JP3151680B2 - Silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic material having high sensitivity, improved photographic sensitivity fluctuation due to storage of raw samples over time, and excellent safelight properties. It relates to a photographic material.

[0002]

BACKGROUND OF THE INVENTION The demand for silver halide photographic light-sensitive materials has become stricter each year, and in addition to the strong demands for high sensitivity and high image quality (particularly excellent graininess and sharpness),
There is a strong demand for low replenishment processing aptitude for reducing environmental pollution and rapid processing for short-time finishing. In most cases, these requirements are solved by achieving high sensitivity of silver halide grains.
It is no exaggeration to say that increasing the sensitivity of silver halide grains is the biggest challenge in the industry.

As one method of increasing the sensitivity, supersensitization (Supe)
rsensitization) is known to be useful. For supersensitization, see Photographic Science and Engenee
ring. Volume 13, P.13-17 (1969), Volume 18, P.418-
430 (1974); H. Themes of the P
hotographic Process 4th edition, Macmillan publisher, 1977
Year, p. 259, etc., and a suitable sensitizing dye,
It is known that high sensitivity can be obtained by selecting a supersensitizer.

Conventionally, supersensitizers for red-sensitive and infrared-sensitive spectral sensitizing dyes include, for example, stilbene,
Azaindene, mercaptoheterocyclic compounds, thiourea, many compounds such as condensates of phenol and hexamethylenetetramine are known, for example, US Patent 2,875,
058, 3,340,064, 3,457,078, 3,458,318
Nos. 3,6615,632, 3,695,888, 4,011,083,
It is disclosed in JP-A-61-203447.

However, when the silver halide emulsion is supersensitized by these conventional techniques, there are disadvantages that the photographic sensitivity fluctuates greatly with the lapse of time and the safelight property deteriorates, and improvement thereof has been desired. .

The term "safelight" as used in the present invention refers to a safe light used when handling a photosensitive material in a dark room.
The safelight property is good when the latitude is high.

There has been a demand for a new sensitizing method which does not have the above-mentioned disadvantages from the viewpoints of increasing the sensitivity of photographic light-sensitive materials, stabilizing quality and improving productivity.

[0008] A technique using a combination of a cyanine dye and a macrocyclic compound is described in, for example, JP-A-55-89359.

The specification states that the photographic application of cyanine dyes is in opposition to the traditionally very low photostability of cyanines (except for their use as sensitizers), It is clear that the invention does not envisage the use of cyanine as a sensitizer.

[0010] In the claims, the invention clearly shows that the crown ether is a quenching substance, and has a technical idea of efficiently leading a fluorescence process from an excited state of a dye, When high sensitivity is to be obtained with a photographic dye as in the present invention, the above quenching action is completely contrary to the purpose.

[0011] Accordingly, in the specification, there is no description suggesting the object of the present invention, which is to increase the sensitivity and improve the raw storage stability and safelight property of the photographic material.

As described above, the present invention relates to the above-mentioned JP-A-55-89359.
The issue is completely different from the technical idea.

[0013]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a red-sensitive silver halide photographic light-sensitive material having high sensitivity, excellent storage stability over time in raw samples, excellent safelight properties, and stable photographic characteristics. is there.

[0014]

The present inventors have made intensive studies and as a result, have found that the object of the present invention can be achieved by the following method, and have accomplished the present invention. That is, in a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion is spectrally sensitized with a sensitizing dye, and at least one oxygen-containing crown compound is used. This is achieved by a silver halide photographic material containing a complex. Hereinafter, the present invention will be described in detail.

The crown compound of the present invention is described in "Crown Compound-Characteristics and Application-" (Mitsuo Hiraoka, Kodansha Scientific), page 4, "O, N as electron donor donor atoms. , S or the like having a heteroatom in the ring structure and having a function of incorporating into the vacancy of the cationic ring. "

Here, the macrocyclic compound is a compound having a ring composed of 12 or more atoms.

The oxygen-containing crown compound according to the present invention includes:
Among these crown compounds, those having at least one oxygen atom in the molecule are referred to.

This oxygen atom is preferably on the ring constituting the crown from the viewpoint of sensitivity, and more preferably two or more oxygen atoms are present on the ring constituting the crown.

The size of the ring may be a 12-membered ring or more,
From the viewpoint of sensitivity, the ring is preferably 12 to 24 members, more preferably 15 to 21 members. Hetero atoms constituting the ring include O, N, S, Se and the like, but it is preferable that only oxygen atoms are used from the viewpoint of sensitivity.

