JPH0869077A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain a photosensitive material high in sensitivity and small in fluctuation of performance due to temperature change at the time of exposure and due to storage at high temperature by mixing a silver halide emulsion containing a specified compound with a dispersion of a phenol type cyan coupler immediately before application of the emulsion to form the silver halide emulsion leyer. CONSTITUTION: The silver halide emulsion layer is obtained by mixing the emulsion containing at least one of the compounds represented by the formula with the dispersion of the phenol type cyan coupler immediately before coating and coating a support with this mixture. In the formula, =Z- is =CH- or =N-; each of R<1a> and R<2a> is a halogen atom or a hydroxyl or alkylamino or the like; M is a univalent metal atom. Mixing immediately before coating means that mixing is executed within a time of <=5min, preferably, <=2min, especially, <=1min after the mixing before the coating, and it is preferred to control the temperature of the mixture in the range of 28 to 70 deg.C, preferably, 32 to 60 deg.C.

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, it has high sensitivity and less variation in performance due to temperature change during exposure, and less variation in performance when raw samples are stored at high temperature. The present invention relates to a silver halide photographic light-sensitive material having a silver halide emulsion layer.

[0002]

2. Description of the Related Art The demand for silver halide photographic light-sensitive materials has become stricter year by year, and in addition to the strong demand for high sensitivity and high image quality (especially excellent graininess and sharpness),
There is a strong demand for low replenishment processing suitability to reduce environmental pollution, and rapid processing for the request for short-time finishing. These requirements are mostly solved by achieving high sensitivity of silver halide grains, and it is no exaggeration to say that increasing the sensitivity of silver halide grains is the biggest problem in the art.

Supersensitization method (Supe
rsensitization) is known to be useful. Regarding supersensitization, Photographic Science and Engenee
ring. Volume 13, p.13-17 (1969), Volume 18, p.418-43
0 (1974), TH James, The Theory of the Ph
otographic Process 4th edition, Macmillan Publishers, 1977
P.259, etc., and it is known that high sensitivity can be obtained by selecting an appropriate sensitizing dye and supersensitizer (Supersensi-tizer).

Conventionally, as supersensitizers, many compounds such as stilbene, azaindene, mercaptoheterocycle, thiourea or condensates of phenol and hexamethylenetetramine are known. For example, US Pat.
2,875,058, 3,340,064, 3,457,078, 3,45
No. 8,318, No. 3,615,632, No. 3,695,888, No. 4,011,083
And JP-A-61-203447.

However, as a result of experiments conducted by the inventors of the present invention, when the sensitivity is increased by these conventional techniques so as to sufficiently satisfy the requirements for the light-sensitive material, the performance variation due to the humidity change at the time of exposure is large, and further, It was found that the deterioration in photographic sensitivity due to high temperature storage of the sample was large. Further, when a supersensitizer as disclosed in JP-A-4-25833 is applied to a photographic emulsion, there is a defect that development is suppressed during development processing and the requirement for rapid processing is not met. The stability of the performance of a photographic light-sensitive material during exposure is extremely important for obtaining stable image quality. The storage stability of raw samples over time is
Since it is desired to make the photographic performance uniform, it is extremely important that the deterioration of performance during storage at high temperature poses a serious obstacle in practical use such as handling of the sample in high temperature areas.

As described above, in the known art, there has been a demand for a technology capable of achieving high sensitivity without deteriorating various characteristics of photography.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide emulsion layer having high sensitivity and less performance fluctuation due to temperature change during exposure, and less performance fluctuation when a raw sample is stored at high temperature. The present invention relates to a silver halide photographic light-sensitive material having

[0008]

As a result of intensive studies, the inventors of the present invention have found that the object of the present invention can be achieved by the following invention, and have completed the invention. That is, (1) obtained by mixing a silver halide emulsion containing one or more compounds represented by the following general formula (1) and a dispersion liquid of a phenolic cyan coupler immediately before coating, and then coating the mixed liquid. A silver halide photographic light-sensitive material having a silver halide emulsion layer on a support.

[0009]

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In the formula, = Z- represents = CH- or = N-,
R ^1a and R ^2a each represent a halogen atom, a hydroxyl group, an alkylamino group, an alkoxy group, an alkylthio group, an arylamino group, an aryloxy group and an arylthio group, and M represents a monovalent metal atom.

