispersion of at least one compound selected from the group consisting of (XIV) can be mentioned.

[0019]

[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. ]

[0021]

[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. ]

[0023]

[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 L ³¹ and L ³² each represent 0 or 1.

[0025]

[Chemical 5]

[In the formula, X ⁴¹ and X ⁴² are a hydrogen atom, a hydroxyl group, a carboxy group, -COOR ⁴¹ , -COR ⁴¹ and -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. ]

[0027]

[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.

[0029]

[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.)

[0031]

[Chemical 8]

In the formula, L ⁷¹ is a nitrogen atom, or 5 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.

[0033]

[Chemical 9]

[In the formula, X ⁸¹ is a hydrogen atom, a hydroxyl group, or COO.
R ⁸⁷ , CONR ⁸⁷ R ⁸⁸ , an alkyl group, and an aryl group, Y represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, and NR ⁸⁷ R ⁸⁸ , and Z ⁸¹ represents a hydrogen atom, an alkyl group, an aryl group, Cyano group, COOR ⁸⁹ , CONR ⁸⁷ R
⁸⁸ , COR ⁸⁹ , SO ₂ R ⁸⁹ , NR ⁸⁸ COR ⁸⁹ , nitro group and pyridinium group, and R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴
Is a hydrogen atom, an alkyl group, OR ⁸⁹ , NR ⁸⁹ CO
R 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 hydrogen. Represents an atom, an alkyl group, an aryl group, or a heterocyclic group,
However, 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 may be independently linked to each other to form a 5- or 6-membered ring. ]

[0035]

[Chemical 10]

(In the formula, R ⁹¹ , R ⁹² , and R ⁹³ represent a hydrogen atom, an alkyl group, or an aryl group, and Q ₁ represents a group of atoms necessary for forming a basic heterocycle. L ⁹¹ , L ⁹² ,
L ⁹³ , L ⁹⁴ , L ⁹⁵ and L ⁹⁶ each represent a methine group. L ⁹¹ ,
m ⁹¹ and n ⁹¹ represent 0 or 1, and L ⁹¹ + m ⁹¹ + n ⁹¹ is an integer of 2 or more. However, the compound represented by the general formula (XIV) has at least one carboxyl group, sulfonic acid arylamide group, or phenolic hydroxyl group in the molecule. )

Next, specific examples of the compounds represented by the general formulas (I) to (V) which can be used in the present invention will be given. However, the present invention is not limited to the following compounds.

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20]

[0048]

[Chemical 21]

[0049]

[Chemical formula 22]

[0050]

[Chemical formula 23]

[0051]

[Chemical formula 24]

[0052]

[Chemical 25]

[0053]

[Chemical formula 26]

[0054]

[Chemical 27]

[0055]

[Chemical 28]

[0056]

[Chemical 29]

[0057]

[Chemical 30]

[0058]

[Chemical 31]

These compounds are available in the international patent WO 88/0.
4794, European Patent EP 0274723A1
No. 276566, No. 299435, JP-A-52.
-92716, 55-155350, 55-1
55351, 61-205934, 48-68.
623, U.S. Pat. Nos. 2,527,583, 34,868.
It can be easily synthesized by the method described in Nos. 97, 3746539, 3933798, 4130429, 4040841, and the like, and methods equivalent thereto.

Specific examples of the compounds represented by the general formulas (VI) to (XIV) which can be used in the present invention are shown below. However, the present invention is not limited to the following compounds.

[0061]

[Chemical 32]

[0062]

[Chemical 33]

[0063]

[Chemical 34]

[0064]

[Chemical 35]

[0065]

[Chemical 36]

[0066]

[Chemical 37]

[0067]

[Chemical 38]

[0068]

[Chemical Formula 39]

[0069]

[Chemical 40]

[0070]

[Chemical 41]

[0071]

[Chemical 42]

[0072]

[Chemical 43]

[0073]

[Chemical 44]

[0074]

[Chemical formula 45]

[0075]

[Chemical formula 46]

[0076]

[Chemical 47]

[0077]

[Chemical 48]

[0078]

[Chemical 49]

[0079]

[Chemical 50]

Regarding the synthesis of these compounds, published patent publications (JP-A-2-173630 and JP-A-2-23013).
5, No. 2-277044, No. 2-282244,
No. 3-7931, No. 3-13937, No. 3-206
No. 443, No. 3-208047, No. 3-192157.
No. 3, No. 3-216645, No. 3-274043, No. 4-37841, No. 4-45436, No. 4-138.
No. 449), and can be easily synthesized.