The complex of the crown compound of the present invention is a complex in which the crown compound serves as a host molecule, and a cation moiety is incorporated into the crown ring using a salt of various metals, an ammonium salt, an organic ionic compound or the like as a guest.

Here, the salts of various metals refer to salts of typical metals or transition metals, and Ia, Ib, IIa, IIb, IIb of the periodic table.
Salts of metals of the groups Ia, IIIb and IVb are preferred in terms of sensitivity.

Examples of ammonium salts include NH ₄ ⁺ , HONH
₃ Cl, NH ₂ NH ₃ Cl, (CH ₃ ) ₂ CHCH ₂ NH ₃ Cl, (CH ₃ ) ₂ CHCH ₂ CH ₂ NH ₃
Cl, (CH ₃ ) ₂ CNH ₃ Cl, PhNH ₃ Cl, NH ₂ CH ₂ CH ₂ NH ₃ Cl, HOOCH ₂
NH ₃ Cl, [NH ₂ C (= NH ₂ ) NH ₂ ] Cl, [NH ₂ C (= NH ₂ ) NH ₂ ] ₂ CO _{3 and the} like.

Examples of the organic ionic compound include p-toluenediazonium BF ₄ , benzenediazonium BF ₄ ,
- methoxy, p- chloro, p- nitro, 3,4-dimethyl - aromatic diazonium salts such as diazonium BF _4, in addition to the aromatic Ashironiumu salts such as benzoyl cation PF ₆ salts, amphoteric by tautomerism Thiourea, N-phenylthiourea, 1-phenylsemicarbazide, 1 and 4-phenylthiosemicarbazide,
-Including thiazolidinethione, thiobenzamide and the like.

Hereinafter, specific examples of the oxygen-containing crown compound and its complex used in the present invention will be shown, but the present invention is not limited thereto.

[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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[0032]

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[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

The above compounds are described, for example, in CJPedersen, "Jou
rnal of American chemical Society ”Vol.86 (2495), 70
17〜7036 (1967), GWGokel, SHKorzeniowski, “Mac
rocyclic Polyether Synthesis, ”Springer-Verlag (19
82), Oda, Shono, Tabushi, "Crown ether chemistry"
Kagaku Doujin (1978), "Host-guest" Kyoritsu Publishing (1
979), Sasaki, Koga, Synthetic Organic Chemistry, Vol. 45 (6) .571-5
82 (1987), "Crown compound" by Hiraoka, Kodansha Scientific, etc., and can be easily synthesized with reference to these.

Next, the sensitizing dyes referred to in the present invention refer to cyanine dyes such as cyanine, merocyanine, and holopolar, and complex cyanines and complex merocyanines, and are preferably represented by the following general formulas [I] and / or [II] And a cyanine dye represented by the formula:

[0038]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group, an alkenyl group, an alkynyl group or an aryl group. L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each represent a methine group. Z ₁ , Z ₂ , Z ₃ and Z ₄ are each 5 or 6
Represents an atom or group of atoms necessary to complete a membered heterocyclic nucleus. Z ₅ represents a group of hydrocarbon atoms necessary to form a 5- or 6-membered ring. m ₁ , m ₂ , m ₃ and m ₄ each represent 0 or 1. n ₁ and n ₂ represents 0 or 1. X ^- represents an acid anion. Y ₁ and Y ₂ each represent 0 or 1, and when the compound forms an internal salt, Y ₁ and Y ₂ each represent 0.

In the sensitizing dye used in the present invention, the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ in the general formula [I] or [II] may be branched. More preferably, it has 10 or less carbon atoms and may have a substituent. As the substituent, sulfo, aryl, carboxy,
Examples include amine (primary, secondary, and tertiary), alkoxy, aryloxy, hydroxy, alkoxycarbonyl, acyloxy, acyl, aminocarbonyl, sulfonyl, and cyano groups and halogen atoms. Illustrative examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, sulfoethyl, sulfopropyl, sulfobutyl, benzyl, phenethyl, carboxyethyl,
Carboxymethyl group, dimethylaminopropyl group, methoxyethyl group, phenoxypropyl group, methylsulfonylethyl group, pt-butylphenoxyethyl group, cyclohexyl group, octyl group, decyl group, carbamoylethyl group, sulfophenethyl group, sulfobenzyl group, 2-hydroxy-3-sulfopropyl group, ethoxycarbonylethyl group, 2,3-disulfopropoxypropyl group, sulfopropoxyethoxyethyl group, trifluoroethyl group, carboxybenzyl group, cyanopropyl group, p-carboxyphenethyl group, Ethoxycarbanylmethyl group, pivaloylpropyl group, propionylethyl group, anisyl group, acetoxyethyl group, benzoyloxypropyl group, chloroethyl group, morpholinoethyl group, acetylaminoethyl group, N-ethylaminocarboni Propyl group, cyanoethyl group and the like.

