JPH0996889A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject sensitive material less liable to a variation in performance due to a humidity change at the time of exposure and ensuring a stable finish. SOLUTION: At least one silver halide emulsion layer of this sensitive material contains silver halide particles having 95-99.9mol% silver chloride content spectrally sensitized so that the particles have the spectral max. in the wavelength region of 400-650nm and at least one of the photographic constituent layers contains a compd. represented by the formula, wherein R11 is H or lower alkyl, Y is O, S or Se, Z is a group of nonmetallic atoms required to complete a 5-or 6-membered N-contg. hetero ring, R12 is alkyl or alkenyl and X1 <-> is an acid anion.

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 which has a small performance fluctuation due to a change in humidity during exposure and which can provide a stable finish.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter also simply referred to as "light-sensitive material"), especially a color light-sensitive material, has high sensitivity, excellent gradation and sharpness.
It is used very often today.

However, the development processing of the color photographic material is a so-called wet processing, which requires a lot of trouble in preparation of a processing solution, becomes dirty, generates a waste liquid containing various chemicals, requires a dark room, and requires a dark room. There are drawbacks such as a long time until the first print is obtained.

In order to compensate for these disadvantages and take advantage of the above-mentioned advantages of the color photographic material, skilled engineers have concentrated on developing color negative films to producing color prints only in a few large developing laboratories. The scheme has been adopted.

However, although the essence of wet processing has not changed in recent years, improvements in equipment such as printers and automatic developing machines, improvements in developing solutions, improvements in color photosensitive materials and their packaging forms have been accumulated, and they have been used by photo shops. The so-called minilab, which consistently processes from the development of color negative films to the production of color prints in a small space such as at a store, is rapidly becoming popular.

[0006] In recent years, the development processing time has been remarkably reduced by employing a silver halide emulsion containing silver chloride at a high concentration. However, it was not observed when using a light-sensitive material containing a silver halide emulsion composed of silver chlorobromide which does not contain silver chloride at a high concentration, which is not suitable for processing with a shortened development processing time. With a light-sensitive material containing a silver halide emulsion containing silver, there has been a problem that the same scene has different finishes depending on the environmental conditions of exposure.

As a result of analyzing these problems, it was found that the finish differs depending on the humidity condition during exposure. It has also been found that this problem is particularly remarkable when an emulsion spectrally sensitized to 400 to 650 nm is used. For example, 65
When a specific sensitizing dye is added so as to have a spectral sensitivity of 0 nm or more, even if a silver halide emulsion containing a high concentration of silver chloride is used, it will be finished depending on the humidity conditions during exposure as described above. But no different problems were seen.

Japanese Patent Publication Nos. 55-12581 and 62-20
1440, JP-A-62-260241, JP-A-1-
Nos. 291250 and 4-253053 disclose techniques for improving latent image stability by incorporating a specific thiazolium compound into a light-sensitive material. These techniques describe the stability of the resulting latent image for a relatively long time, and nothing about the efficiency of the electron latent image formation process during exposure.

Further, JP-A-59-191032, JP-A-2-157749, JP-A-3-109547 and JP-A-3-2.
44667, 4-63337, 4-36293.
Nos. 2, 5-88292, and the like, peculiar problems when an infrared sensitizing dye is used by incorporating a specific thiazolium compound into the photosensitive material using the infrared sensitizing dye, for example, use of the photosensitive material Techniques for improving performance deterioration during storage, sensitization, and temperature dependence during exposure have been disclosed. However, these techniques are basically techniques for solving the essential problem of the compound of the infrared sensitizing dye, and no mention is made about the solution of the problem that the finish is different depending on the humidity condition at the time of exposure. Not not.

These techniques are problems relating to infrared sensitizing dyes, and encounter the problem itself that the finish differs depending on the humidity conditions during exposure, which is remarkable when an emulsion spectrally sensitized to 400 to 650 nm is used. I haven't.

Japanese Unexamined Patent Publication No. 61-95348 discloses a technique of incorporating a specific benzothiazolium compound and a specific phenylmercaptotetrazole compound. This describes a technique for preventing deterioration of photographic performance during storage of a light-sensitive material over time and for preventing sensitivity deterioration due to development inhibition. The embodiments in the publication are limited to silver iodobromide emulsions, and do not mention anything about silver halide emulsions containing a high concentration of silver chloride, which is a problem peculiar to the silver halide emulsions at the time of exposure. No mention is made of the improvement of the problem that the finish differs depending on the humidity conditions.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material which has a small performance fluctuation due to a change in humidity during exposure and which can provide a stable finish.

[0013]

The present inventors have found that the above problems can be achieved by the following constitution in the course of earnestly researching a silver halide photographic emulsion used for a silver halide photographic light-sensitive material. Came to complete.

(1) Halogenation with a silver chloride content of 95 to 99.9 mol% which has been spectrally sensitized so that at least one silver halide emulsion layer has a spectral maximum in a specific wavelength range of 400 to 650 nm. A silver halide photographic light-sensitive material containing silver particles, and at least one of photographic constituent layers containing a compound represented by the following formula (I).

[0015]

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In the formula, R ₁₁ represents a hydrogen atom or a lower alkyl group. Y represents an oxygen atom, a sulfur atom or a selenium atom, and Z represents a non-metal atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. This ring may be fused with a benzene ring or a naphthalene ring. R ₁₂ represents an alkyl group or an alkenyl group. X ₁ ^- represents an acid anion.

(2) Halogenation having a silver chloride content of 95 to 99.9 mol% which is spectrally sensitized so that at least one silver halide emulsion layer has a spectral maximum in a specific wavelength region of 400 to 650 nm. A silver halide photographic light-sensitive material containing silver particles and at least one of photographic constituent layers containing a compound represented by the following general formula (II).

[0018]

[Chemical 6]

Where R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R
Each ₂₅ represents a hydrogen atom or a lower alkyl group. R ₂₆ and R ₂₇ each represent a hydrogen atom, a lower alkyl group or a lower alkoxy group, or a group in which R ₂₆ and R ₂₇ are linked to each other to form a condensed ring. X ₂ ⁻ represents an acid anion.

(3) The silver halide photographic light-sensitive material described in (1) or (2), wherein at least one silver halide emulsion layer contains a compound represented by the following general formula (III).

[0021]

[Chemical 7]

In the formula, R ₃₁ represents an alkyl group or a cycloalkyl group, R ₃₂ represents a chlorine atom or —OR ₃₂ , and R ₃₂
Represents an alkyl group, a cycloalkyl group or an aryl group. R ₃₃ represents a substitutable group on the benzene ring, and m is 0
Represents an integer of 4; However, when m is 2 or more, multiple R
₃₃ may be the same or different. R ₃₄ is a substituent having a Hammett's substituent constant σp value of −0.12 to 0.15 or a hydrogen atom, and R ₃₅ and R ₃₆ are a hydrogen atom, an alkyl group, an alkoxy group or an aryl group.

(4) At least one of the photographic constituent layers contains a compound represented by the following general formula (IV) (1),
The silver halide photographic light-sensitive material according to (2) or (3).