Microcrystalline dispersions of these compounds can be prepared by the same method as described in the description of the first dye layer. The particle size of the fine crystal dispersion and the amount of the compound used are also the same as those described in the description of the first dye layer. The hydrophilic colloids that can be used in the second dye layer are also the same as those described in the description of the first dye layer. In the present invention, a microcrystalline dispersion of a compound having a maximum absorption wavelength in the absorption spectrum on the shorter wave side than the exposure wavelength is used in the first dye layer, and the maximum absorption wavelength in the absorption spectrum of the above compound is used in the second dye layer. It is common to use a fine crystal dispersion of a compound located on the long-wave side of the maximum absorption wavelength. In the first dye layer and the second dye layer, in addition to the compounds and hydrophilic colloids described above, various additives described below (excluding photosensitive silver halide emulsion) are optionally used. be able to. The silver halide in 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. Among them, those having a silver chloride content of 30 mol% or more, and more preferably 60 mol% are preferable. The silver iodide content is preferably 5 mol% or less, more preferably 2 mol% or less. The shape of the silver halide grains may be cubic, tetradecahedron, octahedron, amorphous or plate-like, but is preferably cubic or plate-like. The average grain size of the silver halide grains is preferably 0.01 μm to 1 μm, more preferably 0.4 μm or less, and the fluctuation represented by {(standard deviation of grain size) / (average grain size)} × 100. Coefficient is less than 15%,
More preferably, it has a narrow particle size distribution of 10% or less. 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
published by el, 1967), by GF Duffin Photographic
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 and the like 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 and the like 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
0, 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 4,242,445.
As described in JP-A No. 55-158124, it is preferable to use the method of changing the concentration of the aqueous solution to grow early in 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. Patent No. 3,574,628) comprising at least one compound group wherein oxygen atom and a sulfur atom are separated by an ethylene (e.g. -O-CH ₂ CH ₂ -S-) in the like, especially Alkyl groups at both ends described in Kai 54-155828 (U.S. Pat. No. 4,276,374), each of which 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, and iridium complex salts having halogens, amines, oxalates, etc. as ligands, such as hexachloroiridium (III) or (IV) complex salts, hexaammineiridium (III) or (IV) Examples thereof include complex salts and trioxalatoiridium (III) or (IV) complex salts. 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 the water-soluble iridium, it is also possible to add and dissolve another silver halide grain which is previously doped with iridium at the time of 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 first iridium (III) chloride and first bromine bromide.
Iridium (III), secondary iridium chloride (IV), sodium hexachloroiridium (III), hexachloroiridium (III) salt, hexaamineiridium (IV) salt,
Halogen amines such as trioxalatoiridium (III) salt and trioxalatoiridium (IV) salt, and oxalato complex salts are preferable.

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 lactate ferrous lactate ferrous phosphate ferrous succinate ferrous sulfate ferrous thiocyanate ferrous nitrate ferrous ammonium nitrate basic ferric acetate ferric albuminate 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 where M is rhenium, ruthenium, osmium, L is a bridging ligand, y is an integer 0, 1, or 2, and n is-. 2, -3 or -4. As a specific example, [Re (CN) ₅ ] ^-4 [Ru (CN) ₅ ] ^-4 [Os (CN) ₅ ] ^-4 [ReF (CN) ₅ ] ^-4 [RuF (CN) ₅ ] ^-4 [ OsF (CN) ₅ ] ^-4 [ReCl (CN) ₅ ] ^-4 [RuCl (CN) ₅ ] ^-4 [OsCl (CN) ₅ ] ^-4 [ReBr (CN) ₅ ] ^-4 [RuBr (CN) _5] ] ^-4 [OsBr (CN) _5] ^-4 [ReI (CN) _5] ^-4 [RuI (CN) _5] ^-4 [OSI (CN) _5] ^-4 [ReF ₂ (CN) _4] ^-4 [ RuF ₂ (CN) ₅ ] ^-4 [OsF ₂ (CN) 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 (CN) 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 ₂ 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 may be spectrally sensitized by a sensitizing dye to red light or infrared light having a relatively long wavelength. 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, RESEARCH DISCLOSURE Item 17643 IV-
Item A (p.23, December 1978), Item 1831X
Section (August 1979, p.437) or cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. The present invention is particularly useful as a light-sensitive material for LEDs or semiconductor lasers spectrally sensitized to 750 to 850 nm. For the LED light source, Japanese Patent Publication No. 48-
No. 42172, No. 51-9609, No. 55-3981.
No. 8, thiacarbocyanines described in JP-A No. 62-284343, and tricarbocyanines described in JP-A Nos. 59-191032 and 60-80841 for semiconductor laser light sources, JP-A-59-1922
Dicarbocyanines containing a 4-quinoline nucleus described in No. 42, etc. 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 1) Silver halide emulsion and JP-A-2-68539, page 8, lower right column, line 6 from the manufacturing method to page 10, upper right column, line 12, line 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, left lower column, line 14 and JP-A-2-12236, 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-3-94249, page 6, lower left column, line 15 to Page 11, upper right column 19, line 9.