(2) A silver halide emulsion containing at least one crown ether condensed with at least one aromatic ring and a dispersion of a phenolic cyan coupler are mixed immediately before coating, and then the mixture is coated. A silver halide photographic light-sensitive material characterized by having a silver halide emulsion layer obtained by the method on a support.

(3) The silver halide photographic light-sensitive material as described in 2 above, wherein the crown ether condensed with at least one aromatic ring is a crown ether forming an 18-membered ring.

(4) The halogen according to 1, 2 or 3 above, wherein the compound represented by the general formula (1) or the crown ether is a supersensitizer of a red-sensitizing dye. Silver halide photographic light-sensitive material.

The present invention will be described in detail below.

In the present invention, mixing immediately before coating means
It means that the time from the mixing of the silver halide emulsion and the dispersion liquid of the phenolic cyan coupler to the coating is 5 minutes or less, preferably 2 minutes or less, and more preferably 1 minute or less. The temperature of the mixed solution is 28 to 70 ° C, preferably
32 to 60 ° C.

The compound represented by the general formula (1) of the present invention will be described.

In the general formula (1), = Z- is = CH-
Alternatively, it represents ═N—, but ═CH— (2-pyrimidyl ring) is preferable. R ^1a and R ^2a are each a halogen atom (for example,
Chlorine atom, bromine atom, etc.), hydroxyl group, alkylamino group (eg, dimethylamino, diethylamino, dihydroxyethylamino, etc.), alkoxy group (eg, methoxy, ethoxy, butoxy, etc.), alkylthio group (eg, methylthio, ethylthio, Propiothio etc.), arylamino group (eg substituted or unsubstituted phenylamino, substituted or unsubstituted naphthylamino etc.), aryloxy group (eg substituted or unsubstituted phenyloxy, substituted or unsubstituted naphthyloxy etc.), arylthio group (Eg, substituted or unsubstituted phenylthio, substituted or unsubstituted naphthylthio, etc.), and M represents a monovalent metal atom (eg, sodium atom, potassium atom, etc.).

Specific examples of the compound represented by the general formula (1) are shown below.

[0019]

[Chemical 3]

[0020]

[Chemical 4]

The compound represented by the general formula (1) is dissolved in water or an organic solvent arbitrarily miscible with water, for example, methanol, ethanol, dioxane, acetone, triethylene glycol, triethanolamine, etc., and then silver halide. Add to emulsion. The time of addition may be any time before the emulsion is coated, but it is preferably before the completion of chemical sensitization.

The compound represented by the general formula (1) of the present invention is preferably used as a supersensitizer for a red-sensitive sensitizing dye, but the order of addition may be any one. Well, they may be added simultaneously or as a mixed solution. The addition amount of the compound represented by the general formula (1) of the present invention varies depending on the kind of the compound, but is usually 1 per mol of silver halide.
It is in the range of x10 ^{-7 to} 5x10 ^-2 mol, preferably 5x10.
^-6 to 1 × 10 ^-2 mol.

Next, the crown ethers used in the present invention are crown ethers condensed with at least one or more substituted or unsubstituted aromatic rings. Representative examples of the substituent include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups, but in addition to these, a halogen atom, cycloalkenyl, alkynyl, and heterocyclic group. Ring, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy and the like can be mentioned. In addition to the oxygen atom, the hetero atom forming the crown ring may be replaced with a nitrogen atom, a sulfur atom, a selenium atom or the like. A typical example of these compounds is crown ether, which was synthesized by Pedersen in 1967 and reported its unique properties. These compounds are available from CJPedersen, Journal of American chemical Soci
etyvol.86 (2495), 7017 to 7036 (1967), GWGokel,
SH, Korzeniowski, “Macrocyclic polyethr synthesi
s ”, Springer-Verlag. (1982), Oda, Shono, Tabushi eds.“ Chemistry of Crown Ether ”Chemistry Dojin (1978), Tabushi et al.“ Host-Guest ”Kyoritsu Publishing (1979), Sasaki, Koga“ Organic Synthetic Chemistry ” Vol 45 (6), 571 to 582 (1987), etc. The crown ether preferably used in the present invention is a crown ether forming a 15 to 18-membered ring.

