JP2006071703A - Silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material free of image unevenness and excellent in crazing resistance. <P>SOLUTION: For the silver halide photographic sensitive material having a hydrophilic colloidal layer on a side of a support opposite to a silver halide emulsion layer, the time from coating to cooling of the hydrophilic colloidal layer is ≤1 s. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a printing proof for confirming the finished product in advance, and more particularly to a silver halide photographic light-sensitive material having no image unevenness and excellent crack resistance.

  Silver halide photographic light-sensitive materials (hereinafter also referred to as light-sensitive materials) have high sensitivity, excellent color reproducibility, and are suitable for continuous processing. Therefore, not only in the general photographic field but also in the printing field, In the middle of printing, it has come to be widely used in the field of so-called proof for checking the finished state of the final printed matter in advance.

  In the proof field, an image edited on a computer is formed on a color photographic paper, which is a photosensitive material, using a printing film that outputs the image, and the final printed matter layout and color suitability are judged. It has been broken. That is, yellow (Y), magenta (M), and cyan are placed on a flat original table and subjected to scanning exposure using a light source such as a fluorescent lamp, and the film is subjected to decomposition exposure while appropriately replacing the film. Each image of (C) is formed on color photographic paper.

  However, in recent years, so-called digitization has progressed in the field of printing, and there is an increasing demand for obtaining images directly from data in a computer. As an example of an image forming method of a photosensitive material that obtains a proof without using a medium such as a film in the middle, there is a method of holding the photosensitive material with an external exposure drum. That is, after the photosensitive material is cut to an appropriate size, it is closely attached to an exposure drum having suction holes or the like under reduced pressure, and the exposure head is moved in parallel with the rotation axis while rotating the exposure drum. Scanning exposure is performed while modulating the light source with a digital signal. By changing the wavelength of the exposure light source, yellow (Y), magenta (M), and cyan (C) images are formed.

  However, the above-described method using a flat document table is suitable for scanning exposure using a fluorescent lamp or the like, but in an exposure method using a light beam using a laser or LED, the optical system becomes large and complicated. As a result, it becomes very expensive, which is not preferable.

  In addition, in the exposure method using the outer surface exposure drum, in order to complete the exposure in a short time, it is necessary to rotate the exposure drum at a high speed or to make a multi-channel to increase the number of exposure light sources (number of channels). When rotated at high speed, the photosensitive material is easily detached from the drum due to centrifugal force and resistance to air. In order to avoid this, it is necessary to increase the degree of reduced-pressure adhesion to the exposure drum. However, if it is increased too much, the effect of image unevenness or the like is likely to occur due to the influence of the drum surface such as a suction hole.

  In addition, in the case of multi-channeling, the exposure head portion becomes large and cost increases cannot be avoided, and image unevenness due to variations in each channel tends to occur.

Alternatively, the smoother value on the side not containing the silver halide emulsion is defined using a transparent film, but when a reflective support, particularly a thin reflective support, is used, there is a slight effect on image unevenness. Although there is, the curl problem has not been solved. (For example, see Patent Document 1)
Furthermore, although it is characterized by the mass ratio of fine powder to gelatin and the pH of the gelatin layer being higher than the isoelectric point of gelatin, it is effective against curling but hardly effective against image unevenness. . (For example, see Patent Document 2)
Further, the balance of the amount of gelatin applied on the emulsion side and the opposite side of the support is regulated, but it has been found that curl is effective but image unevenness is not effective. (For example, see Patent Document 3)
Japanese Patent Application Laid-Open No. 5-224348 Japanese Patent Laid-Open No. 9-304899 JP 2000-181014 A

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a silver halide photographic light-sensitive material having no image unevenness and excellent crack resistance.

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

(Claim 1)
A silver halide photographic light-sensitive material having a hydrophilic colloid layer on the opposite side of a silver halide emulsion layer with a support interposed therebetween, wherein the time required for coating and cooling the hydrophilic colloid layer is 1 second or less. A silver halide photographic light-sensitive material.

(Claim 2)
2. The silver halide photographic light-sensitive material according to claim 1, wherein the time from application of the hydrophilic colloid layer to cooling is 0.5 second or less.

(Claim 3)
In a silver halide photographic light-sensitive material having a hydrophilic colloid layer on the side opposite to the silver halide emulsion layer with a support interposed therebetween, the hydrophilic colloid layer contains a matting agent, and the coating amount A ( The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the relationship between g / m ² ) and matting agent coating amount B (g / m ² ) satisfies the following general formula (1).

General formula (1)
0.05 ≦ B / A ≦ 0.15
(Claim 4)
4. The silver halide photographic light-sensitive material according to claim 1, wherein the support is a paper support coated with polyolefin.

  The silver halide photographic light-sensitive material according to the present invention is free from image unevenness and has an effect of excellent crack resistance.

  The present invention will be described in detail below.