As the alkenyl group, an alkenyl group having 10 or less carbon atoms is preferable, and examples thereof include an allyl group, 2-butenyl group and 2-propynyl group. Examples of the alkynyl group include a propargyl group.

The aryl group includes, for example, a phenyl group, a carboxyphenyl group and a sulfophenyl group. These alkenyl group, alkynyl group and aryl group may be substituted by the groups mentioned as substituents of the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ .

L ₁ , L ₂ , L ₃ , L of the general formula [I] or [II]
_The methine groups represented by ₄ and L ₅ may have a substituent, and if they have a substituent, they are represented by the formula (-CR ₅ =);
_{As the} group represented by ₅ , a linear or branched alkyl group having about 1 to 8 carbon atoms (eg, a methyl group, an ethyl group,
Examples include a propyl group, a butyl group, a carboxyl group, a benzyl group, etc., an alkoxy group (eg, a methoxy group, an ethoxy group, etc.), and an aryl group (eg, a phenyl group, a tolyl group, etc.).

Z ₁ , Z ₂ , Z ₃ and Z ₄ each represent an atom or a group of atoms necessary to complete a 5- or 6-membered heterocyclic nucleus, for example, thiazole, benzothiazole, naphthothiazole, selenazole, benzol Selenazole, naphthoselenazole, imidazole, benzimidazole,
Examples include naphthoimidazole, oxazole, benzoxazole, naphthoxazole, pyridine, quinoline ring and the like.

[0045] X in the general formula [I] and [II] ^- anion represented by, for example, chloride, bromide, iodide, perchlorate ion, fluoride Moto硼periodate ions, p-
Toluenesulfonic acid ion, ethylsulfonic acid ion,
Methyl sulfonate ion, nitrate ion and the like can be mentioned.

Further, among the sensitizing dyes represented by the general formulas [I] and [II], particularly useful sensitizing dyes can be represented by the following general formulas [III] and [IV].

[0047]

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In the formula, Y ₁ , Y ₂ , Y ₃ and Y ₄ each represent an oxygen atom, a sulfur atom or a selenium atom.

A ₁ , A ₂ , A ₃ , B ₁ , B ₂ , B ₃ , B ₄ , C ₁ , C ₂ ,
_{C 3, C 4, D 1} , D 2, D 3 and D ₄ are each a hydrogen atom, a halogen atom, an alkyl atom, an alkoxy group, a phenyl group, a cyano group, a nitro group or an alkoxycarbonyl group, A ₁ and B ₁ , B ₁ and C ₁ , C ₁ and D ₁ , A ₂ and B ₂ , B ₂ and C ₂ ,
At least one of the combinations of C ₂ and D ₂ , A ₃ and B ₂ , B ₃ and C ₃ , C ₃ and D ₃ , A ₄ and B ₄ , B ₄ and C ₄ and C ₄ and D ₄ It may combine to form a benzene ring. R ₅ and R ₆ each represent a lower alkyl group. R ₁ , R ₂ , R ₃ , R ₄ , L ₁ , L ₂ , L ₃ ,
L ₄ , L ₅ , X ⁻ , n ₁ , n ₂ , q ₁ and q ² each represent R ₁ , R ₂ , R ₃ , R ₄ , L ₁ , L ₁ in the general formula (I) or (II).
_{2, L 3, L 4,} L 5, X -, the same meanings as n _1, n _2, Y ₁ and Y _2.

In the general formula [III] or [IV], A ₁ , A ₂ ,
The alkyl group represented by A ₃ , B ₁ , B ₂ , B ₃ , B ₄ , C ₁ , C ₂ , C ₃ , C ₄ , D ₁ , D ₂ , D ₃ and D ₄ has 1 carbon atom ~
About 5 linear or branched lower alkyl groups (eg, methyl group, ethyl group, propyl group, butyl group, trifluoromethyl group, etc.) and alkoxy groups each having 1 carbon atom
Approximately 5 straight or branched alkoxy groups (eg, methoxy group, ethoxy group, etc.), halogen atoms include fluorine, chlorine, bromine and iodine atoms, and phenyl groups include, for example, phenyl having no substituent Examples of the alkoxycarbonyl group such as a group, a hydroxyphenyl group and a carboxyphenyl group include a methoxycarbonyl group and an ethoxycarbonyl group. Further, n ₁ and n ₂ represent 0 or 1, and the sum thereof is preferably 1.