[0024]

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In the formula, R ₄₁ is a hydroxyl group, an alkyl group, an alkoxy group, a carbonyl group, --COOM, --SO.
₃ M or —NHR ₄₂ , and n represents an integer of 0 to 4.
However, when n is 2 or more, a plurality of R ₄₁ may be the same or different. R ₄₂ represents a hydrogen atom, an alkyl group or an acyl group. M represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group.

The present invention will be described in detail below.

The composition of the silver halide photographic emulsion according to the present invention (hereinafter referred to as the emulsion of the present invention) is substantially silver iodide-free silver chlorobromide containing 95 mol% or more of silver chloride. . From the viewpoint of rapid processability and process stability, it is preferably 97 mol% or more, more preferably 98 to 99.9 mol%.
Silver chlorobromide emulsions containing silver chloride are preferred.

For the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing a high concentration of silver bromide can also be preferably used. In this case, the portion containing silver bromide at a high concentration may be epitaxy-bonded to silver halide emulsion grains, may be a so-called core-shell emulsion, or may be only partially formed without forming a complete layer. May simply have regions with different compositions. The composition may change continuously or may change discontinuously. The portion in which silver bromide is present at a high concentration is particularly preferably the apex of crystal grains on the surface of silver halide grains.

In order to obtain the emulsion of the present invention, it is advantageous to contain heavy metal ions. Heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt, and Group 12 metals such as cadmium, zinc, and mercury. Examples thereof include group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, iron, iridium,
Platinum, ruthenium, gallium and osmium metal ions are preferred.

These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

When the heavy metal ion forms a complex, its ligands are cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl, ammonia. Etc. can be mentioned. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to contain heavy metal ions in the emulsion of the present invention, the heavy metal compound is subjected to each step during the physical ripening before the formation of silver halide grains, during the formation of silver halide grains and after the formation of silver halide grains. It may be added at any place. In order to obtain an emulsion satisfying the above-mentioned conditions, the heavy metal compound can be dissolved together with the halide and continuously added during the whole or part of the grain forming process.

The amount of heavy metal ions added to the emulsion is 1 × 10 ^-9 to 1 × 10 ^-2 per mol of silver halide.
The amount is preferably mol, and particularly preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁵ mol.

The silver halide grains of the present invention may have any shape. One preferable example is (10
It is a cube having a (0) plane as a crystal surface. US Pat. Nos. 4,183,756 and 4,225,666,
JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 21, 39.
By the method described in the literature such as (1973), etc., particles having a shape such as an octahedron, a tetradecahedron and a dodecahedron are produced,
It can also be used. Further, particles having a twin plane may be used.

As the silver halide grains, grains having a single shape are preferably used, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

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 0.1 to 1.2 μm, more preferably 0.2. Is in the range of 1.0 μm.

This particle size can be measured using the projected area of the particle or an approximate diameter. When the particles have a substantially uniform shape (5 or less particles in 1000 particles having different shapes), the particle size distribution can be represented fairly accurately as a diameter or a projected area.

The grain size distribution of the silver halide grains of the present invention is preferably monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and a coefficient of variation of 0 is particularly preferred. It is to add two or more monodisperse emulsions of 0.15 or less to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution and R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains. Further, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The emulsion of the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The particles may be grown at a time, or may be grown after seed particles have been produced. The method for producing seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt with the soluble halide may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method is preferable. preferable. Further, as one form of the simultaneous mixing method, p described in JP-A-54-48521 and the like is used.
It is also possible to use the Ag-controlled double jet method.

In addition, JP-A-57-92523 and 57-57
A device for supplying a water-soluble silver salt and an aqueous solution of a water-soluble halide from an addition device arranged in a reaction mother liquor described in No. 92524, a water-soluble silver salt described in German Published Patent No. 2,921,164, and the like. Device for continuously changing the concentration of a water-soluble halide aqueous solution and adding it, Japanese Patent Publication No.
For example, an apparatus described in No. 776, etc., in which the reaction mother liquor is taken out of the reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant, may be used.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added and used during the formation of silver halide grains or after the completion of grain formation.

The emulsion of the present invention can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the emulsion of the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but the sulfur sensitizer is preferable. As the sulfur sensitizer, thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine,
Examples thereof include p-toluenethiosulfonate, rhodanine, and inorganic sulfur.

The addition amount of the sulfur sensitizer is preferably changed depending on the kind of silver halide emulsion to be applied and the magnitude of expected effect, but it is 5 × 10 ^{-10 to} 5 per mol of silver halide. × 10 ⁻⁵ mol, preferably 5
The range of × 10 ^{-8 to} 3 × 10 ^-5 mol is preferable.

As the gold sensitizer, various gold complexes can be added in addition to chloroauric acid, gold sulfide and the like. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole.

The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually 1 × 1 per mol of silver halide.
It is preferably 0 ⁻⁴ to 1 × 10 ⁻⁸ mol. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

A reduction sensitization method may be used as the chemical sensitization method for the emulsion of the present invention.

The compound represented by formula (I) of the present invention will be described in detail.

[0052]

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The lower alkyl group represented by R ₁₁ is
Examples thereof include methyl and ethyl groups. The non-metal atom group represented by Z is Y, —N ⁺ (R ₁₂ ) =, and the nitrogen-containing heterocycle formed with a carbon atom may be bonded to a benzene ring or a naphthalene ring. For example, a thiazolium ring (thiazolium, 4 -Methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5
-Methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,1-d] thiazolium, etc.), oxazolium ring (oxazolium,
4-methyloxazolium, benzoxazolium, 5
-Methylbenzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, naphtho [1,2-d] oxazolium, etc., selenazolium ring (benzoselenazolium, 5-methylbenzoselenazolium) , 5-chlorobenzoselenazolium, 5-methoxybenzoselenazolium, naphtho [1,2-d] selenazolium, etc.) and the like.

The alkyl group represented by R ₁₂ is preferably a group having 8 or less carbon atoms such as methyl, ethyl, propyl,
Butyl, pentyl groups and the like can be mentioned. Examples of the alkenyl group represented by R ₁₂ include allyl and 2-methylallyl group. The alkyl group represented by R ₁₁ and R ₁₂ may be a substituted alkyl group. Examples of the acid anion represented by X ₁ ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ^{− and the} like.

Next, the compound represented by formula (II) of the present invention will be described in detail.

[0056]

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The lower alkyl group represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include methyl and ethyl.

The lower alkyl group represented by R ₂₆ and R ₂₇ is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group and ethyl. The lower alkoxy group also has an alkoxy group having 1 to 4 carbon atoms. Are preferred, and methoxy, ethoxy and the like can be mentioned. The condensed ring formed by connecting R ₂₆ and R ₂₇ to each other includes a benzene ring and the like. Examples of the acid anion represented by X ₂ ⁻ include the same acid anions as X ₁ ^{− in the} general formula (I).

Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the invention is not limited thereto.