  The present invention is characterized in that after applying the hydrophilic colloid layer, it is cooled in 1 second or less. Preferably it is 0.5 second or less. Specifically, the coated photosensitive material is exposed to an atmosphere of 15 ° C. or lower. Preferably, the photosensitive material is exposed to an atmosphere of 10 ° C. or lower, more preferably 5 ° C. or lower. Cooling is performed until the coating film is gelled and fixed. According to the method described in JP-A-2000-189875, the cooling method is preferably a cooling method in a box called a cooling set zone in which cold air of 15 ° C. or less can be blown onto the coating film. The lower limit is 0.1 seconds or more.

  In this invention, after passing through the said cooling process, it is preferable to dry at 30-80 degreeC.

  Drying is performed until the moisture in the coating film is evaporated, and the surface temperature of the heated support is adjusted to 20 to 70 ° C, preferably 25 to 60 ° C.

  In the present invention, when a plurality of cooling methods are used in combination, the time from one cooling step to another cooling step is 1 second or less, preferably the two cooling steps overlap or the two cooling steps are Preferably, they overlap or the two cooling steps are continuous and cooling can continue.

  The coating method in the present invention is not particularly limited, such as curtains, slides, extrusions, rods, blades or rolls. However, when performing multi-layer coating in which a plurality of layers are coated simultaneously, a curtain coater or a slide coater is preferable.

  The material of the matting agent used in the present invention may be either organic or inorganic. Examples of inorganic materials include silica described in Swiss Patent No. 330,158 and French Patent No. 1,296,995. The described glass powder, alkaline earth metals or carbonates such as cadmium and zinc described in British Patent No. 1,173,181 can be used.

  Examples of organic substances include starch derivatives described in US Pat. No. 2,322,037, starch derivatives described in Belgian Patent No. 625,451 and British Patent No. 981,198, and Japanese Patent Publication No. 44-3643. Polyvinyl alcohol described in US Pat. No. 330,158, polystyrene or polymethacrylate described in US Pat. No. 3,079,257, polyacrylonitrile described in US Pat. No. 3,022,169, etc. The described polycarbonate or the like can be used.

  Further, as the matting agent used in the present invention, amorphous silica, boron nitride, aluminum nitride, spherical silica, titanium dioxide, magnesium oxide, aluminum oxide, calcium carbonate, hydroxyapatite, magnesium carbonate, barium sulfate, strontium sulfate, polymethacrylate , Polymethyl acrylate, polystyrene, polyacrylonitrile, cellulose acetate, cellulose propionate, silicone, Teflon (registered trademark), and the like. In addition, a material in which wax or silicone oil is impregnated to give the fine particles a slip property, or a surface modified with a silane coupling agent or a titanium coupling agent can be used.

The shape of the matting agent may be either a regular shape or an irregular shape, but is preferably a regular shape, and a spherical shape is preferably used. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle size of the matting agent is preferably 0.5 to 10 μm, more preferably 1.0 to 8.0 μm. More preferably, both of those having an average particle diameter of 4 μm or less and a matting agent having an average particle diameter larger than 4 μm are used. The variation coefficient of the particle size distribution is 40% or less, more preferably 30% or less.
Here, the variation coefficient of the particle size distribution is a value represented by the following formula.

(Standard deviation of particle size) / (Average particle size) × 100
The matting agent used in the present invention can be contained in the silver halide emulsion layer side and the back surface constituting layer, but in order to achieve the object of the present invention, it is preferably a back surface constituting layer, more preferably a support. This is the outermost back surface constituent layer (outermost surface layer) as viewed from the top.

  The method for adding the matting agent used in the present invention may be a method in which the matting agent is dispersed and applied in advance in the coating solution, or a method of spraying the matting agent after the coating solution is applied and before the drying is completed. It may be used. Further, when a plurality of types of matting agents are added, both methods may be used in combination.

  In the present invention, gelatin is preferably used as the hydrophilic colloid. In particular, the gelatin extract was treated with hydrogen peroxide to remove the colored components of gelatin, extracted from the raw material ossein treated with hydrogen peroxide, or manufactured from uncolored raw bone By using ossein, gelatin with improved transmittance can be obtained. The gelatin may be any of alkali-treated ossein gelatin, acid-treated gelatin, gelatin derivatives, and modified gelatin, but alkali-treated ossein gelatin is particularly preferable.

In the present invention, the hydrophilic colloid layer contains a matting agent, and the relationship between the hydrophilic colloid coating amount A (g / m ² ) and the matting agent coating amount B (g / m ² ) is expressed by the following general formula (1). ) Is preferably satisfied.

General formula (1)
0.05 ≦ B / A ≦ 0.15
If it is lower than 0.05, image unevenness occurs, and if it is higher than 0.15, cracks are likely to occur.

The support of the present invention, using paper, preferably has a weight (basis weight) is 50 to 300 g / m ^2, more preferably from 80 to 150 g / m ^2.

  The substrate (base paper) of the support can be selected from raw materials generally used for photographic printing paper. For example, natural paper, synthetic pulp, a mixture of natural pulp and synthetic pulp, as well as various types of combined paper materials can be mentioned. Natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood and hardwood pulp, and the like can be widely used.

  Furthermore, additives such as a sizing agent, a fixing agent, a strength enhancer, a filler, an antistatic agent, a dye, and a fluorescent brightening agent that are generally used in papermaking may be blended in the support. A sizing agent, a surface strengthening agent, an antistatic agent, or the like may be appropriately applied to the surface.

