JP2001255621A - Method for producing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a silver halide photographic sensitive material excellent in pressure resistance and sticking resistance. SOLUTION: In the method for producing the silver halide photographic sensitive material with at least one silver halide emulsion layer and at least one non-photosensitive layer on the base, the concentration of gelatin in a coating solution used for forming a layer situated farthest from the silver halide emulsion layer side of the base is adjusted to >=6 mass % and a compound which has a molecular weight of <=1,000 and increases the viscosity of the coating solution in the range of 5-15 mPa.s when it is added to the coating solution and the coating solution is allowed to stand at 40 deg.C for 1 hr is added to the coating solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silver halide photographic material, and more particularly to a method for producing a silver halide photographic material having excellent pressure resistance and sticking resistance.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials (sometimes simply referred to as light-sensitive materials or light-sensitive materials) have high sensitivity,
It is widely used today because of its excellent color reproducibility and suitability for continuous processing. Due to these characteristics, silver halide photographic materials are widely used not only in the field of photography but also in the field of printing, for example, in the field of so-called proofing for checking the state of a finished printed matter in the middle of printing. It is becoming.

[0003] In the field of proofing, an image edited on a computer is output to a printing film, and the developed film is appropriately exposed and decomposed and exposed, so that yellow (Y), magenta (M), and cyan (C) are obtained. ), Each image is formed, and the appropriateness of the layout and color of the final printed matter has been determined.

In recent years, a method of directly outputting an edited image on a computer to a printing plate has gradually become widespread. In such a case, color printing is performed directly from data on the computer without using a film. The method of forming on paper is disclosed in Japanese Patent Application Nos. 11-263269 and 11-263269.
No. 47913, which has been realized.

In any of the above methods, development must be performed after exposure. Generally, color photographic paper is dried after color development, bleach-fix, washing or stabilization. The photographic paper used in this field is generally A1 or B
Because of the large size of two sizes, the surfaces of the color photographic paper on which the images are obtained after drying are sometimes stuck to each other, making it difficult to peel off, which is a major problem in quality.

Various methods are known to solve this problem. Japanese Patent Application Laid-Open No. 7-92603 discloses a method for defining components of organopolysiloxane and gelatin, but fails to provide a sufficient effect.

If the drying temperature is increased to increase the drying capacity, the drying section is clogged due to the problem of curling. In addition, although the effect can be seen when the amount of the binder (especially gelatin) applied is reduced, scratches generated on the projections during processing become a problem.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for producing a silver halide photographic light-sensitive material having excellent pressure resistance and sticking resistance.

[0009]

The above object of the present invention has been attained by the following means.

[0010] 1. In a method for producing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-light-sensitive layer on a support, a layer furthest from the support having the silver halide emulsion layer The gelatin concentration in the coating solution used for coating was set to 6% by mass or more, the molecular weight in the coating solution was 1,000 or less, and when added to the coating solution and left at 40 ° C. for 1 hour, 5 m
A method for producing a silver halide photographic light-sensitive material, comprising adding a compound that increases the viscosity in the range of Pa · s to 15 mPa · s.

2. When the molecular weight is 1000 or less, and when added to the coating solution and left at 40 ° C. for 1 hour, 5 mPa
2. The method for producing a silver halide photographic light-sensitive material as described in 1 above, wherein the compound that increases the viscosity in the range of s to 15 mPa · s is a dialkyl sulfosuccinate compound.

3. In a method for producing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-light-sensitive layer on a support, a layer furthest from the support having the silver halide emulsion layer The gelatin concentration in the coating solution used for coating is set to 6% by mass or more, and a vinyl sulfone hardener and the above-mentioned general formula [HI] or [H-II] are contained in the coating solution. A method for producing a silver halide photographic light-sensitive material, characterized by containing one of the compounds represented by the formula (I).

4. In a method for producing a silver halide photographic material having at least one silver halide emulsion layer and at least one non-light-sensitive layer on a support, a humidity of 40%
A method for producing a silver halide photographic light-sensitive material, comprising: winding at the end of coating in a state of RH or more and 70% RH or less, and thereafter performing heat treatment in a state of 30 to 40 ° C.

Hereinafter, the present invention will be described in detail. In the present invention, gelatin is preferably used as a binder. In particular, in order to remove colored components of gelatin, gelatin extract is subjected to hydrogen peroxide treatment, ossein as a raw material is extracted from hydrogen peroxide treated, or ossein produced from uncolored bone. By using, a gelatin having improved transmittance can be obtained. The gelatin is an alkali-treated ossein gelatin, an acid-treated gelatin, a gelatin derivative,
Although any of modified gelatin may be used, alkali-treated ossein gelatin is particularly preferable. The transmittance of the gelatin is 10
% Solution is preferably 70% or more when the transmittance is measured at 420 nm with a spectrophotometer.

The gelatin has a jelly strength (based on the Paggy method) of preferably 250 or more, particularly preferably 270 or more.

In the present invention, the gelatin concentration in the coating solution of the layer farthest from the support on the side having the silver halide emulsion layer is preferably at least 6% by mass. This coating solution is kept warm at 40 ° C., and various additives can be added thereto. The coating solution has a molecular weight of 1,000 or less and is added to the coating solution at 1 ° C. By adding a compound that increases the viscosity in the range of 5 mPa · s to 15 mPa · s when left for a long time, a silver halide photographic material having excellent pressure resistance and sticking resistance can be obtained.

In the present invention, the gelatin concentration in the coating solution used for coating the layer farthest from the support having the silver halide emulsion layer is 6% by mass or more. 5 mPa when left at 40 ° C. for 1 hour
Adding a dialkyl sulfosuccinate compound so as to increase the viscosity in the range of s to 15 mPa · s, and adding a vinyl sulfone hardener to the above-mentioned general formula [HI]
Alternatively, it is preferable to include one of the compounds represented by [H-II].

In order to set the viscosity of the coating solution to a preferable range suitable for coating, it is usual to add a polymer substance having a molecular weight of 1000 or more to adjust the viscosity in addition to the gelatin concentration. When a polymer containing a sulfonic acid group, a carboxylic acid group, or a quaternary ammonium group, which is a normal thickener having a molecular weight of 1,000 or more, is used, a preferable thickening effect can be obtained with a small amount. A problem arises in certain pressure resistance and sticking properties. On the other hand, when the molecular weight is 10
A compound which increases the viscosity of the coating solution of the layer farthest from the support in the above-mentioned viscosity range, for example, the coating solution of the protective layer, in the above-mentioned viscosity range when added to the coating solution. It has been found that the use of a polymer can avoid or suppress the disadvantages caused by using these polymer molecules.

As a compound having a low molecular weight and increasing the viscosity of the coating solution to a preferred range, a dialkyl sulfosuccinate compound is preferred. The sulfosuccinic acid dialkyl ester compound is also considered to contribute to thickening by causing the sulfonic acid group in the molecule to interact with gelatin. This is considered to be due to the fact that it acts in a form different from the thickening by the polymer, but it was found that problems such as sticking property hardly occur. In addition, a favorable thickening effect can be obtained by containing a vinyl sulfone-based hardener and one of the compounds represented by the general formulas [HI] and [H-II]. This is a method with few problems in pressure resistance. These vinyl sulfone hardeners and the above-mentioned general formula [H
The thickening when the compound represented by -I] or [H-II] is used in combination is considered to increase the viscosity by partially exerting its dura action. The mechanism is obviously different. These molecular weights are 1000
The following low-molecular compounds thicken by interacting with gelatin in such a different form as compared with the case of a high-molecular thickener having a molecular weight of 1000 or more, so that the light-sensitive material has pressure resistance, stickiness, and stickiness. This is considered to be effective in improving the properties.