Next, specific examples of the sensitizing dye used in the present invention will be described, but the present invention is not limited thereto.

[0052]

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[0053]

[Table 4]

[0054]

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[0055]

[Table 5]

[0056]

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The sensitizing dyes described above are described, for example, in FM Hammer, The Chemistry of Heterocyclic Compound.
s) Volume 18, (The Cyanine Dyes and Related Compound
s) (A. Weissherger ed. Interscience, New York 1
964).

The addition amount of the sensitizing dye in the present invention is not particularly limited, but it is preferable to use 2 × 10 ^-8 mol to 1 × 10 ^-2 mol per mol of silver halide.

To add the oxygen-containing crown compound of the present invention to a hydrophilic colloid containing silver halide grains, the compound is dissolved, dispersed or suspended in water or a hydrophilic organic solvent such as methanol, ethanol or fluorinated alcohol. It may be added later. The timing of addition may be any timing before coating the emulsion.

The order of adding the sensitizing dye and the crown compound is as follows.
Either of them may be added first, or they may be added simultaneously or as a mixed solution. The addition amount of the crown compound of the present invention varies depending on the kind of the compound, but is usually in the range of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide, preferably 5 × 10 ^-1 mol.
× 10 ^-6 to 1 × 10 ^-2 mol.

The silver halide used in the present invention includes any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. You. Silver halide grains preferably used in the present invention are silver chloride or silver chlorobromide. More preferably, the silver bromide content is 0.01 to
2 mol% silver chlorobromide. The composition of the silver halide grains may be uniform from the inside to the outside of the grains, or the inside and outside compositions of the grains may be different.
When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous. Also, JP
-183647, it may have a localized phase having a locally different halogen composition.

The grain size of the silver halide grains is not particularly limited, but is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2 in consideration of other photographic properties such as rapid processing and sensitivity.
It is in the range of μm. The particle diameter is represented by an average based on a projected area, wherein a spherical or approximate spherical particle diameter is a particle diameter, and a cubic particle is a ridge length, which is a particle diameter. The particle size distribution of the silver halide grains may be polydisperse or monodisperse. Preferably, in the particle size distribution of silver halide grains, the coefficient of variation is 0.22 or less, more preferably
Monodispersed silver halide grains of 0.15 or less.

In the present invention, the silver halide grains used in the emulsion may be obtained by any of an acidic method, a neutral method and an ammonia method. The particles may be grown at one time, or may be grown after seed particles have been made. The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Octahedron, 14-hedron,
Particles having a shape such as a dodecahedron can also be used.
Further, the particles may be spherical, rod-shaped, plate-shaped or the like. Further, particles having a twin plane may be used.

When the compound of the present invention is used in a red-sensitive silver halide emulsion layer, it preferably has a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer.

The silver halide emulsion of the present invention is subjected to chemical ripening for the purpose of preventing fog during the production process, storage, or photographic processing of the light-sensitive material, or maintaining chemical ripening for the purpose of maintaining stable photographic performance. An antifoggant or stabilizer can be added at the time and / or after the completion of chemical ripening and before coating the silver halide emulsion. As the binder for the silver halide photographic light-sensitive material used in the present invention, it is advantageous to use gelatin, but if necessary, gelatin derivatives, gelatin and other polymer graft polymers, other proteins, sugar derivatives, A hydrophilic colloid such as a cellulose derivative, a synthetic hydrophilic polymer substance such as a homopolymer or a copolymer can also be used. Dye-forming couplers such as yellow couplers, magenta couplers, and cyan couplers may be used in the silver halide photographic light-sensitive material according to the present invention. Further, a silver image may be used without using a dye-forming coupler.

In the present invention, an acylacetanilide-based coupler can be preferably used as the yellow coupler. Among them, benzoylacetoanilide compounds and pivaloylacetoanilide compounds are advantageous, and particularly, exemplified compounds Y-1 to Y-146 and JP-A-63-97951 described in JP-A-63-85631. The exemplified compounds Y-1 to Y-98 described and JP-A-1-156748 (67 to
Exemplified compounds Y-1 to Y-24 described on page 78) are preferably used.

