JP2001022018A - Silver halide photographic sensitive material and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material small in occurrence of fog in color development at high developing temperature and high in aptitude to ultrahigh speed processing and sensitivity and stable in performances in manufacturing lots and to provide its manufacture. SOLUTION: The silver halide photographic sensitive material is provided with at least one of silver halide emulsion layer containing >=90 mol% silver chloride on a support and at least one kind of N-containing heterocyclic mercapto compound is added into this emulsion between a process before the end of chemical ripening (process A) and the following process (process B), and an addition amount in the process B is more than that in the process A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter also simply referred to as a "light-sensitive material") and a method for producing the same. The present invention relates to a silver halide photographic material having high sensitivity and stable performance in a production lot, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, processing has been accelerated, and a large amount of color photographic light-sensitive materials for printing have been rapidly processed. Accelerated development is a very strong demand in the color photographic industry, with numerous improvements being made and new rapid systems being developed every few years.

[0003] Acceleration of processing includes color development, bleach-fixing,
It is necessary to separately devise the time for each of the washing and drying processes. As a method of accelerating the processing, for example, WO 87-04,534 discloses a rapid processing using a color photographic light-sensitive material using high silver chloride as a photographic emulsion (hereinafter, also simply referred to as "light-sensitive material"). Is disclosed, and from the viewpoint of rapid processing,
It has been shown that it is preferable to use silver chloride or a silver chlorobromide emulsion having a high silver chloride content.

For example, US Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-A-58-91444, JP-A-58-95339, and JP-A-58-95339.
No. 94340, No. 58-95736, No. 58-106
No. 538, No. 58-107531, No. 58-1075
No. 32, No. 58-107533, No. 58-10853
No. 3 describes the above technology.

With the introduction of these technologies, current color papers have been devised so that a high-quality image can be obtained in a developing process of only several tens of seconds. In order to shorten the development processing time, a method of increasing the processing temperature of color development is known.

[0006] In the market, with the rapid development processing, there is a demand for a service for giving prints to customers on the spot in resorts and a service for producing prints during shopping at a shopping center and giving the prints when returning. It seems that this is a business format that makes the most of the advantages of the minilab for ultra-rapid processing.

It is generally known that color paper has poor fog resistance, particularly in color development at a high processing temperature.

[0008] In recent years, there has been a demand for ultra-rapid development processing and even higher sensitivity, so that the fogging preventing ability of these antifoggants has become insufficient. Until now, there is no description about improvement of the antifogging ability by the method of adding the antifoggant. For example, JP-A-51-36130
JP-A-62-177539 and JP-A-62-253.
No. 142 and JP-A-62-253161 disclose a technique for preventing fog by adding a nitrogen-containing heterocyclic mercapto compound.

However, these techniques are not techniques for preventing fogging in color development at a high processing temperature, and do not disclose any method for adding a nitrogen-containing heterocyclic mercapto compound.

On the other hand, in order to supply a stable color paper, a method for improving performance fluctuation due to variations has been devised. JP-A-4-323645, JP-A-6
JP-A-222523 discloses a technique for stabilizing fluctuations in sensitivity and fog in an emulsion solution using a cyanine dye and a nitrogen-containing mercapto compound.

However, although this technique has the effect of preventing performance fluctuations due to aging during dissolution from emulsion dissolution to coating, it is not a technique for preventing fogging in color development at a high processing temperature, but has a rapid processing stability. No suggestion is made as to the effect of the conversion and the method for adding the nitrogen-containing heterocyclic mercapto compound.

JP-A-1-197740 discloses a technique for adding a nitrogen-containing heterocyclic mercapto compound to a coating solution and stabilizing the performance in the coating solution. Also, JP-A-62-17
No. 4,743, discloses the addition of a nitrogen-containing heterocyclic mercapto compound to an emulsion layer and a non-photosensitive layer.

However, these techniques are similar to those described above.
Although the effect of preventing performance fluctuation due to aging during dissolution from emulsion dissolution to coating can be seen, there is no suggestion for the effect of rapid processing stabilization, not fog prevention technology in color development at high processing temperatures. No description is made regarding the degree of dissociation of the inhibitor.

[0014]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photograph which is color developing at a high processing temperature, has low fog, has excellent suitability for rapid processing, and has high sensitivity and stable performance in a production lot. An object of the present invention is to provide a photosensitive material and a method for producing the same.

[0015]

The above object of the present invention is achieved by the following constitution.

1. In a method for producing a silver halide photographic material in which a photosensitive emulsion layer and a non-photosensitive layer are coated on a support, the coating solution used for forming the photosensitive emulsion layer has a silver chloride content of 90 mol% or more. And the nitrogen-containing heterocyclic mercapto compound is added until the completion of the chemical ripening of the silver halide grains (Step A), and is contained until the coating (Step B) after the completion of the chemical ripening. A nitrogen heterocyclic mercapto compound is added, and the amount of the nitrogen-containing heterocyclic mercapto compound in the step B is adjusted so as to be larger than the amount of the nitrogen-containing heterocyclic mercapto compound to the step A, and the coating is performed. A method for producing a silver halide photographic light-sensitive material, comprising:

2. In a method for producing a silver halide photographic material in which a photosensitive emulsion layer and a non-photosensitive layer are coated on a support, the coating solution used for forming the photosensitive emulsion layer has a silver chloride content of 90 mol% or more. And the nitrogen-containing heterocyclic mercapto compound is added until the completion of the chemical ripening of the silver halide grains (Step A), and between the completion of the chemical ripening and the coating (Step B). The nitrogen-containing heterocyclic mercapto compound is added in an aqueous solution having a dissociation degree of 0.99 or more, and the nitrogen-containing heterocyclic mercapto compound has a dissociation degree of 0.99 or more in a coating solution used for forming the non-photosensitive layer. A method for producing a silver halide photographic light-sensitive material, characterized in that it is added so as to be an aqueous solution of and coated.

3. A coating solution used for forming the photosensitive emulsion layer and a coating solution used for forming the non-photosensitive layer are coated so as to form an adjacent layer on a support. A method for producing a silver photographic light-sensitive material.

4. In a method for producing a silver halide photographic material in which a photosensitive emulsion layer and a non-photosensitive layer are coated on a support, the coating solution used for forming the photosensitive emulsion layer has a silver chloride content of 90 mol% or more. Wherein the nitrogen-containing heterocyclic mercapto compound is added and coated within 60 minutes after mixing the silver halide emulsion containing the silver halide grains with the coupler. For producing a silver halide photographic light-sensitive material.

[5] 5. A silver halide photographic light-sensitive material produced by the method for producing a silver halide photographic light-sensitive material according to any one of the above items 1 to 4.

Hereinafter, the present invention will be described in more detail.

