JP2000066324A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having contrasty photographic characteristics and rapid processability, excellent in scratch resistance and suitable for forming an image by using an image setter. SOLUTION: This silver halide photographic sensitive material has a photosensitive silver halide emulsion layer contg. a hydrazine compd. on a substrate, the ratio of the amt. of silver to the amt. of a hydrophilic binder on the side having the emulsion layer is 0.7-2 and a hydrophilic colloidal layer adjacent to the emulsion layer contains a halogenated compd. Then, it is featured that the hydrophilic colloidal layer adjacent to the emulsion layer contng. the hydrazine compd. contains the halogenated compd. This hydrophilic colloidal layer is however preferably located on the surface rather than the emulsion layer in order to exhibit a function to suppress blackening due to a scratch.

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 (hereinafter, also referred to as a "photosensitive material"), and more particularly, to a silver halide photographic material suitable for forming an image using an image setter in the field of printing and plate making. It relates to a photosensitive material.

[0002]

2. Description of the Related Art In order to faithfully reproduce a halftone dot image or a line drawing image, a photographic material for printing plate making is required to have high photographic characteristics. There are various photographic techniques for obtaining these high-contrast photographic characteristics. Among them, for example, US Pat.
There is known a method for developing a silver halide photographic light-sensitive material containing a hydrazine derivative as disclosed in JP-A-269,929.

In recent years, an image setter capable of producing an original film for plate making using image data via a computer has been rapidly spreading.

[0004]

However, in recent years, the photographic constituent layers of the light-sensitive material have become thinner in response to a demand for faster development processing, and a thin-film light-sensitive material containing active hydrazine has been used in an image setter. Exposure with long transport distance
When an image is formed using a development processing device, a problem of blackening of a scratch occurs.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide an image setter using an image setter which has high contrasting photographic characteristics and rapid processing suitability, and has excellent scratch resistance. An object of the present invention is to provide a silver halide photographic light-sensitive material.

[0006]

An object of the present invention is to provide a photosensitive silver halide emulsion layer containing a hydrazine compound on a support, and the amount of silver based on the amount of the hydrophilic binder on the side having the emulsion layer. Is 0.7-2, and the hydrophilic colloid layer adjacent to the emulsion layer is a silver halide photographic material containing a halide compound.

That is, the inventor of the present invention intends to reduce the silver potential on the surface of the emulsion layer by suppressing the development of the scratched portion by allowing the halide compound to be present on the surface of the silver halide emulsion layer of the light-sensitive material and in the vicinity thereof. This has led to the present invention.

Hereinafter, the present invention will be described in detail.

The light-sensitive material of the present invention contains a hydrazine compound in a silver halide emulsion layer.

In the present invention, the hydrazine compound is preferably a compound represented by the following general formula [H].

[0011]

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In the formula, A represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents a — (CO) _n — group, a sulfonyl group, a sulfoxy group, a —P
(＝ O) represents an R ₂ — group or an iminomethylene group;
Represents an integer of 1 or 2; A ₁ and A _{2 each} represent a hydrogen atom or one of them is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group or a substituted or unsubstituted acyl group; Represents a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, or oxycarbonyl group. R ₂ is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group,
Represents an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an amino group, or the like.

Among the compounds represented by the general formula [H], the compounds represented by the following general formula [Ha] are more preferable.

[0014]

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In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, chenyl group, Furyl group),
As these groups, those further substituted with a suitable substituent are preferably used. Further, R ¹ preferably contains at least one diffusion-resistant group or silver halide adsorption promoting group.

As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group having a carbon number of 8 or more which is relatively inert to photographic properties, for example, an alkyl group Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

The silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [Ha], X represents a group that can be substituted on a phenyl group, m represents an integer of 0 to 4,
Is 2 or more, X may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and both are preferably hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ² _{is, -CF 3, -CF 2 H,} -CFH 2, -
CF ₂ CF ₂ COOH, —COOR ³ group and —CON
(R ⁴ ) (R ⁵ ) groups (R ³ represents an alkynyl group or a saturated heterocyclic group, R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; R ⁵ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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Specific examples of other preferred hydrazine compounds are described in US Pat. No. 5,229,248, columns 4 to 60, (1) to (252).
Is mentioned.

These hydrazine compounds can be synthesized by known methods. For example, US Pat.
The method as described in the column to the 80th column can be referred to.

The amount of addition may be any amount that makes the contrast high (the amount of the contrast enhancement).
Although the optimum amount varies depending on the degree of chemical sensitization, the type of the inhibitor, etc., it is generally 10 ^-6 to 10 ^-1 per mol of silver halide.
Molar range, preferably from 10 ^-5 to 10 ^-2 mol.

In order to effectively promote the contrast enhancement by the hydrazine derivative, a quaternary onium compound (also referred to as an onium salt compound) having a quaternary nitrogen compound and / or a quaternary phosphorus compound in the structure is selected from amine compounds. It is preferable to use at least one nucleation accelerator used.

As the quaternary onium compound (also referred to as an onium salt compound), a compound represented by formula (P) is preferable.

[0037]

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Further, R _{1 to} R ₄ may be linked to each other to form a ring.

Examples of the substituent represented by R _{1 to} R ₄ include groups such as alkyl, alkenyl, alkynyl, aryl, heterocycle, amino and the like. Specifically, alkyl groups (methyl, ethyl, propyl, Butyl, hexyl, cyclohexyl, etc.), alkenyl group (allyl, butenyl, etc.), alkynyl group (propargyl, butynyl, etc.), aryl group (phenyl, naphthyl, etc.), heterocyclic group (piperidinyl,
Piperazinyl, morpholinyl, pyridyl, furyl, thienyl, tetrahydrofuryl, tetrahydrothienyl, sulfolanyl, etc.).

Examples of the ring which R _{1 to} R ₄ can form by linking each other include rings of piperidine, morpholine, piperazine, quinuclidine, pyridine and the like.

The groups represented by R _{1 to} R ₄ include substituents (hydroxyl, alkoxy, aryloxy, carboxyl,
Sulfo, alkyl, aryl groups, etc.).

As R ₁ , R ₂ , R ₃ and R ₄ , a hydrogen atom and an alkyl group are preferred.

[0043] X ^- include anions represented by the halogen ion, sulfate ion, nitrate ion, acetate ion, and inorganic and organic anions, such as p- toluenesulfonic acid ion.

More preferably, the following general formulas (Pa) and (P
It is a pyridinium compound represented by b) or (Pc).

[0045]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetal atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ include a 5- to 6-membered ring (pyridine,
Imidazole, thiozole, oxazole, pyrazine,
Each ring such as pyrimidine), and a more preferred example is a pyridine ring.

B _p represents a divalent linking group, and m is 0 or 1
Represents Examples of the divalent linking group include an alkylene, arylene, _{alkenylene, -SO 2 -, - SO -} , - O -, -
S -, - CO -, - N (R 6) - (R 6 is an alkyl group, an aryl group, a hydrogen atom) represents what is configured alone or in combination. Preferably, B _p is an alkylene or alkenylene group.

R ¹ , R ² and R ⁵ each have 1 to 20 carbon atoms
Represents an alkyl group. R ¹ and R ² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and examples of the substituent include A ¹ , A ² , A ³ , A ⁴
And the substituents mentioned as the substituents for A ⁵ .

Preferred examples of R ¹ , R ² and R ⁵ include:
Each is an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0050] X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt. Next, specific examples of the quaternary onium compound are shown below, but the present invention is not limited thereto.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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As the amine compound, a compound represented by the following general formula [Na] is preferable.