  The thickness of the reflective support is preferably 70 to 200 μm, more preferably 90 to 150 μm. The surface of the reflective support is smooth, and the resin for laminating both surfaces is a homopolymer such as ethylene, α-olefins such as polypropylene, at least two copolymers of the olefins or these. It can be selected from a mixture of at least two kinds of various polymers. Particularly preferred polyolefin resins are low density polyethylene, high density polyethylene or mixtures thereof.

The molecular weight of the polyolefin resin laminated on the reflective support is not particularly limited, but is usually preferably in the range of 20,000 to 200,000.
The polyolefin used for laminating the back side (BC side) of the reflective support is usually a melt laminate of a mixture of low density polyethylene and high density polyethylene itself. In general, this layer is often matted.

  In general, the laminate on both sides of the reflective support can be formed by melt extrusion coating the polyolefin resin composition on the support. Moreover, it is preferable to perform corona discharge treatment, flame treatment, or the like on the surface of the support or on both the front and back surfaces as necessary. Moreover, it is preferable to provide a subcoat layer for improving the adhesion to the hydrophilic colloid layer on the surface of the laminate layer, or a backcoat layer for improving the print writing property and antistatic property on the laminate layer on the back surface.

  The polyolefin resin used for the laminate on the surface of the reflective support (the side on which the silver halide emulsion layer is provided) is preferably 13 to 20% by mass, more preferably 15 to 20% by mass, white pigment dispersed and mixed. As white pigments, inorganic and organic white pigments can be used, preferably inorganic white pigments, such as alkaline earth metal sulfates such as barium sulfate, alkalis such as calcium carbonate, and the like. Examples include earth metal carbonates, finely divided silicic acid, synthetic silicate silicas, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, and clay. Among these, barium sulfate, calcium carbonate, and titanium oxide are preferable, and barium sulfate and titanium oxide are more preferable. Titanium oxide may be a rutile type or anatase type, and those whose surfaces are coated with a metal oxide such as hydrous alumina or hydrous ferrite are also used. In addition, it is preferable to add an antioxidant, a colored pigment for improving whiteness, and a fluorescent brightening agent.

  In addition, it is preferable to coat 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.

  The shape of the surface of the reflective support may be smooth or may have an appropriate surface roughness, but it is preferable to select a reflective support that has a gloss close to that of printed matter. For example, it is preferable to use a white support having an average surface roughness SRa defined in JIS-B-0601-1976 of 0.30 to 3.0 μm.

  Blue photosensitive emulsion, green photosensitive emulsion, red photosensitive emulsion, and infrared photosensitive emulsion are at least 6 times the sensitivity of other emulsions at that wavelength in the spectral sensitivity region of any emulsion. Is desirable. Here, the sensitivity is the reciprocal of the exposure amount necessary for setting the density of a certain image layer to a density of (maximum density−0.3). More preferably, it is 8 times or more.

  Each photosensitive emulsion can be realized by selecting and sensitizing a conventionally known spectral sensitizing dye.

  In another embodiment of the present invention, a yellow image, a magenta image, and a cyan image are formed with three types of photosensitive emulsions, that is, an infrared photosensitive emulsion, a green photosensitive emulsion, and a red photosensitive emulsion. The combination of the three types of photosensitive emulsion and the image to be formed can be arbitrarily selected. This form is particularly 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 at the same time when bleaching silver generated in an image-like manner, a dye is simultaneously bleached to form a positive image. Photosensitive materials using a silver dye bleaching method and photosensitive materials using a color diffusion transfer method are also included in the present invention.

  The grain size of each emulsion of the light-sensitive material of the present invention can be selected from a wide range in consideration of the required performance, particularly various performances such as sensitivity, sensitivity balance, color separation, sharpness, and graininess. .

  The silver halide emulsion used in the light-sensitive material of the present invention is a surface latent image type silver halide emulsion that forms a latent image on the surface by image exposure, and a silver halide emulsion that forms a negative image by development. But you can. In addition, an internal latent image type silver halide emulsion whose grain surface is not previously fogged is used. After image exposure, fog processing (nucleation processing) is performed, and then surface development is performed, or after image exposure, fog processing is performed. Those capable of directly obtaining a positive image by performing surface development while applying are also preferably used. An emulsion containing an internal latent image type silver halide emulsion grain means a silver halide grain having a photosensitive nucleus mainly inside a silver halide crystal grain and forming a latent image inside the grain upon exposure. Contains emulsion.

  The fogging treatment may be performed by exposing the entire surface, chemically using a fogging agent, using a strong developer, or by heat treatment.

  The entire surface exposure is performed by immersing the image-exposed photosensitive material in a developer or other aqueous solution or moistening, and then uniformly exposing the entire surface. The light source used here may be any light source as long as it has light in the photosensitive wavelength region of the photosensitive material, and can be exposed to high-intensity light such as flash light for a short time. May be applied for a long time. The overall exposure time can be varied over a wide range so that the best positive image is finally obtained, depending on the photosensitive material, development processing conditions, type of light source used, and the like. Further, the exposure amount of the entire surface exposure is preferably given in a certain range in combination with the photosensitive material. Usually, when an excessive exposure amount is given, the minimum density increases and desensitization tends to occur, and the image quality tends to deteriorate.