[0060]

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[0061]

[Chemical 12]

[0062]

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[0063]

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[0064]

[Chemical 15]

[0065]

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[0066]

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The compounds represented by the general formulas (I) and (II) can be used in the steps of preparing silver halide emulsion grains, chemical sensitization step, completion of chemical sensitization step, coating solution preparation step and the like. Although it is added, it is preferably added at the end of the chemical sensitization step or in the coating solution preparation step. When added at the end of chemical sensitization, 1 × 10
^-6 to 1 × 10 ^-2 mol is preferable, and 1 × 10 ^-5 to
5 × 10 ⁻³ mol is more preferred. When added in the coating solution preparation step, 1 × 1 per mol of silver halide
The amount is preferably about 0 ^-6 to 1 × 10 ^-1 mol, and 1 × 10 ^-5 is preferred.
More preferably, it is 1 × 10 ⁻² mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1
The amount is preferably about 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol per m ² .

As a method of adding the compound, methanol,
It may be added as a solution by dissolving it in a water-miscible organic solvent such as ethanol, fluorinated alcohol, acetone, dimethylformamide or the like, but it is preferably added as an aqueous solution adjusted to an appropriate pH.

The 1-phenyl-5-mercaptotetrazole derivative represented by the general formula (IV) of the present invention will be described.

[0070]

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M represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group, preferably a hydrogen atom.
Specific examples of R ₄₁ include methyl, methoxy, ethoxy, hydroxyl, amino, carboxyl, sulfo, acetamino, 3-methylureido and the like.

Specific examples of the compound represented by formula (IV) are shown below, but the invention is not limited thereto.

[0073]

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[0074]

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The compound represented by the general formula (IV) is added in the steps of preparing silver halide emulsion grains, chemical sensitization step, completion of chemical sensitization step, coating solution preparation step and the like. It is preferably added at the end of the chemical sensitization step or in the coating solution preparation step. When added at the end of chemical sensitization, 1 × 10 ⁻⁶ to 1 × 10 ⁻² per mol of silver halide
The amount is preferably about mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. When it is added in the coating liquid preparation step, it is 1 × 10 ⁻⁶ to 1 × 10 ⁶ per mol of silver halide.
^-1 mol is preferable, and ^{1x10 -5} to ^{1x10 -2} mol is more preferable. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 × m ^{2 /} m ^2.
The amount is preferably about 10 ⁻⁹ to 1 × 10 ⁻³ mol.

As the method of adding the compound, the same methods as those described in the above general formulas (I) and (II) can be applied.

The emulsion of the present invention has the above general formula (IV) for the purpose of preventing fogging during the process of preparing a light-sensitive material, reducing performance fluctuations during storage, and preventing fogging during development. In addition to the above compounds, known antifoggants and stabilizers can be used. Examples of the compound that can be used for such purpose include compounds represented by the general formula (II) described in JP-A-2-146036, page 7, lower column. Examples thereof include compounds (IIa-1) to (IIa-8) described on page 8 of the publication.

These compounds are represented by the general formula (IV) of the present invention.
It can be used similarly to the compound represented by.

Dyes having absorption in various wavelength regions can be used in the light-sensitive material for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. Particularly, as the dye having absorption in the visible region, the dyes of AI-1 to 11 described in JP-A-3-251840, page 308, and JP-A-6- The dye described in No. 3770 is preferably used, and as the infrared absorbing dye, the compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A No. 1-280750 are preferable. It is preferable because it has spectral characteristics, does not affect photographic characteristics, and does not cause contamination by residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication.

For the purpose of improving the sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of the untreated sample of the light-sensitive material is 0.7 or more, more preferably 0.8 or more. Is more preferable.

It is preferable to add a fluorescent whitening agent to the light-sensitive material because the whiteness can be improved. Preferred examples of the compound include a compound represented by the general formula II described in JP-A-2-232652.

When the light-sensitive material of the present invention is used as a color photographic light-sensitive material, it is used in combination with a yellow coupler, a magenta coupler and a cyan coupler to obtain 400 to 650n.
It has a layer containing a silver halide emulsion spectrally sensitized to a specific region of the m wavelength range. A light-sensitive material having a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength range of 400 to 500 nm is preferable because the effect of the present invention can be obtained highly.

The silver halide emulsion spectrally sensitized in the specific region of the wavelength region of 400 to 650 nm according to the present invention can be obtained by containing one or more sensitizing dyes in combination in the emulsion.

The light-sensitive material of the present invention is 400 to 650 nm.
In addition to the layer containing the silver halide emulsion spectrally sensitized in the specific region of the wavelength range of, a layer containing the spectrally sensitized silver halide emulsion in the specific region of the wavelength range of 650 to 900 nm can be included.

Any known compound can be used as the spectral sensitizing dye used in the emulsion of the present invention, and as the blue-sensitive sensitizing dye, JP-A-3-251840 28
BS-1 to BS-8 described on the page can be preferably used alone or in combination. As the green-sensitized sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. Further, for red, green and blue light-sensitive sensitizing dyes, JP-A-4-285950 8-
Supersensitizers SS-1 to SS-9 described on page 9 and JP-A No. 5-109839.
-66515, compounds S-1 to S described on pages 15 to 17
It is preferable to use -17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water and adding it as a solution, or as a solid dispersion. Although it may be added, it is preferably added as a solid dispersion.

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized product of a color developing agent. Can also be used, but a typical example is the wavelength range 3
Known as a yellow dye forming coupler having a spectral absorption maximum wavelength in 50 to 500 nm, a magenta dye forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a cyan dye forming coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm. It is what has been.

Examples of cyan couplers that can be preferably used in the present invention include couplers represented by formulas (CI) and (C-II) described in JP-A-4-114154, page 5, lower left column. Examples of specific compounds include those described as CC-1 to CC9 in the same publication, page 5, lower right column to page 6, lower left column.

Examples of magenta couplers that can be preferably used include couplers represented by the general formulas (MI) and (M-II) described in JP-A-4-114154, page 4, upper right column, Specific compounds include those described as MC-1 to 11 on page 4, lower left column to page 5, upper right column. Among the above-mentioned magenta couplers, more preferred is the general formula (M-
Among them, the couplers represented by I), and among them, couplers in which R _{M in the} general formula (M-I) is a tertiary alkyl group are excellent in light resistance and particularly preferable. MC-8 to 11 described in the upper column of page 5 of the same publication are preferable because they are excellent in the reproduction of colors from blue to purple and red and are excellent in the depiction of details.

Known photosensitive yellow couplers such as pivaloyl acetanilide type yellow couplers and benzoyl acetanilide type yellow couplers can be used in the light-sensitive material of the present invention, but the compound represented by formula (III) is particularly preferable. Is preferred.