[0062]

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In the general formula [Na], R ₁₁ , R ₁₂ , R
₁₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group, such as a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group, an aryl group, a heterocyclic group, a mercapto group, a thioether group, a thione group, and a thiourea group. No. R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable. Preferred adsorbing groups include a heterocyclic ring, a mercapto group, a thioether group,
And a thione group and a thiourea group. General formula [N
Particularly preferred as a) is a compound having at least one thioether group as a silver halide adsorptive group in the molecule.

Specific examples of these nucleation accelerators [Na] are described below.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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The present invention is characterized in that the hydrophilic colloid layer adjacent to the hydrazine compound-containing silver halide emulsion layer contains a halogenated compound, and the hydrophilic colloid layer is blackened by abrasion. In order to exhibit the function of suppressing the occurrence of an emulsion layer, it is preferably on the surface rather than the emulsion layer.

In the present invention, the halogenated compound is water-soluble because it exhibits a function of lowering the silver potential. Preferred compounds include alkali metal (eg, lithium, sodium, potassium) salts, magnesium salts, calcium salts, strontium salts, ammonium salts, zinc salts and the like of chlorine, bromine and iodine. Further, a chloride or bromide of an organic cation having a molecular weight of up to about 350 can also be used. These may be added to the coating liquid for the hydrophilic colloid layer, or may be applied as an aqueous solution after the formation of the hydrophilic colloid layer.

[0072] As usage, 1 to 100 mg / m ² about, and preferably 10 to 40 mg / m ^2.

As the hydrophilic colloid, it is advantageous to use gelatin. In addition, for example, gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin and phthalated gelatin, and an ethylene group capable of polymerizing with gelatin are used. Graft polymers with monomers, carboxymethylcellulose, hydroxymethylcellulose, cellulose derivatives such as cellulose sulfate, polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylamide, poly-N, N-dimethylacrylamide, poly-N-vinylpyrrolidone, poly Synthetic hydrophilic polymers such as methacrylic acid, agar, gum arabic, alginic acid, albumin, casein and the like can be used. These may be used in combination of two or more.

According to the present invention, the ratio of the amount of silver to the amount of the hydrophilic binder on the side having the emulsion layer is 0.7 to 2, more preferably 1 to 2
The effect is regretfully exhibited in an extremely thin film system.

Spectral sensitizing dyes used for spectrally sensitizing a light-sensitive material corresponding to the light source of an image setter are preferably those having high sensitivity and low residual color contamination.

[0076]

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In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each represent a substituted or unsubstituted aliphatic group, and at least one of R ¹² and R ¹⁴ substitutes for a water-solubilizing group. ^11, V ^12,
V ¹³ , V ¹⁴ , V ¹⁵ , V ¹⁶ , V ¹⁷ and V ¹⁸ each represent a hydrogen atom or a substituent, and V ¹¹ and V ¹² , V ¹² and V ¹³ , V ¹³ and V ¹⁴ , V ¹⁵ and V ^{18 16} , V ¹⁶ and V ^17, and V ¹⁷ and V ¹⁸ , respectively, may form a condensed ring, provided that V ^{11 to} V ^{14 and} V ^{15 to} V ¹⁸ are each the sum of the Hammett σp values added. Is a substituent greater than 0.12, and L ¹¹ , L ¹² , L
^13, each L ¹⁴ and L ¹⁵ represent methine groups, M ¹¹ represents an ion required to offset the total intramolecular charge, the number of ions required to l ¹¹ is to offset the total intramolecular charge Represents

Examples of the aliphatic group represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ include, for example, a branched or straight-chain alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, n-propyl, each group such as n-pentyl and isobutyl), a vinyl group, an alkenyl group having 2 to 10 atoms (for example, each group such as 3-butenyl and 2-propenyl) or 3 to 3 carbon atoms;
And 10 aralkyl groups (for example, respective groups such as benzyl and phenethyl). Examples of the water-solubilizing group that substitutes for at least one of R ¹² and R ¹⁴ include acid groups such as a sulfo group, a carboxy group, a phosphono group, a sulfate group, and a sulfino group.

Each of the aliphatic groups represented by R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is a hydroxy group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (eg, a methoxy group, An ethoxy group, etc.), an aryloxy group (for example, phenoxy group, p-sulfophenoxy group, etc.), a cyano group, a carbamoyl group (for example, carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), Sulfamoyl group (for example,
Sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (eg, phenyl group, carboxyphenyl group, etc.) ), An acyl group (for example,
Acetyl group, benzoyl group, etc.), acylamino group (eg, acetylamino group, etc.) may be substituted with a substituent, and specific examples of the aliphatic group substituted with a water solubilizing group include carboxymethyl, Sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, ω-sulfopropoxycarbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3-phosphonopropyl, Each group includes 4-sulfo-3-butenyl, 2-carboxy-2-propenyl, O-sulfobenzyl, P-sulfophenethyl, P-carboxybenzyl and the like.

V ¹¹ , V ¹² , V ¹³ , V ¹⁴ , V ¹⁵ , V ¹⁶ , V
Examples of the substituent represented by each of ¹⁷ and V ¹⁸ include an electron donating group and an arbitrary electron withdrawing group selected so that the sum of the added Hammett σp values becomes larger than 0.12.
Specifically, a cyano group, a carboxy group, a linear or branched alkyl group (for example, each group such as methyl, ethyl, iso-propyl, t-butyl, iso-butyl, t-pentyl, hexyl, etc.), an alkoxy group ( For example, each group such as methoxy, ethoxy, propoxy, etc.), an alkylthio group (eg, methylthio group), for example, a halogen atom such as fluorine, chlorine, bromine and the like, a carbamoyl group (eg, carbamoyl, N-methylcarbamoyl, N, N- Each group such as pentamethylenecarbamoyl), sulfamoyl group (for example,
N-methylsulfamoyl, morpholinosulfonyl,
Groups such as piperidinosulfonyl), an acylamino group (eg, each group such as acetylamino, propionylamino, benzoylamino), a sulfonylamino group (eg, methanesulfonylamino, benzenesulfonylamino, m
Each group such as -chlorobenzenesulfonylamino, perfluoromethanesulfonylamino), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc.), an alkylsulfonyl group (e.g., methanesulfonyl, ethanesulfonyl,
Each group such as trifluoromethanesulfonyl), an arylsulfonyl group (for example, a group such as benzenesulfonyl), an acyl group (for example, each group such as acetyl and benzoyl), and a perfluoroalkyl group (for example, trifluoromethyl,
Groups such as pentafluoroethyl), perfluoroalkoxy groups (such as trifluoromethoxy and pentafluoroethoxy), perfluoroalkylthio groups (such as trifluoromethylthio and pentafluoroethylthio) and aryl groups ( For example, phenyl, m
-Chlorophenyl, etc.) and heterocyclic groups (e.g., pyrrolyl, pyridyl, imidazolyl, furyl, thiphenyl, etc.).

The Hammett's σp value is a substituent constant determined from the electronic effect of the ring group on the hydrolysis rate of benzoic acid ethyl ester by Hammett et al. The value of each group is, for example, Chemical Review (Chemical Review).
Reviews, 17, 125-136 (1935), Journal of Organic Chemistry (Jou)
rnal of Organic Chemistr
y) Volume 23, 420-427 (1958), Experimental Chemistry Course 14 (Maruzen Publishing Co., Ltd.), Physical Organic
Chemistry (Physical Organic C
hemistry; McGraw Hill Boo
k: 1940), Drug Design Volume VII (Drug)
design VII Academic Press;
New York: 1970), Structure-activity relationship of drugs (Nankodo: 1979), Substitute Constants for Correlation Analysis in Chemistry and Biology (Subst)
title Constants for Corr
elation Analysis in Chemi
try and Biology; John Wil
eye and Sons: 1979).