  As the technique of the fogging agent that can be used for the light-sensitive material, it is preferable to use the technique described in JP-A-6-95283, page 18, right column, line 39 to page 19, left column, line 41.

  The non-fogged internal latent image type silver halide grains that can be used in the light-sensitive material of the present invention mainly form a latent image inside the silver halide grains and have most of the photosensitive nuclei inside the grains. An emulsion having silver halide grains, including any silver halide such as silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, etc. .

Particularly preferably, a portion of the sample coated on the transparent support so that the amount of coated silver is in the range of about 1 to 3.5 g / m ² is determined from about 0.1 seconds to about 1 second. The same when developed at 20 ° C. for 4 minutes using the following surface developer A which is exposed to a light intensity scale over a long period of time and develops only the surface image of grains substantially free of silver halide solvent. Another portion of the emulsion sample is also exposed and developed at 20 ° C. for 4 minutes with the following internal developer B which develops the image inside the grains, and the maximum density not greater than 1/5 of the maximum density obtained. Is an emulsion. More preferably, the maximum density obtained using surface developer A is not greater than 1/10 of the maximum density obtained with internal developer B.
(Surface developer A)
Metol 2.5g
L-ascorbic acid 10.0g
Sodium metaborate (tetrahydrate) 35.0g
Potassium bromide 1.0g
1000ml with water
(Internal developer B)
Metol 2.0g
Sodium sulfite (anhydrous) 90.0g
Hydroquinone 8.0g
Sodium carbonate (monohydrate) 52.5g
Potassium bromide 5.0g
Potassium iodide 0.5g
1000ml with water
Further, the internal latent image type silver halide emulsion preferably used in the present invention includes those prepared by various methods. For example, conversion type silver halide emulsions described in US Pat. No. 2,592,250, or US Pat. Nos. 3,206,316, 3,317,322 and 3,367,778 A silver halide emulsion having internally chemically sensitized silver halide grains, or a polyvalent metal ion described in US Pat. Nos. 3,271,157 and 3,447,927; A silver halide emulsion having a weakly chemically sensitized grain surface of a silver halide grain containing a dopant described in U.S. Pat. No. 3,761,276, or A silver halide emulsion comprising grains having a laminated structure described in JP 50-8524, 50-38525, 53-2408, etc. Silver halide emulsions or the like as described in JP and Nos 55-127549.

  The shape of the silver halide grains used in the present invention is any of cubic, octahedron, 14-hedron composed of a mixture of (100) face and (111) face, shape having (110) face, spherical shape, flat plate shape, etc. There may be. An average particle diameter of 0.05 to 3 μm can be preferably used. The particle size distribution may be a monodispersed emulsion having a uniform particle size and crystal habit, or an emulsion having no uniform particle size or crystal habit. It is preferable that

In the present invention, the monodispersed silver halide emulsion is one in which the mass of silver halide contained within a grain size range of ± 20% around the average grain size rm is 60% or more of the total silver halide grain mass. That is, it is 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 maximized (three significant digits, the smallest digit is Round to 4). The particle diameter referred to here is the diameter in the case of spherical silver halide grains, and the diameter when the projected image is converted into a circular image of the same area in the case of grains other than a spherical shape. . The particle size can be obtained by, for example, photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times and measuring the particle diameter on the print or the projected area (the number of measured particles is not limited). It is assumed that there are 1000 or more in discrimination).

Particularly preferred highly monodisperse emulsions are:
(Standard deviation of particle size / average particle size) × 100 = width of distribution (%)
The width of the distribution defined by is 20% or less. Here, the average particle size and the particle size standard deviation are determined from ri defined above.

  A monodispersed emulsion can be obtained by adding a water-soluble silver salt solution and a water-soluble halide solution to a gelatin solution containing seed grains by a double jet method under the control of pAg and pH. In determining the addition rate, JP-A Nos. 54-48521 and 58-49938 can be referred to. As a method for obtaining a more advanced monodisperse 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 monodispersed emulsions to the same color sensitive layer.

  The silver halide grain size of each emulsion layer can be determined from a wide range in consideration of required properties, particularly sensitivity, sensitivity balance, color separation sharpness, graininess and the like.

  In one preferred embodiment of the present invention, the silver halide grain size is 0.1 to 0.6 μm for the red-sensitive emulsion, 0.15 to 0.8 μm for the green-sensitive emulsion, and 0 for the blue-sensitive emulsion. A range of 3 to 1.2 μm can be preferably used.

  The photosensitive material preferably contains a nitrogen-containing heterocyclic compound having a mercapto group. As preferred compounds, general formula [XI] described in JP-A-6-95283, page 19, right column, lines 20 to 49, particularly preferably the general formula described in the same publication, page 20, left column, line 5 to page 20, right column, line 2; [XII], general formula [XIII], and general formula [XIV]. Specific examples of the compound include compounds (1) to (39) described in, for example, JP-A 64-73338, pages 11 to 15.