[0092]

[Chemical 21]

In formula (III), the alkyl group represented by R ₃₁ is a linear or branched alkyl group such as methyl, ethyl, i-propyl, t-butyl, dodecyl and
Examples thereof include 1-hexylnonyl group. Examples of the cycloalkyl group represented by R ₃₁ include cyclopropyl, cyclohexyl and adamantyl groups. These alkyl group and cycloalkyl group may further have a substituent, and examples of the substituent include a halogen atom (chlorine, bromine and the like), a cyano group, a nitro group, an aryl group (phenyl, p-t-octylphenyl, 2,4-di-t-amylphenyl, etc.), hydroxyl group, alkoxy group (methoxy, 2-ethoxyethoxy, etc.), aryloxy group (phenoxy, 2,4-di-t-amylphenoxy, 4
-(4-hydroxyphenylsulfonyl) phenoxy etc.), heterocyclic oxy group (4-pyridyloxy, 2-hexahydropyranyloxy etc.), carbonyloxy group (acetyloxy, pivaloyloxy etc. alkylcarbonyloxy group, benzoyloxy etc.) Arylcarbonyloxy group, etc.), a sulfonyloxy group (methanesulfonyloxy, trifluoromethanesulfonyloxy, dodecanesulfonyloxy, etc., alkylsulfonyloxy group,
Benzenesulfonyloxy, arylsulfonyloxy group such as p-toluenesulfonyloxy), carbonyl group (alkylcarbonyl group such as acetyl and pivaloyl, benzoyl, arylcarbonyl group such as 3,5-di-t-butyl-4-hydroxybenzoyl) Etc.), an oxycarbonyl group (alkoxycarbonyl group such as methoxycarbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, etc., phenoxycarbonyl, 2,4-di-t-
Aryloxycarbonyl groups such as amylphenoxycarbonyl and 1-naphthyloxycarbonyl, and 2-pyridyloxycarbonyl and 1-phenylpyrazolyl-5-
A heterocyclic oxycarbonyl group such as oxycarbonyl),
Carbamoyl group (dimethylcarbamoyl, 4- (2,4
An alkylcarbamoyl group such as -di-t-amylphenoxy) butylaminocarbonyl, phenylcarbamoyl,
1-naphthylcarbamoyl and other arylcarbamoyl groups), sulfonyl groups (methanesulfonyl, trifluoromethanesulfonyl and other alkylsulfonyl groups, p-toluenesulfonyl and other arylsulfonyl groups), sulfamoyl groups (dimethylsulfamoyl, 4- (2, 4-di-t-amylphenoxy) butylaminosulfonyl and other alkylsulfamoyl groups, phenylsulfamoyl and other arylsulfamoyl groups), amino groups (dimethylamino, cyclohexylamino, dodecylamino and other alkylamino groups, Arylamino groups such as anilino and p-t-octylanilino), sulfonylamino groups (alkylsulfonylamino groups such as methanesulfonylamino, heptafluoropropanesulfonylamino, hexadecylsulfonylamino, etc.), -Arylsulfonylamino groups such as toluenesulfonyl and pentafluorobenzenesulfonylamino), acylamino groups (alkylcarbonylamino groups such as acetylamino and myristoylamino groups, arylcarbonylamino groups such as benzoylamino), alkylthio groups (methylthio, t- Octylthio etc.), arylthio groups (eg phenylthio etc.), and heterocyclic thio groups (1-phenyltetrazole-5-thio, 5-methyl-1,3,4-oxadiazole-2-thio etc.) and the like. .

R ₃₁ is preferably an alkyl group, more preferably a branched alkyl group, and particularly preferably a t-butyl group.

R ₃₂ is preferably -OR ₃₀ , and examples of the alkyl group and cycloalkyl group represented by R ₃₀ include the same groups as the alkyl group and cycloalkyl group described for R ₃₁ above. . Moreover, examples of the aryl group represented by R ₃₀ include a phenyl group and a 1-naphthyl group. The alkyl group, cycloalkyl group or aryl group represented by R ₃₂ may have a substituent, and examples of the substituent include a group synonymous with the alkyl group and cycloalkyl group represented by R ₃₁ above, and Examples thereof include the groups defined as the substituents of the alkyl group and cycloalkyl group represented by R ₃₁ . R ₃₀ is preferably an alkyl group, more preferably an unsubstituted alkyl group, and particularly preferably a methyl group.

Examples of the substitutable group on the benzene ring represented by R ₃₃ in the general formula (III) include the groups exemplified as the substituents of the alkyl group, cycloalkyl group and aryl group represented by R ₃₂ above. And a group synonymous with. When m is 2 or more, a plurality of R ₃₃ 's may be the same or different, but m is preferably 1. In that case, the substitution position of R ₃₃ is preferably the 5-position of the anilide ring.

The group represented by R ₃₃ is preferably a substituent represented by the following general formula (IIIb).

In formula (IIIb) —NH—X — (— L—Y—) _n —R ₃₇ , X represents a carbonyl group or a sulfonyl group, preferably a carbonyl group.

L represents an alkylene group, for example, a linear or branched alkylene group such as methylene, ethylene, 2,
Examples include 3-propylene and a 1,2-cyclohexylene group. Of these alkylene groups, an alkylene group having 1 to 6 carbon atoms is preferable.

Y represents a divalent linking group, for example, sulfinyl group, sulfenyl group, sulfonyl group, sulfamoyl group, carbonyl group, carbonyloxy group, carbamoyl group, oxy group, oxycarbonyl group, amino group, acylamino group, Examples thereof include a sulfonylamino group. Of these linking groups, a sulfonyl group, a sulfamoyl group, a carbonyloxy group, a carbamoyl group, an oxy group, an oxycarbonyl group and an acylamino group are preferable, and a sulfonyl group, an oxycarbonyl group and a carbamoyl group are particularly preferable. n represents 0 or 1, but 0 is preferable.

R ₃₇ represents an alkyl group, a cycloalkyl group or an aryl group. An alkyl group represented by R ₃₇ ,
Examples of the cycloalkyl group and the aryl group include groups having the same meanings as the alkyl group, the cycloalkyl group and the aryl group represented by R ₃₂ in the general formula (III). These groups may further have a substituent, and examples of the substituent include the same groups as the groups mentioned as the substituents of the alkyl group, cycloalkyl group and aryl group represented by R _32. .

The substituent represented by the above general formula (IIIb) is preferably a substituent represented by the following general formula (IIIc), (IIId) or (IIIe).

General formula (IIIc) -NHCOR ₃₈

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In the general formula (IIIe) —NHCO—L ₂ —SO ₂ R ₃₈ general formulas (IIIc) and (IIIe), R ₃₈ represents an alkyl group or a cycloalkyl group, and the general formula (III)
Examples of the alkyl group and the cycloalkyl group represented by R ₃₁ in R. These alkyl group and cycloalkyl group may further have a substituent, and the substituent has the same meaning as the groups mentioned as the substituents of the alkyl group, cycloalkyl group and aryl group represented by R _30. Can be mentioned. R ₃₈ is preferably an alkyl group.

R ₃₈ in the general formula (IIIc) is preferably an unsubstituted alkyl group, more preferably an unsubstituted linear alkyl group, and particularly preferably an unsubstituted linear alkyl group having 13 to 21 carbon atoms. .