These effects are effective within the above viscosity range when the gelatin concentration is 6% by mass or more. If the viscosity is too high, there is a problem in the uniformity of the coated surface.

As the dialkyl sulfosuccinate compound, a compound represented by the following general formula [III] is preferable.

[0022]

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In the formula, R ₁₁ and R ₁₂ represent a substituted or unsubstituted alkyl group, aryl group or alkoxy group.

Typical compounds are shown below, but are not limited thereto.

[0025]

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The dialkyl sulfosuccinate compound is preferably added in an amount of 0.002 mol% or more per gram of gelatin in the coating solution of the layer furthest from the support on the side having the silver halide emulsion layer. As a method of adding, it may be dissolved in water or a solvent miscible with water (for example, methanol, ethanol or the like) and added to the coating liquid for the constituent layer.

In the present invention, the gelatin concentration in the coating solution used for coating the layer farthest from the support having the silver halide emulsion layer is 6% by mass or more.
It is preferable that the coating solution contains a vinyl sulfone-based hardening agent and one of the compounds represented by the general formula [HI] or [H-II].

The vinyl sulfone hardener used in the present invention is, for example, an aromatic compound as described in German Patent No. 1,100,942, and JP-B-44-29622.
And alkyl compounds linked with a hetero atom as described in JP-B-47-25373.
No. 6, sulfonamides and ester compounds, and 1,3,5-tris [β- (vinylsulfonyl) -propionyl] -hexahydro-s- as described in JP-A-49-24435. It includes triazine or an alkyl compound as described in JP-A-51-44164.

Representative compounds are shown below, but are not limited thereto.

[0030]

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[0031]

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[0032]

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The vinyl sulfone hardener in the present invention may be a compound having at least three vinyl sulfone groups in its molecular structure, for example, the compounds [H-5] to [H-22], in addition to the above-mentioned compounds. Includes compounds having a group that reacts with a vinyl sulfone group and a compound having a water-soluble group, such as a reaction product obtained by reacting a compound having diethanolamine, thioglycolic acid, sarcosine sodium salt, or taurine sodium salt.

Next, the compound represented by the general formula [HI] or [H-II] according to the present invention will be described in detail.

In the general formulas [HI] and [H-II], the alkyl group, alkoxy group and alkylthio group represented by R ₁ may be an alkyl group having 1 to 3 carbon atoms. Examples include a methyl group, an ethyl group, a methoxy group, an ethoxy group, a methylthio group, and an ethylthio group.

As M ₁ representing a monovalent metal atom of the —OM ₁ group represented by R ₁ , for example, sodium, potassium,
And the alkyl group represented by R ₅ and R ₆ of the —NR ₅ R ₆ group includes 1 to 3 carbon atoms.
There are alkyl groups such as methyl group, ethyl group and the like,
The aryl group includes a phenyl group.

Further, R of the --NHCOR ₇ group represented by R _1
The alkyl group and the aryl group represented by ₇ are each represented by the above R ₅
And an alkyl group and an aryl group represented by R ₆ .

R ₂ is the same group as R ₁ except for the above-mentioned chlorine atom. Next, the groups represented by R ₃ and R ₄ are those described above for R ₁
Represents the same group as the group represented by

As the alkylene group represented by L,
An alkylene group having 1 to 3 carbon atoms, for example, a methylene group,
Examples include ethylene groups. Examples of the arylene group include a phenylene group.

Next, the general formulas [HI] and [HI]
Representative examples of the hardener according to the present invention represented by I] will be described.

[0041]

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[0042]

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[0043]

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In order to add the vinyl sulfone hardener according to the present invention and the hardeners represented by formulas [HI] and [H-II] to a silver halide emulsion layer and other constituent layers. , Water or a solvent miscible with water (eg, methanol,
(E.g., ethanol) and added to the coating solution for the above-mentioned constituent layer. The addition method may be either a batch method or an inline method. The addition time is not particularly limited, but is preferably added immediately before coating.

The vinyl sulfone hardener and the hardeners represented by the general formulas [HI] and [H-II] according to the present invention are particularly preferably a vinyl sulfone hardener and a general formula [H-
I] or a vinyl sulfone hardener and a compound of the general formula [H-II]
Are preferred.

These hardeners are added in an amount of 0.5 to 100 mg, preferably 5.0 to 50 mg, per gram of gelatin applied.

The silver halide photographic material is usually coated on a support on a long roll, dried, and wound up on a roll. In the present invention, the humidity at the time of winding is 40%.
It is desirable that the heat treatment be performed in a state of RH or more and 70% RH or less, and then in a state of 30 ° C. or more and 40 ° C. or less.

The time period in which the temperature is kept between 30 ° C. and 40 ° C. is preferably between 2 days and 14 days.

One of the preferred embodiments of the present invention is a four-type emulsion comprising an infrared-sensitive emulsion, a blue-sensitive emulsion, a green-sensitive emulsion and a red-sensitive emulsion, and includes a yellow image, a magenta image and a cyan image. And a black image is formed. The combination of the four photosensitive emulsions and the image to be formed can be arbitrarily selected.

The emulsion for forming a black image may be any emulsion capable of forming a black image by image exposure and development. In a preferred example, the emulsion can be used in combination with a black imaging layer containing a black coupler,
Also, a plurality of couplers having different maximum wavelengths can be used in place of the black coupler. It is also a preferable example that the emulsion contributes to image formation of a plurality of layers and a black image is formed by combining a plurality of images by developing the emulsion. As an example of forming a black image by combining a plurality of images, for example, a yellow image layer for forming a yellow image contains the emulsion, and a blue image that is a complementary color of the yellow image (for example, a magenta image and a cyan image are simultaneously formed) Some of the forming layers contain the emulsion, and a black image is formed by developing the emulsion. Further, the emulsion may be contained in the magenta image forming layer and its complementary color image forming layer, or the emulsion may be contained in the cyan image forming layer and its complementary color image forming layer.

Another preferred example is that the emulsion is contained in any of a yellow image forming layer, a magenta image forming layer and a cyan image forming layer, and the emulsion is developed to form a black image. In that case, the yellow image forming layer, the magenta image forming layer, and the cyan image forming layer may contain other emulsions or may not contain the other emulsions.

The yellow image-forming silver halide emulsion layer, magenta image-forming silver halide emulsion layer, and cyan image-forming silver halide emulsion layer of the present invention may be composed of a single layer or a plurality of layers. Good. The order of application from the support can be arbitrarily selected.

The blue-sensitive emulsion, the green-sensitive emulsion, the red-sensitive emulsion and the infrared-sensitive emulsion each have at least the spectral sensitivity of any emulsion relative to the sensitivity of other emulsions at the wavelength. It is desirable that the sensitivity is 6 times higher. Here, the sensitivity is defined as the density of a certain image layer (maximum density−0.3).
Is the reciprocal of the amount of exposure required to achieve a density of More preferably, it is eight times or more.

Each photosensitive emulsion can be realized by selecting from known spectral sensitizing dyes and sensitizing them.

In another embodiment of the present invention, there are three types of infrared-sensitive emulsion, green-sensitive emulsion and red-sensitive emulsion.
A yellow image, a magenta image, and a cyan image are formed with various types of photosensitive emulsions. The combination of the three types of photosensitive emulsion and the image to be formed can be arbitrarily selected. This mode is effective in that it can be combined with an inexpensive semiconductor laser light source.