The mercapto compound may be appropriately added depending on the type of compound used and the layer to be added. Generally, when added to a silver halide emulsion layer, the mercapto compound is added in an amount of 10 ⁻⁸ to 10 ⁻⁸ per mol of silver halide. ^{It is in} the range of ⁻² mol, more preferably 10 ⁻⁶ to 10 ⁻³ mol.

  In the silver halide photographic light-sensitive material according to the present invention, the yellow image-forming silver halide emulsion layer, the magenta image-forming silver halide emulsion layer, and the cyan image-forming silver halide emulsion layer have different spectral sensitivity wavelength regions. And at least one of the yellow, magenta and cyan image-forming silver halide emulsion layers is contained in the yellow, magenta and cyan image-forming silver halide emulsion layers. It is preferable that a silver halide emulsion having a spectral sensitivity portion common to any emulsion having different spectral sensitivity wavelength regions is contained.

  As the magenta coupler used in the light-sensitive material according to the present invention, a compound represented by the general formula [M-1] described in the right column of page 7 of JP-A-6-95283 is preferable because of its good spectral absorption characteristics. Specific examples of preferred compounds include compounds M-1 to M-19 described on pages 8 to 11 of the publication. Furthermore, other specific examples include compounds M-1 to M-61 described in European Published Patent No. 0273712 pages 6 to 21 and compounds 1 to 223 described in European Published Patent No. 0359913 pages 36 to 92. There are other than the above-described representative examples.

The magenta coupler can be used in combination with other types of magenta couplers and is usually 1 × 10 ⁻² mol to 1 mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻¹ mol per mol of silver halide. Can be used in a range.

  The λmax of spectral absorption of the magenta image formed in the photosensitive material according to the present invention is preferably 530 to 560 nm, and λL0.2 is preferably 580 to 635 nm.

  Here, λL0.2 and λmax of spectral absorption of the magenta image formed by the photosensitive material according to the present invention are amounts measured by the following method.

  That is, the density of the ND filter is adjusted so that the maximum value of the absorbance of the magenta image when the spectral absorption is measured is developed by applying green light through the ND filter. λL0.2 is a wavelength at which the absorbance of the magenta image is 0.2 longer than the wavelength at which the maximum absorbance is 1.0 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 a magenta coupler. The difference in pKa between these couplers is preferably within 2 and more preferably within 1.5. A preferred yellow coupler to be contained in the magenta image forming layer according to the present invention is a coupler represented by the general description [Y-Ia] described in JP-A-6-95283, page 12, right column. Among the couplers represented by the general formula [Y-1] of the same publication, particularly preferred are couplers represented by [M-1] when combined with a magenta coupler represented by the general formula [M-1]. It is a coupler having a pKa value not lower than 3 by the pKa.

  Specific examples of yellow couplers include compounds Y-1 and Y-2 described on pages 12 to 13 of JP-A-6-95283, and compounds described on pages 13 to 17 of JP-A-2-139542 ( Y-1) to (Y-58) can be preferably used, but of course not limited thereto.

  In the light-sensitive material according to the present invention, a known phenol-based, naphthol-based or imidazole-based coupler can be used as the cyan coupler contained in the cyan image forming layer. Representative examples include phenol couplers substituted with alkyl groups, acylamino groups, or ureido groups, naphthol couplers formed from a 5-aminonaphthol skeleton, and 2-equivalent naphthol couplers introduced with an oxygen atom as a leaving group. Is done. Among these, preferred compounds include the general formula [CI] [C-II] described in JP-A-6-95283, page 13.

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

  In the light-sensitive material according to the present invention, a known acylacetanilide coupler or the like can be preferably used as the yellow coupler contained in the yellow image forming layer.

  Specific examples of the yellow coupler include compounds represented by YI-1 to YI-55 described on pages 5 to 9 of JP-A-3-241345, or 11 to 11 of JP-A-3-209466. Compounds represented by Y-1 to Y-30 described on page 14 can also be preferably used. Furthermore, the coupler etc. which are represented by general formula [YI] of page 21 of Unexamined-Japanese-Patent No. 6-95283 can also be mentioned.

  The λmax of the spectral absorption of the yellow image formed by the photosensitive material according to the present invention is preferably 425 nm or more, and λL0.2 is preferably 515 nm or less. Here, λL0.2 is defined for the yellow image as in the case of the magenta image.

The yellow coupler can be used usually in the range of 1 × 10 ⁻² to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol per mol of silver halide in the silver halide emulsion layer.

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

  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 laminated and applied on the support, but 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 to this, an intermediate layer, a filter layer, a protective layer, and the like can be disposed as necessary.

  Each of the magenta, cyan, and yellow couplers can be used in combination with an anti-fading agent in order to prevent fading due to light, heat, humidity, and the like of the formed dye image. 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. An amine compound represented by the general formula A described in JP-A-64-90445 and a metal complex represented by the general formulas XII, XIII, XIV and XV described in JP-A-62-187441 are particularly preferable for magenta dyes. . Further, compounds represented by the general formula I ′ described in JP-A-1-196049 and 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 emulsion dispersion method used to add couplers and other organic compounds used in the light-sensitive material according to the present invention is usually low in water-insoluble high-boiling organic solvents having a boiling point of 150 ° C. or higher. It dissolves using a boiling point and / or a water-soluble organic solvent in combination, and is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant.