R _{38 in the} general formula (IIIe) is preferably an unsubstituted alkyl group, more preferably an unsubstituted linear alkyl group, and particularly preferably an unsubstituted linear alkyl group having 8 to 18 carbon atoms. .

In the general formula (IIId), R ₃₉ represents a substitutable group on the benzene ring, and for example, R ₃₉
Examples thereof include the groups defined as the substituents of the alkyl group, cycloalkyl group and aryl group represented by R ₃₀ in I). R ₃₉ is preferably an unsubstituted alkyl group, more preferably an unsubstituted branched alkyl group, and particularly preferably an unsubstituted alkyl group having 3 to 12 carbon atoms.

K represents an integer of 0 to 5, and when k is 2 or more, a plurality of R ₃₉ may be the same or different.
k is preferably 2.

In the general formulas (IIId) and (IIIe),
L ₁ and L ₂ each represent an alkylene group, and examples thereof include the same groups as those described as the alkylene group represented by L in the general formula (IIIb).

In the general formula (IIId), L ₁ is preferably an alkylene group having 3 to 7 carbon atoms, 1,3-propylene, 1,1-propylene, 1,1-pentylene, 1,1
More preferably a hexylene group, 1,3-propylene,
The 1,1-propylene group is particularly preferred.

In the general formula (IIIe), L ₂ is preferably an alkylene group having 3 to 7 carbon atoms, and 1,3-propylene, 2,2-propylene, 2,3-propylene, 1,1
-A propylene group is more preferred, 1,3-propylene,
The 2,3-propylene group is particularly preferred.

The substituent represented by the general formula (IIIb) is represented by the general formulas (IIIc) and (IIIe) among the substituents represented by the general formula (IIIc), (IIId) or (IIIe). Are more preferred, and the substituents represented by formula (IIIc) are particularly preferred.

In the general formula (III), the Hammett's substituent constant σp value represented by R ₃₄ is -0.12 to 0.1.
Representative examples of the substituent of 5 include benzyl, chloromethyl, hydroxymethyl, vinyl, allyl, acetoxymethyl, dimethylaminomethyl, cyclopentyl, 2-phenethyl, phenyl, and the like.
J. MeD. Chem. 16, 1207 (1973),
ibid. 20, 304 (1977) and the like include substituents having a .sigma.p value of -0.12 to 0.15. Of these, particularly preferred groups are benzyl and allyl groups. Examples of the alkyl group, alkoxy group and aryl group represented by R ₃₅ and R ₃₆ include the same groups as the alkyl group, alkoxy group and aryl group represented by R ₃₁ above, preferably R ₃₅ and R ₃₆ are both hydrogen atoms.

Typical examples of the yellow coupler represented by formula (III) (referred to as the yellow coupler of the present invention) are shown below, but the invention is not limited thereto.

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[0117]

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[0118]

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In the light-sensitive material of the present invention, in addition to the above-mentioned yellow coupler, a coupler represented by the general formula (YI) described in the upper right column of JP-A-4-114154 can be used. Specific compounds include those described as YC-1 to YC-9 in the lower left column of page 3 of the same publication. Further, a coupler represented by the general formula [I] described in JP-A-6-67388 can also be used, and specifically, Y described in JP-A-4-114154, page 4, lower left column.
C-8, YC-9, and JP-A-6-67388, 13-
Examples thereof include compounds represented by Nos. (1) to (47) on page 14. Further, compounds represented by the general formula [Y-1] described in JP-A-4-81847, page 1 and pages 11 to 17 thereof can also be used.

When the oil-in-water type emulsion dispersion method is used to add the coupler according to the present invention or other organic compound, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, if necessary. A low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. Examples of the high boiling point organic solvent that can be used to dissolve and disperse the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate and dibutyl phthalate, and phosphoric acid such as tricresyl phosphate and trioctyl phthalate. Esters are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. It is also possible to use two or more high boiling point organic solvents in combination.

Further, instead of the method using a high-boiling point organic solvent, or in combination with a high-boiling point organic solvent, a water-insoluble and organic-solvent-soluble polymer compound is optionally added to a low-boiling point and / or water-soluble organic solvent. It is also possible to employ a method in which the surfactant is dissolved in a hydrophilic binder such as an aqueous gelatin solution and various emulsion means are used for emulsion dispersion. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

Preferred compounds as the surfactant used for dispersing the photographic additives and adjusting the surface tension at the time of coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfo group (or a salt thereof) in one molecule. And the like. Specifically, A-1 to A- described in JP-A 64-26854.
11 are mentioned. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used.

These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time after the dispersion is added to the coating solution and the time after the addition to the coating solution and before the coating are carried out. It is better to be shorter, preferably within 10 hours each,
It is more preferably within 3 hours and within 20 minutes.

An anti-fading agent is preferably used in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include the compounds of formula I described on page 3 of JP-A-2-66541.
Phenyl ether compounds represented by II, JP-A-3-1
No. 74150, a phenolic compound represented by the general formula IIIB, JP-A-64-90445, an amine compound represented by the general formula A, JP-A-62-182741, general formulas XII, XIII and XIV; The metal complex represented by XV is particularly preferable for the magenta dye. In addition, JP-A-1-1
The compound represented by the general formula I ′ described in 96049 and the compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-11) described in JP-A-4-114154, page 9, lower left column, the compound (A'-1), described in page 10, lower left column of the same. And other compounds can be used. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material, a compound which reacts with an oxidized product of a developing agent is added to an intermediate layer between the light-sensitive layers to prevent color turbidity, or added to an emulsion layer to improve fog and the like. Preferably. The compound for this purpose is preferably a hydroquinone derivative, more preferably 2,5-di-
It is a dialkyl hydroquinone compound such as t-octyl hydroquinone. A particularly preferable compound is a compound represented by the general formula II described in JP-A-4-133056, and compounds II-1 to II described on pages 13 to 14 of the publication.
The compound 1 described in -14 and 17 is mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or improve the light resistance of the dye image. Benzotriazoles are mentioned as a preferable ultraviolet absorber, and as a particularly preferable compound, a general formula III-3 described in JP-A-1-250944 is used.
A compound represented by the general formula III described in JP-A-64-66646, and JP-A-63-187240.
UV-1L to UV-27L described in JP-A-4-163
Compounds represented by formula I described in JP-A No. 3-16 / 1993
There are compounds represented by the general formulas (I) and (II) described in No. 5144.

In the light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary,
A hydrophilic colloid such as a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer substance such as a homopolymer or a copolymer can also be used.

As a hardener for these binders, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in No. 9054 and No. 61-245153. Further, in order to prevent the growth of mold and bacteria that adversely affect photographic performance and image storability, it is preferable to add an antiseptic and an antifungal agent as described in JP-A-3-157646 to the colloid layer. Further, in order to improve the physical properties of the surface of the light-sensitive material or the sample after processing, it is preferable to add a slipping agent or a matting agent described in JP-A Nos. 6-118543 and 2-73250 to the protective layer.

Any material may be used as the support of the light-sensitive material, including paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, and white pigment. Polypropylene, polyethylene terephthalate support, baryta paper or the like may be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, hydrated alumina, titanium oxide, Examples thereof include zinc oxide, talc and clay. Barium sulfate and titanium oxide are preferred as white pigments.