The photosensitive material of the present invention is preferably a positive photosensitive material. This positive-type photosensitive material includes a direct-positive type and a color reversal type photosensitive material, and also forms a positive image by bleaching a dye at the same time as bleaching silver produced imagewise. A photosensitive material using a silver dye bleaching method, a photosensitive material using a color diffusion transfer method, and the like are also included in the present invention.

The particle size of each emulsion of the light-sensitive material of the present invention depends on its required performance, particularly sensitivity, sensitivity balance, color separation,
It can be selected from a wide range in consideration of various properties such as sharpness and granularity.

As the silver halide emulsion used in the light-sensitive material of the present invention, a surface latent image type silver halide emulsion which forms a latent image on the surface by image exposure is used, and a halogen which forms a negative image by developing is used. A silver halide emulsion may be used.
In addition, using an internal latent image type silver halide emulsion in which the surface of the grains is not fogged in advance, fog processing (nucleation processing) is performed after image exposure, and then surface development is performed, or fog processing is performed after image exposure. Those capable of directly obtaining a positive image by performing surface development while performing the coating are also preferably used. The emulsion containing the internal latent image type silver halide emulsion grains is a silver halide grain having a photosensitive nucleus mainly inside silver halide crystal grains and forming a latent image inside the grains upon exposure. Containing emulsion.

The fogging treatment may be performed by exposing the entire surface, may be performed chemically using a fogging agent, may use a strong developing solution, and may be performed by heat treatment or the like.

The whole surface exposure is performed by immersing or moistening the image-exposed photosensitive material in a developing solution or other aqueous solution, and then performing uniform exposure over the entire surface. The light source used here may be any light source as long as it has light in the photosensitive wavelength range of the photosensitive material,
High illuminance light such as flash light may be applied for a short time, or weak light may be applied for a long time. Further, the time of the entire surface exposure can be varied over a wide range so as to finally obtain the best positive image depending on the photosensitive material, the development processing conditions, the type of the light source used, and the like. Further, it is preferable that the exposure amount of the entire surface exposure is given in a certain range in combination with the photosensitive material. Usually, when an excessive amount of exposure is given, the minimum density increases or desensitization occurs, and the image quality tends to deteriorate.

Techniques for fogging agents that can be used in photosensitive materials include JP-A-6-95283, page 18, right column 39.
It is preferable to use the technique described in line 41 to page 19, left column, line 41.

The non-pre-fogged internal latent image type silver halide grains usable in the light-sensitive material of the present invention include:
An emulsion having a silver halide grain that mainly forms a latent image inside the silver halide grain and has most of the photosensitive nuclei inside the grain, and includes any silver halide such as silver bromide and silver chloride. Silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide and the like are included.

Particularly preferably, the coated silver amount is about 1 to 3.5.
g / m ² , exposing a portion of the sample coated on the transparent support to a light intensity scale for a defined period of time from about 0.1 seconds to about 1 second; When developed at 20 ° C. for 4 minutes using the following surface developer A, which develops only the surface image of grains substantially containing no silver halide solvent, another part of the same emulsion sample is similarly exposed. This is an emulsion showing a maximum density not more than 1/5 of the maximum density obtained when developing at 20 ° C. for 4 minutes with the following internal developing solution B for developing an image inside the grains. More preferably, the maximum density obtained with the surface developer A is not greater than 1/10 of the maximum density obtained with the internal developer B.

(Surface developer A) Methol 2.5 g L-ascorbic acid 10.0 g Sodium metaborate (tetrahydrate) 35.0 g Potassium bromide 1.0 g Add water 1000 ml (Internal developer B) Methol 2 0.0g Sodium sulfite (anhydrous) 90.0g Hydroquinone 8.0g Sodium carbonate (monohydrate) 52.5g Potassium bromide 5.0g Potassium iodide 0.5g Add water 1000ml Addition of water preferably used in the present invention Latent image silver halide emulsions include those prepared by various methods. For example, a conversion-type silver halide emulsion described in U.S. Pat. No. 2,592,250, or U.S. Pat.
6,316, 3,317,322 and 3,36
No. 7,778,749, and silver halide emulsions having internally chemically sensitized silver halide grains, or US Pat.
No. 271,157 and 3,447,927, emulsions having silver halide grains containing polyvalent metal ions, or doping agents described in U.S. Pat. No. 3,761,276. Silver halide emulsion in which the surface of the silver halide grains to be weakly chemically sensitized
No. 8524, No. 50-38525 and No. 53-240
And silver halide emulsions having a laminated structure described in JP-A No. 8 and No. 8 and the like and silver halide emulsions described in JP-A Nos. 52-156614 and 55-127549.

The shape of the silver halide grains used in the present invention may be cubic, octahedral, tetrahedral composed of a mixture of (100) and (111) planes, shape having (110) plane, sphere, flat plate, etc. Any of these may be used. Average particle size is 0.0
Those having a size of 5 to 3 μm can be preferably used. The grain size distribution may be a monodisperse emulsion having a uniform grain size and crystal habit or an emulsion having no uniform grain size or crystal habit, but a monodisperse silver halide emulsion having a uniform grain size and crystal habit It is preferred that

In the present invention, a monodisperse silver halide emulsion is defined as having a silver halide content within a range of ± 20% of the center of the average particle size rm, wherein the mass of silver halide is 6% of the total mass of silver halide grains.
0% or more, preferably 70% or more, more preferably 80% or more. Here, the average particle size rm is defined as the particle size ri when the product ni × ri ³ of the frequency ni and ri ³ of the particles having the particle size ri is maximum (three significant digits, the minimum digit is Round off to the nearest 4). The particle size referred to here is the diameter of spherical silver halide grains, or the diameter of a projected image converted to a circular image of the same area for grains having a shape other than spherical. . The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is 1000 or more indiscriminately).

Particularly preferred highly monodisperse emulsions are those having a distribution width of not more than 20% as defined by (particle size standard deviation / average particle size) × 100 = width of distribution (%).
Here, the average particle size and the particle size standard deviation are determined from ri defined above.

The monodispersed emulsion is prepared by adding a water-soluble silver salt solution and a water-soluble halide solution to a pAg solution in a gelatin solution containing seed particles.
And controlled pH and addition by the double jet method. In determining the addition rate, JP-A-54-48521 and JP-A-58-49938 can be referred to. As a method for obtaining a more highly monodispersed emulsion, the growth method in the presence of a tetrazaindene compound disclosed in JP-A-60-122935 can be applied. It is also preferable to add two or more monodisperse emulsions to the same color-sensitive layer.

The grain size of the silver halide in each emulsion layer depends on the required performance, especially sensitivity, sensitivity balance, color separation sharpness,
It can be determined from a wide range in consideration of various properties such as graininess.

In one of the preferred embodiments of the present invention, the grain size of the silver halide is 0.1 to 0.6 μm for the red-sensitive layer emulsion.
m, the green-sensitive emulsion preferably ranges from 0.15 to 0.8 μm, and the blue-sensitive emulsion preferably ranges from 0.3 to 1.2 μm.

The light-sensitive material preferably contains a nitrogen-containing heterocyclic compound having a mercapto group. Preferred compounds are described in JP-A-6-95283, p.
General formula [XI] described in line 49, particularly preferably the same publication 2
General formula [XII] described on page 0, left column, 5 lines to page 20, right column, 2 lines,
They are represented by the general formulas [XIII] and [XIV]. Specific examples of the compound include, for example, JP-A-64-73338, 11-1.
Compounds (1) to (39) described on page 5 can be mentioned.