Examples of the magenta coupler that can be used in the present invention include pyrazoloazole couplers such as oil-protected indazolone couplers and cyanoacetyl couplers, preferably 5-pyrazolone and pyrazolotriazoles. The magenta coupler preferably used in the present invention includes magenta couplers represented by the following formulas [MI] and [M-XI].

[0068]

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In the formula, Z represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

R represents a hydrogen atom or a substituent. The substituent represented by R is not particularly limited, but typically includes groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. Atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy and the like.

Specific examples of the compound represented by the formula [MI] include M-1 to M-61 described in JP-A-63-167360, page 5, lower right column to page 9, lower left column. And JP-A-62-16633
No. 1 to 4, 6, 8 to 17, 19 to 24, 26 to 4 among the compounds described in the upper right column on page 18 to the upper right column on page 32 of No. 9
Compounds represented by 3,45 to 59, 61 to 104, 106 to 121, 123 to 162, and 164 to 223 can be exemplified.

[0072]

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In the formula, Ar represents an aryl group, X represents a halogen atom, an alkoxy group or an alkyl group, and R represents a group that can be substituted on a benzene ring. n represents 1 or 2. When n is 2, R may be the same group or different groups. Y represents a group which can be removed by a coupling reaction with an oxidized form of an aromatic primary amine color developing agent.

In the general formula [M-XI], Y is a group which can be removed by a coupling reaction with an oxidized form of an aromatic primary amine-based color developing agent, for example, a halogen atom, an alkoxy group, an aryloxy group, Examples include an acyloxy group, an arylthio group, an alkylthio group, and a 5- to 6-membered heterocyclic group. Here, Y does not represent a hydrogen atom.

The coupler represented by the general formula [M-XI] includes, for example, Compound No. 2 described in JP-A-63-52138.
18 to No. 244 and the like, and further, U.S. Pat.
788, 3,061,432, 3,062,653, 3,127,269
Nos. 3,311,476, 3,152,896, 3,419,391,
3,519,429, 3,555,318, 3,684,514, 3,8
88,680, 3,907,571, 3,928,044, 3,930,86
No. 1, 3,930,866, 3,933,500, JP-A-49-29639
No. 49-111631, No. 49-129538, No. 50-13041, No.
52-58922, 55-62454, 55-118034, 56-3804
No. 3, No. 57-35858, No. 60-2953, No. 60-23855, No. 60
-60644, UK Patent 1,247,493, Belgium Patent 789,116
No. 792,525, West German Patent No. 2,156,111, JP-B-46-604
No. 79, 57-36577 and the like.

As the cyan coupler, a phenol cyan coupler and a naphthol cyan coupler are preferably used. Cyan couplers preferably used in the present invention include the following general formulas [C-I] and [C-II]
And a cyan coupler represented by

[0077]

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In the formula, R ₁ represents an alkyl group having 2 to 6 carbon atoms. R ₂ represents a ballast group. Z represents a hydrogen atom or an atom or group which can be removed by reaction with an oxidized form of a color developing agent. The alkyl group represented by R ₁ may be linear or branched, and includes those having a substituent.

The ballast group represented by R ₂ has a size and shape that gives the coupler molecules sufficient bulk to prevent the coupler from substantially diffusing from the layer to which the coupler is applied to other layers. Organic group.

Preferred examples of the ballast group are those represented by the following general formula.

[0081]

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R ₃ represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and the aryl groups include those having a substituent. General formula [C-
Specific examples of the cyan coupler represented by I) include the exemplified compounds PC-1 to PC-19 described on pages 116 to 119 of JP-A-1-156748 and JP-A-62-249151. In addition to the exemplified compounds C-1 to C-28,
No., JP-A-61-3142, No. 61-9652, No. 61-9653, No. 6
1-39045, 61-50136, 61-99141, 61-105545
And the like.

[0083]

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In the formula, R ¹ represents an alkyl group or an aryl group. R ² represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ³ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ³ is R ¹
And may form a ring together with. Z represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent.