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. 3,623,888, second column, line 34 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 From antistatic agent, 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 From plasticizer, same 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 of the same.

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 To page 11, upper left 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 description, JP 3-174143, page 20, lower right column General formula (II) and compound examples II-1 to II-54 from line 1 to page 27, upper right column, line 20. 17) Nucleation accelerator 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 example II- 1 to II-22, compounds described in JP-A No. 1-179939.

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

[0096]

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 a halogen salt aqueous solution containing 4M potassium bromide and 0.1M sodium chloride,
Sodium chloride and 1,3-dimethylimidazolidine-2
-In a gelatin aqueous solution containing thione, with stirring 4
Nucleation was carried out at 3 ° C. for 12 minutes by the double jet method to obtain silver chlorobromide grains having an average grain size of 0.15 μm and a silver chloride content of 70 mol%. Subsequently, similarly, a 0.87% silver nitrate aqueous solution, a 0.26M potassium bromide and a 0.65M sodium chloride aqueous solution containing 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, pH 6.5, pAg7.
Adjust to 5, and then add 20 mg of sodium benzenethiosulfonate, 5 mg of sodium thiosulfate and 8 mg of chloroauric acid per 1 mol of silver, heat at 75 ° C for 75 minutes, perform chemical sensitization treatment, and use 4-hydroxy as a stabilizer. 150 mg of -6-methyl-1,3,3a, 7-tetraazaindene was added. The obtained grains have an average size of 0.26 μm, a silver chloride content of 70 mol%, and 1 × Rh compound per mol of silver.
10 ^-7 mol to give the Ir compound 5 × 10 ^-7 mol content to silver chlorobromide cubic grains (10% coefficient of variation).

Preparation of Dye Dispersion 2.5 g of dye, surfactant (trade name: Triton X-20
0, Rohm & Haas) 4.3% aqueous solution 10.3 g
And 50.5 g of water were mixed by stirring in advance to obtain a diameter of 0.
Eiger motor mill containing 40cc of 8mm-1.2mm zirconia beads (M-50, Eiger Japan)
And was dispersed at a rotation speed of 5000 rpm to obtain a fine crystal dispersion of a dye having a particle size of 1 μm or less. 50 g of a microcrystalline dispersion of the obtained dye, 1.8 g of gelatin and 1 part of water
3.3 g of the mixture was stirred and mixed at 40 ° C. and used for preparation of the photographic light-sensitive material of the present invention.

(Preparation of Photographic Light-sensitive Materials 1 to 13) Emulsion Layer Coating Solution To Emulsion A was added a 0.05% methanol solution of the following sensitizing dye-1 in an amount of 30 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. 3 mol of iodo salt for each mol of silver
00 mg and 450 mg were added.

[0099]

[Chemical 51]

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 0.4 g / m ² 2-Bis (vinylsulfonylacetamide) ethane 86 mg / m ²

Dye layer-1 Gelatin 0.5 g / m ² Dye type and amount are listed in Table 1. Polymethylmethacrylate having a particle size of 2.5 μm 60 mg / m ² Colloidal silica having a particle size of 10 μm 70 mg / m ² Dodecylbenzenesulfonic acid Sodium 38 mg / m ² Dye layer-2 Gelatin 0.5 g / m ² Dye type and amount are listed in Table 1 Sodium dodecylbenzene sulfonate 17 mg / m ² Sodium polystyrene sulfonate 44 mg / m ² 2-bis (vinylsulfonylacetamide) Ethane 33mg / m ²

[0102]

[Chemical 52]

With the above coating amount, the dye layer-1, on the support,
Photosensitive materials 1 to 13 were prepared by simultaneously coating multiple layers in the order of emulsion layer and dye layer-2 (from the support side).