V ¹¹ , V ¹² , V ¹³ , V ¹⁴ , V ¹⁵ , V ¹⁶ , V
^The aryl group, the heterocyclic group, and the alkyl group represented by ¹⁷ and V ¹⁸ may have any of the above-described substituents at any positions. V ¹¹ and V ^12, V ¹² and V ^13, V ¹³ and V ^14, V
Each between ¹⁵ and V ^16, V ¹⁶ and V ¹⁷ and V ¹⁷ and V ^18, 5 to 7-membered saturated carbocycle as fused ring formed, aromatic carbon ring, ring groups heterocycles mentioned And may have any of the aforementioned substituents at any position.

Examples of the group substituted by the methine carbon represented by L ¹¹ , L ¹² , L ¹³ , L ¹⁴ and L ¹⁵ include a lower alkyl group (for example, each group such as methyl and ethyl) and a cyclic alkyl group (For example, each group such as cyclopropyl and cyclopentyl), a substituted alkyl group (for example, each group such as 2-methoxyethyl and 2-thienylmethyl), an aralkyl group (for example, each group such as benzyl and phenethyl), and a phenyl group (E.g., phenyl, carboxyphenyl, etc.),
Heterocyclic groups (eg, thienyl, furyl, imidazolyl,
And alkoxy groups (for example, methoxy, ethoxy and the like) and fluorine atoms. L ¹¹ can form a condensed ring with R ¹¹ or R ¹² , and L ¹² can form a condensed ring with R ¹³ or R ¹⁴ , respectively. M ¹¹ represents a cation or an acid anion. Specific examples of the cation include a proton, an organic eummonium ion (for example, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (for example, lithium, sodium, calcium and the like). Specific examples of the acid anion include, for example, a halogen ion (for example, chloride ion, bromine ion,
Iodine ion), p-toluenesulfonic acid ion, perchlorate ion, boron tetrafluoride ion and the like.

L ¹¹ is 0 when an internal salt is formed and the total charge is offset.

Specific examples of the spectral sensitizing dye represented by the general formula (1) are shown below, but it should not be construed that the invention is limited thereto.

[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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These compounds are described, for example, in FM
Hama, "Cyanine Soybeans and Related
Compounds "(1964, published by Inter Science Publishers), UK Patent No. 980,234, U.S. Patent No. 3,684,517, JP-A-61-2034.
No. 46, Ukr. Khim. Zh. , 197
The compound can be easily synthesized with reference to a conventionally known method described in 7, 43 (4) 381-4.

[0107]

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[0108] In the formula, Y ^21, Y ^22, Y ²³ and Y ²⁴ are each independently -N (R ²⁴⁾ - group, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, Y ²³ and Y Any one of ²⁴ is a —N (R ²⁴ ) — group, and Y ²¹ , Y ²² and Y ²³ or Y ²¹ , Y ²² and Y ²⁴ are not simultaneously a sulfur atom;
R ²¹ represents an aliphatic group having 8 or less carbon atoms obtained by replacing water-solubilizing group, each R ^24, R ²² and R ²³ represents an aliphatic group, an aryl group or a heterocyclic group, and R ^24, R ^At least two groups of ²² and R ²³ substitute a water-solubilizing group; Z ²¹ represents a group of nonmetal atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group which may be condensed; W ²¹ represents an oxygen atom, sulfur atom, ＝ N (AR) group, ＝ C <(E ²¹ ) (E ²² ) group, AR represents an aromatic ring or a heterocyclic group, and L ²¹ and L ²² each represent substituted independently represent unsubstituted methine carbon, respectively E ²¹ and E ²² independently represent an electron-withdrawing group, it may form a heterocyclic ring of keto ring or an acidic bonded to each other, l ²¹ is 0 or 1 represents, M ²¹ represents an ion required to offset the total intramolecular charge, ion necessary n ²¹ is to offset the total intramolecular charge It represents the number.

[0109]

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In the formula, Y ²⁵ , Y ²⁶ and Y ²⁷ each independently represent an —N (R ²⁹ ) — group, an oxygen atom, a sulfur atom, or a selenium atom, and R ²⁵ has a substituent for a water solubilizing group. It represents an aliphatic group having 8 or less carbon ^{atoms, R 29, R 26, R} 27 and R ²⁸ each represent an aliphatic group, an aryl group or a heterocyclic group, and R ^29,
At least three groups of R ^26, R ²⁷ and R ²⁸ is substituted with a water-solubilizing group, Z ²² represents a nonmetallic atomic group necessary for forming a condensed nitrogen-containing heterocyclic group, L ²³ , L ²⁴ each represents a substituted or unsubstituted methine carbon, M ²² represents an ion required to offset the total charge in the molecule, and n ²² represents an ion required to offset the total charge in the molecule. Represents a number.

R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R
^27, as the water-solubilizing group substituting on R ²⁸ and R ^29, for example sulfo group, a carboxy group, a phosphono group, a sulfate group, and each acid group such as a sulfino group.

R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R
Examples of the aliphatic group represented by ²⁷ , R ²⁸ and R ²⁹ include:
A branched or straight-chain alkyl group having 1 to 8 carbon atoms (for example, each group such as methyl, ethyl, n-propyl, n-pentyl, and isobutyl), and an alkenyl group having 3 to 8 carbon atoms (for example, 3- Examples include groups such as butenyl and 2-propenyl) and aralkyl groups having 3 to 8 carbon atoms (eg, groups such as benzyl and phenethyl).

R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R
^27, examples of the aryl group represented by R ²⁸ and R ²⁹ for example, include a phenyl group, a heterocyclic group for example,
Pyridyl group (2-, 4-), pyrazyl group, furyl group (2
-), Thienyl group (2-), sulfolanyl group, tetrahydrofuryl group, piperidinyl group, pyrrole group, imidazolyl group and the like.

R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R
²⁷ , R ²⁸ and R ²⁹ each represent a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (eg, a methoxy group, an ethoxy group, etc.), an aryloxy group (eg, a phenoxy group, p-tolyloxy group, etc.), cyano group, carbamoyl group (for example, carbamoyl group, N
-Methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (eg, ethoxy group) It may be substituted with a substituent such as a carbonyl group, a butoxycarbonyl group, an aryl group (for example, a phenyl group, a carboxyphenyl group, etc.), an acyl group (for example, an acetyl group, a benzoyl group, etc.).

Specific examples of the aliphatic group substituted with a water-solubilizing group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, and ω-sulfopropoxy. Carbonylmethyl, ω-sulfopropylaminocarbonylmethyl, N-ethyl-N-sulfopropyl, 3-sulfinobutyl, 3-phosphonopropyl,
4-sulfo-3-butenyl, 2-carboxy-2-propenyl, O-sulfobenzyl, P-sulfophenethyl,
Specific examples of the aryl group in which each group such as p-carboxybenzyl is substituted with a water-solubilizing group include p-sulfophenyl groups and p-carboxyphenyl groups, and the water-solubilizing group is substituted. Specific examples of such heterocyclic groups include groups such as a 4-sulfothienyl group and a 3-carboxypyridyl group.

In these, R ²¹ and R ²⁵ are alkyl groups substituted with a sulfo group, and R ²² , R ²³ , R ²⁴ , R ^24
26, Izure or at least two groups of R ^27, R ²⁸ and R ²⁹ are each a is preferable carboxymethyl group.