[0072] The above mercapto compound may vary appropriately depending on the kind and layer the addition of compounds to be used as an additive amount, in general, when added to a silver halide emulsion layer, per mol of silver halide 10 ^{- It is in} the range of ⁸ to 10 ^-2 mol, more preferably 10 ^-6 to 10 ^-3 mol.

The yellow image forming silver halide emulsion layer, the magenta image forming silver halide emulsion layer and the cyan image forming silver halide in the silver halide photographic light-sensitive material (hereinafter also referred to as light-sensitive material) according to the present invention. The emulsion layers each contain a silver halide emulsion having a spectral sensitivity wavelength region different from each other, and at least one of the yellow, magenta and cyan image-forming silver halide emulsion layers contains the yellow, magenta and cyan It is preferable that the silver halide emulsion having a common spectral sensitivity portion be contained in any of the emulsions having different spectral sensitivity wavelength regions contained in the image-forming silver halide emulsion layer.

As the magenta coupler used in the light-sensitive material of the present invention, a compound represented by the general formula [M-1] described in the right column on page 7 of JP-A-6-95283 includes
Spectral absorption characteristics of the coloring dye are good and preferable. Specific examples of preferred compounds include compounds M-1 to M-19 described on pages 8 to 11 of the same publication. Further, as another specific example, European Patent Publication No. 0273712 is disclosed.
Nos. M-1 to M-61 described on pages 6 to 21
And Compounds 1 to 223 described in JP-A No. 0235913, pp. 36-92, other than the above-mentioned representative specific examples.

The magenta coupler can be used in combination with other types of magenta couplers.
1 × 10 ^-2 mol to 1 mol per mol, preferably 1 × 1
It can be used in the range of 0 ^-2 mol to 8 × 10 ^-1 mol.

The λ _max of the spectral absorption of the magenta image formed in the photosensitive material according to the present invention is 530 to 560 n
m, and λ _L0.2 is 580 to 63
Preferably it is 5 nm.

Here, formed by the photosensitive material according to the present invention.
Λ of the spectral absorption of the magenta image _L0.2And λ_maxIs
It is an amount measured by the following method.

That is, development processing is performed by applying green light through an ND filter, and the density of the ND filter is adjusted so that the maximum absorbance of the magenta image when spectral absorption is measured is 1.0. λ _L0.2 refers to a wavelength at which this magenta image has a longer absorbance than the wavelength at which the maximum absorbance shows 1.0 and the absorbance shows 0.2 on the spectral absorbance curve.

The magenta image forming layer of the light-sensitive material according to the present invention preferably contains a yellow coupler in addition to the magenta coupler. The difference in pKa between these couplers is preferably within 2 and more preferably within 1.5. Preferred yellow couplers to be contained in the magenta image-forming layer according to the present invention are described in JP-A-6-9.
It is a coupler represented by General Description General Formula [Y-Ia] described in the right column of page 12 of JP-A-5283. Among the couplers represented by the general formula [Y-1] in the same publication, particularly preferred are couplers represented by the formula [M-1] when combined with the magenta coupler represented by the formula [M-1]. Is a coupler having a pKa value not lower than 3 or less than the pKa of the above.

Specific examples of the yellow coupler include compounds Y-1 and Y-2 described on pages 12 to 13 of JP-A-6-95283, as well as JP-A-2-13954.
No. 2, pages 13 to 17 (Y-
Although 1) to (Y-58) can be preferably used, they are of course not limited thereto.

In the light-sensitive material according to the present invention, as the cyan coupler contained in the cyan image forming layer, a known phenol, naphthol or imidazole coupler can be used. For example, a phenol coupler substituted with an alkyl group, an acylamino group or a ureido group, a naphthol coupler formed from a 5-aminonaphthol skeleton, a bi-equivalent naphthol coupler having an oxygen atom introduced as a leaving group, and the like are representative. Is done.
Among them, preferred compounds are described in JP-A-6-9528.
General formulas [C-I] and [C-II] described in No. 3, page 13 are mentioned.

The cyan coupler is usually used in the silver halide emulsion layer in an amount of 1 × 10 ⁻³ to 1 × 10 ⁻³ per mol of silver halide.
It can be used in an amount of 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol.

In the light-sensitive material according to the present invention, the yellow coupler contained in the yellow image forming layer includes
Known acylacetanilide-based couplers and the like can be preferably used.

As a specific example of the yellow coupler, for example, a yellow coupler described on pages 5 to 9 of JP-A-3-241345.
-I-1 to Y-I-55 or Y-1 described on page 11 to 14 of JP-A-3-209466.
~ Y-30 can also be preferably used. Furthermore, couplers represented by the general formula [Y-I] described on page 21 of JP-A-6-95283 can be mentioned.

The λ _max of the spectral absorption of the yellow image formed by the photosensitive material according to the present invention is preferably at _{least 425} nm, and the λ _L0.2 is preferably at _most 515 nm. Here, λ _L0.2 is defined for the yellow image in the same way as for the magenta image.

The yellow coupler is usually used in the silver halide emulsion layer in an amount of 1 × 10 ^-2 per mol of silver halide.
To 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol.

In order to adjust the spectral absorption characteristics of the magenta image, cyan image and yellow image, it is preferable to add a compound having a color tone adjusting action. Compounds for this purpose are described in JP-A-6-95283, 22
General formulas [HBS-I] and [HBS-I]
The compound represented by I] is preferable, and the compound represented by the general formula [HBS-II] described on page 22 of the same publication is more preferable.

The yellow image forming layer, magenta image forming layer and cyan image forming layer in the light-sensitive material according to the present invention are:
Coating is performed on the support, and the order from the support may be any order. One preferred embodiment is, for example, a cyan image forming layer, a magenta image forming layer, and a yellow image forming layer from the side close to the support. In addition, an intermediate layer, a filter layer, a protective layer, and the like can be provided as necessary.

A discoloration inhibitor can be used in combination with each of the magenta, cyan and yellow couplers in order to prevent discoloration of the formed dye image due to light, heat, humidity and the like. Preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541 and phenolic compounds represented by general formula IIIB described in JP-A-3-174150. Amine compounds represented by the general formula A described in JP-A-64-90445 and metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A-62-182741 are particularly preferable for magenta dyes. . In addition, Japanese Patent Laid-Open No. 1-1
The compounds represented by the general formula I 'described in 96049 and the compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

The oil-in-water type emulsification dispersion method used for adding a coupler or other organic compound used in the light-sensitive material according to the present invention is usually required for a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or more. If necessary, a low boiling point and / or water-soluble organic solvent is used in combination and dissolved, 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. As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler and the like, the compound represented by the general formula (2) according to the present invention is most preferable, but phthalic acid such as dioctyl phthalate, diisodecyl phthalate and dibutyl phthalate is preferred. High boiling organic solvents such as esters, phosphate esters such as tricresyl phosphate and trioctyl phosphate, and phosphine oxides such as trioctyl phosphine oxide can also be preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

Preferred compounds as a surfactant used for dispersing a photographic additive used in the light-sensitive material of the present invention and adjusting the surface tension at the time of coating are hydrophobic compounds having 8 to 30 carbon atoms in one molecule. And those containing a sulfonic acid group or a salt thereof. Specifically, Japanese Patent Application Laid-Open
A-1 to A-11 described in JP-A-26854. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution after coating are preferably shorter. It is preferably within an hour, preferably within 3 hours, more preferably within 20 minutes.