The base used in this example has a back layer and a back protective layer having the following compositions. [Back layer] Gelatin 2.0 g / m ² Sodium dodecylbenzenesulfonate 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 2 mg / m ² silicone oil 100 mg / m ²

Evaluation of Photographic Performance The obtained sample was subjected to scanning exposure using a semiconductor laser having an emission peak at 780 nm. The exposure time corresponds to 10 ^-7 sec / spot. Subsequently, sensitometry was performed using an automatic processor FG-710NH manufactured by Fuji Photo Film Co., Ltd. at the temperature and time shown below.

Current image 38 ° C. 14 seconds 9 seconds Settling 37 ° C. 9.7 seconds 6.2 seconds Washing with water 26 ° C. 9 seconds 5.8 seconds Squeeze 2.4 seconds 1.5 seconds Dry 55 ° C. 8.3 seconds 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 3.0 was taken as the sensitivity, and the relative sensitivity is shown in Table 1.

Safelight Safety evaluation The surface of the photographic light-sensitive 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.

[0109]

[Table 1]

From the above results, the photographic light-sensitive material according to the present invention has good safelight safety and excellent sharpness,
It can be seen that it has high sensitivity. Further, as in Sample 13, if the amount of the water-soluble dye added to the first dye layer and the second dye layer is small, the sensitivity is sufficient, but the image is unclear and the safelight safety is insufficient. Only material was available.

Example 2 (Preparation of photographic light-sensitive materials 21 to 33) Used in the preparation of the emulsion layer coating solution of Example 1. Sensitizing dye-1 0.05%
Instead of the methanol solution, 0.1 of the following sensitizing dye-2 was used.
% Methanol solution was used at 50 mg per silver mole. Also, 320 mg of 4,4-bis (4,6-dinaphthoxypyrimidin-2-ylamino) -stilbenedisulphonic acid disodium salt was used per 1 mol of silver.
An emulsion layer coating solution was prepared in the same manner as in Example 1 except that 2,5-dimethyl-3-allylbenzothiazole iodo salt was not used.

[0112]

[Chemical 53]

Next, except that the kinds and amounts of the dyes used in Example 1 in the dye layer were changed to those shown in Table 2,
Photosensitive materials 21 to 33 were prepared in the same manner as in Example 1.

[0114]

[Chemical 54]

(Evaluation of Photographic Performance) Instead of the method of sensitometry of Example 1, the obtained sample was processed through an interference filter having a peak at 633 nm and a continuous wedge to obtain xenon having an emission time of 10 ⁻⁶ sec. After exposure with flash light, sensitometry was performed under the same conditions as in Example 1 using an automatic processor FG-710NH manufactured by Fuji Photo Film Co., Ltd. (Evaluation of Safelight Safety) Instead of the filter No. 4LD (manufactured by Fuji Photo Film Co., Ltd.) used in the evaluation of safelight safety of Example 1, filter No. 4 (manufactured by Fuji Photo Film Co., Ltd.) ), The safelight safety was evaluated in the same manner as in Example 1 except that the exposure was performed for 4 minutes. The results are shown in Table 2.

[0116]

[Table 2]

From the above results, it can be seen that the photographic light-sensitive material according to the present invention has high safelight safety, excellent sharpness and high sensitivity. Further, like Sample 33, if the amount of the water-soluble dye added to the first dye layer and the second dye layer is small, the sensitivity is sufficient, but the image is not clear,
Only a photographic light-sensitive material having insufficient safelight safety was obtained.

Example 3 (Preparation of emulsion B) The emulsion of Example 1 was prepared.
In place of 0.04 M potassium bromide and 0.1 M sodium chloride, 1.3 × 10 ⁻³ M potassium bromide and 0.
Nucleation was carried out in the same manner as in Example 1 except that 14 M sodium chloride was used to obtain silver chlorobromide grains having a silver chloride content of 99 mol%. Then, instead of the halogen salt aqueous solution containing 0.26M potassium bromide and 0.65M sodium chloride used in Example 1, 8.
Silver chlorobromide cubic grains having a silver chloride content of 99 mol% in the same manner as in Example 1 except that an aqueous halogen salt solution containing 7 × 10 ⁻³ M potassium bromide and 0.91 M sodium chloride was used. Got (Emulsion B)