Specific examples of the crown ether used in the present invention are shown below, but the present invention is not limited thereto.

[0025]

[Chemical 5]

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

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[0029]

[Chemical 9]

The crown ether of the present invention may be added to a hydrophilic colloid containing silver halide grains after it is dissolved in water or a hydrophilic organic solvent such as methanol, ethanol or fluorinated alcohol and then added. It may be added at any time before the emulsion is coated, but it is preferably added before the completion of the chemical sensitization.

The crown ether of the present invention is preferably used as a supersensitizer for a red-sensitive sensitizing dye, but the order of addition may be either first, simultaneous or simultaneous in a mixed solution. You may. The addition amount of the crown ether 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, preferably 5 × 10 ⁻⁶ to 1 per mol of silver halide. × 10 ^-2 mol.

The red-sensitizing sensitizing dye in the present invention refers to cyanine dyes such as cyanine, merocyanine and holopolar, and complex cyanine and complex merocyanine, and preferably the following general formula [I] and / or general formula [II] ] It says the cyanine dye represented by.

[0033]

[Chemical 10]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group, an alkenyl 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 5 or 6 respectively.
Represents an atom or group of atoms necessary to complete a heterocyclic nucleus of a member. Z ₅ represents a hydrocarbon atom group necessary for forming a 6-membered ring. m ₁ , m ₂ , m ₃ and m ₄ are 0 or 1 respectively
Represents n 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 intramolecular salt, Y ₁ and Y ₂ each represent 0.

In the sensitizing dye used in the present invention, the alkyl group represented by R ₁ , R ₂ , R ₃ and R _{4 in the} formula [I] or [II] may be branched. More preferably, it has 10 or less carbon atoms and may have a substituent. Examples of the substituent include sulfo, aryl, carboxy, amine (primary, secondary, tertiary), alkoxy, aryloxy, hydroxy, alkoxycarbonyl, acyloxy, acyl, aminocarbonyl, cyano, and other groups, and a halogen atom. be able to. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Sulfoethyl group, sulfopropyl group, sulfobutyl group,
Benzyl group, phenethyl group, carboxyethyl group, carboxymethyl group, dimethylaminopropyl group, methoxyethyl group, phenoxypropyl group, methylsulfonylethyl group, pt-butylphenoxyethyl group, cyclohexyl group, octyl group, decyl group, carbamoylethyl Base,
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, ethoxycarbonylmethyl group, pivaloylpropyl group, propionylethyl group, Anisyl group, acetoxyethyl group, benzoyloxypropyl group, chloroethyl group, morpholinoethyl group, acetylaminoethyl group, N-
Examples thereof include an ethylaminocarbonylpropyl group and a cyanoethyl group.

The alkenyl group is preferably an alkenyl group having 10 or less carbon atoms, and examples thereof include an allyl group, a 2-butenyl group and a 2-propynyl group.

The aryl group is, for example, a phenyl group, a carboxyphenyl group, a sulfophenyl group or the like.

The methine group represented by L ₁ , L ₂ , L ₃ , L ₄ and L ₅ in the general formula [I] may have a substituent, and in the case of having a substituent, the methine group represented by the formula (-CR ₅ =), and the group represented by R ₅ is a linear or branched alkyl group having about 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, benzyl group, etc. ), An alkoxy group (eg, methoxy group, ethoxy group, etc.), and an aryl group (eg, phenyl group, tolyl group, etc.) and the like.

[0039] X in the general formula [I] and [II] ^- anion represented by, for example, chloride, bromide, iodide, perchlorate ion, boron fluoride ion, p-
Toluenesulfonic acid ion, ethylsulfonic acid ion,
Examples thereof include methyl sulfonate ion and nitrate ion.

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

[0041]

[Chemical 11]

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 , A ⁴ , 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 is a hydrogen atom, a halogen atom, an alkyl group,
Representing 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 , C ² And D ² ; A ³ and B ³ , 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 , at least one of which is bonded. 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 , Y ¹ and Y ² are respectively R ₁ , R ₂ in the general formula [I] or [II],
It is synonymous with R ₃ , R ₄ , L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , X ⁻ , n, Y ₁ and Y ₂ .