The composition of the silver halide emulsion of the present invention is characterized by containing 90 mol% or more of silver chloride, and silver chloroiodide, silver chlorobromide, and salt containing 95 mol% or more of silver chloride. Silver iodobromide is preferred. From the viewpoint of rapid processing property and processing stability, it is preferably 97 mol% or more, more preferably 98 to 98 mol%.
Silver chlorobromide containing 99.9 mol% of silver chloride.

The composition of the halogenated emulsion may be uniform or may have a portion containing silver bromide at a high concentration. In this case, the portion containing silver bromide at a high concentration is a so-called epitaxy junction in which a region having a partially different composition does not form a complete layer on the silver halide grains but exists only partially. It may be a core-shell emulsion. The composition may change continuously or may change discontinuously. The portion where silver bromide exists at a high concentration may be on the surface of silver halide grains or inside thereof, but is preferably on the surface of silver halide grains. The silver bromide content of the portion containing silver bromide at a high concentration is preferably 30 mol% or more, more preferably 30 to 50 mol%.

In the present invention, the grain size of the silver halide grains is not particularly limited, but is preferably not more than 3.0 μm, and more preferably not more than 2.0 μm in consideration of photographic performance such as rapid processing and sensitivity. Is more preferable.

The size of the silver halide grains can be measured by various methods generally used in the art. A representative method is described in Loveland's “Particle Size Analysis Method” (ASTM Symposium on Right Microscopy, pp. 94-122, 19).
55) or "Theory of Photographic Process Third Edition" (Mies and James, Chapter 2, published by Macmillan, 196)
The method described in 6) can be mentioned.

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

In the present invention, the silver halide emulsion may be obtained by any of an acidic method, a neutral method and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Further, JP-A-57-92523, JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in German Offenlegungsschrift 2,921,164, etc. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Also, aminoazaindene, pyrimidine, aminoazine, thiourea, triazole, 3-amino-1H-1,2,4 triazole, 3,
A compound such as a crystal habit control agent such as 5-diamino-1H-1,2,4 triazole, imidazole, or xanthoid or a sensitizing dye may be added during the formation of silver halide grains.

In the present invention, as the nitrogen-containing heterocyclic mercapto compound, any known compound can be preferably used, but a compound represented by the following general formula (1), (2) or (3) is more preferable. .

[0032]

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In the general formula (1), R ₁ is a hydrogen atom,
It represents an alkoxy group, a carboxyl group, a hydroxyl group, or a sulfonic acid group.

The following are specific examples of the compound represented by the general formula (1). However, the present invention is not limited to these exemplified compounds.

[0035]

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[0036]

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In the formula, R ₂ represents a hydrogen atom or an alkyl group having up to 4 carbon atoms, R ₃ represents —COR or —CONHR, and R represents an alkyl group or an aryl group.

The following are specific examples of the compound represented by the general formula (2). However, the present invention is not limited to these exemplified compounds.

[0039]

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Next, the compound represented by formula (3) will be described.

[0041]

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In the general formula (3), Y represents a hydrogen atom, an amino group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a -CONHR ₃₂ group, a -COR ₃₃ group,
Represents an NHCOR ₃₄ group or a —HNSO ₂ R ₃₄ group. Z represents a nitrogen atom, a sulfur atom or an oxygen atom. n represents 1 when Z is a nitrogen atom, and 0 when Z is an oxygen atom or a sulfur atom.
Represents R ₃₁ represents a hydrogen atom, an amino group, a hydroxyl group,
Hydrazino group, alkyl group, alkenyl group, aryl group, cycloalkyl group, mercapto group, -NHCOR ₃₅
Represents a group, —NHSO ₂ R ₃₅ group or —SR ₃₆ group. R ₃₂ ,
_{R 33, R 34, R 35} , R 36 are each an alkyl group, an alkenyl group, a cycloalkyl group or an aryl group.

The following are specific examples of the compound represented by the general formula (3). However, the present invention is not limited to these exemplified compounds.

[0044]

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[0045]

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The step of preparing a silver halide emulsion includes a nucleation step for generating nuclei of silver halide microcrystals, a subsequent crystal growth step, a physical ripening step, a desalting step for removing excess salts, and a photosensitive nucleus. A chemical / color sensitization step of forming and performing color sensitization, and a chemical / color sensitization stopping step of stopping formation of a photosensitive nucleus and color sensitization. The step A in which the nitrogen-containing heterocyclic mercapto compound of the present invention is added refers to the steps from the nucleation step to the chemical / color sensitization stopping step.

The silver halide emulsion is completed as a silver halide photographic material through a coating solution preparation step for preparing a coating solution suitable for coating, a coating step, and a subsequent drying step.
The step B of adding the nitrogen-containing heterocyclic mercapto compound according to the present invention refers to the above-mentioned coating solution preparation step to immediately before coating in the coating step.

The nitrogen-containing heterocyclic mercapto compound of the present invention is used in an amount of 1 × 10 ^-6 mol to 1 × 1 per mol of silver halide.
About 0 ^-2 mol is preferable.

The invention of claim 1 will be described.

The amount of the nitrogen-containing heterocyclic mercapto compound of the present invention to be added in the step B is larger than that in the step A.

The addition amount of the nitrogen-containing heterocyclic mercapto compound of the present invention in the step B is 1.1 to 1 times the addition amount in the step A.
The amount is preferably 10 times, more preferably 1.1 times to 5 times.

The invention of claim 2 will be described.

The addition of the nitrogen-containing heterocyclic mercapto compound in the step A of the present invention is not limited, and the dissociation degree is not limited, as long as the nitrogen-containing heterocyclic mercapto compound is added.

It is essential that the nitrogen-containing heterocyclic mercapto compound in the step B of the present invention and the non-photosensitive layer is added as an aqueous solution having a degree of dissociation of 0.99 or more, and particularly, in an adjacent silver halide emulsion layer. Reduces the processing fogging effect and high temperature processing fogging effect. The aqueous solution having a dissociation degree of the nitrogen-containing heterocyclic mercapto compound of 0.99 or more of the present invention may be a solvent and other additives so that the dissociation degree of the nitrogen-containing heterocyclic mercapto compound is 0.99 or more, It can be prepared by keeping the dissolved solution for a certain period of time.
It is more preferable to use a solution prepared as described above. The degree of dissociation of the nitrogen-containing heterocyclic mercapto compound is defined as the concentration of the dissociated nitrogen-containing heterocyclic mercapto compound in the solution divided by the concentration of the total nitrogen-containing heterocyclic mercapto compound. The degree of dissociation can be determined, for example, by measuring the spectral absorption of the nitrogen-containing heterocyclic mercapto compound, obtaining the concentration of the dissociated nitrogen-containing heterocyclic mercapto compound, and then obtaining the concentration.