(Preparation of Photographic Light-sensitive Materials 41 to 53) Sensitizing Dye-1 used in the preparation of the emulsion layer coating solution of Example 1.
In place of the 0.05% methanol solution of No. 2, a 0.2% methanol solution of the following sensitizing dye-3 was used so as to be 85 mg per mol of silver of emulsion B. In addition, 4,4-bis (4,6-dinaphthoxypyrimidin-2-ylamino)
-Stilbene disulfonic acid disodium salt, 2,5-
An emulsion layer coating solution was prepared in the same manner as in Example 1 except that dimethyl-3-allylbenzothiazole iodo salt was not used.

[0120]

[Chemical 55]

Next, photographic light-sensitive materials 41 to 53 were prepared in the same manner as in Example 1 except that the type and amount of the dye in the dye layer used in Example 1 were changed to those shown in Table 3.

[0122]

[Chemical 56]

(Evaluation of Photographic Performance) Used in Example 2,
67 in place of the interference filter having a peak at 633 nm
Sensitometry was performed in the same manner as in Example 2 except that an interference filter having a peak at 0 nm was used. (Evaluation of Safelight Safety) Instead of the filter No. 4LD (manufactured by Fuji Photo Film Co., Ltd.) used in the evaluation of safelight safety of Example 1, filter No. 4 (manufactured by Fuji Photo Film Co., Ltd.) ), The safelight safety was evaluated in the same manner as in Example 1 except that the exposure was performed for 5 minutes. The results are shown in Table 3.

[0124]

[Table 3]

From the above results, it can be seen that the photographic light-sensitive material according to the present invention has high safelight safety, excellent sharpness and high sensitivity. Further, if the amount of the water-soluble dye added to the first dye layer and the second dye layer is small like Sample 53, the sensitivity is sufficient, but the image is not clear,
Only a photographic light-sensitive material having insufficient safelight safety was obtained.

Example 4 (Preparation of Emulsion C) 40 g of gelatin was dissolved in 1 liter of H ₂ O, and sodium chloride 5 was added to a container heated at 53 ° C.
g, potassium bromide 0.4 g, and the following compound (A)

[0127]

[Chemical 57]

After adding 60 mg of water, 1000 ml of water-soluble solution containing 200 g of silver nitrate and hexachloroiridium (I) having a molar ratio of iridium to finished silver halide of 10 ^-7.
II) Potassium acid and water-soluble 1080 ml containing 21 g of sodium chloride and 100 g of potassium bromide were added by the double jet method to give an average particle size of 0.35 μm.
Cubic monodisperse silver chlorobromide grains were prepared. After demineralizing this emulsion, 40 g of gelatin was added to pH 6.0, pAg
Sodium thiosulfate (2.5 mg) and chloroauric acid (4 mg) were added according to 8.5, and chemical sensitization was performed at 60 ° C., and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaine. 0.2 g of den was added and rapidly solidified (Emulsion C).

(Preparation of Photographic Light-Sensitive Materials 61-73) Emulsion Layer Coating Solution A container in which 1000 g of Emulsion C was weighed was heated to 40 ° C., and additives were added by the following method to prepare an emulsion coating solution.

(Formulation of emulsion coating solution)

A. Emulsion C 1000 g b. Sensitizing dye-1 1.2 × 10 ^-4 mol c. Supersensitizer [3] 0.8 × 10 ⁻³ mol d. Shelf life improving agent [4] 1 × 10 ⁻³ Morpho. Polyacrylamide (molecular weight 40,000) 7.5 g f. Trimethylolpropane 1.6 g To polystyrene sulfonate Na 1.2 g Chi. Poly (ethyl acrylate / methacrylic acid) latex 12 g N, N'-ethylenebis- (vinyl sulfone acetamide) 3.0 g Lu. 1-phenyl-5-mercapto-tetrazole 50mg

Supersensitizer [3]

[0133]

[Chemical 58]

Storability improver [4]

[0135]

[Chemical 59]

Emulsion layer Coating was carried out so that the coated silver amount was 2.5 g / m ² .