In the light-sensitive material according to the present invention, 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. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17 of the same specification. Can be

It is preferable to add an ultraviolet absorber to the light-sensitive material according to the present invention to prevent static fog or improve the light fastness of a dye image. Preferred ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the formula III-3 described in JP-A-1-250944, and JP-A-64-666.
No. 46, a compound represented by the general formula III;
UV-1L to UV-27L described in -187240, compounds represented by the general formula I described in JP-A-4-1633,
General formulas (I) and (II) described in JP-A-5-165144
The compound shown by these is mentioned.

It is preferable that the light-sensitive material according to the present invention contains an oil-soluble dye or pigment, since the white background is improved. Representative specific examples of the oil-soluble dyes include compounds 1 to 27 described in pages (8) to (9) of JP-A-2-842.

In the light-sensitive material according to the present invention, the reflection density of the raw sample at the maximum wavelength of the spectral sensitivity of the cyan image-forming silver halide emulsion layer is preferably 0.7 or more. The above-mentioned light-sensitive material can be obtained by incorporating a coloring material such as a dye having absorption at the above-mentioned wavelength and a black colloidal silver into any of the photographic constituent layers of the present invention. In the light-sensitive material according to the present invention, a water-soluble dye can be contained in any of the silver halide emulsion layers and / or other hydrophilic colloid photographic constituent layers. Further, in the light-sensitive material according to the present invention, a dye having at least one of a carboxyl group, a sulfonamide group and a sulfamoyl group in an arbitrary silver halide emulsion layer and / or in another hydrophilic colloid photographic constituent layer. Can be contained as a solid dispersion.

Examples of the dye having at least one of the carboxyl group, sulfamoyl group and sulfonamide group include compounds represented by formulas [I] to [IX] described in JP-A-6-95283, pp. 14-16. be able to.

In the general formulas [I] to [IX], [I] to [I]
Specific examples of the dye represented by [VIII] include, for example, I-I described in JP-A-4-18545, pp. 13-35.
1 to VIII-7, but are not limited thereto.

The layer containing the dye or colloidal silver is not particularly limited, but is preferably contained in a non-photosensitive hydrophilic colloid layer between the support and the emulsion layer closest to the support.

The silver halide in the light-sensitive material according to the present invention can be optically spectrally sensitized by a commonly used sensitizing dye. Use of a combination of sensitizing dyes used for supersensitization, such as an internal latent image type silver halide emulsion and a negative type silver halide emulsion, is also useful for the silver halide emulsion of the present invention. For sensitizing dyes, Research Disclosure (Research Disc)
loss, hereinafter abbreviated as RD) No. 15162 and No. 17
No. 643 can be referred to.

It is preferable to add a compound for adjusting the foot tone to the light-sensitive material according to the present invention. Preferred compounds are those represented by the general formula [AO-II] described on page 17 of JP-A-6-95283. Preferred examples of the compound include compounds II-1 to II-8 described on page 18 of the same publication.

The amount of the compound [AO-II] added is 0.1.
Preferably 001~0.50g / m ^2, more preferably from 0.005~0.20g / m ^2. The compounds may be used alone or in combination of two or more. Further, a quinone derivative having 5 or more carbon atoms can be used by being added to the compound of [AO-II]. However, in any of these cases, the amount used is 0.001 to 0.5 as a whole.
It is preferably in the range of 0 g / m ² .

It is preferable to include a fluorescent whitening agent in the light-sensitive material and / or the processing solution according to the present invention in order to improve the whiteness.

When the silver halide photographic light-sensitive material according to the present invention is developed with a color developing solution, a developing solution, a bleach-fixing solution,
The stabilizing solution can be continuously developed while replenishing a replenishing developer, a replenishing bleaching solution, a replenishing fixing solution, a replenishing bleach-fixing solution, a replenishing stabilizing solution, and the like.

Examples of the color developing agents which can be used in the developer which can be used for developing the light-sensitive material according to the present invention include aminophenols and phenylenediamines, and p-phenylenediamines are preferred. Specifically, N, N-diethyl-p-phenylenediamine, diethylamino-o-toluidine, 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 4-amino-3 -Methyl-N
-Ethyl-N- (β-hydroxyethyl) aniline, 4
-Amino-N-ethyl-N- (β-hydroxyethyl)
Aniline, 4-amino-3-methyl-N-ethyl-N-
And color developing agents such as (γ-hydroxypropyl) aniline.

Other auxiliary developing agents include ordinary silver halide developers, for example, polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and the like, or mixtures thereof. And specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1
-Phenyl-4,4-dimethyl-3-pyrazolidone, 1
-Phenyl-4-methyl-4-hydroxymethyl-3-
All or some of these developing agents, such as pyrazolidone and ascorbic acid, may be included in the emulsion in advance so that they act on the silver halide during immersion in a high pH aqueous solution.

The developer used in the light-sensitive material according to the present invention may further contain specific antifoggants and development inhibitors, or these additives may be added to the constituent layers of the photographic light-sensitive material. Arbitrarily.

In the present invention, the color developing solution is adjusted to an arbitrary pH.
PH 9.5 to pH
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 according to the present invention is 35.
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, it is preferable that the temperature is not too high.

In the color developing solution, in addition to the color developing agent,
Known developer component compounds can be added. Usually, an alkaline agent having a pH buffering action, chloride ion,
Development inhibitors such as benzotriazoles, preservatives, chelating agents and the like are used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, the pH is usually adjusted with various alkali agents during the stabilization process before use. It is preferable that the film surface pH of the silver halide photographic light-sensitive material after processing and drying is adjusted to 7 or less.

As a method for measuring the pH of the surface, the photosensitive material was left in an atmosphere of 23 ° C. and 55% RH for 24 hours, and then two drops of a 0.3 M aqueous solution of potassium nitrate were dropped on the surface with a pipette. Membrane pH electrode (GST-521
3F) is brought into contact, equilibrated for 3 minutes, and the pH value may be read.

The photographic material according to the present invention may further contain known photographic additives. Examples of the known photographic additives include the compounds described in RD17643 and RD18716 shown below.

Additive RD17643 RD18716 Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right sensitizing dye 23 IV 648 Upper right Upper development accelerator 29 XXI 648 Upper right antifoggant 24 VI 649 Lower right stabilizer 24 VI 649 Lower right Color stain inhibitor 25 VII 650 left-right Image stabilizer 25 VII UV absorber 25-26 VII 649 right-650 left Filter dye 25-26 VII 649 right-650 left Brightener 24 V Hardener 26 X 651 right Coating aid 26-27 XI 650 right Surfactant 26-27 XI 650 right Plasticizer 27 XII 650 right Sliding agent 27 XII 650 right Static inhibitor 27 XII 650 right Matting agent 28 XVI 650 right Binder 29 IX 651 right book The reflective support used in the photosensitive material according to the present invention is based on base paper and has polyolefins on both sides thereof. Those laminated with resin are preferably used.

The base paper used as the support can be selected from raw materials generally used for photographic printing paper. Examples include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various kinds of laminated paper raw materials. In general, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, and the like can be widely used.

The support may further contain additives generally used in papermaking, such as a sizing agent, a fixing agent, a strength enhancer, a filler, an antistatic agent and a dye.
Further, a surface sizing agent, a surface strengthening agent, an antistatic agent and the like may be appropriately applied to the surface.