A ¹ , A ^{2 of} the general formula [III] or [IV],
A ³ , A ⁴ , B ¹ , B ² , B ³ , B ⁴ , C ¹ , C ² , C ³ , C ⁴ ,
The alkyl group represented by D ¹ , D ² , D ³ and D ⁴ is a linear or branched lower alkyl group having about 1 to 5 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, Trifluoromethyl group, etc.), alkoxy group as a linear or branched alkoxy group having about 1 to 5 carbon atoms (eg, methoxy group, ethoxy group, etc.), and halogen atom as fluorine, chlorine, bromine or iodine. Examples of each atom and phenyl group include a phenyl group having no substituent, a hydroxyphenyl group, a carboxyphenyl group, and the like, and an alkoxycarbonyl group includes, for example, a methoxycarbonyl group and an ethoxycarbonyl group.
In addition, n ¹ represents 0 or 1, but is preferably 1.

Next, specific examples of the red-sensitive sensitizing dye of the present invention will be described, but the present invention is not limited thereto.

[0046]

[Chemical 12]

[0047]

[Chemical 13]

[0048]

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[0049]

[Chemical 15]

The above red-sensitizing sensitizing dye is, for example, The Chemistry of Heterocylic Compou by F.M.Harmer.
nds Volume 18, The Cyanine Dyes and Related Compounds
(A. Weissherger ed. Interscience, New York 1964
It can be easily synthesized by the method described in (1).

The addition amount of the red sensitizing dye in the present invention is not particularly limited, but it is 2 per 1 mol of silver halide.
It is preferable to use x10 ^-8 mol to ^{1x10 -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. It The silver halide grain preferably used in the present invention is silver chlorobromide. More preferably, it is a silver chlorobromide having a silver bromide content of 0.01 to 2 mol%. The composition of the silver halide grains may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. When the composition inside and outside the particle is different, the composition may change continuously or may be discontinuous. Further, as described in JP-A-1-183647, a localized phase having a different halogen composition may be locally contained.

The grain size of the silver halide grain is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2.
It is in the μm range. The above-mentioned particle diameter is expressed as an average based on the projected area, where the particle diameter is the particle diameter in the case of spherical or spherical particles, and the edge length is the particle diameter in the case of cubic particles. The grain size distribution of the silver halide grains may be polydisperse or monodisperse. Monodisperse silver halide grains having a variation coefficient of 0.22 or less, more preferably 0.15 or less in the grain size distribution of silver halide grains are preferred.

In the present invention, the silver halide grains used in the emulsion may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains.

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. It is also possible to use particles having a shape of octahedron, tetrahedron, dodecahedron or the like. Further, spherical, rod-shaped, plate-shaped particles or the like may be used. Further, grains having twin planes may be used.

The silver halide photographic light-sensitive material used in the present invention preferably has a blue-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer in addition to the red-sensitive silver halide emulsion layer. These layers are optically sensitized with a sensitizing dye.

As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxanol dye can be used. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and contains a supersensitizer that enhances the sensitizing effect of the sensitizing dye in the emulsion. Good.

Further, these sensitizing dyes can be used for the purpose of gradation adjustment, development adjustment, etc. in addition to the original purpose of the spectral sensitizing action.

The silver halide emulsion of the present invention can be used to prevent fog during the process of manufacturing a light-sensitive material, during storage, or during photographic processing.
Or during chemical aging for the purpose of keeping photographic performance stable,
Antifoggants or stabilizers can be added at the end of chemical ripening and / or for coating the silver halide emulsion after the completion of chemical ripening.

As the binder of the silver halide photographic light-sensitive material used in the present invention, it is advantageous to use gelatin, but if necessary, gelatin derivative, gelatin and other high molecular weight graft polymer, other proteins, Hydrophilic colloids such as sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers or copolymers can also be used.