  As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used.

  A step of removing the low-boiling organic solvent after the dispersion or simultaneously with the dispersion may be added. As the high-boiling organic solvent that can be used for dissolving and dispersing couplers 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. High boiling point 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. Moreover, as a dielectric constant of a high boiling point organic solvent, it is preferable that it is 3.5-7.0. Two or more high-boiling organic solvents can be used in combination.

  As a preferable compound as a surfactant used for dispersion of photographic additives used in the light-sensitive material according to the present invention and adjustment of surface tension during coating, a hydrophobic group having 8 to 30 carbon atoms and sulfone in one molecule. The thing containing an acid group or its salt is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant having a fluorine atom substituted on an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is preferable that the time required for addition to the coating solution after dispersion and the time required for coating after addition to the coating solution are short, and each 10 Within hours, preferably within 3 hours, and more preferably within 20 minutes.

  In the light-sensitive material according to the present invention, a compound that reacts with the oxidized developer is added to the layer between the light-sensitive layer to prevent color turbidity, or added to the silver halide emulsion layer to cause fogging, etc. It is preferable to improve. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula II described in JP-A-4-13356, and examples thereof include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17.

  In the light-sensitive material according to the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of a dye image. Preferred ultraviolet absorbers include benzotriazoles. Particularly preferred compounds include compounds represented by general formula III-3 described in JP-A-1-250944, and general formula III described in JP-A-64-66646. The compounds shown, UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula I described in JP-A-4-16333, and general formula (I) described in JP-A-5-165144 And compounds represented by (II).

  The light-sensitive material according to the present invention preferably contains an oil-soluble dye or pigment, since the white background is improved. Typical examples of oil-soluble dyes include compounds 1-27 described on 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 spectral sensitivity wavelength of the cyan image-forming silver halide emulsion layer is preferably 0.7 or more. The above light-sensitive material can be obtained by incorporating a coloring material such as a dye having absorption at the above-mentioned wavelength or 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 silver halide emulsion layer and / or other hydrophilic colloid photographic composition layer. 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 other hydrophilic colloid photographic constituent layer. Can be contained as a solid dispersion.

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

  Specific examples of the dyes represented by [I] to [VIII] among the general formulas [I] to [IX] include, for example, I-1 to VIII- described in JP-A-4-18545, pages 13 to 35. However, the present invention is not limited to these.

  The layer containing the dye or colloidal silver is not particularly limited, but is preferably contained in the 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 with a commonly used sensitizing dye. It is also useful for the silver halide emulsion of the present invention to use a combination of sensitizing dyes used for supercolor sensitization such as an internal latent image type silver halide emulsion and a negative type silver halide emulsion. Regarding the sensitizing dye, Research Disclosure (hereinafter abbreviated as RD) 15162 and 17643 can be referred to.

  It is preferable to add a compound for adjusting the step gradation to the photosensitive material according to the present invention. As a preferable compound, a compound represented by the general formula [AO-II] described on page 17 of JP-A-6-95283 is preferable. Preferable compound examples include compounds II-1 to II-8 described on page 18 of the publication.

The addition amount of the compound of [AO-II] is preferably 0.001 to 0.50 g / m ² , more preferably 0.005 to 0.20 g / m ² . A compound may be used independently and may use 2 or more types together. Furthermore, a quinone derivative having 5 or more carbon atoms can be used by adding to the compound [AO-II]. However, in any of these cases, the amount used is preferably in the range of 0.001 to 0.50 g / m ² as a whole.

  In order to form an image using the photosensitive material according to the present invention, it is preferable to use a light source scanning exposure type automatic developing machine. Specific examples of particularly preferable devices and systems for image formation include Digital Konsensus manufactured by Konica.

  The present invention is preferably applied to a photosensitive material in which a developing agent is not incorporated in the photosensitive material, and is particularly preferably applied to a photosensitive material that forms an image for direct viewing having a reflective support. For example, a photosensitive material for color proof can be mentioned.

  In the present invention, it is preferable that the photosensitive material wound in a roll is loaded in advance in a cartridge that can be handled in a bright room. In cartridges that can be handled in a bright room, there is a means to shield the photosensitive material in the bright room from receiving light, and at the same time, there is a photosensitive material drawer that can be smoothly pulled out of the cartridge when it is installed in equipment. Normally, when handled in a bright room, the photosensitive material therein is not exposed to light.

  In the present invention, it is preferable that the light-sensitive material wound in a roll is loaded in advance in the bright room cartridge, and that the emulsion surface of the light-sensitive material is wound outside the roll.

  Various types of bright room cartridges have been proposed, but all known bright room cartridges can be used. In addition, by covering the outer periphery of the roll photosensitive material having a light-shielding flange with a light-shielding reader, the photosensitive material can be handled in a bright room while being shielded from light, and after loading the exposure apparatus, a dark room is required by removing the leader. In addition, a so-called easy-loading photosensitive material that can easily be loaded with a roll of photosensitive material in the apparatus is also included in the bright room cartridge in the image forming method of the present invention. In that case, readable information can be given to the reader, or can be given to a flange or the like.