The reflection support is usually 50 to 300 g / m2.
A resin having a smooth surface having a mass of ² is used, and a resin for laminating both surfaces thereof is ethylene, polyethylene terephthalate, α-olefins, for example, a homopolymer such as polypropylene, and at least two kinds of the olefins. Copolymer or at least 2 of these various polymers
It can be selected from a mixture of species and the like. Particularly preferred polyolefin resins are low density polyethylene, high density polyethylene or mixtures thereof.

The molecular weight of the polyolefin resin to be laminated on the reflection support is not particularly limited.
Usually, those having a range of 20,000 to 200,000 are used.

The polyolefin resin coating layer on the side of the reflection support used for the light-sensitive material of the present invention on which the photographic emulsion is coated is preferably 25 to 50 μm, more preferably 25 to 35 μm.

As the polyolefin used for laminating the back side of the reflection support (the reflection side of the side on which the emulsion layer is provided), a mixture of low-density polyethylene and high-density polyethylene is usually melt-laminated. In general, this layer is often subjected to a matting process.

In forming the laminate on the front and back of the support used in the photosensitive material according to the present invention, the density of the resin layer on the front side is generally made slightly larger than that on the back side in order to increase the flatness of the developed photographic paper in a normal environment. For example, means for increasing the amount of lamination on the back side than on the front side is used.

In general, the lamination on both the front and back surfaces of the reflective support can be formed by melt extrusion coating a polyolefin resin composition on the support. In addition, corona discharge treatment on the surface of the support or on both the front and back if necessary,
It is preferable to apply a flame treatment or the like. Further, it is preferable to provide a sub-coat layer on the surface of the surface laminate layer for improving the adhesion to the photographic emulsion, or a back coat layer on the back surface of the laminate layer for improving the printability and antistatic property.

The polyolefin resin used for laminating the support surface (the surface on which the emulsion layer is provided) of the light-sensitive material according to the present invention has preferably 13 to 20% by mass, more preferably 15 to 20% by mass of a white pigment dispersed therein. Mixed.

As the white pigment, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments, such as alkaline earth metal sulfates such as barium sulfate; Alkaline earth metal carbonates such as calcium carbonate, finely divided silica, synthetic silicate silicas,
Examples include calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like.

Among these, barium sulfate, calcium carbonate and titanium oxide are preferred, and barium sulfate and titanium oxide are more preferred.

The titanium oxide may be of a rutile type or an anatase type, and a titanium oxide whose surface is coated with a metal oxide such as hydrated alumina or hydrated ferrite is also used.

In addition, it is preferable to add an antioxidant, a colored pigment for improving whiteness, and a fluorescent whitening agent.

Further, it is preferable to provide a hydrophilic colloid layer containing a white pigment on the reflective support because sharpness is improved. As the white pigment, the same white pigment as described above can be used, but titanium oxide is preferable. It is more preferable to add a hollow fine particle polymer or a high boiling point organic solvent to the hydrophilic colloid layer containing a white pigment because sharpness and / or curl resistance can be improved.

Further, as the reflective support used in the photosensitive material according to the present invention, a synthetic resin film support such as polypropylene, the surface of which is further coated with polyolefin, can be used.

The thickness of the reflection support is not particularly limited.
Those having a thickness of 80 to 160 μm are preferably used. In particular, those having a thickness of 90 to 130 μm are more preferable.

The surface shape of the reflective support may be smooth or may have an appropriate surface roughness.
It is preferable to select a reflective support having a gloss close to that of the printed matter. For example, JIS-B0601-1976
Has an average surface roughness SRa of 0.30 to 3.0 μm
It is preferred to use a white support having a m.

In the light-sensitive material according to the present invention, it is preferable that the surface roughness of the image-forming surface is 0.30 to 3.0 μm. May contain a matting agent. The layer to which the matting agent is added includes a silver halide emulsion layer, a protective film, an intermediate layer, an undercoat layer, and the like, and may be added to a plurality of layers, and is preferably the uppermost layer of the photosensitive material.

The surface gloss on the image forming layer side of the photosensitive material according to the present invention preferably has a gloss close to that of a printed matter.
For example, JIS-Z8741 of the surface after processing of the image forming layer
Having a glossiness G _S (60 °) of 5 to 60 measured by the method defined in.

In the step of producing a color proof according to the present invention, the photosensitive material is exposed to light based on the halftone image information forming the color-separated yellow image information, magenta image information, cyan image information and black image information. I do. In the step of creating a color proof, at least a part of the halftone dot image information is halftone dots such that the number of halftone dots per inch ² is 200 × 10 ³ or more when the halftone dot area ratio is 40%. Use the one that has been image converted.
Preferably, it is 300 × 10 ³ or more, more preferably 40 × 10 ³ or more.
It is 0 × 10 ^{3 to} 2000 × 10 ³ .

The number of the halftone dots can be measured by counting halftone images taken by an optical microscope or the like.

A halftone image produced by using the photosensitive material according to the present invention is particularly effective when the halftone image is used for high-definition printing by the AM screening method generally used conventionally. The present invention is most effective in the case of a dot image formed by a frequency-modulated screening method called a so-called FM screening method.

The halftone image information used for creating these halftone images is a halftone image recorded on a film. The halftone image information is exposed by bringing the film into close contact with the silver halide photographic material and scanning a light source. Is preferably performed. For the adhesion, a vacuum adhesion method can be preferably used.

In these exposures, it is preferable to carry out the exposure through an optical means for improving the parallelism of the light from the light source. Means for improving the parallelism of light emitted from the light source include those that absorb components other than parallel light on the wall surface by passing through a linear tubular optical path such as an optical lens, a reflecting mirror, or a honeycomb structure. Can be Also,
The collimated light can also be improved by an aggregate of optical fibers.

Exposure is preferably performed by laser scanning based on the dot image information.

In order to form an image using the photosensitive material according to the present invention, it is preferable to use an automatic developing machine of a light source section scanning exposure system. A specific example of a particularly preferable image forming system is Konsensus manufactured by Konica Corporation.
L, Konsensus570, Konsensus2
Can be mentioned.

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 having a reflective support and forming an image for direct viewing. For example, a light-sensitive material for color proof can be used.

[0141]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention.

Example 1 << Preparation of Emulsion EM-P1 >> While controlling the aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (KBr: NaCl = 95: 5) at the same time by the control double jet method.
A 30 μm cubic silver chlorobromide core emulsion was obtained. At that time, the pH and pAg were controlled so that a cube was obtained as the particle shape.

To the obtained core emulsion, an aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in a molar ratio) were simultaneously added by a control double jet method. The shell was formed until the average particle size became 0.42 μm. At this time, p is set so that a cube is obtained as the particle shape.
H and pAg were controlled.

After washing with water to remove water-soluble salts, gelatin was added to obtain an emulsion EM-P1. This emulsion EM-P1
Was 8%.

<< Preparation of Emulsion EM-P2 >> While controlling the aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (KBr: NaCl = 95: 5 by molar ratio). ) Was added simultaneously by the control double jet method to obtain a cubic silver chlorobromide core emulsion having a particle size of 0.18 μm. At this time, p is set so that a cube is obtained as the particle shape.
H and pAg were controlled.

To the obtained core emulsion, an aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in molar ratio) were simultaneously added by a control double jet method. The shell was formed until the average particle size became 0.25 μm. At this time, p is set so that a cube is obtained as the particle shape.
H and pAg were controlled.

After washing with water to remove water-soluble salts, gelatin was added to obtain an emulsion EM-P2. This emulsion EM-P2
Was 8%.