Examples of the 5- or 6-membered nitrogen-containing heterocyclic group represented by Z ²¹ and Z ²² include a basic heterocyclic ring forming a cyanine dye, and include, for example, an oxazole ring (eg, oxazole, benzoxazole) , Naphthoxazole, etc.), thiazole ring (eg, thiazolidine, thiazole, benzothiazole, naphthothiazole, etc.), imidazole ring (eg, imidazole, benzimidazole, naphthimidazole, etc.), selenazole ring (eg, selenazole, benzoselenazole, naphtho. Selenazole, etc.), tetrazole ring (for example, tetrazole,
Benzotetrazole, naphthotetrazole and the like), pyridine ring (for example, pyridine, quinoline and the like), and pyrrole ring (for example, pyrrole, indole, indolenine and the like) can be mentioned.

Examples of the nitrogen-containing 5-membered heterocyclic ring represented by Z ²¹ include 5-membered heterocyclic rings described above for Z ²¹ .

The above-mentioned heterocyclic ring represented by Z ²¹ and Z ²² may have a substituent at any position, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), Trifluoromethyl group, alkoxy group (for example,
Methoxy, ethoxy, butoxy, etc., unsubstituted alkoxy groups, 2-methoxyethoxy, benzyloxy, etc., substituted alkoxy groups, hydroxy group, cyano group, aryloxy group (eg, phenoxy, tolyloxy, etc.
Unsubstituted groups), aryl group (substituted or unsubstituted groups such as phenyl, p-chlorophenyl, p-tolyl, and p-methoxyphenyl), styryl group, and heterocyclic group (e.g., furyl, thienyl) Carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl, etc.), sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, etc.), acylamino group (eg, acetyl) Amino, propionylamino, benzoylamino, etc.), acyl group (eg, acetyl, benzoyl, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl, etc.), sulfonamide group (eg, methanesulfonylamide, benzene) Each group such as sulfonamide), a sulfonyl group (for example, methanesulfonyl, p Each group of such toluenesulfonyl),
Carboxy group, alkyl group (for example, methyl, ethyl,
Arbitrary groups such as isopropyl and the like).

Examples of the group substituted on the methine carbon represented by L ²¹ , L ²² , L ²³ and L ²⁴ include, for example, a lower alkyl group (for example, each group such as methyl and ethyl) and a phenyl group (for example, Phenyl, carboxyphenyl, etc.),
There are groups such as an alkoxy group (for example, each group such as methoxy and ethoxy), an aryloxy group (for example, each group such as phenoxy and carboxyphenoxy), an aralkyl (for example, a group such as benzyl), and a fluorine atom.

These dyes generally provide high spectral sensitivity when either one of the methine carbons represented by L ²¹ and L ²² is substituted, but provide a property that the dye is liable to drift in a processing bath. This has a favorable effect of reducing residual color contamination.

The electron-withdrawing groups represented by E ²¹ and E ²² are selected from groups having a Hammett σ _p value of more than 0.3, and specifically include a cyano group and a carbamoyl group (for example, carbamoyl group, morpholino group). Carbonyl group, N-methylcarbamoyl group, etc.), alkoxycarbonyl group (for example,
Methoxycarbonyl group, ethoxycarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl group, morpholinosulfonyl group, N, N-dimethylsulfamoyl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), sulfonyl group (For example, methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.).

The keto ring formed by E ²¹ and E ²² and the acidic heterocyclic ring include, for example, the following compounds.

[0124]

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In the formula, R ^a and R ^b each represent a lower alkyl group, an aryl group or a heterocyclic group, and specific examples of the lower alkyl group include methyl, ethyl, propyl, 2-hydroxyethyl and 2-methoxyethyl. , Trifluoroethyl,
Examples include substituted and unsubstituted groups such as allyl, carboxymethyl, carboxyethyl, 2-sulfoethyl, and benzyl. The aryl group and heterocyclic group represented by R ^a and R ^b include R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , and R ^27.
And those of the content shown in R ^28.

M ²¹ and M ²² each represent a cation or an acid anion. Specific examples of the cation include a proton,
Examples thereof include an organic ammonium ion (for example, each ion such as triethylammonium and triethanolammonium) and an inorganic cation (for example, each cation such as lithium, sodium, and calcium). Specific examples of the acid anion include, for example, a halogen ion (for example, chlorine ion, Bromide ion, iodine ion, etc.), p-toluenesulfonic acid ion,
Examples include perchlorate ion and 4-boron fluoride ion. n ²¹ and n ²² become 0 when an internal salt is formed to cancel the total charge in the molecule.

Specific examples of the spectral sensitizing dye represented by formula (2-a) or (2-b) are shown below, but it should not be construed that the invention is limited thereto.

[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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The above-mentioned compounds are described in, for example, "Cyanine Soybeans and Related Compounds" by FM Hammer (1964, published by Inter Science Publishers), US Pat. No. 2,454,629,
No. 2,493,748, British Patent No. 489,335
, And can be easily synthesized with reference to a conventionally known method described in, for example, European Patent No. 730,008.

[0136]

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In the formula, Y ³¹ , Y ³² and Y ³³ each independently represent a —N (R ³⁴ ) — group, an oxygen atom, a sulfur atom or a selenium atom, and R ³¹ is substituted with a water solubilizing group. Represents an aliphatic group having 10 or less carbon atoms, R ³⁴ , R ³² and R ³³ each represent an aliphatic group, an aryl group or a heterocyclic group, and at least two groups of R ³⁴ , R ³² and R ³³ are Substituting a water solubilizing group,
V ³¹ and V ³² each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a group bonded to V ³¹ or V ³² to form a condensed ring with an azole ring, and L ³¹ and L ³² each represent M ³¹ independently represents a substituted or unsubstituted methylene carbon; M ³¹ represents an ion required to offset the total charge in the molecule;
³¹ represents the number of ions required to offset the total charge in the molecule.

Examples of the water-solubilizing group substituted for R ³¹ , R ³² and R ³³ include, for example, acid groups such as a sulfo group, a carboxy group, a phosphono group, a sulfate group and a sulfino group.

As the aliphatic group represented by R ³¹ , R ³² and R ³³ , for example, a branched or straight-chain alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, n-propyl, n-
-Each group such as pentyl and isobutyl), having 3 to 1 carbon atoms
Examples thereof include an alkenyl group of 0 (for example, each group such as 3-butenyl and 2-propenyl) and an aralkyl group having 3 to 10 carbon atoms (for example, each group of benzyl and phenethyl).

Examples of the aryl group represented by R ³² , R ³³ and R ³⁴ include a phenyl group, and examples of the heterocyclic group include a pyridyl group (2-, 4-) and a furyl group (2
-), Thienyl group (2-), sulfolanyl group, tetrahydrofuryl group, piperidinyl group and the like.

Each of R ³¹ , R ³² and R ³³ is a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group, etc.), an aryloxy group (for example, Phenoxy group, p-tolyloxy group, etc.), cyano group, carbamoyl group (eg, carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N -3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group,
Alkoxycarbonyl group (for example, ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (for example,
It may be substituted with a substituent such as a phenyl group, a carboxyphenyl group, or an acyl group (eg, an acetyl group, a benzoyl group, etc.).

Specific examples of the aliphatic group substituted with a water-solubilizing group include carboxymethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfopentyl, 3-sulfobutyl, 6-sulfo-3-oxahexyl, and ω-sulfopropoxy. Carbonylmethyl, ω-sulfopropylaminocarbonylmethyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-2-propenyl, O-sulfobenzyl, P-sulfophenethyl, P Specific examples of the aryl group substituted with a water-solubilizing group include each group such as -carboxybenzyl and the like, and examples thereof include a p-sulfophenyl group and a p-carboxyphenyl group, each of which is substituted with a water-solubilizing group. Specific examples of the heterocyclic group include groups such as a 4-sulfothienyl group and a 5-carboxypyridyl group. .