The phenolic cyan coupler used in the present invention is represented by the following general formula [C-I] or [C-II].
A cyan coupler represented by

[0062]

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In the formula, R ₁₁ represents an alkyl group having 2 to 6 carbon atoms. R ₁₂ represents a ballast group. Z ₁₁ represents a hydrogen atom or an atom or group capable of splitting off upon reaction with an oxidized product of a color developing agent, and a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group,
Acylamino group, sulfonylamino group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, imide group, etc. (including those having substituents)
Are preferred, and a halogen atom, an aryloxy group and an alkoxy group are preferred. The alkyl group represented by R ₁₁ may be linear or branched and includes those having a substituent.

The ballast group represented by R ₁₂ is of a size and shape that provides the coupler molecule with sufficient bulk to prevent the coupler from substantially diffusing from the layer to which it is applied to other layers. It is an organic group having.

Preferred as the ballast group is one represented by the following general formula.

[0066]

[Chemical 17]

R ₁₃ represents an alkyl group having 1 to 12 carbon atoms, Ar represents an aryl group such as a phenyl group, and the aryl group includes those having a substituent. General formula [C-
Specific examples of the cyan coupler represented by the formula [I] are described in JP-A 1-156748, exemplifying compounds PC-1 to PC-19 described on pages 116 to 119 and JP-A-62-249151. In addition to the exemplified compounds C-1 to C-28 described above, JP-B-49-11572
No. 6, JP-A-61-3142, No. 61-9652, No. 61-9653, No. 6
1-39045, 61-50136, 61-99141, 61-105545
Cyan couplers described in, for example, No.

[0068]

[Chemical 18]

In the formula, R ₂₁ represents an alkyl group or an aryl group. R ₂₂ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₂₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. Also, R ₂₃ is R
_It may form a ring together with ₂₁ . Z ₂₁ represents a group having the same meaning as Z ₁₁ .

In the cyan coupler represented by the above general formula [C-II], the alkyl group represented by R ₂₁ is
Those having 1 to 32 carbon atoms are preferable, and these may be linear or branched and include those having a substituent. The aryl group represented by R ₂₁ is preferably a phenyl group, and includes those having a substituent. The alkyl group represented by R ₂₂ preferably has 1 to 32 carbon atoms, and these alkyl groups may be linear or branched and include those having a substituent. R
_The cycloalkyl group represented by ₂₂ preferably has 3 to 12 carbon atoms, and these cycloalkyl groups include those having a substituent. The aryl group represented by R ₂₂ is preferably a phenyl group, and includes those having a substituent. R
_The heterocyclic group represented by ₂₂ is preferably a 5- to 7-membered heterocyclic group, which may have a substituent and may be condensed.

R ₂₃ 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 ₂₃ is preferably a hydrogen atom.

The ring formed by R ₂₁ and R _{23 in combination} is preferably a 5- or 6-membered ring, and examples thereof include:

[0073]

[Chemical 19]

Among the above-mentioned cyan couplers, those represented by the following general formula [C-II-A] are particularly preferable.

[0075]

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In the formula, R _A1 represents a phenyl group substituted with at least one halogen atom, and these phenyl groups further include those having a substituent other than a halogen atom.
R _A2 has the same meaning as R _{21 in the} above general formula [C-II]. Z _A
Represents a group having the same meaning as Z ₁₁ .

It represents a halogen atom, an aryloxy group or an alkoxy group, and includes those having a substituent.

Typical examples of the cyan coupler represented by the general formula [C-II] are exemplified compounds C-1 to C-25 described in JP-A-63-96656 and JP-A-1- No. 156748, pages 124 to 127, exemplary compounds PC-II-
1-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, JP-A-60-222853, page 6, upper left column to page 8, lower right column, and JP-A-59-185335, page 6, lower left column to page 9, upper left column 2,5- Examples thereof include diacylamino cyan couplers.

In addition to the cyan couplers described above, dye-forming couplers such as yellow couplers and magenta couplers are used in the silver halide photographic light-sensitive material according to the present invention.

Examples of yellow couplers preferably used include acylacetanilide type couplers.
Of these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous, and are particularly preferred.
Exemplary compounds Y-1 to Y-14 described in No. 63-85631
6. Exemplified compound Y-described in JP-A-63-97951
1 to Y-98 and the exemplified compounds Y-1 to Y-24 described in JP-A 1-156748 (pages 67 to 78) are preferably used.