The amount of the white pigment contained in the water resistant resin layer on the surface of the support is preferably 13% by weight or more, more preferably 15 to 50% by weight in order to improve the sharpness.

The degree of dispersion of the white pigment in the water resistant resin layer of the paper support can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the variation coefficient described in the publication.

Further, it is more preferable that the value of the center surface average roughness (SRa) of the support is 0.15 μm or less, further 0.12 μm or less because the effect of good gloss can be obtained.
Further, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after the treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer, ultramarine blue, oil-soluble dyes, etc. It is preferable to add a slight amount of a bluing agent or a reddishing agent.

The photosensitive material may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or in an undercoat layer (adhesiveness on surface of support, antistatic property, dimensional stability). Properties, abrasion resistance, hardness, antihalation properties, one or more subbing layers for improving frictional properties and / or other properties).

At the time of coating the light-sensitive material, a thickener may be used in order to improve coatability. The coating method is 2
Extrusion coatings and curtain coatings, which allow for the simultaneous application of more than one layer, are particularly useful.

To form a photographic image using the light-sensitive material of the present invention, the image recorded on the negative may be optically imaged and printed on the light-sensitive material to be printed. Once converted into digital information, the image may be imaged on a CRT (cathode ray tube), and this image may be imaged and printed on a photosensitive material to be printed. You may print by changing the intensity of light and scanning.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably to a light-sensitive material for forming an image for direct viewing. For example, color paper, color reversal paper, photosensitive material for forming a positive image, photosensitive material for display,
A light-sensitive material for color proof can be used. Particularly, application to a light-sensitive material having a reflective support is preferable.

As the aromatic primary amine developing agent used for color development, known compounds can be used. Typical examples of these are the following compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4: 4- (N-ethyl-N-β-hydroxyethylamino) aniline CD-5: 2-methyl-4- (N-ethyl-N-β-hydroxyethylamino) aniline CD-6: 4- Amino-3-methyl-N-ethyl-N-
(Β-Methanesulfonamidoethyl) aniline CD-7: 4-amino-3-β-methanesulfonamidoethyl-N, N-diethylaniline CD-8: N, N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline CD-10: 4-amino-3-methyl-N-ethyl-N
-(Β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N
-(Γ-hydroxypropyl) aniline The color developing solution can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0.
The pH is more preferably in the range of 9.8 to 12.0.

The processing temperature for color development is preferably 35 to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, it is preferable that the temperature is not too high from the viewpoint of the stability of the processing solution.

Conventionally, the color development time is generally 3 minutes 30.
Although it is carried out in about 2 seconds, in the present invention, it is preferably within 40 seconds, more preferably within 25 to 5 seconds.

To the color developing solution, known developer component compounds can be added in addition to the above color developing agent.
Usually, an alkaline agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazole, a preservative, a chelating agent and the like are used.

The photographic material is subjected to bleaching processing and fixing processing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed.
Further, as a substitute for the washing treatment, a stabilizing treatment may be performed.

As the developing processing apparatus used for the developing processing,
It may be a roller transport type in which the photosensitive material is sandwiched between the rollers arranged in the processing tank and conveyed, or an endless belt method in which the photosensitive material is fixed on the belt and conveyed, but the processing tank is formed into a slit shape. Forming and supplying the processing liquid to the processing tank and conveying the photosensitive material, spraying method in which the processing liquid is sprayed, web method by contact with a carrier impregnated with the processing liquid, method using viscous processing liquid Etc. can also be used.

When a large amount of a light-sensitive material is processed, it is usually run by using an automatic processor. At this time, the smaller the replenishing amount of the replenisher is, the more preferable the processing form is from the environmental suitability. Is to add a treating agent in the form of tablets as a supplement method.
The method described in No. 935 is most preferable.

[0147]

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

Example 1 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However,
On the side to which the emulsion layer was applied, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed was laminated to prepare a reflective support.
After subjecting this reflective support to corona discharge treatment, a gelatin subbing layer was provided, and each layer having the constitution shown below was coated to prepare a single-layer color light-sensitive material. The coating liquid was prepared as follows.

23.4 g of a yellow coupler (Y-1),
Dye image stabilizer (ST-1) 3.34 g, (ST-
2) 3.34 g, (ST-5) 3.34 g, stain inhibitor (HQ-1) 0.34 g, image stabilizer A 5.0 g
3.33 g of high boiling point organic solvent (DBP) and (DN
P) (1.67 g) was dissolved by adding 60 cc of ethyl acetate,
A 10% gelatin aqueous solution (220 cc) containing 0% surfactant (SU-1) 7 cc was emulsified and dispersed using an ultrasonic homogenizer to obtain a yellow coupler dispersion.

This dispersion was mixed with a silver halide emulsion (Em-B101; containing 8.50 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. A second layer (protective layer) coating solution and the support were simultaneously coated to prepare Sample 101. In addition, (H-1) was added to the second layer as a hardener. As the coating aid, surfactants (SU-2), (S
U-3) was added to adjust the surface tension.

[0151]

[Table 1]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Di (sulfo succinate) (2,2,3,3,4) , 4,
5,5-octafluoropentyl) sodium salt H-1: tetrakis (vinylsulfonylmethyl) methane HQ-1: 2,5-di-t-octylhydroquinone DBP: dibutylphthalate DNP: dinonylphthalate Compound A: p- t-octylphenol

[0153]

[Chemical formula 26]

(Preparation of high silver chloride monodisperse emulsion (EMP-1)) In 1 liter of a 2% gelatin aqueous solution kept at 40 ° C., the following (A solution) and (B solution) had pAg = 7.3 and pH =
Simultaneously added over 30 minutes while controlling at 3.0, the following (C solution) and (D solution) were further added, pAg = 8.0, pH = 5.5.
The temperature was controlled to 180 ° C. and the simultaneous addition was performed. At this time, p
The Ag was controlled by the method described in JP-A-59-45437, and the pH was controlled by using a sulfuric acid or sodium hydroxide aqueous solution.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 cc (Solution B) Silver nitrate 10 g Water was added to 200 cc (Solution C) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag potassium bromide 1.0 g Water added 600 cc (solution D) Silver nitrate 300 g Water added 600 cc After the addition, Kao Atlas Desalination was performed using a 5% aqueous solution of DEMOL N and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.71μ.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained.

(Preparation of Silver Chlorobromide Monodisperse Emulsion (EMP-2)) In the preparation of emulsion (EMP-1), (C solution) and (D solution) were replaced with the following (C2 solution) and (D2 solution). Except that the average particle size was 0.71 μm and the variation coefficient was 0.
07, a monodisperse cubic emulsion EM having a silver chloride content of 90 mol%
P-2 was obtained.