As the alkyl group represented by V ³¹ and V ³² , a linear or branched group (eg, methyl, ethyl, iso
-Propyl, t-butyl, iso-butyl, t-pentyl, hexyl, etc.). Alkoxy groups represented by V ³¹ and V ³² (for example, methoxy, ethoxy,
Groups such as propoxy).

The aryl group represented by V ³¹ and V ³² may have a substituent at any position, and examples thereof include phenyl, p-tolyl, p-hydroxyphenyl, p-methoxyphenyl and the like. Groups. Examples of the condensed ring formed by V ³¹ and V ³² bonded together with an azole ring include benzoxazole, 4,5,6,7-tetrahydrobenzoxazole, naphtho [1,2-d] oxazole, naphtho [2, 3-d] oxazole, benzothiazole, 4,5,6,7-tetrahydrobenzothiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, benzoselenazole, naphtho [1,2 -D] condensed rings such as selenazole;

The above-mentioned substituents represented by V ³¹ and V ³² and the condensed ring formed may have a substituent at any position, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom). Atom, iodine atom), trifluoromethyl group, alkoxy group (for example, unsubstituted alkyl groups such as methoxy, ethoxy, butoxy, substituted alkoxy groups such as 2-methoxyethoxy, benzyloxy, etc.), hydroxy group, cyano group, An aryloxy group (for example, a substituted or unsubstituted group such as phenoxy or tolyloxy), or an aryl group (for example, a substituted or unsubstituted group such as phenyl or p-chlorophenyl), a styryl group, or a heterocyclic group (for example) Carbamoyl group (e.g., carbamoyl, N-ethylcarbamoyl, etc.), sulfamoyl group (e.g., , Sulfamoyl, N, N-dimethylsulfamoyl, etc.), acylamino group (eg, acetylamino, propionylamino, benzoylamino, etc.), acyl group (eg, acetyl, benzoyl, etc.), alkoxy Carbonyl group (eg, ethoxycarbonyl group), sulfonamide group (eg, methanesulfonylamide, benzenesulfonamide group, etc.), sulfonyl group (eg, methanesulfonyl group, p-toluenesulfonyl group, etc.) carboxy group And the like.

Examples of the group substituted on the methine carbon represented by L ³¹ and L ³² include a lower alkyl group (for example, each group such as methyl and ethyl) and a phenyl group (for example, each group such as phenyl and carboxyphenyl). Groups), alkoxy groups (for example, groups such as methoxy and ethoxy), and aralkyl (for example, groups such as benzyl).

M ³¹ represents a cation or an acid anion. Specific examples of the cation include a proton, an organic ammonium ion (eg, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (eg, lithium, sodium, calcium and the like). Cation), and specific examples of the acid anion include, for example, a halogen ion (eg, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid ion, perchlorate ion, 4-boron fluoride ion and the like. Can be n ³¹ is 0 when an internal salt is formed and the total charge in the molecule is offset.

In the above formula (3), R ³¹ is an alkyl group substituted with a sulfo group, and R ³² , R ³³ and R ³⁴
Wherein at least two groups are carboxymethyl.

Specific examples of the spectral sensitizing dye represented by formula (3) are shown below, but it should not be construed that the invention is limited thereto.

[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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The above-mentioned compounds are described, for example, in "Cyanine Soybeans and Related Compounds" by FM Hammer (1964, published by Inter Science Publishers), US Pat. Nos. 2,454,629 and 2 , 493, 748, and the like, and can be easily synthesized with reference to a conventionally known method.

[0156]

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In the formula, Z ⁴¹ represents a nonmetallic atom necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be condensed, and Y ⁴¹ and Y ⁴² each independently represent —N ( ^R44 )-
W ⁴¹ represents a ＮN (AR) group, an oxygen atom, a sulfur atom, ＝ C
<(E ⁴¹ ) represents a (E ⁴² ) group, R ⁴¹ represents an aliphatic group having a carbon number of 8 or less substituted with a water solubilizing group, and R ⁴⁴ , R ⁴² and R
⁴³ represents an aliphatic group, an aryl group or a heterocyclic group, and at least two groups of R ⁴⁴ , R ⁴² and R ⁴³ substitute a water-solubilizing group, and E ⁴¹ and E ⁴² each independently represent an electron. withdrawing group or E ⁴¹ and E ⁴² are bonded to each other represents a nonmetallic atom group forming an acidic heterocycle, AR represents an aromatic ring or a heterocyclic ^{group, L 41, L 42, L} 43, L ⁴⁴ each represents a substituted or unsubstituted methine carbon independently, l ⁴¹ is an integer of 0 or 1, M ⁴¹ represents an ion required to offset the total charge of the molecule, n ⁴¹ is intramolecular It represents the number of ions required to offset the total charge.

[0158]

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In the formula, Z ⁴² represents a nonmetal atom necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may be condensed, and Y ⁴³ and Y ⁴⁴ each independently represent -N ( ^R48 )-group,
Oxygen, sulfur, selenium, tellurium,
R ⁴⁵ represents a substituted aliphatic group having 8 or less carbon water-solubilizing group, a R ^48, R ⁴⁶ and R ⁴⁷ are each an aliphatic group, an aryl group or a heterocyclic group, and R ^48, R ⁴⁶ And at least two groups of R ⁴⁷ replace a water solubilizing group, W ⁴² is an oxygen atom,
Represents a sulfur atom, each ^{L 45, L 46, L 47} , L 48 represents a methine carbon at least one of the substituted methine carbon of L ^45, L ^46, L ⁴⁷ and L ^48, M ⁴² is It represents an ion required to offset the total intramolecular charge, n ⁴² represents the number of ions necessary to offset the total intramolecular charge.

R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ and R ⁴⁵ ,
Examples of the aliphatic group represented by R ⁴⁶ , R ⁴⁷ and R ⁴⁸ include a branched or linear alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, n-propyl, n-pentyl, isobutyl, etc.). Each), an alkenyl group having 3 to 8 atoms (for example, each group such as 3-butenyl and 2-propenyl) or an aralkyl group having 3 to 8 carbon atoms (for example, each group such as benzyl and phenethyl). Is mentioned.

R ⁴² , R ⁴³ and R ⁴⁴ and R ⁴⁶ , R ⁴⁷ and R
Examples of the aryl group represented by ⁴⁸ include a phenyl group, and examples of the heterocyclic group include a pyridyl group (2
-, 4-), a pyrazyl group, a furyl group (2-), a thienyl group (2-), a sulfolanyl group, a tetrahydrofuryl group,
Examples include a piperidinyl group, a pyrrole group, and an imidazolyl group.

R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ , R ⁴⁵ , R ⁴⁶ ,
Each of R ⁴⁷ and R ⁴⁸ is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkoxy group (eg, methoxy group, ethoxy group, etc.), an aryloxy group (eg, phenoxy group, p- A cyano group, a hydroxyl group, a carbamoyl group (eg, a carbamoyl group, an N-methylcarbamoyl group, an N, N-tetramethylenecarbamoyl group, etc.), a sulfamoyl group (eg, a sulfamoyl group, N, N-3-). Oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (eg, phenyl group, carboxyphenyl group, etc.), acyl group (eg, acetyl group) , Benzoyl group, etc.), amide group (for example, acetamido group Methanesulfonamide group,
Benzoylamide group) or the like.