These methods are described, for example, in “Experimental Chemistry Lecture Series 11”, paragraphs 524 to 552 (Maruzen 19
1965) can be referred to. For the purpose of adjusting the degree of dissociation, main inorganic compounds and organic compounds can be used. These compounds are added to a silver halide photographic light-sensitive material and selected from compounds that do not substantially affect the silver halide photographic light-sensitive material. Examples thereof include sodium hydroxide, potassium hydroxide, and sodium carbonate. And compounds such as sodium hydrogencarbonate, potassium carbonate, sodium acetate, triethylamine and triethanolamine, and those having a buffer effect in a solution are particularly preferably used. As the solvent, water, a low-boiling alcohol, a mixture thereof can be used,
It is preferable to use water from the viewpoint of little change in the degree of dissociation and pH of the solution over time and the working environment of the manufacturing process.

The silver halide emulsion used in the present invention is:
A sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer can be used.

As the chalcogen sensitizer, a sulfur sensitizer,
A selenium sensitizer, a tellurium sensitizer, or the like can be used, but a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur.

The amount of the sulfur sensitizer to be added is preferably changed depending on the kind of the silver halide emulsion to be applied, the size of the expected effect, and the like, but is preferably 5 × 10 ^{-10 to} 5 × 10 -5 per mol of the silver halide. In the range of ^10-5 mol, preferably 5
The amount is from ^10-8 to ^310-5 mol.

As a gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold sensitizer used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, and the like.
It is preferably from 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The chemical sensitization of the silver halide emulsion used in the present invention may be a reduction sensitization. Preferred reduction sensitizers include thiourea dioxide, amine borane, sodium sulfite, and the like.

In the light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. In particular, as dyes having absorption in the visible region, JP-A-3-251840.
And the dyes described in JP-A-6-3770 are preferably used. Examples of the infrared-absorbing dyes include the dyes described in the lower left column on page 2 of JP-A-1-280750. The compounds represented by the formulas (I), (II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and do not cause contamination due to residual color. As specific examples of preferred compounds, exemplified compounds (1) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication
To (45).

For the purpose of improving sharpness, the amount of these dyes added is 680 nm for an unprocessed sample of a light-sensitive material.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material because the whiteness can be improved. The compound preferably used is a compound represented by the general formula described in JP-A-2-232652.
Compounds represented by II are mentioned.

When the light-sensitive material of the present invention is used as a color light-sensitive material, the light-sensitive material is used in combination with a yellow coupler, a magenta coupler, and a cyan coupler to have a wavelength of 400 to 900 nm.
Has a layer containing a silver halide emulsion spectrally sensitized to a specific region of the wavelength range of The silver halide emulsion may be one or two kinds.
It contains a combination of two or more sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any of known compounds can be used, and as the blue-sensitive sensitizing dye, JP-A-3-251840, 28 It is preferable to use BS-1 to 8 described on the page alone or in combination. Examples of the green photosensitive sensitizing dye include GS-1 to GS-5 described on page 28 of the same publication.
Is preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used.
In the case of performing image exposure with infrared light using a semiconductor laser or the like, an infrared-sensitive sensitizing dye must be used.
The dyes of IRS-1 to 11 described in No. 85950, pages 6 to 8 are preferably used. In addition, these infrared, red, green,
The blue-sensitive sensitizing dyes are disclosed in JP-A-4-285950
And supersensitizers SS-1 to SS-9 described in
No. 66515, pages 15 to 17, compounds S-1 to S-
It is preferable to use 17 in combination.

The sensitizing dye used in the present invention includes a kind of the sensitizing dye, a halogen composition of a silver halide emulsion to be applied,
Although it depends on the grain size and the like, it is preferably used in a range of 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol, more preferably 1 × 10 ^{−4 to} 7 × 10 ⁻⁴ mol per mol of silver halide.

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

As a method for dispersing the sensitizing dye, other than a method of mechanically pulverizing and dispersing fine particles of 1 μm or less in an aqueous system by using a high-speed stirring type disperser, see JP-A-58-105141.
As described in JP-B-60-6496, a method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system under conditions of pH 6 to 8 and 60 to 80 ° C., and a surface tension of 38 dyne / cm described in JP-B-60-6496. For example, a method of dispersing in the presence of a surfactant suppressed below can be used.

Examples of the dispersing device that can be used for preparing the dispersion include a high-speed stirring type dispersing device shown in FIG. 1 of JP-A-4-125563, a ball mill, a sand mill, an ultrasonic dispersing device, and the like. Can be mentioned.

In using these dispersing apparatuses, a method may be employed in which pretreatment such as dry pulverization is performed in advance and then wet dispersing is performed as described in JP-A-4-125632.

As the sensitizing dye, a plurality of sensitizing dyes can be used in combination as long as the effects of the present invention are not impaired. In this case, the two sensitizing dyes may be added separately or may be added after mixing in advance.

As a coupler used in a color photosensitive material using a silver halide emulsion, a coupling reaction with an oxidized form of a color developing agent is carried out to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Although any compound that can be used can be used, particularly typical compounds include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 5
This is known as a magenta dye-forming coupler having a spectral absorption maximum wavelength in the range of 00 to 600 nm, and a cyan dye-forming coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

As the cyan coupler which can be preferably used, mention may be made of couplers represented by formulas (CI) and (C-II) described in the lower left column of JP-A-4-114154, page 5.

Examples of the magenta coupler which can be preferably used include couplers represented by formulas (MI) and (M-II) described in the upper right column on page 4 of JP-A-4-114154. it can. Preferred from among the magenta couplers is a coupler represented by the general formula described in the publication, page 4, right upper column (M-I), of which, R _M of the formula (M-I) is 3 A coupler which is a lower alkyl group is particularly preferable because of its excellent light resistance. MC-8 to MC-11 described in the upper column of page 5 of the publication are excellent in reproducing colors from blue to purple and red, and are also excellent in detail depiction power, and thus are preferable.

Further, as a yellow coupler which can be preferably used, a coupler represented by formula (Y-I) described in the upper right column on page 3 of JP-A-4-114154 can be mentioned. Specific compounds include those described as YC-1 to YC-9 in the lower left column on page 3 of the publication. Among them, the general formula [Y-
The coupler of the formula [1], wherein R _Y1 is an alkoxy group, or the coupler represented by the general formula [I] described in JP-A-6-67388 can reproduce yellow having a preferable color tone, and is therefore preferable.

When an oil-in-water emulsion dispersion method is used to add a coupler or other organic compound, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or more, and if necessary, to a low boiling point and / or Alternatively, they are dissolved together with a water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. 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 or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

A preferred compound as a surfactant used for dispersing a photographic additive or adjusting the surface tension during coating contains a hydrophobic group having 8 to 30 carbon atoms and a sulfo group or a salt thereof in one molecule. To do. Specific examples include A-1 to A-11 described in JP-A-64-26854. 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, but it is better that the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution after the addition are short. , Preferably within 10 hours, more preferably within 3 hours and within 20 minutes.

It is preferable to use an anti-fading agent 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.

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

In a color light-sensitive material, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer to prevent fog. And the like are preferably improved. It is preferable to add an ultraviolet absorber to prevent static fog or to improve the light fastness of the dye image.