In the cyan coupler represented by the formula [C-II], the alkyl group represented by R ¹ preferably has ¹ to 32 carbon atoms, and may be linear or branched. Also includes those having a substituent. The aryl group represented by R ¹ is preferably a phenyl group, including those having a substituent. Preferably has 1 to 32 carbon atoms as the alkyl group represented by R ^2, includes those These alkyl groups with well, and substituents be linear or branched. The cycloalkyl group represented by R ² has 3 carbon atoms.
To 12 are preferred, and these cycloalkyl groups include those having a substituent. The aryl group represented by R ² is preferably a phenyl group, including those having a substituent. The heterocyclic group represented by R ² is preferably a 5- to 7-membered heterocyclic group, including those having a substituent, and may be condensed.

R ³ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, and R ³ is preferably a hydrogen atom.

The ring formed by R ¹ and R ³ together is preferably a 5- to 6-membered ring.

[0088]

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In the general formula [C-II], the group capable of leaving by reaction with an oxidized form of the color developing agent represented by Z includes a halogen atom, an alkoxy group, an aryloxy group,
Examples include an acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those each having a substituent), preferably a halogen atom, an aryl An oxy group and an alkoxy group.

Particularly preferred among the above-mentioned cyan couplers are those represented by the following general formula [C-II-A].

[0091]

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In the formula, R _A1 represents a phenyl group substituted with at least one halogen atom, and these phenyl groups include those having a substituent other than a halogen atom.
R _A2 has the same meaning as R ^{1 in} formula [C-II]. X _A represents a halogen atom, an aryloxy group or an alkoxy group, including those having a substituent.

Typical specific examples of the cyan coupler represented by the general formula [C-II] include the exemplified compounds C-1 to C-25 described in JP-A-63-96656, Illustrative compound PC-II- described on pages 124 to 127 of 156748
In addition to PC-II-31, JP-A-62-178962, page 7, lower right column to page 9, lower left column, JP-A-60-225155, page 7, lower left column to page 10, lower right column Column, the upper left column of page 6 of JP-A-60-222853 to the lower right column of page 8, and the column of lower left of page 6 to the upper left column of page 9 of JP-A-59-185335 are described. And diacylamino cyan couplers.

The above-mentioned hydrophobic compound such as a dye-forming coupler is usually used in combination with a high-boiling organic solvent having a boiling point of about 150 ° C. or higher or a water-insoluble polymer compound, if necessary, with a low-boiling organic compound and / or a water-soluble organic solvent. After dispersing and emulsifying and dispersing using a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flow jet mixer, and an ultrasonic device in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, What is necessary is just to add to a hydrophilic colloid layer.

In the present invention, a high-boiling organic solvent having a dielectric constant of less than 6.0 is preferably used.

The lower limit is not particularly limited, but preferably has a dielectric constant of 1.9 or more. Examples thereof include esters such as phthalic acid esters and phosphoric acid esters having a dielectric constant of less than 6.0, organic acid amides, ketones, and hydrocarbon compounds. Specific examples of the high-boiling organic solvent include the organic solvents 1 to 22 described on page 41 of JP-A-62-166331.

The silver halide photographic light-sensitive material according to the present invention includes a water-soluble dye, a color fogging inhibitor, an image stabilizer, a hardener, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger, a mordant, a development accelerator. An agent, a development retarder, a fluorescent brightener, a matting agent, a lubricant, an antistatic agent, a surfactant and the like can be optionally used.

The photographic constituent layers of the silver halide photographic light-sensitive material according to the present invention include baryta paper or paper laminated with an α-olefin polymer or the like, a paper support and a paper support from which the α-olefin layer can be easily peeled, and synthetic paper. Such as a flexible reflective support such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, or a semi-synthetic or synthetic polymer film such as a polyamide containing or coated with a white pigment; It can be applied to rigid bodies such as metals and ceramics.
Also, a thin reflective support having a thickness of 120 to 160 μm can be used.

As the white pigment, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments such as alkaline earth metal sulfates such as barium sulfate and alkaline earth metal such as calcium carbonate. Carbonate, fine silicic acid, silica of synthetic silicate, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like. The white pigment is preferably barium sulfate or titanium oxide.

The silver halide light-sensitive material according to the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion of the support surface, charging, etc.). It may be applied via one or more subbing layers to improve anti-static properties, dimensional stability, friction resistance, hardness, anti-halation properties, frictional properties and / or other properties.

In coating a photographic light-sensitive material using the silver halide emulsion according to the present invention, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method. The photosensitive material of the present invention can form an image by performing a color development process known in the art.

The developing agents used in the developer in the present invention include aminophenol-based phenidone-based and p-phenylenediamine-based derivatives widely used in various photographic processes.