Specific examples of the aliphatic group substituted with a water-solubilizing group include (for example, carboxymethyl, sulfoethyl,
Sulfopropyl, sulfobutyl, sulfopentyl, 3-
Sulfobutyl, 6-sulfo-3-oxahexyl, ω-
Sulfopropoxycarbonylmethyl, ω-sulfopropylaminocarbonylmethyl, N-ethyl-N-sulfopropyl, N-ethyl-N-sulfopropyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-
3-butenyl, 2-carboxy-2-propenyl, O-
Each group such as sulfobenzyl, P-sulfophenethyl and p-carboxybenzyl), and specific examples of the aryl group substituted with a water-solubilizing group (for example, p-sulfophenyl group, p-carboxyphenyl group, etc.). Each group),
Specific examples of the heterocyclic group substituted with a water-solubilizing group include (for example, respective groups such as a 4-sulfothienyl group and a 3-carboxypyridyl group).

In these, R ⁴¹ and R ⁴⁵ are alkyl groups substituted with a sulfo group, and at least two of R ⁴⁴ , R ⁴² , R ⁴³ and R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are each a carboxy group. Those which are methyl groups are preferred.

Examples of the 5- or 6-membered nitrogen-containing heterocyclic group represented by Z ⁴¹ and Z ⁴² include a basic heterocyclic ring forming a cyanine dye, and include, for example, an oxazole ring (eg, oxazole, benzoxazole) , A ring of naphthoxazole or the like), a thiazole ring (for example, a ring of thiazolidine, thiazole, benzothiazole, naphthothiazole or the like), an imidazole ring (for example, each ring of imidazole, benzimidazole, naphthimidazole or the like), a selenazole ring ( For example, each ring such as selenazole, benzoselenazole, naphthoselenazole, etc., a tellurazole ring (eg, each ring such as tellurazole, benzotellurazole, naphthotellazole), a pyridine ring (eg, each ring such as pyridine, quinoline, etc.) , A pyrrole ring (e.g., pyrrole, indole, indole Each ring such as drainin).

The above-mentioned heterocyclic rings represented by Z ⁴¹ and Z ⁴² may have a substituent at an arbitrary position, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), Trifluoromethyl group, alkoxy group (for example,
Methoxy, ethoxy, butoxy, etc., unsubstituted alkoxy groups, 2-methoxyethoxy, benzyloxy, etc., substituted alkoxy groups, hydroxy group, cyano group, aryloxy group (eg, phenoxy, tolyloxy, etc.
Unsubstituted groups), aryl group (substituted or unsubstituted groups such as phenyl, p-chlorophenyl, p-tolyl, and p-methoxyphenyl), styryl group, and heterocyclic group (e.g., furyl, thienyl) Carbamoyl group (eg, carbamoyl, N-ethylcarbamoyl, etc.), sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, etc.), acylamino group (eg, acetyl) Amino, propionylamino, benzoylamino, etc.), acyl group (eg, acetyl, benzoyl, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl, etc.), sulfonamide group (eg, methanesulfonylamide, benzene) Each group such as sulfonamide), a sulfonyl group (for example, methanesulfonyl, p Each group) carboxy groups such as toluenesulfonyl, alkyl groups (e.g., methyl, ethyl, include any group in each group), isopropyl and the like.

L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴ and L ⁴⁵ , L ⁴⁶ ,
Examples of the group substituted with the methine carbon represented by L ⁴⁷ and L ⁴⁸ include a lower alkyl group (for example, each group such as methyl and ethyl) and a phenyl group (for example, each group such as phenyl and carboxyphenyl). , An alkoxy group (for example, each group such as methoxy and ethoxy), an aryloxy group (for example,
Good groups such as phenoxy and carboxyphenoxy, and aralkyl groups (for example, benzyl and the like), and heterocyclic groups (for example, pyridyl, pyrrolyl, tetrahydrofuryl, thienyl, furyl, and pentahydrooxa) Each group such as a dinyl group) and a fluorine atom.

These dyes are represented by L ⁴¹ , L ⁴² , L ⁴³ , L ⁴⁴
And when one of the methine carbons represented by L ⁴⁵ , L ⁴⁶ , L ⁴⁷ , and L ⁴⁸ is substituted, a high spectral sensitivity is generally obtained, but the dye is provided with a property of being easily drifted in a processing bath. This has a favorable effect of reducing residual color contamination.

W ⁴¹ and W ⁴² are an oxygen atom, a sulfur atom, and ＣC <
(E ⁴¹ ) (E ⁴² ) or ＣC <(E ⁴³ ) (E ⁴⁴ ), and E ⁴¹ and E ⁴² or E ⁴³ and E ⁴⁴ each independently represent an electron-withdrawing group, and are bonded to each other To form a keto ring or an acidic heterocyclic ring, l ⁴¹ represents an integer of 0 or 1,
M ⁴¹ and M ^{42 each} represent a cation or an acid anion. Specific examples of the cation include a proton, an organic ammonium ion (for example, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (for example, each of lithium, sodium, calcium, and the like). Cation). Specific examples of the acid anion include, for example, a halogen ion (eg, a chloride ion, a bromine ion, an iodine ion, etc.),
p-toluenesulfonic acid ion, perchlorate ion, 4-
And boron fluoride ions. n ⁴¹ and n ⁴² become 0 when an internal salt is formed to cancel the total charge in the molecule.

The electron-withdrawing groups represented by E ⁴¹ and E ⁴² or E ⁴³ and E ⁴⁴ are selected from groups having a Hammett σp value of more than 0.3, and specifically include a cyano group and a carbamoyl group (for example, , A carbamoyl group, a morpholinocarbonyl group,
N-methylcarbamoyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl group, morpholinosulfonyl group, N, N-dimethylsulfamoyl group, etc.), acyl Group (eg, acetyl group, benzoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group,
Toluenesulfonyl group, etc.).

The keto ring formed by E ⁴¹ or E ⁴² or E ⁴³ or E ⁴⁴ and the acidic heterocyclic ring are represented by the aforementioned general formula (2)
The same as the keto ring and the acidic heterocyclic ring formed by E ²¹ and E ²² in -a).

In the formula, R ^a and R ^b each represent a lower alkyl group, an aryl group, or a heterocyclic group, and specific examples of the lower alkyl group include methyl, ethyl, propyl, 2-hydroxyethyl, and 2-methoxyethyl. , Trifluoroethyl,
Examples include substituted and unsubstituted groups such as allyl, carboxymethyl, carboxyethyl, 2-sulfoethyl, and benzyl. The aryl group and the heterocyclic group represented by R ^a and R ^b include those represented by R ⁴⁴ , R ⁴² , R ⁴³ , R ⁴⁸ , R ⁴⁶ and R ⁴⁷ .

Specific examples of the spectral sensitizing dyes represented by formulas (4-a) and (4-b) are shown below, but are not limited to these compounds.

[0174]

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[0175]

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[0176]

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[0177]

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[0178]

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[0179]

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[0180]

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The above-mentioned compounds are described, for example, in "Cyanine Soybeans and Related Compounds" by FM Hammer (1964, published by Inter Science Publishers), US Pat. Nos. 2,454,629 and 2, , 493, 748, and the like, and can be easily synthesized with reference to a conventionally known method.

[0182]

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In the formula, R ⁵¹ represents an aliphatic group having 10 or less carbon atoms substituted with a water-solubilizing group, and R ⁵² , R ⁵³ and R ⁵⁴ each represent an aliphatic group, an aryl group or a heterocyclic group; And R ⁵² ,
At least two groups of R ⁵³ and R ⁵⁴ substitute a water solubilizing group. V ⁵¹ and V ⁵² are each bonded to a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or V ⁵¹ and V ⁵² to form an azole ring. And L ⁵¹ and L ⁵² each represent a substituted or unsubstituted methine carbon, and W ⁵¹ represents ＮN
(AR) group, oxygen atom, sulfur atom, = C <(E ⁵¹ ) (E
⁵² ) represents a group, AR represents an aromatic ring or a heterocyclic group,
⁵¹ and E ⁵² each independently represent an electron-withdrawing group, or may combine with each other to form a keto ring or an acidic heterocyclic ring,
M ⁵¹ represents an ion required to offset the total charge in the molecule, and n ⁵¹ represents the number of ions required to offset the total charge of the molecule.