Emulsions EM-P1 and EM-P2 were coated on a transparent cellulose triacetate support so that the amount of silver was 2 g / m ² in terms of silver. Then, development was performed at 20 ° C. for 4 minutes using the surface developer A, a part of another sample was similarly exposed, and then developed at 20 ° C. for 4 minutes with the internal developer B. The maximum density for surface development was about 1/12 of the maximum density for internal development. Emulsions EM-P1, EM-
P2 was confirmed to be an internal latent image type silver halide emulsion.

<< Preparation of Green-Sensitive Silver Halide Emulsion >> Emulsion E
After sensitizing dye GS-1 was added to M-P1 for optimal color sensitization, T-1 (4-hydroxy-6-methyl-1,3,3
a, 7-tetrazaindene) in an amount of 600 m
g was added to prepare a green-sensitive silver halide emulsion Em-G1.

<< Preparation of Red-Sensitive Silver Halide Emulsion >> Emulsion E
Sensitizing dyes SP-I-21 and SP-I-22 on MP-2
And red-sensitive silver halide emulsion Em-G1 in the same manner as green-sensitive silver halide emulsion Em-G1 except that the color sensitization was optimized by adding
R1 was prepared.

<< Preparation of Infrared-Sensitive Silver Halide Emulsion >> Red was prepared in the same manner as the green-sensitive emulsion Em-G1 except that the sensitizing dye SP-I-7 was added to the emulsion EM-P2 to optimize the color. An external light-sensitive silver halide emulsion Em-IFR1 was prepared.

[0152]

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<< Preparation of Multilayer Silver Halide Photosensitive Material Sample >>
A high-density polyethylene on one surface and a fused polyethylene containing anatase-type titanium oxide dispersed at a content of 15% by mass on the other surface, a polyethylene-laminated paper reflective support having a mass per square meter of 115 g (Taber stiffness) = 3.5, PY value = 2.7 μm)
Using each emulsion of m-G1, Em-R1, and Em-IFR1, each layer having the following layer structure was coated on the side of the polyethylene layer containing titanium oxide, and further, 6.00 g / m 2 of gelatin was formed on the back side. ^2. A multilayer silver halide photosensitive material sample coated with a silica matting agent of 0.65 g / m ² was prepared. Incidentally, H-1 and H-2 were added as hardeners. Surfactants SU-1, SU-2, S
U-3 was added and prepared. The amount of each material was represented by the mass per 1 m ² of the polyethylene terephthalate support.

SU-1: sodium sulfosuccinate di (2-ethylhexyl) ester SU-2: sulfosuccinate di (2,2,3,3,4,4,4)
5,5-octafluoropentyl) ester sodium SU-3: sodium tri-i-propylnaphthalenesulfonate H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium H-2: tetrakis (vinyl) Sulfonylmethyl) methane << Layer Configuration of Sample 1 >> Eighth Layer (Ultraviolet Absorbing Layer) Gelatin 1.60 Ultraviolet Absorber (UV-1) 0.070 Ultraviolet Absorber (UV-2) 0.025 Ultraviolet Absorber (UV -3) 0.120 Surfactant (SU-3) 0.002 Silica matting agent 0.01 Hardener 0.008 7th layer (red sensitive layer) Gelatin 0.90 Red sensitive emulsion (Em-R1) 0 0.35 cyan coupler (C-1) 0.35 stain inhibitor (HQ-1) 0.02 surfactant (SU-3) 0.002 inhibitor (T-1, T-2, T) 3) (Molar ratio 1: 1: 1) 0.002 High boiling organic solvent (SO-2) 0.40 6th layer (intermediate layer) Gelatin 0.80 Stain inhibitor (HQ-2) 0.04 Stain prevention Agent (HQ-3) 0.02 Surfactant (SU-1) 0.002 High boiling organic solvent 0.005 Irradiation prevention dye (AI-2) 0.050 Hardener (H-2) 0.012 Fifth layer (green-sensitive layer) Gelatin 1.25 Green-sensitive emulsion (Em-G1) 0.37 Magenta coupler (M-1) 0.25 Yellow coupler (Y-3) 0.02 Stain inhibitor (HQ-1) ) 0.035 Surfactant (SU-3) 0.003 Inhibitor (T-1, T-2, T-3) (molar ratio 1: 1: 1) 0.0036 High boiling organic solvent (SO-1) ) 0.38 4th layer (middle layer) Gelatin 0.08 Stain prevention (HQ-2) 0.04 Stain inhibitor (HQ-3) 0.02 High boiling point organic solvent (SO-2) 0.005 Surfactant (SU-1) 0.001 Irradiation preventing dye (AI-1) 0.04) Hardener (H-2) 0.012 Third layer (infrared-sensitive layer) Gelatin 1.10 Infrared-sensitive emulsion (Em-IFR1) 0.33 Yellow coupler (Y-1) 19 Yellow coupler (Y-2) 0.19 Stain inhibitor (HQ-1) 0.04 Surfactant (SU-3) 0.002 Inhibitor (T-1, T-2, T-3) (mol Ratio 1: 1: 1) 0.004 High boiling organic solvent (SO-1) 0.30 Second layer (intermediate layer) Gelatin 1.20 Stain inhibitor (HQ-2) 0.04 Stain inhibitor (HQ- 3) 0.02 High boiling organic solvent (SO-2) 0.005 Interface Hardener (SU-1) 0.001 Anti-irradiation dye (AI-3) 0.150 Hardener (H-2) 0.017 First layer (white pigment-containing layer) Gelatin 2.00 Styrene / n- Butyl methacrylate / 2-sulfoethyl methacrylate sodium salt 0.12 Black colloidal silver 0.08 Polyvinylpyrrolidone 0.10 Titanium oxide (average primary particle size 0.25 μm) 0.50 Surfactant (SU-2) 0.002

[0155]

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[0156]

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SO-1: trioctylphosphine oxide SO-2: di (i-decyl) phthalate HQ-1: 2,5-di (t-butyl) hydroquinone HQ-2: 2,5-di ((1, 1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone, 2,5-di-sectetradecylhydroquinone and 2-sec-dodecyl-5-sec-tetra Mixture of decyl hydroquinone at a mass ratio of 1: 1: 2 T-2: 1- (3-acetamidophenyl) -5-mercaptotetrazole T-3: N-benzyladenine However, regarding application of the eighth layer (ultraviolet absorbing layer) Is the eighth
The gelatin concentration of the coating solution constituting the layer was changed, and
As shown in Table 1, coating and drying were carried out in the usual manner using the components prepared by adding the components according to the present invention, to thereby produce photosensitive materials 1 to 29 as shown in Table 1.

A drum exposure type laser printer using a helium neon laser (544 nm), a semiconductor laser (650 nm), and a semiconductor laser (780 nm) as a light source was assembled with the prepared photosensitive material, and each sample was exposed. A development process was performed.

<< Processing Step >> Processing Step Temperature Time Immersion (Developer) 37 ° C. 12 seconds Fog exposure −12 seconds Development 37 ° C. 95 seconds Bleach-fix 35 ° C. 45 seconds Stabilization processing 25-35 ° C. 90 seconds Drying 50-85 ° C. 40 seconds <Composition of color developer> Benzyl alcohol 15.0 ml Ethylene glycol 8.0 ml Diethylene glycol 15.0 ml Potassium sulfite 2.5 g Potassium bromide 1.0 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate 5. 0 g pentasodium diethylenetriaminepentaacetic acid 2.0 g 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Optical brightener (4,4′-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Add water to make the total volume 1000 ml, p Adjusted to 10.15.