In the color developing solution used for processing the light-sensitive material of the present invention, a known developer component compound can be added in addition to the above-mentioned primary aromatic amine-based color developing agent.

The pH value of the color developing solution is usually 9 or more, preferably about 10 to 13.

The color development temperature is usually 15 ° C. or higher, and is generally in the range of 20 ° C. to 50 ° C.

For rapid processing, it is preferred to carry out at 30 ° C. or higher.

The developing time is generally from 5 seconds to 4 seconds.
Although it is a minute, it is preferably performed in the range of 5 seconds to 1 minute for the purpose of rapid processing, and is preferably performed in the range of 5 to 30 seconds when further speeding is required. The effect of the present invention is more effectively exhibited when such rapid processing is performed.

When the light-sensitive material of the present invention is subjected to running processing while continuously replenishing a color developing replenisher, the replenishing amount of the color developing solution is preferably 20 to 150 ml per m ² of the light-sensitive material. The volume is more preferably 20 to 120 ml, and still more preferably 20 to 100 ml. The effect of the present invention is more effectively exhibited when such a low replenishment running process is performed.

After the bleach-fixing process, a washing process, a stabilizing process, or a combination of both processes is usually performed.

[0110]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

Example 1 An aqueous solution containing potassium bromide and sodium chloride in a molar ratio of 1:99 and an aqueous solution of silver nitrate were added to a gelatin aqueous solution containing sodium chloride under vigorous stirring conditions, and chlorobromination was performed by a simultaneous mixing method. A silver agent (silver chloride content: 99 mol%, average particle size: 0.45 μm, coefficient of variation: 9%) was prepared.

This emulsion was divided and, at 65 ° C., sodium thiosulfate, sodium chloroaurate, and sensitizing dyes shown in Table 3 were added in an amount of 4.0 × 10 ⁻⁵ mol / mol silver and the compound of the present invention. To give Em-1 to Em-25.

Next, the cyan couplers CC-1 and CC-2 were dissolved in a mixture of dioctyl phthalate (DOP) and ethyl acetate together with the stain inhibitor HQ-1 and the dye image stabilizer ST-1 to obtain alkanol B ( Emulsified and dispersed in an 8% aqueous gelatin solution containing Dupont.

This emulsified dispersion was used to prepare the emulsions Em-1 to Em-25
To prepare a coating solution, which was applied to a paper support coated on both sides with polyethylene to prepare Samples 101 to 125. Gelatin is applied as a protective layer,
Sodium 2,4-dichloro-6-hydroxy-S-triazine (H-1) was contained as a hardener.

Table 6 shows the details of the coating.

Addition amount (g / m ² ) Protective layer Gelatin 1.0 Red-sensitive layer Silver chlorobromide emulsion (Em-1 to Em-10) Silver 0.3 Cyan coupler (CC-1) 0.3 Cyan coupler (CC-2) 0.1 Dye image stabilizer (ST-1) 0.2 Anti-stain agent (HQ-1) 0.01 DOP 0.2 Gelatin 1.0 Support Polyethylene laminated paper

[0117]

[Table 6]

[0118]

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[0119]

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The samples thus obtained were evaluated for relative sensitivity, safelight properties and raw sample preservability by the following methods.

(Evaluation of Relative Sensitivity) Each sample was subjected to gradation exposure for sensitometry in 0.5 seconds through a red filter, and then subjected to the following development processing. The concentration of the obtained sample was measured using an optical densitometer (PDA-65, manufactured by Konica Corporation), the sensitivities of the samples were compared, and the relative sensitivities were determined.

(Evaluation of Safelight Property) The safelight property was evaluated by using a 10 W light bulb and manufactured by Eastman Kodak Company No. 13
After exposing the sample for 5 minutes from a distance of 1 m through a filter, the sample was processed according to the following processing steps, and the fog density of cyan was measured and determined.

Safelight property = Cyan fog value of exposed sample−Cyan fog value of unexposed sample (Evaluation of raw sample preservability) Each sample was subjected to an environment of 25 ° C. and 60% (relative humidity) for 3 months. After storage over time, exposure as above,
Processing was performed.

The density change (ΔD) of the coated sample stored over time at the exposure dose giving a density of 1.0 when the sample not stored over time was exposed was determined.

Table 7 shows the results thus obtained.

[0126]

[Table 7]

[0127] Color developing solution Pure water 800ml Triethanolamine 10 g N, N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid 1.0g catechol - Disodium 3,5-diphosphonate 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative 1.0 g Potassium carbonate 27 g Add water to make the total volume 1 liter, and adjust to pH = 10.10.