Dye layer-1 Gelatin 0.5 g / m ² Dye type and amount are listed in Table 4. Polymethylmethacrylate having a particle size of 2.5 μm 60 mg / m ² Colloidal silica having a particle size of 10 μm 70 mg / m ² Dodecylbenzenesulfonic acid Sodium 38 mg / m ² Dye layer-2 Gelatin 0.5 g / m ² Dye type and amount are listed in Table 4 Sodium dodecylbenzene sulfonate 17 mg / m ² Sodium polystyrene sulfonate 44 mg / m ² 2-bis (vinylsulfonylacetamide) Photosensitive materials 61 to 73 were prepared by coating in the same manner as in Example 1 with a coating amount of ethane of 33 mg / m ² or more.

(Evaluation of Photographic Performance) The photographic materials 61 to 73 thus prepared were subjected to sensitometry by the following method to measure the sensitivity. Photographic materials 61-73 25
Keep the temperature and humidity at ℃ 60% and leave it for 7 days after application.
Scanning exposure was carried out for 10 ⁻⁷ seconds using a semiconductor laser of 80 nm, and development processing was carried out with the following developing solution [I] and fixing solution [I]. The developing time was 15 seconds. Sensitivity value is D =
The reciprocal of the amount of exposure giving 1.0 was expressed as a relative value. Safelight safety was measured as in Example 1. The results are shown in Table 4.

Composition of developer [I]

Potassium hydroxide 29 g Sodium sulfite 31 g Potassium sulfite 44 g Ethylenetriaminetetraacetic acid 1.7 g Boric acid 1 g Hydroquinone 30 g Diethylene glycol 29 g 1-Phenyl-3-pyrazolidone 1.5 g Glutaraldehyde 4.9 g 5-Methylbenzotriazole 60 mg 5- Nitroindazole 0.25g Potassium bromide 7.9g Acetic acid 18g upto 1000ml pH 10.3 Fixer [I] composition

Ammonium thiosulfate 140 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid disodium dihydrate 20 mg Sodium hydroxide 7 g Aluminum sulfate 10 g Boric acid 10 g Sulfuric acid 3.9 g Acetic acid 15 g H ₂ O upto 1000 ml pH 4.30

[0142]

[Table 4]

From the results in Table 4, it is clear that the present invention is effective as in Example 1.

Specific examples of the infrared sensitizing dye that can be used in the present invention include the following compounds in addition to the above compounds.

[0145]

[Chemical 60]

[0146]

[Chemical formula 61]

[0147]

According to the present invention, a silver halide photographic light-sensitive material having high safelight safety and less residual color can be obtained.
Therefore, the light-sensitive material of the present invention is extremely useful as a scanner film which can be handled in a bright room and can be processed rapidly.

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[Procedure amendment]

[Submission date] November 13, 1992

[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 on a support and having a maximum absorption wavelength in the absorption spectrum. A hydrophilic colloid layer (first dye layer) containing a microcrystalline dispersion of at least one compound in the range of 300 to 750 nm is provided outside the photosensitive emulsion layer with respect to the support, and has an absorption spectrum. Having a hydrophilic colloid layer (second dye layer) containing a microcrystalline dispersion of at least one compound having a maximum absorption wavelength in the range of 600 to 1200 nm between the support and the photosensitive emulsion layer. It is achieved by using a silver halide photographic light-sensitive material characterized by

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

[0023]

[Chemical 4]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

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.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

[0035]

[Chemical 10]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

(In the formula, R ⁹¹ , R ⁹² , and R ⁹³ represent a hydrogen atom, an alkyl group, or an aryl group, and Q ₁ represents a group of atoms necessary for forming a basic heterocycle. L ⁹¹ , 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 (XIV) has at least one carboxyl group, sulfonic acid arylamide group, or phenolic hydroxyl group in the molecule. )

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0103

[Correction method] Change

[Correction content]

With the above coating amount, the dye layer-2 on the support,
Photosensitive materials 1 to 13 were prepared by simultaneously coating multiple layers in the order of emulsion layer and dye layer-1 (from the support side).

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, having a maximum absorption wavelength of 300 to 7 in the absorption spectrum.
A hydrophilic colloid layer (first dye layer) containing a microcrystalline dispersion of at least one compound in the range of 50 nm is provided outside the photosensitive emulsion layer with respect to the support, and the absorption spectrum A hydrophilic colloid layer (second dye layer) containing a microcrystalline dispersion of at least one compound having a maximum absorption wavelength in the range of 600 to 1200 nm is provided between the support and the photosensitive emulsion layer. A silver halide photographic light-sensitive material.