In the general formula (5), R ⁵¹ , R ⁵² and R ⁵³
And the water-solubilizing group substituted for R ⁵⁴ include, for example, acid groups such as a sulfo group, a carboxy group, a phosphono group, a sulfate group, and a sulfino group.

As the aliphatic group represented by R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ , for example, a branched or linear alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, n-propyl, n
Each group such as pentyl and isobutyl), having 3 to 8 carbon atoms
(E.g., 3-butenyl, 2-propenyl, etc.) or an aralkyl group having 3 to 8 carbon atoms (e.g., benzyl, phenethyl, etc.).

Examples of the aryl group represented by R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ include a phenyl group, and examples of the heterocyclic group include a pyridyl group (2-, 4-) and a pyrazyl group. , A furyl group (2-), a thienyl group (2-), a sulfolanyl group, a tetrahydrofuryl group, a piperidinyl group,
Pyrrole group, imidazolyl group, etc.).

Each of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ includes a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and the like), an alkoxy group (for example, a methoxy group and an ethoxy group), an aryloxy group and the like. Group (for example, phenoxy group, p-
Tolyloxy group, etc.), cyano group, carbamoyl group (for example, carbamoyl group, N-methylcarbamoyl group, N,
N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.) ), An aryl group (eg, phenyl group, carboxyphenyl group, etc.), an acyl group (eg, acetyl group, benzoyl group, etc.).

Specific examples of the aliphatic group substituted with a water-solubilizing group include (for example, carboxymethyl, sulfoethyl,
Sulfopropyl, sulfobutyl, sulfopentyl, 3-
Sulfobutyl, 6-sulfo-3-oxahexyl, ω-
Sulfopropoxycarbonylmethyl, ω-sulfopropylaminocarbonylmethyl, N-ethyl-N-sulfopropyl, 3-sulfinobutyl, 3-phosphonopropyl, 4-sulfo-3-butenyl, 2-carboxy-
2-propenyl, O-sulfobenzyl, P-sulfophenethyl, p-carboxybenzyl, etc.), and specific examples of the aryl group substituted with a water-solubilizing group include (for example, p-sulfophenyl group, Specific examples of the heterocyclic group substituted with a water-solubilizing group include (for example, a 4-sulfothienyl group and a 3-sulfothienyl group).
Each group such as -carboxypyridyl group).

In these, R ⁵² and R ⁵³ are alkyl groups substituted with a sulfo group, and those in which at least two of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ are each a carboxymethyl group. preferable.

[0190] The nitrogen-containing heterocyclic group having 5-membered or 6-membered represented by Z ⁵¹ include heterocyclic basic forming a cyanine dye, for example, an oxazole ring (e.g., oxazole, benzoxazole, naphthoxazole etc),
Thiazole ring (for example, each ring of thiazolidine, thiazole, benzothiazole, naphthothiazole, etc.), imidazole ring (for example, imidazole, benzimidazole, naphthimidazole, etc.), selenazole ring (for example, selenazole, benzoselenazole, naphthoselenazole, etc.) ), Tetrazole ring (eg, tetrazole,
Benzotetrazole, naphthotetrazole and the like), pyridine ring (for example, each ring of pyridine and quinoline), and pyrrole ring (for example, each ring of pyrrole, indole, indolenine and the like) and the like can be mentioned.

Examples of the group substituted by the methine carbon represented by L ⁵¹ and L ⁵² include a lower alkyl group (for example, each group such as methyl and ethyl) and a phenyl group (for example, phenyl and carboxyphenyl). Each group), an alkoxy group (for example, each group such as methoxy and ethoxy), an aryloxy group (for example, each group such as phenoxy and carboxyphenoxy), an aralkyl (for example, a group such as benzyl), and a group such as a fluorine atom. is there.

[0192] dyes of the invention, when one any of methine carbon represented by L ⁵¹ and L ⁵² are substituted, but generally higher spectral sensitivity is obtained, the easy characteristic dye is bleached by treatment bath It has a favorable effect of reducing residual color contamination.

W ⁵¹ is an oxygen atom, a sulfur atom, ＝ C <
L ⁵¹ and L ⁵² each represent a group represented by the formula (E ⁵¹ ) or (E ⁵² ),
Represents an unsubstituted methylene carbon; E ⁵¹ and E ⁵² each independently represent an electron-withdrawing group, which may be bonded to each other to form a keto ring or an acidic heterocyclic ring;

The electron-withdrawing groups represented by E ⁵¹ and E ⁵² are selected from groups having a Hammett σp value of more than 0.3, and specifically include a cyano group and a carbamoyl group (for example, carbamoyl group, morpholinocarbonyl Group, N-methylcarbamoyl group, etc.), alkoxycarbonyl group (for example,
Methoxycarbonyl group, ethoxycarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl group, morpholinosulfonyl group, N, N-dimethylsulfamoyl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), sulfonyl group (For example, methanesulfonyl group, ethanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.).

The keto ring formed by E ⁵¹ and E ⁵² and the acidic heterocyclic ring are, for example, the same as the keto ring formed by E ²¹ and E ²² and the acidic hetero ring in formula (2-a). It is.

Examples of the heterocyclic group include the aforementioned R ⁵¹ , R ⁵² and R ⁵³
And those of the content shown in R ^54.

M ⁵¹ represents a cation or an acid anion. Specific examples of the cation include a proton, an organic ammonium ion (eg, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (eg, lithium, sodium, calcium, etc.). Examples of the acid anion include, for example, a halogen ion (for example, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid ion, perchlorate ion, 4-boron fluoride ion and the like. Is mentioned. n ⁵¹
Is 0 when an internal salt is formed and the total charge in the molecule is offset.

Specific examples of the photosensitive dye represented by formula (5) are shown below, but the invention is not limited to these compounds.

[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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The above compounds are described, for example, in "Cyanine Soybeans and Related Compounds" by F.M.Hama (1964, published by InterScience Publishers), US Pat. No. 2,454,629,
No. 2,493,748, British Patent No. 489,335
, And can be easily synthesized with reference to a conventionally known method described in, for example, European Patent No. 730,008.

The addition amount of the compounds of the general formulas (1) to (5) varies greatly depending on the conditions used and the type of emulsion, but is preferably 1 × 10 ^{−6 to} 5 × 10 ⁻⁶ per mol of silver halide.
× 10 ⁻³ mol, more preferably 2 × 10 ⁻⁶ to 2 × 10 ⁻³
Range of moles.

The compounds represented by formulas (1) to (5) can be added to a silver halide emulsion by a conventionally known method. For example, JP-A-50-80826, 50
No. 3,822,135, JP-A-50-1141.
9, a method of dispersing and adding together with a surfactant, U.S. Pat. Nos. 3,676,147 and 3,469,987;
No. 4,247,627, JP-A-51-59942,
No. 53-16624, No. 53-102732, No. 5
Nos. 3-102733 and 53-137131, the method of dispersing and adding to a hydrophilic substrate, East German Patent No. 143,
No. 324, or a method disclosed in Research Disclosure No. 21,802, JP-B-50
-40659, and water-soluble solvents such as low-boiling solvents such as water, methanol, ethanol, propyl alcohol, acetone, and fluorinated alcohol; dimethylformamide, methyl High boiling point solvents such as cellosolve and phenyl cellosolve) alone or in a mixed solvent thereof may be added and dissolved in the solvent.