  On the other hand, the core around which the roll is wound (hereinafter referred to as the core) has strength, moisture resistance, stretchability, surface shape and slipperiness with respect to the innermost surface of the photosensitive material, how the photosensitive material is pressed by the cushion, and further to cost and photosensitive material. It is preferable to make a comprehensive determination in terms of the influence of the above. Specifically, natural paper such as virgin pulp, waste paper, recycled paper, synthetic paper, plastic or a moisture-proof film, metal foil, metal-deposited film, and laminate around it, as well as polyurethane foam, foamed polyethylene sheet on its surface, A foamed polyethylene paper or the like laminated to give cushioning properties can be appropriately employed.

  In the present invention, it is preferable that the photosensitive material is coated and then wound around a core having a diameter of 70 to 100 mm and stored after being stored at 25 to 40 ° C. for 3 to 10 days. More preferably, it is wound around a core of 70 to 85 mm and stored under conditions of 30 to 40 ° C.

  Next, the process will be described. The light-sensitive material or the developing solution according to the present invention preferably contains a fluorescent brightening agent in order to improve the white background.

  When developing the light-sensitive material according to the present invention, the color developer, bleach-fix solution, and stabilizing solution are replenishment color developer, replenishment bleach solution, replenishment fixing solution, replenishment bleach-fixing solution, and replenishment stability, respectively. The development process can be continuously performed while replenishing the forming solution.

  In the development processing of the light-sensitive material according to the present invention, examples of color developing agents that can be used in a color developer 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 conventional silver halide developers such as polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, and mixtures thereof. Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl -4-hydroxymethyl-3-pyrazolidone, ascorbic acid, and the like. All or a part of these developing agents may be previously contained in the light-sensitive material so as to act on silver halide during immersion in a high pH aqueous solution.

  The color developer used for processing the photosensitive material according to the present invention may further contain a specific antifoggant and a development inhibitor, or these developer additives may be contained in the constituent layers of the photosensitive material. It is also possible to incorporate arbitrarily.

  In the present invention, the color developer can be used in any pH range, but from the viewpoint of rapid processing, the pH is preferably from 9.5 to 13.0, more preferably from 9.8 to 12.0. It is used in the range.

  The processing temperature for color development is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature, the shorter the treatment is possible and the better. However, it is preferable that the temperature is not so high from the stability of the treatment liquid, and the treatment is preferably performed at 37 ° C. or more and 60 ° C. or less.

  A known developer component compound can be added to the color developer in addition to the color developing agent. For example, a development inhibitor such as an alkaline agent having a pH buffering action, chloride ion, or benzotriazole, a retention agent. Fixing agents, chelating agents, etc. are used.

  The light-sensitive material according to the present invention may be subjected to bleaching and fixing after color development, and the bleaching may be performed simultaneously with the fixing. After the fixing process, it is usually preferable to perform a stabilizing process, adjust the pH with various alkaline agents, and set the film surface pH of the photosensitive material after the process to dry to 7 or less.

  As an example of the method for measuring the film surface pH, after leaving the photosensitive material in an atmosphere of 23 ° C. and 55% RH for 24 hours, two drops of 0.3 mol / L potassium nitrate aqueous solution are dropped on the surface with a pipette, It can be determined by contacting a membrane surface pH electrode (GST-5213F) manufactured by Toa Denpa Co., Ltd., equilibrating for 3 minutes, and reading the pH value.

  In the photographic material according to the present invention, further known photographic additives can be used, and examples thereof include compounds described in RD17643 and RD18716 shown in Table 1.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the embodiment of this invention is not limited to these.

Example 1
On the back side (back coat layer), the BC-1 layer and BC-2 layer are arranged in the order of BC-1 layer and BC-2 layer from the side closer to the support, as shown in Table 2, and the gelatin and hardener (H -1 and 20 mg per 1 g of gelatin are added to the BC-2 layer), and silica matting agent (Silicia 430 manufactured by Fuji Silysia Chemical Co., Ltd.) is applied in the amounts shown in Table 2 and disclosed in JP-A 2000-189876. A multilayer silver halide photographic light-sensitive material was produced by changing the temperature and time until cooling shown in Table 2 at a coating speed of 250 m / min. In addition, drying after cooling was performed at 40 ° C. until there was no moisture in the sample.

  A silver halide emulsion layer was coated on the front side of the dried sample according to the following procedure.

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 and an aqueous solution containing potassium bromide were simultaneously added by a controlled double jet method to obtain cubic silver bromide having a particle size of 0.25 μm. A core emulsion was obtained. At that time, pH and pAg were controlled so that a cubic shape was obtained as the particle shape.

  To the obtained core emulsion, an aqueous solution further containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (in terms of molar ratio KBr: NaCl = 50: 50) were simultaneously added by the control double jet method to obtain an average. Shells were formed until the particle size was 0.42 μm. At that time, pH and pAg were controlled so that a cubic shape was obtained as the particle shape.