Preferred examples of the ultraviolet absorber include benzotriazoles. Particularly preferred compounds are those represented by the general formula III-3 described in JP-A-1-250944 and those represented by the general formula described in JP-A-64-66646. III
A compound represented by the general formula I described in JP-A-4-1633; a compound represented by the general formula I described in JP-A-4-16333;
And the compounds represented by the general formulas (I) and (II).

In the light-sensitive material of the present invention, it is advantageous to use gelatin as a binder. If necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives Alternatively, a hydrophilic colloid such as a single or copolymerized hydrophilic polymer material such as a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination.

That is, it is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. Further, in order to prevent the growth of fungi and bacteria which adversely affect the photographic performance and image storability, JP-A-3-15.
It is preferable to add a preservative and an antifungal agent as described in No. 7646.

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-6-118543 or JP-A-2-73250 to the protective layer.

As the support used for the photosensitive material, any material may be used, such as paper coated with polyethylene (PE) or polyethylene terephthalate (PET), a paper support made of natural pulp or synthetic pulp, and vinyl chloride. Sheet, polypropylene (P
P), PET support, baryta paper and the like can be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. PE or PET as water-resistant resin
Or their copolymers are preferred.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used.

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

The photosensitive material may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, directly or undercoating (adhesion, antistatic properties, dimensional stability of the support surface). , One or more subbing layers to improve rub resistance, hardness, antihalation properties, friction properties and / or other properties).

In coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As a coating method, extrusion coating and curtain coating, which can simultaneously apply two or more layers, are particularly useful.

In order to form a photographic image using the photosensitive material of the present invention, an image recorded on a negative may be optically formed on a photosensitive material to be printed and printed. Is once converted into digital information, the image is formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed, or a laser based on the digital information may be used. The printing may be performed by scanning while changing the light intensity.

The silver halide emulsion is preferably applied to a light-sensitive material which directly forms an image for direct viewing, for example, color paper, color reversal paper, a light-sensitive material for forming a positive image, a light-sensitive material for display, a color proof. Photosensitive material. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

Known compounds can be used as an aromatic primary amine developing agent used for color development of a color light-sensitive material.

In the present invention, the color developing solution may be any p
Can be used in the H range, but from the viewpoint of rapid processing, pH 9.5 to
It is preferably 13.0, more preferably pH
It is used in the range of 9.8 to 12.0.

The processing temperature for color development used in the present invention is preferably 35 ° C. to 70 ° C., and the higher the temperature, the more preferable the effect of the present invention is exhibited.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but is preferably 45 seconds or less, and more preferably 20 seconds or less in the present invention.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

After the color development, the light-sensitive material is subjected to a bleaching process and a fixing process. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed.
Further, as an alternative to the washing process, a stabilizing process may be performed.

The developing apparatus used for developing the photosensitive material of the present invention may be a roller transport type in which the photosensitive material is conveyed by sandwiching the photosensitive material between rollers disposed in a processing tank. An endless belt method may be used, in which the processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is transported, or a spray method in which the processing liquid is sprayed Alternatively, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can be used. When processing in large quantities, it is usual to perform a running process using an automatic developing machine. At this time, the replenishment amount of the replenisher is preferably as small as possible. And the method described in JP-A-94-16935 is most preferable.

[0101]

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

Embodiments of the first and fifth aspects of the present invention will be described.

Example 1 Preparation of Blue-Sensitive Silver Halide Emulsion In 1 liter of a 2% aqueous gelatin solution kept at 40 ° C.
The following (solution A) and (solution B) were treated with pAg 7.3, pH 3.0.
Over 30 minutes while controlling at the same time.
Solution) and (D1 solution), (C2 solution) and (D2 solution), (E
Solution) and (Solution F) were simultaneously added over 150 minutes while controlling the pAg to 8.0 and the pH to 5.5.

At this time, the control of pAg is described in JP-A-59-4.
No. 5437, and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 0.99 g Potassium bromide 0.008 g Water was added to 58 ml (Solution B) Silver nitrate 2.9 g Water was added to 58 ml (Solution C1) Sodium chloride 3.26 g Hexachloroiridium (IV) Potassium acidate 2 × 10 ^-9 mol Potassium hexacyanoferrate (II) 1 × 10 ^-6 mol Potassium bromide 0.006 g Add water 19 ml (D1 solution) 9.5 g silver nitrate Add water 19 ml (C2 solution) Chloride Sodium 13.6 g Potassium hexachloroiridate (IV) 2 × 10 ⁻⁹ mol Potassium hexacyanoferrate (II) 1 × 10 ⁻⁶ mol Potassium bromide 0.02 g Add water 79.2 ml (D2 solution) Silver nitrate 39. 6g Add water to 79.2ml (Solution E) Sodium chloride 5.49g Potassium hexachloroiridate (IV) 2 × 10 ^-9 mol potassium hexacyanoferrate (II) 1 × 10 ^-6 mol potassium bromide 0.01 g water 32.1 ml (solution F) silver nitrate 16 g water 32.1 ml after completion of addition, manufactured by Kao Atlas After desalting was performed using a 10% aqueous solution of Demol N and a 30% aqueous solution of magnesium sulfate, the resulting mixture was mixed with an aqueous gelatin solution to give an average particle diameter of 0.85.
μm, coefficient of variation 0.07, silver chloride content 99.5 mol%
Was obtained as a monodispersed cubic emulsion EM-B.

After heating the EMB to 60 ° C., a sensitizing dye, sodium thiosulfate, and chloroauric acid were added, and the mixture was chemically sensitized for 120 minutes. Compound (1-4) was added, and the temperature was lowered. A blue-sensitive silver halide emulsion EMB-1 was obtained. The addition amount and chemical formula are shown below.

Sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX Sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX Sodium thiosulfate 0.8 mg / mol AgX 0.5 mg / mol chloroauric acid AgX compound (1-4) 4 × 10 ⁻⁴ mol / mol AgX

[0108]

Embedded image

Next, EMB-2 was prepared in the same manner as in the preparation of EMB-1, except that the amount of compound (1-4) was changed to 6 × 10 ⁻⁴ mol / mol AgX.

Hereinafter, EMB-3 to EMB-3 to EMB-2 were prepared in the same manner as in the preparation of EMB-2, except for the types of the compounds shown in Table 2 and the amounts added.
EMB-6 was produced. At this time, the compound was added as a methanol solution. Further, an aqueous solution having a degree of dissociation of 0.99 or more according to the kind and amount of the compound shown in Table 2 was added, and EMB was added.
-7 was produced.

(Preparation of Coated Sample) A high-density polyethylene was laminated on both sides of a paper pulp weighing 180 g / m ² to prepare a paper support. However, on the side on which the emulsion layer is coated, 15% of anatase-type titanium oxide subjected to surface treatment is applied.
, A molten polyethylene dispersed and contained at a content of was laminated to prepare a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and two layers having the following constitutions were further provided to prepare a monochromatic photosensitive material. The coating solution was prepared as follows.