<Composition of bleach-fixing solution> Ferric ammonium diethylenetriaminepentaacetate 90.0 g Ammonium thiosulfate (70% aqueous solution) 180.0 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-mercapto-1,2,4-triazole 0.15 g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to make the total volume 1000 ml.

<Composition of Stabilizing Solution> o-phenylphenol 0.1 g 1-hydroxyethylidene-1,1-diphosphonic acid 4.0 g diethylenetriaminepentaacetic acid 2.0 g ammonium hydroxide (28% aqueous solution) 0.7 g fluorescent brightening Agent (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Water is added to make the total volume 1000 ml, and the pH is adjusted to 7.5 with ammonium hydroxide or sulfuric acid.

Note that the stabilization treatment was of a countercurrent type having a three-tank configuration. The formula of the replenisher for performing the running process is shown below.

<Composition of Color Developer Replenisher> Benzyl alcohol 18.5 ml Ethylene glycol 10.0 ml Diethylene glycol 18.0 ml Potassium sulfite 2.5 g Potassium bromide 0.2 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate Salt 5.0g Diethylenetriaminepentaacetic acid pentasodium 2.0g 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 5.4g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Water is added to adjust the total volume to 1 liter, and the pH is adjusted to 10.35.

<Bleach-fix replenisher composition> Same as the above-mentioned bleach-fix solution.

<Composition of stabilizer replenisher> Same as the above stabilizer.

The replenishment rate was 320 ml per m ^{2 of} the light-sensitive material for the developing solution, the bleach-fixing solution and the stabilizing solution.

The drying temperature after the stabilization treatment was 55 ° C. << Evaluation of Sticking Resistance >> The sample that has been subjected to the development processing as described above is allowed to stand at 30 ° C. and 90% RH for 2 hours. Thereafter, the surfaces having the silver halide emulsion layer are stuck together and pressed with a rubber roller. Subsequently, the adhered sample is peeled off by hand, and the touch is used to make a determination.

1 Can be peeled off without difficulty (usable) 2 Sounds slightly, but can be peeled off without failure on the film surface (usable) 3 Difficult to peel off, damaging the film surface (unusable) 4 Almost no peeling ( (Unavailable) << Evaluation of pressure resistance >> Each of unexposed samples was subjected to 25 ° C.
After standing for 2 hours, a ball point needle having a ball diameter of 0.1 mm is set upright on the sample surface, and the sample surface is moved in parallel at a speed of 1 cm / sec.
The developing process is performed by continuously changing the load of 100 g. The load on the ball point needle when the pressure causes a decrease in cyan density is recorded. In this case, it is evaluated that the larger the value of the load, the higher the pressure resistance during drying.

Table 1 shows the results.

[0170]

[Table 1]

[0171]

Embedded image

As shown in Table 1, the coating liquid viscosity of the eighth layer was 6
A compound having a molecular weight of 1000% by mass or more and
5 to 15 mPa · s increase in viscosity after leaving at 0 ° C for 1 hour
It can be seen that the sample of Example 2 has excellent sticking resistance and pressure resistance.

It can also be seen that the addition of the dialkyl sulfosuccinate compound provides excellent sticking resistance and pressure resistance.

Example 2 A sample was prepared in the same manner as in Example 1, except that a sample using a hardener as shown in Table 2 was used and the same evaluation was performed.

[0175]

[Table 2]

As shown in Table 2, the sample of the present invention containing a vinyl sulfone hardener and one of the compounds represented by the general formulas [HI] or [H-II] is excellent. I understand.

Example 3 A sample was prepared in the same manner as in Example 1, and the environment at the end of coating and the subsequent heating conditions were changed as shown in Table 3. The evaluation was performed in the same manner as in Example 1.

[0178]

[Table 3]

As shown in Table 3, a humidity of 40% or more and 70% R
H is taken up at the end of coating in the state of H or less.
It can be seen that the sample of the present invention heat-treated at a temperature of 0 to 40 ° C. has excellent sticking resistance and pressure resistance.

Example 4 The development process used in Example 1 was performed using the sample manufactured in Example 1. However, the pH of the film surface after drying was measured by changing the pH of the stabilizing solution by the following method.

After the photosensitive material is allowed to stand for 24 hours in an atmosphere of 23 ° C. and 55% RH, two drops of a 0.3 M potassium nitrate aqueous solution are dropped on the surface with a pipette. Then, a membrane surface pH electrode (GST-5213F) manufactured by Toa Denpa Co., Ltd. was brought into contact and equilibrated for 3 minutes, and the pH value was read.

Table 4 shows the results.

[0183]

[Table 4]

It is understood that the sticking resistance is further improved by setting the pH of the film surface to 7 or less.

Example 5 A sample similar to that of Example 1 of Japanese Patent Application No. 11-109148 was prepared. However, the twelfth layer (ultraviolet absorber layer) was changed in the same manner as in Examples 1 to 3 of the present invention, and the sticking resistance and the pressure resistance were evaluated. As a result, it was confirmed that a similar effect was obtained.

[0186]

According to the present invention, there is provided a method for producing a silver halide photographic light-sensitive material which is excellent in sticking resistance, which is a phenomenon in which the image surfaces of color photographic paper are stuck to each other after drying is completed, and which is less desensitized by pressure. I was able to do it.

Claims (4)

[Claims] In a method for producing a silver halide photographic material having at least one silver halide emulsion layer and at least one non-light-sensitive layer on a support, a support having a silver halide emulsion layer is provided. The gelatin concentration in the coating solution used for coating the layer farthest from the body is 6% by mass or more. The coating solution has a molecular weight of 1,000 or less, and is added to the coating solution for 1 hour at 40 ° C. 5mP when left unattended
A method for producing a silver halide photographic light-sensitive material, comprising adding a compound that increases the viscosity in the range of a · s to 15 mPa · s. 2. A polymer having a molecular weight of 1,000 or less and having a molecular weight of 5 mPa ·
The method for producing a silver halide photographic material according to claim 1, wherein the compound that increases the viscosity in the range of s to 15 mPa · s is a dialkyl sulfosuccinate compound. 3. A method for producing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-light-sensitive layer on a support, wherein a support having a silver halide emulsion layer is provided. The gelatin concentration in the coating solution used for coating the layer farthest from the body is 6% by mass or more, and a vinyl sulfone-based hardener and the following general formula [HI] or general formula [HI] H-II]. A method for producing a silver halide photographic material, comprising: Embedded image Wherein R ₁ is a chlorine atom, a hydroxy group, an alkyl group,
An alkoxy group, an alkylthio group, a —OM ₁ group (M ₁ is a monovalent metal atom), a —NR ₅ R ₆ group (R ₅ and R ₆ are each a hydrogen atom, an alkyl group, an aryl group) or —NHCO
R _{7 represents a} group (R ₇ represents a hydrogen atom, an alkyl group or an aryl group), and R ₂ represents a group having the same meaning as R ₁ except for a chlorine atom. ] [Wherein, R ₃ and R ₄ are each a chlorine atom, a hydroxy group, an alkyl group, an alkoxy group or a —OM ₁ group (M ₁
Represents a monovalent metal atom). Q ₁ and Q ₂ are each-
L represents a linking group selected from O-, -S-, and -NH-, and represents an alkylene group or an arylene group. l and m each represent 0 or 1. ] 4. A method for producing a silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive layer on a support, wherein the humidity is 40% R
A method for producing a silver halide photographic light-sensitive material, comprising: winding at the end of coating in a state of not less than H and not more than 70% RH, followed by heat treatment in a state of not less than 30 ° C and not more than 40 ° C.