The photosensitive dyes represented by formulas (1) to (5) may be added at any stage during the emulsion production process from physical ripening to chemical ripening and coating. It is preferably added during the period from to the end of chemical ripening. Addition of the compound according to the present invention during physical ripening, prior to the addition of the chemical sensitizer in the chemical ripening step, or immediately after the addition of the chemical sensitizer, has the effect of obtaining higher spectral sensitivity. Are preferably used.

The silver halide emulsion of the light-sensitive material of the present invention comprises:
Those having a halogen composition in which silver chloride is at least 50 mol% are preferred. Preferably 10 ^-8 to 10 per mol of silver
Silver chloride containing at least ⁴ moles of rhodium compound
Mol% or more, more preferably ^10-7 to ^10-5 per mole of silver.
It is an emulsion that contains moles.

The silver halide grains of the silver halide emulsion of the light-sensitive material of the present invention are cubic, octahedral, and have an aspect ratio of 5
Although any of the above tabular crystals and the like can be used, monodisperse particles having a coefficient of variation represented by (standard deviation of particle size) / (average value of particle size) × 100 of 15% or less are preferable.

The average grain size of the silver halide grains is not particularly limited, but is 0.05 to 2.0 μm, preferably 0.1 to 2.0 μm.
1.0 μm.

It is preferable to employ the following techniques for the light-sensitive material of the present invention.

1) Solid dispersed fine particles of dye: JP-A-7-5
No. 629 (3), paragraph “0017” to page (16), paragraph “0024” 2) Compound having an acid group: JP-A-62-237445, page 292 (8), lower left column, line 11 to 309 (25) 3) acid polymer: lower right column, third line, page 3) JP-A-6-186659 (10)
Page paragraph "0036" to page 17 paragraph "0062" 4) Supersensitizer JP-A-6-347938, page (3) page "0011"
To page (16), paragraph "0066" 5) Redox compounds JP-A-4-245253, 235 (7) to 250
(29) 6) Syndiotactic polystyrene support JP-A-3-131843, pages 324 (2) to 327
(5) Other additives are described in, for example, Research Disclosure No. No. 17643 (December 1978); No. 18716 (November 1979) and the same No. Three
08119 (December, 1989).

[0215]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of silver halide emulsion) Aqueous solution of silver nitrate and NaC
A silver halide grain composed of 70 mol% of silver chloride and the remainder of silver bromide was grown from an aqueous solution of a mixture of 1 and KBr by a double jet method. In this case, mixing was performed at 50 ° C., pAg 7.8, p
The reaction was performed under the conditions of H3.0, and a water-soluble rhodium salt was added at 2 × 10 ⁻⁷ mol per mol of silver during grain formation. afterwards,
After washing with desalinated water by flocculation, a bactericide consisting of a mixture of the following compounds [A], [B] and [C] and ossein gelatin were added and redispersed. Silver potential E after redispersion
Ag was 220 mV. The resulting emulsion was a monodisperse emulsion having an average particle size of 0.19 μm and a variation coefficient of the particle size distribution of 12%.

The pH of the thus obtained emulsion was adjusted with citric acid, and the pAg was adjusted with KBr.
7 mg of chloroauric acid and 0.57 mg of sulfur were added, and 5
Chemical ripening was performed at 3 ° C. for 50 minutes. After ripening, 600 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mole of silver, and KI was further added.
After adding 00 mg, sensitizing dye 3-3 was added at 170 mg / mo.
IAg and 3-11 were added at 70 mg / molAg to obtain a silver halide emulsion.

(Preparation of photosensitive material sample)
A photosensitive silver halide emulsion layer having the following formulation (1) and a photosensitive silver halide emulsion layer having the following formulation (1) were provided on one side of a 100 μm-thick polyethylene terephthalate support provided with a 0.1 μm-thick undercoat layer described in Example 1 of US Pat. The lower layer and the upper layer of the emulsion protective layer of (2) and (3) are simultaneously coated, and the backing layer of the following formula (4) and the backing protective layer of the following formula (5) are simultaneously coated on the other surface. A sample was obtained.

Formulation (1) (Composition of photosensitive silver halide emulsion layer) Gelatin 1.5 g / m ² Silver halide emulsion silver amount 3.5 g / m ² Hydrazine compound; H-7 3 × 10 ⁻⁵ mol / m ² 5-nitroindazole 16.5 mg / m ² polymer latex 1 0.5 g / m ² colloidal silica 0.25 g / m ² water-soluble polymer V-1 20mg / m ² surfactant: saponin 0.1 g / m ² surface Activator: Sodium sulfosuccinate iso Pentyl normal decyl ester 8.0 mg / m ² Formula (2) (Emulsion protective layer lower layer composition) Gelatin Amount adjusted to the Ag amount / binder amount described in the table Surfactant: Sodium sulfosuccinate iso preparing the Ag amount / amount of binder according to pentyl n-decyl ester 10 mg / m ² formulation (3) (emulsion protective layer upper composition) gelatin table Nucleation accelerator: Na-12 10mg / m ² Matting agent: average particle size 3.5μm polymethyl methacrylate beads 30 mg / m ² halogenated compounds: Listed in Table 1 22 mg / ^{m 2} Surfactant: Sodium sulfosuccinic acid di (2-ethylhexyl) ester 15 mg / m ² Surfactant: F-1 0.6 mg / m ² Silicone oil 45 mg / m ² HA-1 110 mg / m ² Formulation (4) (Backing layer composition) Gelatin 2.3 g / m ² surfactant: saponin ^{0.12g / m 2 D-1 65mg} / m 2 D-2 16.8mg / m 2 D-3 94.4mg / m 2 colloidal silica 0.2 g / m ² polymer latex 2 0 ^{.3g / m 2 HA-2 110mg} / m 2 formulation (5) (backing protective layer composition) gelatin ^{1.0g / m 2 D-1 24.7mg} / m 2 D-2 6. ^{mg / m 2 D-3 35.7mg} / m 2 Matting agent: average particle size 4.0μm polymethyl methacrylate beads 19 mg / m ² Silica 19 mg / m ² Surfactant: Sodium sulfosuccinic acid di (2-ethylhexyl) ester 10 mg / m ² HA-3 110 mg / m ²

[0220]

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[0221]

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[0222]

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(Evaluation of Drying Property) Processing was carried out using an automatic developing machine manufactured by Dainippon Screen Co., Ltd. under the following conditions.

(Process) (Temperature) (Time) Developing 35 ° C. 30 seconds Fixing 35 ° C. 20 seconds Rinse at room temperature 20 seconds Squeeze / Drying 45 ° C. 30 seconds (Evaluation of scratch resistance) After continuously applying a load in the range of 0 to 200 g using a 0.1 mm sapphire needle with a meter Heidon 18 type, the state of the sample obtained by performing the above-mentioned development processing is shown as a level unusable for use in ranks 4 and below. Was evaluated on a 10-point scale.

Table 1 shows the above results.

[0226]

[Table 1]

[0227]

As has been demonstrated in the examples, according to the present invention, it is possible to obtain a silver halide photographic material having rapid processing suitability and excellent scratch resistance.

Claims (1)

[Claims] 1. A photosensitive silver halide emulsion layer containing a hydrazine compound on a support, wherein the ratio of the amount of silver to the amount of hydrophilic binder on the side having the emulsion layer is 0.7 to 2, And a hydrophilic colloid layer adjacent to the emulsion layer contains a halide compound.