First layer coating solution 23.4 g of yellow coupler (Y-1), additive (ST)
-1) 3.34 g, (ST-2) 3.34 g, (ST-
5) 3.34 g, antistain agent (HQ-1) 0.34
g, image stabilizer A 5.0 g and high boiling organic solvent (DB
P) 3.33 g, (DNP) 1.67 g and ethyl acetate 6
0 ml was added and dissolved, and 20% of a surfactant (SU-
1) 200 ml of a 10% gelatin aqueous solution containing 7 ml
The mixture was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion.

This dispersion was prepared under the following conditions to prepare a first layer coating liquid TB-1.

An aqueous gelatin solution was prepared as a coating solution for the second layer, and (H-1) and (H-2) were added as hardeners. Surfactants (SU-2), (S
U-3) was added to adjust the surface tension. Table 1 shows the layer structure
Shown in

[0115]

[Table 1]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone Image stabilizer A: pt-octylphenol

[0117]

Embedded image

Next, the compound (1) was added to the first layer coating solution TB-1.
-4) was added with 4 × 10 ^-4 mol / mol AgX, and TB-
2 was produced.

In the following, TB-3 was prepared in the same manner as in the preparation of TB-2, except that the type of the compound, the solvent and the amount of addition shown in Table 2 were changed.
To TB-7. At this time, the compound was added as a methanol solution. Further, an aqueous solution having a degree of dissociation of 0.99 or more according to the types and amounts of the compounds shown in Table 2 was added, and TB-
No. 8 was produced.

(Sensitivity evaluation) Sensitivity evaluation was performed using a sensitometer KS-7.
Wedge exposure using a mold (manufactured by Konica Corporation) for 0.1 second and color development according to the following processing steps,
Density is measured using an optical densitometer PDA-65 (manufactured by Konica Corporation), and the sensitivity is represented by the reciprocal of the exposure required to obtain a density 0.8 higher than the fog density. Sample 1 obtained
The sensitivity of No. 02 was set to 100 and expressed as a relative value.

(Evaluation of fog) Fog was evaluated by subjecting the obtained sample to color development according to the processing steps in the same manner as the evaluation of sensitivity without exposure, and then measuring the density using X-Rite 310 (manufactured by X-Rite). , Fog density.

(Evaluation of high-temperature processing fog) A color development temperature of 4
Except that the color development processing time was 5 seconds at 5 ° C., color development was performed according to the processing steps, and X-Rite 3 was evaluated in the same manner as the fog evaluation.
10 (manufactured by X-Rite).

The developing process is described below.

Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Drying 60-80 30 ° C. The composition of the developing solution is shown below.

Color developer tank liquid and replenisher tank liquid Replenisher Pure water 800 ml 800 ml 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 pentasodium 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 a total volume of 1 liter. Is pH = 10.10 and replenisher is Adjusted to H = 10.60.

Bleach-fixing solution tank replenisher and replenisher ammonium ferric diethylenetriaminepentaacetate dihydrate 65 g diethylenetriaminepentaacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust the pH to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution 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 ( Polyvinylpyrrolidone) 1.0 g Ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Water was added to bring the total volume to 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia. adjust.

Table 2 summarizes the results.

[0129]

[Table 2]

As is clear from Table 2, Samples 101 and 1
In the comparative sample No. 02, when the nitrogen-containing heterocyclic mercapto compound was added to the step B, the fog at high temperature treatment was reduced, but the level was not at a satisfactory level and the sensitivity was greatly reduced.

As can be seen from the comparative samples of Samples 102 and 103 and 105 and 106, when the ratio of the addition of the nitrogen-containing heterocyclic mercapto compound to the step A is larger than that to the step B, the sensitivity is significantly reduced. High temperature treatment fog has little effect.

Comparative Samples 102 and 105 and Sample 1 of the Present Invention
As can be seen from FIGS. 04 and 107, it was found that when the ratio of the addition of the nitrogen-containing heterocyclic mercapto compound to the step B was larger than that to the step A, the fog at high sensitivity was improved with high sensitivity.

Further, as can be seen from Samples 104 and 108 of the present invention, the dissociation degree of the nitrogen-containing heterocyclic mercapto compound was 0.1%.
It was found that the sample added as an aqueous solution of 99 or more further improved the high-temperature treatment fog.

Example 2 Preparation of Green-Sensitive Silver Halide Emulsion Addition time of (Solution A) and (Solution B) and (Solution C) and (Solution D)
A monodisperse cubic emulsion EMG having an average particle size of 0.4 μm, a variation coefficient of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained in the same manner as in EMB except that the addition time was changed.

Optimum chemical sensitization was carried out at 55 ° C. using the following compounds in EMG, and a green-sensitive silver halide emulsion EMG-
1 was obtained.

Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Compound (1-1) 4 × 10 ⁻⁴ mol / mol AgX

[0137]

Embedded image

Next, EMG-2 was prepared in the same manner as in the preparation of EMG-1, except that the amount of compound (1-1) added was changed to 6 × 10 ⁻⁴ mol / mol AgX.

Hereinafter, EMG-3 to EMG-3 were prepared in the same manner as in the preparation of EMG-2, except for the types of the compounds and the addition amounts shown in Table 3.
EMG-6 was produced. At this time, the compound was added as a methanol solution. Further, an aqueous solution having a degree of dissociation of 0.99 or more according to the kind and amount of the compound shown in Table 2 was added, and EMG was added.
-7 was produced.

First layer coating liquid 12.14 g of magenta coupler (M-1), additive (S
T-3) 12.14 g, (ST-4) 10.32 g, high boiling organic solvent (DBP) 7.9 g, (DIDP) 7.
To 9 g, 60 ml of ethyl acetate was added and dissolved, and the mixture was emulsified and dispersed in 200 ml of a 10% aqueous gelatin solution containing 12 ml of a 20% surfactant (SU-1) using an ultrasonic homogenizer to prepare a magenta coupler dispersion.

This dispersion was prepared under the following conditions to prepare a first layer coating liquid TG-1. A gelatin aqueous solution was prepared as the coating solution for the second layer in the same manner as in Example 1, and (H-1) and (H-2) were added as hardeners. Surfactants (SU-2) and (SU-3) are added as coating aids,
The surface tension was adjusted, and a coated sample was prepared in the same manner as in Example 1.

Next, the compound (1) was added to the first layer coating solution TG-1.
-1) was added with 4 × 10 ⁻⁴ mol / mol AgX, and TG-
2 was produced.

Hereinafter, TG-3 was prepared in the same manner as in the preparation of TG-2, except that the kind of the compound, the solvent and the amount of addition shown in Table 3 were changed.
To TG-7. At this time, the compound was added as a methanol solution. Further, an aqueous solution having a degree of dissociation of 0.99 or more according to the type and amount of the compound shown in Table 4 was added, and TB was added.
-8 was produced. Table 3 shows the layer structure.