(Solution C2) Sodium chloride 92.9 g K ₂ IrCl ₆ 4 × 10 ⁻⁸ mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ⁻⁵ mol / mol Ag potassium bromide 21.0 g Water was added. 600 cc (D2 solution) Silver nitrate 300 g Water was added to 600 cc (Preparation of silver chlorobromide monodisperse emulsion (EMP-3)) Emulsion (E
MP-1) was prepared in the same manner except that (C liquid) and (D liquid) were changed to the following (C3 liquid) and (D3 liquid), the average particle size was 0.71 μm, and the coefficient of variation was 0.07. A monodisperse cubic emulsion EMP-3 having a silver chloride content of 80 mol% was obtained.

(Solution C3) Sodium chloride 82.6 g K ₂ IrCl ₆ 4 × 10 ⁻⁸ mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ⁻⁵ mol / mol Ag potassium bromide 42.0 g Water was added. 600 cc (solution D3) 300 g of silver nitrate Water 600 cc (preparation of blue-sensitive silver halide emulsion) EMP-1 to 3 above
On the other hand, the following compounds were optimally chemically sensitized at 60 ° C. to obtain a blue-sensitive silver halide emulsion (Em-B101 to B1).
03) was obtained.

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-4 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-4: 4-hydroxy-6-methyl-1,3
3a, 7-Tetrazaindene The sensitizing dyes BS-1 and BS-2 are disclosed in Japanese Patent Application No. 5-98.
The additive solution obtained by the method described in No. 094, page 87, in which the sensitizing dye is dispersed in solid fine particles, was used.

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(Preparation of Green-Sensitive Silver Halide Emulsion) E above
The following compounds were optimally chemically sensitized to MP-1 to 55 at 55 ° C. to obtain a green-sensitive silver halide emulsion (Em-G
101-G103) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-4 3 × 10 ⁻⁴ mol / mol AgX Sensitizing Dye GS-1 4 × 10 ⁻⁴ mol / mol AgX As the sensitizing dye GS-1, an additive solution obtained by the method described on page 87 of Japanese Patent Application No. 5-98094 in which the sensitizing dye is dispersed in solid fine particles was used.

(Preparation of Red-Sensitive Silver Halide Emulsion) E above
The following compounds were optimally chemically sensitized to MP-1 at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R10
1) was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-4 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX Further, SS-1 was added to the red photosensitive emulsion in an amount of 2.0 × 10 ⁻³ mol per mol of silver halide.

Here, as the sensitizing dyes RS-1 and RS-2, an additive solution in which the sensitizing dye obtained by the method described on page 87 of Japanese Patent Application No. 5-98094 is dispersed in solid fine particles is used. .

(Preparation of Infrared-Sensitive Silver Halide Emulsion) The above-mentioned EMP-1 was optimally chemically sensitized at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-IR).
101).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-4 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye IRS-1 2 × 10 ⁻⁴ mol / mol AgX Here, as the sensitizing dye IRS-1, an additive solution in which the sensitizing dye obtained by the method described on page 87 of Japanese Patent Application No. 5-98094 was dispersed in solid fine particles was used.

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Samples 102 to 120 were prepared in the same manner as in Sample 101 except that the silver halide emulsion (Em-B101) was changed as shown in Table 2 and the compounds shown in Table 2 were dissolved in ethanol and added. It was made.

Samples 101 to 120 were processed at 25 ° C. and 30% RH.
While maintaining an atmosphere of 25 ° C. and 80% RH, light wedge exposure was performed by an ordinary method with an exposure time of 0.5 seconds, and development processing was performed according to the following development processing steps.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 cc Bleach fixing 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30-34 ° C. 60 seconds 150 cc Dry 60-80 ° C. 30 seconds The composition of each treatment liquid is shown below.

Color developer tank solution and replenisher tank solution Replenisher pure water 800 cc 800 cc triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N-β methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriaminepentaacetic acid Sodium salt 2.0 g 2.0 g Optical brightener (4,4′-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter, and the tank liquid had pH = 10. .10, the replenisher has pH = 10 Adjust to 60.

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetic acid ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc 2-Amino-5-mercapto-1,3,4-thiadiazole 2 0.0 g Ammonium sulfite (40% aqueous solution) 27.5 cc Water is added to bring the total volume to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing liquid tank liquid and replenishing liquid o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP ( Poly-N-vinylpyrrolidone) 1.0 g Ammonia water (ammonium hydroxide 25% aqueous solution) 2.5 g Nitrilotriacetic acid trisodium salt 1.5 g Water is added to bring the total volume to 1 liter, and pH is adjusted with sulfuric acid or ammonia water. Adjust to 7.5.

The processed sample was measured for blue density using a PDA-65 densitometer (manufactured by Konica) to evaluate the sensitivity. The sensitivity is defined based on the reciprocal of the exposure amount that gives a density of 0.75. For the sensitivity of 25 ° C. and 30% RH, in the case of the sample using the blue-sensitive silver halide emulsion, the sample 101 is used and the green-sensitive halogenated one is used. Sample 109 for samples using silver emulsion
Is expressed as a relative value with sample 116 in the case of the sample using the red-sensitive silver halide emulsion and sample 119 as 100 in the case of the sample using the infrared-sensitive silver halide emulsion. Again 2
For the sensitivity of 5 ° C and 80% RH, the same sample at 25 ° C
-It was expressed as a relative value with the sensitivity of 30% RH as 100. Table 2 shows the results.

[0176]

[Table 2]

As can be seen from these results, the sample using the silver halide emulsion having a high silver bromide content is not suitable for the processing having a short processing time, the development is not sufficient, and the high silver chloride emulsion is used. The sensitivity is lower than the original sample. In the sample using the high silver chloride emulsion having the maximum spectral sensitivity in the range of 400 to 650 nm without using the compound of the present invention, the sensitivity decrease is large when exposed under high humidity. On the other hand, it can be seen that the sample using the compound of the present invention has a maximum spectral sensitivity in the range of 400 to 650 nm and has high sensitivity, and the sensitivity reduction when exposed under high humidity is improved.

Example 2 Samples 201 to 214 were prepared in the same manner as in Sample 101 of Example 1 except that the compound to be added, the addition amount, and the yellow coupler were changed as shown in Table 3 below. It evaluated similarly to. At the same time, the maximum concentration of each sample was also measured. The results are also shown in Table 3.

[0179]

[Table 3]

As is clear from these results, the yellow coupler of the present invention has a high maximum density, but a large decrease in sensitivity when exposed under high humidity. However, when the compound of the present invention is added, the decrease in sensitivity when exposed under high humidity is improved, and the maximum concentration of the yellow coupler of the present invention is further increased. That is, by using the yellow coupler of the present invention in combination with the compound of the present invention, it is possible to obtain a light-sensitive material having a high maximum density and a small humidity fluctuation during exposure.

Example 3 Samples 301 to 314 were prepared in the same manner as in Example 1, except that the compound to be added and the addition amount were changed as shown in Table 4 below. evaluated. Table 4 shows the results. The compound of the general formula (IV) of the present invention was added after being dissolved in water whose pH was adjusted using sodium hydroxide.