Examples of the magenta couplers used in the present invention include pyrazoloazole-based, 5-pyrazolone-based, indazolone-based and cyanoacetyl-based, and preferably pyrazoloazole-based and 5-pyrazolone-based such as pyrazolotriazoles. Couplers.

Specific examples of the pyrazoloazole-based magenta coupler are described in JP-A-63-167360, page 5, lower right column to column 9.
M-1 to M-61 described in the lower left column of the page and JP-A-62-166.
Among the compounds described in No. 339, page 18, upper right column to page 32, upper right column, No. 1 to 4, 6, 8 to 17, 19 to 24, 26 to 4
3,45-59,61-104,106-121,123-162,164-223 etc. can be mentioned.

Another preferred type of magenta coupler is a 1-aryl-3-anilino-5-pyrazolone type compound. For example, exemplified compounds No. 218 to No. 218 to No. 218 to No. .244 etc. can be mentioned.

The above-mentioned hydrophobic compounds such as dye-forming couplers are usually used in combination with a high boiling point organic solvent having a boiling point of about 150 ° C. or higher and a water-insoluble polymer compound, if necessary, in combination with a low boiling point and / or a water-soluble organic solvent. Dissolve and emulsify with a dispersing agent such as a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic device, etc., using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. It may be added in the 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 the dielectric constant is preferably 1.9 or more. For example, esters such as phthalic acid ester and phosphoric acid ester having a dielectric constant of less than 6.0, organic acid amides, ketones, hydrocarbon compounds and the like. Specific examples of the high boiling point organic solvent include the exemplified organic solvents 1 and 2 described in JP-A-62-166331, page 41.
2 etc. can be mentioned.

The silver halide photographic light-sensitive material of the present invention includes a water-soluble dye, an antifoggant, an image stabilizer, a hardener, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger, a mordant, and a development accelerator. Agents, development retardants, optical brighteners, matting agents, lubricants, antistatic agents, surfactants 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 α-olefin polymer or the like, and a paper support or synthetic paper from which the paper support and the α-olefin layer can be easily peeled off. Flexible reflective support such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate,
It can be applied to a reflection support or a rigid body such as metal or earthenware which contains or is coated with a white pigment on a film made of a semi-synthetic or synthetic polymer such as polycarbonate or polyamide.
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, preferably inorganic white pigments such as alkaline earth metal sulfates such as barium sulfate and alkaline earth such as calcium carbonate. Examples thereof include carbonates of group metals, finely divided silicic acid, silicas of synthetic silicates, calcium silicate, alumina, hydrated alumina, 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 directly or undercoated (adhesiveness of the surface of the support, charging) after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary. It may also be applied via one or more subbing layers) for improving anti-preventive properties, dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties.

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

The color developing agent used in the color developing solution in the present invention includes aminophenol and p-phenylenediamine derivatives which are widely used in various color photographic processes.

To the color developing solution applied to the processing of the light-sensitive material of the present invention, known developer component compounds can be added in addition to the above-mentioned primary aromatic amine color developing agent.

The pH value of the color developing solution is usually 9 or more, preferably about 10-13. The color developing temperature is usually 15 ° C or higher, and generally 20 ° C to 50 ° C.

For rapid treatment, it is preferable to carry out at 30 ° C. or higher. Further, the development processing time is generally 10 seconds to 4
In terms of minutes, it is preferable to perform the treatment in the range of 10 seconds to 1 minute for the purpose of rapid processing, and in the range of 10 to 30 seconds when further rapid processing 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 a running process while continuously replenishing a color developing replenisher,
The replenishing amount of the color developing solution is preferably 20 to 150 ml, more preferably 20 to 120 ml, and further preferably 20 to 100 ml per m ² of the light-sensitive material. The effects of the present invention are more effectively exhibited when such a low replenishment running process is performed. The light-sensitive material of the present invention is subjected to bleach-fixing processing after color development.

After the bleach-fixing treatment, a washing treatment, a stabilizing treatment, or a combined treatment of both is usually performed.

[0097]

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

Example 1 (Preparation of Red-Sensitive Emulsion) An aqueous solution containing potassium bromide and sodium chloride in a molar ratio of 1:99 and an aqueous silver nitrate solution were added to a gelatin aqueous solution containing sodium chloride under a vigorous stirring condition, and then mixed simultaneously. At the silver chlorobromide agent (silver chloride content 99 mol%,
An average particle size of 0.45 μm and a coefficient of variation of 9%) was prepared.