[0144]

[Table 3]

[0145]

Embedded image

Thereafter, silver halide emulsions and coating solutions as shown in Table 3 were prepared in the same manner as in Example 1 to prepare samples. These samples were evaluated in the same manner as in Example 1, and the results are shown in Table 4.

[0147]

[Table 4]

As is evident from Table 4, the effect of the present invention was obtained when the green photosensitive emulsion was used.

As can be seen from the comparative sample of Samples 201 and 202, when the nitrogen-containing heterocyclic mercapto compound is added to Step B, the fog at high temperature treatment is reduced, but the level is not at a satisfactory level and the sensitivity is greatly reduced.

As can be seen from the comparative samples of Samples 202 and 203 and 205 and 206, when the ratio of the addition of the nitrogen-containing heterocyclic mercapto compound to the step A is larger than that to the step B, the sensitivity is significantly reduced. High temperature treatment fog has little effect.

Comparative Samples 202 and 205 and Sample 2 of the Present Invention
04 and 207, it was found that when the ratio of the addition of the nitrogen-containing heterocyclic mercapto compound to the step B was larger than that to the step A, the fog at high sensitivity was improved with high sensitivity.

Further, as can be seen from the samples 204 and 208 of the present invention, the dissociation degree of the nitrogen-containing heterocyclic mercapto compound is 0.1.
It was found that the sample added as an aqueous solution of 99 or more further improved the high-temperature treatment fog.

(Example 3) (Preparation of Red-Sensitive Silver Halide Emulsion) Addition time of (Solution A) and (Solution B) and (Solution C) and (Solution D)
A monodisperse cubic emulsion EMR having an average particle size of 0.5 μm, a variation coefficient of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained in the same manner as in EMB except that the addition time was changed.

Optimum chemical sensitization was carried out at 56 ° C. using the following compounds in the EMR to obtain a red-sensitive silver halide emulsion EMR-
1 was obtained.

Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX Sodium thiosulfate 1.8 mg / mol AgX 2.0 mg / mol chloroauric acid AgX additive SS-1 2 × 10 ⁻³ mol / mol AgX Compound (1-1) 4 × 10 ⁻⁴ mol / mol AgX

[0156]

Embedded image

Next, EMR-2 was prepared in the same manner as in the preparation of EMR-1, except that the amount of compound (1-1) added was changed to 6 × 10 ⁻⁴ mol / mol AgX.

Hereinafter, EMR-3 was prepared in the same manner as in the preparation of EMR-2, except that the types of the compounds shown in Table 6 and the amounts added were changed.
To EMR-6. At this time, the compound was added as a methanol solution. Further, an aqueous solution having a degree of dissociation of 0.99 or more according to the kind and amount of the compound shown in Table 6 was added.
MR-7 was produced.

First layer coating solution: 10.12 g of cyan coupler (C-1), (C-2)
3.24 g, 4.05 g of additive (ST-1), 0.4 g of stain inhibitor (HQ-1), and high boiling organic solvent (D
BP) 4.05 g, (DOP) 8.1 g and ethyl acetate 6
0 ml was added and dissolved, and 20% of a surfactant (SU-
1) 200 m of 10% gelatin aqueous solution containing 12 ml
The resulting mixture was emulsified and dispersed using an ultrasonic homogenizer to prepare a cyan coupler dispersion.

DOP: dioctyl phthalate

[0161]

Embedded image

This dispersion was prepared under the following conditions to prepare a first layer coating liquid TR-1. A gelatin aqueous solution was prepared as the coating solution for the second layer in the same manner as in Example 1, and (H-1) and (H-2) were added as hardeners. Surfactants (SU-2) and (SU-3) are added as coating aids,
The surface tension was adjusted, and a coated sample was prepared in the same manner as in Example 1.

Next, the compound (1) was added to the first layer coating solution TR-1.
-1) was added with 4 × 10 ⁻⁴ mol / mol AgX, and TR-
2 was produced.

Hereinafter, TR-3 was prepared in the same manner as in the preparation of TR-2, except that the type of the compound, the solvent and the amount of addition shown in Table 6 were changed.
To TR-7. At this time, the compound was added as a methanol solution. Further, an aqueous solution having a degree of dissociation of 0.99 or more was added according to the types and amounts of the compounds shown in Table 4, and TR was added.
-8 was produced. Table 5 shows the layer structure.

[0165]

[Table 5]

Thereafter, silver halide emulsions and coating solutions as shown in Table 6 were prepared in the same manner as in Example 1 to prepare samples. These samples were evaluated in the same manner as in Example 1, and the results are shown in Table 6.

[0167]

[Table 6]

As is clear from Table 6, the effect of the present invention was obtained when the red-sensitive emulsion was used.

(Example 4) (Preparation of multilayer sample) The emulsions prepared in Examples 1 to 3 were prepared in the same manner as in the first layer coating solution of Example 1 so that the coating amounts shown in Tables 7 and 8 were applied to Tables 9 and 8. Samples were prepared by preparing silver halide emulsions and coating solutions as shown in (1). These samples were evaluated in the same manner as in Example 1, and the results are shown in Tables 9 and 10.

[0170]

[Table 7]

[0171]

[Table 8]

PVP: polyvinylpyrrolidone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec- Tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butylhydroquinone

[0173]

Embedded image

[0174]

Embedded image

[0175]

[Table 9]

[0176]

[Table 10]

As is clear from Tables 9 and 10, the effect of the present invention was obtained even with the multilayer sample.

As can be seen from the comparative samples of Samples 1001 and 1002, when the nitrogen-containing heterocyclic mercapto compound is added to Step B, the fog at high temperature treatment is reduced, but the level is not at a satisfactory level and the sensitivity is greatly reduced.

Samples 1002 and 1003 and 1005 and 1
As can be seen from the comparative sample of No. 006, when the ratio of the addition of the nitrogen-containing heterocyclic mercapto compound to the step A is greater than the addition to the step B, the sensitivity is significantly reduced, and the effect of the high-temperature treatment fog is almost nil.

As can be seen from Comparative Samples 1002 and 1005 and Samples 1004 and 1007 of the present invention, when the ratio of addition of the nitrogen-containing heterocyclic mercapto compound to Step B is larger than that to Step A, high sensitivity and high temperature It has been found that the processing fog is improved.

Further, as can be seen from the samples 1004 and 1008 of the present invention, the sample added as an aqueous solution having a dissociation degree of the nitrogen-containing heterocyclic mercapto compound of 0.99 or more was found to further improve the high-temperature treatment fog. .

In the processing step, a color developing solution of 1000 m
3 ml of the bleach-fixing solution was added to the sample No. 1 to evaluate fog.
The comparative sample showed a significant increase in fog, but the sample of the present invention was found to have low fog and good fog resistance.

Next, embodiments of the second, third and fifth aspects of the invention will be described.