[0182]

[Table 4]

As can be seen from these results, the compound represented by the general formula (IV) of the present invention has no effect of improving the sensitivity reduction when exposed to high humidity. However, it is understood that when the compound is used in combination with the compound of the present invention, the effect of improving the sensitivity decrease upon exposure under high humidity is further enhanced.

Example 4 After the same reflective support as in Example 1 was subjected to corona discharge treatment,
A gelatin subbing layer was provided, and each layer having the constitution shown in Tables 5 and 6 was further coated to prepare a multilayer color light-sensitive material sample 401.

Further, as a hardener (H-1), (H-2)
And a surfactant (SU-2) as a coating aid,
(SU-3) was added to adjust the surface tension. Further, a fungicide (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

[0186]

[Table 5]

[0187]

[Table 6]

DOP: dioctyl phthalate DIDP: di-i-decyl phthalate H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-2: 2,5-di-sec-dodecyl hydroquinone HQ- 3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxy) Carbonyl) butyl hydroquinone

[0189]

[Chemical 29]

[0190]

Embedded image

[0191]

[Chemical 31]

[0192]

Embedded image

(Preparation of blue-sensitive silver halide emulsion) In exactly the same manner as in Example 1, a single grain having an average grain size of 0.71 μm, a variation coefficient of grain size distribution of 0.07, and a silver chloride content of 99.5 mol%. A dispersed cubic emulsion EMP-1 was obtained.

Next, the EMP was changed except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
A monodispersed cubic emulsion EMP-1B having an average grain size of 0.64 μm, a variation coefficient of the grain size distribution of 0.07 and a silver chloride content of 99.5 mol% was obtained in the same manner as in Example 1.

The above EMP-1 was optimally chemically sensitized at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 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-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 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 (Preparation of green-sensitive silver halide emulsion) (Solution A) and (Solution B) )
The average particle size was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%. Next, (solution A) and (B
(Solution) and (C solution) and (D solution) were added in the same manner as in EMP-1, except that the addition time was changed to an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5%. A monodisperse cubic emulsion EMP-2B was obtained.

The above-mentioned EMP-2 was optimally chemically sensitized at 55 ° C. using the following compounds. Also, EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 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 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (Solution A) and (Solution B)
The average particle size was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. Similarly, the average grain size is 0.38 μm, the variation coefficient is 0.08, and the silver chloride content is 9
A 9.5% monodisperse cubic emulsion EMP-3B was obtained.

The above EMP-3 was optimally chemically sensitized at 60 ° C. using the following compounds. Also, EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX sensitizing dye RS-2 1 × 10 ^-4 mol / mol AgX Also for red-sensitive emulsions. Added SS-1 in an amount of 2.0 × 10 ⁻³ mol per mol of silver halide.

In the preparation of these emulsions, the addition of the sensitizing dye was carried out in the same manner as in Example 1 by using an addition liquid in which the sensitizing dye was dispersed in solid fine particles.

Samples 402 to 409 were prepared in the same manner except that the compounds shown in Table 7 were added to the first layer, second layer, third layer and fifth layer of sample 401.

[0203]

[Table 7]

These samples 401 to 409 were exposed and developed in the same manner as in Example 1, and the processed samples were measured for blue, green, and red densities using a PDA-65 densitometer (described above), and the results of Example 1
Was evaluated in the same way as Table 8 shows the results.

[0205]

[Table 8]

As can be seen from these results, the sample to which the compound of the present invention is added shows an improvement effect which is the same as that of a single layer even in the case of multiple layers.

Example 5 Samples 401, 406 and 407 prepared in Example 4 were developed using an automatic processor (Nonica NPS-868J manufactured by Konica Corp., ECOJET-P was used as a processing chemical) to develop Konica Color LV. It was exposed and developed through -400 (negative film). This automatic processor is
It has been modified so that it can measure humidity.

An automatic processor was installed in a room where the temperature and humidity could be set constant, the room temperature was kept constant and the humidity was changed, and printing was performed from a negative film of the same scene. Looking at the prints developed during this time, sample 4
In No. 01, a shift was seen in the cyan color direction when the humidity of the exposed portion increased, but in Samples 406 and 407 of the present invention,
It was found that no change in the color of the print was observed regardless of the humidity of the exposed area, and a stable print finish was obtained.

[0209]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which has a small performance fluctuation due to a change in humidity at the time of exposure and can obtain a stable finish.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takahiko Nojima 1 Konica Stock Company, Sakura-cho, Hino City, Tokyo

Claims (4)

[Claims] 1. A silver chloride content of 95 to 99.9 mol% spectrally sensitized so that at least one silver halide emulsion layer has a spectral maximum in a specific wavelength range of 400 to 650 nm.
A silver halide photographic light-sensitive material comprising at least one photographic constituent layer containing a compound represented by the following general formula (I). Embedded image [In the formula, R ₁₁ represents a hydrogen atom or a lower alkyl group. Y
Represents an oxygen atom, a sulfur atom or a selenium atom, and Z represents a non-metal atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocycle. This ring may be fused with a benzene ring or a naphthalene ring. R ₁₂ represents an alkyl group or an alkenyl group. X ₁ ^- represents an acid anion. ] 2. A silver chloride content of 95 to 99.9 mol% spectrally sensitized so that at least one silver halide emulsion layer has a spectral maximum in a specific wavelength range of 400 to 650 nm.
A silver halide photographic light-sensitive material containing at least one photographic constituent layer containing a compound represented by the following general formula (II). Embedded image [In the formula, R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ each represent a hydrogen atom or a lower alkyl group. R ₂₆ and R ₂₇ each represent a hydrogen atom, a lower alkyl group or a lower alkoxy group, or a group in which R ₂₆ and R ₂₇ are linked to each other to form a condensed ring. X ₂ ⁻ represents an acid anion. ] 3. The silver halide photographic light-sensitive material according to claim 1, wherein at least one silver halide emulsion layer contains a compound represented by the following general formula (III). Embedded image [In the formula, R ₃₁ represents an alkyl group or a cycloalkyl group, R ₃₂ represents a chlorine atom or —OR ₃₂ , and R ₃₂ represents an alkyl group, a cycloalkyl group or an aryl group. R ₃₃ represents a substitutable group on the benzene ring, and m represents an integer of 0 to 4. However, when m is 2 or more, a plurality of R ₃₃ may be the same or different. R ₃₄ is a substituent having a Hammett's substituent constant σp value of −0.12 to 0.15 or a hydrogen atom, and R ₃₅ and R ₃₆ are a hydrogen atom, an alkyl group, an alkoxy group or an aryl group. ] 4. The silver halide photographic light-sensitive material according to claim 1, wherein at least one of the photographic constituent layers contains a compound represented by the following general formula (IV). Embedded image [In the formula, R ₄₁ represents a hydroxyl group, an alkyl group, an alkoxy group, a carbonyl group, —COOM, —SO ₃ M or —
Represents NHR ₄₂ , and n represents an integer of 0 to 5. However, n
When is 2 or more, plural R ₄₁ may be the same or different. R ₄₂ represents a hydrogen atom, an alkyl group or an acyl group. M represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group. ]