Bleaching / fixing solution ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g ethylenediaminetetraacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml ammonium sulfite (40% aqueous solution) 27.5 ml Adjust to pH = 5.7 with glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene 1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% Aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.5 g Add water to make the total volume 1 l, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

As is clear from Table 7, it is found that the use of the compound of the present invention provides high sensitivity, and significantly improves the raw sample storage stability and safelight property.

Example 2 An aqueous solution containing potassium bromide and sodium chloride in a molar ratio of 70:30 and an aqueous solution of silver nitrate were added to a gelatin aqueous solution containing potassium bromide under vigorous stirring conditions, and the salt was mixed by a simultaneous mixing method. A silver bromide emulsion (silver bromide content: 70 mol%, average particle size: 0.45 μm, coefficient of variation: 9%) was prepared. Except that this emulsion was used, sensitization was performed in the same manner as in Example 1 to obtain Em-201 to Em-201.
-225 was produced. (However, sodium chloroaurate was excluded in the sensitization.) Coating was performed in the same manner as in Example 1, and the relative sensitivity, raw sample storage stability and safelight property were evaluated.

[0132] However, the following processing was performed.

[0133] [Color developer composition] Pure water 700 ml Benzyl alcohol 15 ml Diethylene glycol 15 ml Hydroxylamine sulfate 2 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.4 g Potassium carbonate 30 g Potassium bromide 0.4 g Potassium chloride 0.5 g Potassium sulfite 2 g Add pure water to make 1 liter (pH = 10.2) [Bleaching and fixing composition] Ethylenediaminetetraacetate ammonium 61 g Ethylenediaminetraacetic acid diammonium 5 g Ammonium thiosulfate 125 g Sodium metabisulfite 13 g Sodium sulfite 2.7 g Water was added to make 1 liter (pH = 7.2). From the results obtained, it was found that the emulsion using the compound of the present invention had high sensitivity and improved raw sample preservability and safelight property. From this example, it was found that the effects of the present invention can be obtained regardless of the composition of silver halide.

<Example 3> A structure shown below was formed on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on another side (the side on which a photographic constituent layer is coated). Were coated to prepare a multilayer silver halide color photographic light-sensitive material sample 201. The coating solution was prepared as described below.

First layer coating solution Yellow coupler (YY-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, ST-2 6.67 g, additive (H
Q-1) 60 ml of ethyl acetate was added to and dissolved in 0.67 g of the high-boiling-point organic solvent (DNP) 6.67 g, and this solution was dissolved in 220 m of a 10% aqueous gelatin solution containing 7 ml of a 20% surfactant (SU-1).
The mixture was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. The dispersion contains a fungicide (B
-1) was added. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

[0136] In addition, as a hardening film, H-2 was used in the second and fourth layers, and H-1 was used.
Was added to the seventh layer.

Samples 202 to 206 were prepared in the same manner as in Sample 201 except that the emulsion used for the red-sensitive layer was changed as shown in Table 5.

(Preparation of blue-sensitive emulsion) Silver chlorobromide emulsion (silver chloride content: 99.8 mol%, average grain size: 0.70 μm, coefficient of variation: 7%)
Then, sodium thiosulfate and the following sensitizing dye (BS) were added in an amount of 4.times.10.sup.- ⁴ mol per mol of silver, and the mixture was optimally sensitized at 60.degree.

(Preparation of green-sensitive emulsion) Silver chlorobromide emulsion (silver chloride content: 99.5 mol%, average grain size: 0.40 μm, coefficient of variation: 8%)
Sodium thiosulfate, sodium chloroaurate and the following sensitizing dye (GS) were added in an amount of 3.times.10.sup.- ⁴ mol per mol of silver, and the mixture was optimally sensitized at 65.degree.

[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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The samples thus obtained were evaluated for the relative sensitivity of the red-sensitive layer and the raw sample storage stability by the method described in Example 1. The results are shown in Table 8 below.

[0147]

[Table 8]

Table 8 shows that the use of the oxygen-containing crown compound of the present invention also improves the sensitivity and the raw sample preservability and safelight properties of a multilayer color printing paper.

[0149]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having excellent storage stability over time, stable high sensitivity, and improved safelight properties. Was.

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein said silver halide emulsion is spectrally sensitized with a sensitizing dye and contains at least one silver halide emulsion. A silver halide photographic material comprising a complex of an oxygen crown compound.