This emulsion was divided into pieces, and sodium thiosulfate (1.8 mg / mol silver) and sodium chloroaurate (1.0 mg / mol) were added at 65 ° C.
Molar silver), red-sensitive sensitizing dye (II-3) (4 × 10 ⁻⁵ mol / mol silver) and supersensitizer (A), compound of the present invention (1-
Each of (1), (S-26) and (S-2) was added with 0.7 g / mol silver and sensitized to obtain Em-1 to Em-5. (Em-1 has no supersensitizer added)

[0100]

[Chemical 21]

Next, C-1 and C-2 of the cyan coupler were dissolved in a mixed solution of dioctyl phthalate (DOP) and ethyl acetate together with an anti-stain agent HQ-1 and a dye image stabilizer ST-1 to give an alkanol B ( It was emulsified and dispersed in an 8% gelatin aqueous solution containing DuPont).

The emulsified dispersion and the red-sensitive emulsion Em-1 to
Coating was performed by changing the time from mixing to coating of Em-5 as shown in Table 3. The coating liquid was used as the fifth layer coating liquid, and the constitutions of the first to seventh layers are shown in Tables 1 and 2. The coating was performed on a paper support coated on both sides with polyethylene, and the samples obtained by coating were designated as Samples 1 to 20.

Further, as a hardener (H-1), (H-2)
Was added. As a coating aid, a surfactant (SU-
1) and (SU-2) were added to adjust the surface tension.
Further, F-1 was added to each layer so that the total amount was 0.04 g / m ² .

[0104]

[Table 1]

[0105]

[Table 2]

SU-1: Di (2-ethylhexyl) sulfosuccinate / sodium salt SU-2: Di (2-2,3,3,4,4,5,5-octafluoropentyl) sulfosuccinate / sodium salt Salt DBP: Dibutyl phthalate DOP: Dioctyl phthalate DIDP: Di-i-decyl phthalate PVP: Polyvinylpyrrolidone H-1: Tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine.
Sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2- sec-dodecyl-5-sec-tetradecyl hydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butyl hydroquinone

[0107]

[Chemical formula 22]

[0108]

[Chemical formula 23]

[0109]

[Chemical formula 24]

[0110]

[Chemical 25]

[0111]

[Chemical formula 26]

(Preparation of blue-sensitive silver halide emulsion) The following (A) was added to 1 liter of a 2% gelatin aqueous solution kept at 40 ° C.
30) while controlling the liquids) and (B liquid) to pAg = 7.3 and pH = 3.0
Simultaneously added over the course of minutes,
Simultaneous addition was carried out over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 cc (Solution B) Silver nitrate 10 g Water added 200 cc (Solution C) K ₂ IrCl ₆ 2 × 10 ^-8 mol / mol Ag Chloride Sodium 102.7 g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mol Ag potassium bromide 1.0 g Water added 600 cc (D liquid) Silver nitrate 300 g Water added 600 cc After addition of Kao Atlas Demol N 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate were used for desalting, and then mixed with an aqueous solution of gelatin to obtain a single particle having an average particle size of 0.85 μm, a particle size distribution variation coefficient of 0.07, and a silver chloride content of 99.5 mol%. A dispersed cubic emulsion EMP-1 was obtained.

The following compounds were used for EMP-1.
Optimal chemical sensitization was performed at 60 ° C. to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-3 8 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (preparation of green-sensitive silver halide emulsion) (solution A) and solution B
A monodisperse cubic emulsion E having an average grain size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) are changed.
MP-2 was obtained.

The following compounds were used for EMP-2.
Optimal chemical sensitization was carried out at 55 ° C. to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4- Ethoxyphenyl) -5-mercaptotetrazole

[0118]

[Chemical 27]

(Evaluation of Sensitivity) After wedge exposure with white light for 0.5 seconds and color development according to the following processing steps,
The density was measured using an optical densitometer (PDA-65 type manufactured by Konica), and the sensitivity was expressed by the logarithm of the reciprocal of the exposure amount required to obtain a density 0.75 higher than the fog density. The sensitivity of Sample 1 was set to 100 and expressed as relative sensitivity.