(Example 5) The silver halide emulsion was prepared in Example 1.
The EMB-4, EMG-4, and EMR-4 produced in the steps No. 3 to No. 3 were used. TB-5X was prepared in the same manner from TB-5 prepared in Example 1 as a coating solution for the blue photosensitive layer, except that the methanol solvent of the nitrogen-containing heterocyclic mercapto compound was changed to an aqueous solution having a dissociation degree of 0.99 or more. did. The coating solution TG-5 for the green photosensitive layer and the coating solution TR-5 for the red photosensitive layer were also prepared by dissolving the methanol solvent of the nitrogen-containing heterocyclic mercapto compound in a dissociation degree of 0.9.
TG-5 in the same manner except that the aqueous solution was changed to 9 or more.
X and TR-5X were produced. In addition, the layers shown in Tables 7 and 8 except that 2 × 10 ⁻⁴ mol / mol AgX were added as the coating solution for the non-photosensitive layer in the type of the nitrogen-containing heterocyclic mercapto compound shown in Table 11 and the solvent, respectively. The sample was prepared by applying the composition. The obtained sample was evaluated for fog and high-temperature treated fog in the same manner as in Example 1. Table 12 shows the results.
Shown in

[0185]

[Table 11]

[0186]

[Table 12]

As is clear from Table 12, Sample 2001
In the comparative samples of Nos. 2002 and 2002, when the dissociation degree of the nitrogen-containing heterocyclic mercapto compound was added as an aqueous solution having a dissociation degree of 0.99 or more, the fog usually treated and the high-temperature treated fog were small, but not at a satisfactory level.

Samples 2001 and 2003, 2002 and 20
As can be seen from the comparative sample No. 04, the addition of the nitrogen-containing heterocyclic mercapto compound of a methanol solvent to the non-photosensitive layer further reduces the fogging in the normal processing and the high-temperature processing, but is not at a satisfactory level.

As can be seen from the comparative sample of Samples 2003 and 2005, when the nitrogen-containing heterocyclic mercapto compound is added as an aqueous solution having a degree of dissociation of 0.99 or more, the fog in the normal processing and the fog in the high-temperature processing are reduced. Since the nitrogen-containing heterocyclic mercapto compound in the hydrophilic layer is a methanol solvent, the level is not at a satisfactory level.

Comparative Samples 2003, 2004 and 2005
As can be seen from Sample 2006 of the present invention, by adding a nitrogen-containing heterocyclic mercapto compound as an aqueous solution having a degree of dissociation of 0.99 or more to the photosensitive layer and the non-photosensitive layer of the second layer, the processing fog and the high temperature It has been found that the processing fog can be greatly improved.

Samples of the Invention 2007, 2008, 200
9, 2010, 2011, 2012,
Similar effects were confirmed by adding the nitrogen-containing heterocyclic mercapto compound as an aqueous solution having a degree of dissociation of 0.99 or more in the fourth layer and the sixth layer as compared with the comparative sample 2008. As can be seen from the sample of the present invention, when the nitrogen-containing heterocyclic mercapto compound is added as an aqueous solution having a degree of dissociation of 0.99 or more to the non-photosensitive layer, the effect of the present invention on the adjacent photosensitive layer is more remarkable. all right.

In the same manner as in Example 4, in the processing step, 3 ml of the bleach-fixing solution was added to 1000 ml of the color developing solution to evaluate fog. The comparative sample showed a significant increase in fog, but the sample of the present invention was found to have low fog and good fog resistance.

Next, embodiments of the present invention will be described.

(Embodiment 6) The EMB-
4 was stored in a refrigerator at 7 ° C. for one week. The EM
B-4 was dissolved at 45 ° C. over 30 minutes, and the yellow coupler dispersion prepared in Example 1 was mixed. After cooling to 38 ° C, the nitrogen-containing heterocyclic mercapto compound (2-10)
× 10 ^-4 mol / mol AgX was added to the coating solution TB-11.
Was prepared. The addition of the nitrogen-containing heterocyclic mercapto compound at this time was 120 minutes after the mixing of the emulsion and the coupler.

Next, after mixing the emulsion and the coupler,
TB-12 to TB-12 in the same manner as TB-11, except that the addition time of the nitrogen-containing heterocyclic mercapto compound shown in 3 was changed.
-14 was prepared.

Further, EMB-4 was dissolved at 45 ° C. for 30 minutes, 10 minutes after the dissolution was completed, a nitrogen-containing heterocyclic mercapto compound was added, and then a coupler was added.
A coating liquid of -15 was prepared, and coating was performed with the same layer configuration as in Example 1 to prepare a sample. The obtained sample was evaluated for fog at high temperature, storage fog at high temperature under the following evaluation conditions, and stagnation property of the coating solution in the same manner as in Example 1. Table 13 shows the results.

(Fog stored under high-temperature conditions) A sample obtained by coating the coating solution 30 minutes after mixing with the emulsion was allowed to stand at 65 ° C. for 10 days, treated in the same manner as for the evaluation of fogging of the coating solution, and then subjected to concentration. A measurement was taken. The fog of the sample left for 10 days at 23 ° C. was set to 0, and the fog obtained for 10 days at 65 ° C. was evaluated as a relative value.

(Coating liquid stagnation) Sensitivity was evaluated using a sensitometer KS
After performing wedge exposure for 0.1 second using Model -7 (manufactured by Konica Corporation) and performing color development processing according to the following processing steps, use an optical densitometer PDA-65 (manufactured by Konica Corporation). The sensitivity is represented by the reciprocal of the exposure required to obtain a density 0.8 higher than the fog density.

The sensitivity of the coating solution stagnation was evaluated by setting the sensitivity obtained by mixing the emulsion with the coating solution 30 minutes later and coating the emulsion to 100, mixing the emulsion and stagnation for 10 hours, and coating. The sensitivity of the sample was expressed as a relative value.

In the fog evaluation, the obtained sample was color-developed according to the processing steps in the same manner as in the sensitivity evaluation without exposure,
The density was measured using X-Rite 310 (manufactured by X-Rite) to show the fog density. The fogging evaluation of the coating solution stagnant is obtained by mixing the emulsion with the coating solution, coating the emulsion 30 minutes later, setting the fogging to 0, mixing the emulsion, stagnating the emulsion for 10 hours, and coating the same as the sensitivity evaluation. The fog value of each sample was expressed as a relative value.

[0201]

[Table 13]

As is clear from Table 13, Comparative Sample 40
In the case of No. 1, if the addition interval of the nitrogen-containing heterocyclic mercapto compound is increased to 120 minutes after mixing the emulsion and the coupler, the fog at high temperature storage and the fog at high temperature treatment become high.

As can be seen from the samples 402 to 404 of the present invention, by mixing the emulsion and the coupler and then adding the nitrogen-containing heterocyclic mercapto compound within 60 minutes, high-temperature storage fog and high-temperature treated fog can be obtained. It turned out that a satisfactory level could be maintained.