(Evaluation of Temperature Dependence during Exposure) Samples 1 to 15 were subjected to wedge exposure with blue light for 0.5 seconds and then subjected to the above-mentioned development treatment. At the time of exposure, set the temperature and humidity at the time of exposure as shown in A and B below, and set the sample to 1 in each atmosphere.
After leaving for a time, exposure was performed.

A: 10 ° C. 50% RH B: 30 ° C. 50% RH The obtained sample was used as an optical densitometer (PDA-65 manufactured by Konica Corporation).
(Type) to measure the concentration and obtain a characteristic curve. Sensitivity is A
The density D (30 ° C., 50% RH) under the condition B was measured at an exposure amount giving a density higher than the fog density by 0.8 condition. And this difference in concentration; ΔD = D (30 ° C 50% RH)-
0.8 (If ΔD is positive and large, it is sensitized at high temperature)
Was taken as the value of temperature dependence during exposure for each sample. The closer this value is to 0, the smaller the temperature dependency during exposure, which is preferable.

(Evaluation of Raw Sample High Temperature Preservability)
After storage for 10 days in an environment of ° C and 40% RH, exposure, treatment, and sensitometry were performed in the same manner as above, and the absolute value of the sensitivity difference from the sample not stored was determined and expressed as ΔS. The smaller ΔS is, the smaller the performance fluctuation due to high temperature storage of the sample is, which is preferable.

The processing conditions used for evaluation are as follows.

[0124] step Temperature Time color development 35.0 ± 0.3 ° C. 45 seconds blix 35.0 60 seconds color developer ± 0.5 ° C. 45 seconds Stabilization of 30 ~ 34 ° C. 90 seconds Drying 60 ~ 80 ° C. pure water 800ml triethanolamine Amine 10g N, N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-diphosphonic acid disodium salt 1.0g N-Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 4.5g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0g Potassium carbonate 27g Water In addition, adjust the total volume to 1 l and adjust the pH to 10.10.

Bleach-fixing solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to bring the total volume to 1 liter and add potassium carbonate or With glacial acetic acid
Adjust to pH = 5.7.

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'-diaminostilbene disulfonic acid derivative) 1.5 g Water is added to make a total volume of 1 l, and sulfuric acid or potassium hydroxide is added to p.
Adjust to H = 7.0.

The evaluation results are shown in Table 3.

[0128]

[Table 3]

From Table 3, the samples of the present invention have high sensitivity,
It can be seen that the silver halide color photographic light-sensitive material has little performance fluctuations due to temperature changes during exposure and has little performance fluctuations when raw samples are stored at high temperatures.

[0130]

According to the present invention, it is possible to obtain a silver halide color photographic light-sensitive material having high sensitivity and having little performance fluctuation due to temperature change during exposure and having little performance fluctuation when a raw sample is stored at high temperature.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03C 7/34

Claims (4)

[Claims] 1. A compound represented by the following general formula (1):
A silver halide emulsion comprising at least one kind of a silver halide emulsion and a dispersion of a phenolic cyan coupler are mixed just before coating, and then the mixture is coated to obtain a silver halide emulsion layer, which is characterized by having on a support. Silver photographic light-sensitive material. Embedded image In the formula, = Z- represents = CH- or = N-, and R ^1a and R ^2a are each a halogen atom, a hydroxyl group, an alkylamino group, an alkoxy group, an alkylthio group, an arylamino group, an aryloxy group, It represents an arylthio group, and M represents a monovalent metal atom. 2. A silver halide emulsion containing at least one crown ether condensed with at least one aromatic ring and a dispersion of a phenolic cyan coupler are mixed immediately before coating, and then the mixture is coated. A silver halide photographic light-sensitive material having a silver halide emulsion layer obtained as described above on a support. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the crown ether condensed with at least one aromatic ring is a crown ether forming an 18-membered ring. 4. The halogen according to claim 1, 2 or 3, wherein the compound represented by the general formula (1) or the crown ether is a supersensitizer of a red-sensitizing dye. Silver halide photographic light-sensitive material.