As can be seen from Comparative Sample 405, even when the addition interval of the nitrogen-containing heterocyclic mercapto compound was added to the emulsion after dissolution at a shorter interval, the addition of the coupler after the addition of the nitrogen-containing heterocyclic mercapto compound resulted in high-temperature storage. Although the fog and the high-temperature treatment fog were at a satisfactory level, it was found that the sensitivity was significantly reduced by storing the coating solution.

Example 7 A nitrogen-containing heterocyclic mercapto compound (Example 7) was prepared in the same manner as in Example 6, except that EMB-4 was changed to EMG-4 and the magenta coupler dispersion prepared in Example 2 was changed. 2-10) to 4 × 10 ^-4 mol / mol A
gX was added to prepare a coating liquid TG-11.

Then, in the same manner as in Example 6, TG-12 to TG were mixed in the same manner as TG-11, except that the addition time of the nitrogen-containing heterocyclic mercapto compound shown in Table 14 was changed after mixing the emulsion and the coupler. -14 was prepared.

EGB-4 was dissolved at 45 ° C. for 30 minutes, and after 10 minutes from the completion of the dissolution, a nitrogen-containing heterocyclic mercapto compound was added.
A coating liquid of -15 was prepared, and coating was performed with the same layer configuration as in Example 2 to prepare a sample. The obtained sample was evaluated in the same manner as in Example 6. Table 14 shows the results.

[0208]

[Table 14]

As is clear from Table 14, the effect of the present invention was obtained when the green photosensitive emulsion was used.

As can be seen from Comparative Sample 501, if the addition interval of the nitrogen-containing heterocyclic mercapto compound is increased to 120 minutes after mixing the emulsion and the coupler, the fog at high temperature and the fog at high temperature are increased.

As can be seen from the samples 502 to 504 of the present invention, by mixing the emulsion and the coupler and then adding the nitrogen-containing heterocyclic mercapto compound within 60 minutes, high-temperature storage fog and high-temperature treated fog can be obtained. It turned out that a satisfactory level could be maintained.

As can be seen from Comparative Sample 505, even if the addition interval of the nitrogen-containing heterocyclic mercapto compound was added to the emulsion after dissolution and the coupler was added after the addition of the nitrogen-containing heterocyclic mercapto compound, the emulsion was stored at a high temperature. Although the fog and the high-temperature treatment fog were at a satisfactory level, it was found that the sensitivity was significantly reduced by storing the coating solution.

Example 8 A nitrogen-containing heterocyclic mercapto compound (Example 8) was prepared in the same manner as in Example 6 except that EMB-4 was changed to EMR-4 and the cyan coupler dispersion prepared in Example 3 was changed. 2-10) to 4 × 10 ^-4 mol / mol Ag
X was added to prepare a coating liquid TR-11.

Next, in the same manner as in Example 6, TR-12 to TR-TR were mixed in the same manner as in TR-11, except that the addition time of the nitrogen-containing heterocyclic mercapto compound shown in Table 15 was changed after mixing the emulsion and the coupler. -14 was prepared.

Further, EGB-4 was dissolved at 45 ° C. for 30 minutes, 10 minutes after the completion of the dissolution, a nitrogen-containing heterocyclic mercapto compound was added, and then a coupler was added.
A coating liquid of -15 was prepared, and coating was performed with the same layer configuration as in Example 2 to prepare a sample. The obtained sample was evaluated in the same manner as in Example 6. Table 15 shows the results.

[0216]

[Table 15]

As is clear from Table 15, the effect of the present invention was obtained when the red-sensitive emulsion was used. Comparative sample 6
As can be seen from FIG. 01, when the addition interval of the nitrogen-containing heterocyclic mercapto compound is increased to 120 minutes after mixing the emulsion and the coupler, the fog at high temperature and the fog at high temperature are increased.

As can be seen from the samples 602 to 604 of the present invention, by mixing the emulsion and the coupler and then adding the nitrogen-containing heterocyclic mercapto compound within 60 minutes, the fog at high temperature and the fog at high temperature can be reduced. It turned out that a satisfactory level could be maintained.

As can be seen from Comparative Sample 605, even if the addition interval of the nitrogen-containing heterocyclic mercapto compound was added to the emulsion after dissolution at a short interval, the addition of the coupler after the addition of the nitrogen-containing heterocyclic mercapto compound resulted in high-temperature storage. Although the fog and the high-temperature treatment fog were at a satisfactory level, it was found that the sensitivity was significantly reduced by storing the coating solution.

[0220]

The silver halide photographic light-sensitive material according to the present invention and the method for producing the same are a production lot which is color developing at a high processing temperature, is excellent in ultra-rapid processing with little fogging, and has high sensitivity and no deterioration of coating solution stagnation. Performance is stable and has excellent effects.

Claims (5)

[Claims] In a method for producing a silver halide photographic material, wherein a photosensitive emulsion layer and a non-photosensitive layer are coated on a support, a coating solution used for forming the photosensitive emulsion layer has a silver chloride content. Contains 90 mol% or more of silver halide grains, and a nitrogen-containing heterocyclic mercapto compound is added until the completion of chemical ripening of the silver halide grains (Step A). In step B), a nitrogen-containing heterocyclic mercapto compound is added, and the addition amount of the nitrogen-containing heterocyclic mercapto compound in step B is adjusted to be larger than the addition amount of the nitrogen-containing heterocyclic mercapto compound in step A. And producing a silver halide photographic material. 2. A method for producing a silver halide photographic material in which a photosensitive emulsion layer and a non-photosensitive layer are coated on a support, wherein the coating solution used for forming the photosensitive emulsion layer has a silver chloride content of Contains 90 mol% or more of silver halide grains, and a nitrogen-containing heterocyclic mercapto compound is added until the completion of chemical ripening of the silver halide grains (Step A). The nitrogen-containing heterocyclic mercapto compound is added to (Step B) so as to form an aqueous solution having a dissociation degree of 0.99 or more, and the nitrogen-containing heterocyclic mercapto compound is added to the coating solution used for forming the non-photosensitive layer. Is added so as to form an aqueous solution of 0.99 or more, followed by coating. 3. A coating solution used for forming the photosensitive emulsion layer and a coating solution used for forming the non-photosensitive layer are coated so as to form an adjacent layer on a support. A method for producing a silver halide photographic material. 4. A method for producing a silver halide photographic material in which a photosensitive emulsion layer and a non-photosensitive layer are coated on a support, wherein the coating solution used for forming the photosensitive emulsion layer has a silver chloride content. Contains 90 mol% or more of silver halide grains, and within 60 minutes after mixing the silver halide emulsion containing the silver halide grains with a coupler, a nitrogen-containing heterocyclic mercapto compound is added. A method for producing a silver halide photographic light-sensitive material. 5. A silver halide photographic light-sensitive material produced by the method for producing a silver halide photographic light-sensitive material according to claim 1.