  After washing with water to remove water-soluble salts, gelatin was added to obtain an emulsion EM-P1. The particle size distribution of this emulsion 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 and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5) were controlled by the control double jet method. At the same time, a cubic silver chlorobromide core emulsion having a particle size of 0.18 μm was obtained. At that time, pH and pAg were controlled so that a cubic shape was obtained as the particle shape.

  To the obtained core emulsion, an aqueous solution further containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (in terms of molar ratio KBr: NaCl = 40: 60) were simultaneously added by the control double jet method to obtain an average. Shells were formed until the particle size was 0.25 μm. At that time, pH and pAg were controlled so that a cubic shape was obtained as the particle shape.

  After washing with water to remove water-soluble salts, gelatin was added to obtain an emulsion EM-P2. The particle size distribution of this emulsion was 8%.

  A portion of a sample coated with emulsions EM-P1 and EM-P2 on a transparent cellulose triacetate support so that the amount of coated silver was 2 g / m 2 as silver was exposed to light wedge for 0.5 seconds, The surface developer A was used for development at 20 ° C. for 4 minutes, and a part of other samples were similarly exposed, and then developed with the internal developer B at 20 ° C. for 4 minutes. The maximum density for surface development was about 1/12 of the maximum density for internal development. Thus, it was confirmed that both EM-P1 and EM-P2 were internal latent image type silver halide emulsions.

<< Preparation of green photosensitive silver halide emulsion >>
After sensitizing dye (GS-1) is added to emulsion EM-P1 for optimal color sensitization, 100 mg of inhibitor (T-1) is added per mole of silver to give green-sensitive silver halide emulsion Em-G1. Prepared.
T-1: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene << Preparation of red-sensitive silver halide emulsion >>
Red-sensitive silver halide emulsion in the same manner as green-sensitive silver halide emulsion Em-G1, except that sensitizing dyes (RS-1, RS-2) were added to emulsion EM-P2 for optimum color sensitization Em-R1 was prepared.

<< Preparation of infrared-sensitive silver halide emulsion >>
A green-sensitive silver halide emulsion Em-G1, except that sensitizing dyes (IRS-1, IRS-2) were added to emulsion EM-P2 for optimum color sensitization and an inhibitor (AF-1) was added. In the same manner, an infrared-sensitive silver halide emulsion Em-IFR1 was prepared.
AF-1: Sodium ascorbate monohydrate

<Preparation of multilayer photosensitive material sample>
The following layers are formed on a 110 μm-thick paper pulp reflective support in which high-density polyethylene is laminated on one side and molten polyethylene containing 15% by mass of anatase-type titanium oxide dispersed on the other side. Each layer of the composition was coated on the side of the polyethylene layer containing titanium oxide. The numerical value of each material indicates the coating amount (g / m ² ). The amount of each emulsion added is the amount converted to silver.

<Layer structure of multilayer photosensitive material sample>
Eighth layer (ultraviolet absorption layer) Application amount (g / m ² )
Gelatin 1.60
Ultraviolet absorber (UV-1) 0.200
Surfactant (SU-3) 0.002
Silica matting agent 0.01
Hardener (H-1) 0.008
7th layer (red-sensitive layer)
Gelatin 1.25
Red-sensitive silver halide emulsion (Em-R1) 0.35
Magenta coupler (M-1) 0.25
Yellow coupler (Y-2) 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 point organic solvent (SO-1) 0.38
6th layer (intermediate layer)
Gelatin 0.80
Hydroquinone (HQ) derivative (HQ-2) 0.04
Hydroquinone (HQ) derivative (HQ-3) 0.02
Surfactant (SU-1) 0.002
High boiling point solvent (SO-2) 0.005
Irradiation preventing dye (AI-2) 0.003
Hardener (H-3) 0.010
5th layer (green-sensitive layer)
Gelatin 0.90
Green sensitive silver halide emulsion (Em-G1) 0.37
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 point organic solvent (SO-2) 0.40
Fourth layer (intermediate layer)
Gelatin 0.08
Hydroquinone (HQ) derivative (HQ-2) 0.04
Hydroquinone (HQ) derivative (HQ-3) 0.02
Surfactant (SU-1) 0.001
High boiling point solvent (SO-2) 0.005
Irradiation preventing dye (AI-1) 0.003
Hardener (H-3) 0.010
Third layer (infrared photosensitive layer)
Gelatin 1.10
Infrared photosensitive silver halide emulsion (Em-IFR1) 0.40
Yellow coupler (Y-1) 0.19
Yellow coupler (Y-2) 0.19
Stain inhibitor (HQ-1) 0.04
Surfactant (SU-3) 0.002
Inhibitor (T-1, T-2, T-3, molar ratio 1: 1: 1) 0.004
High boiling point organic solvent (SO-1) 0.30
Second layer (intermediate layer)
Gelatin 1.20
Hydroquinone (HQ) derivative (HQ-2) 0.04
Hydroquinone (HQ) derivative (HQ-3) 0.02
High boiling point solvent (SO-2) 0.005
Sea surface active agent (SU-1) 0.001
Irradiation preventing dye (AI-3) 0.003
Hardener (H-3) 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
Support Polyethylene laminated paper (containing a small amount of colorant)
Details of other additives used in the preparation of the above samples are shown below.

SO-1: Trioctylphosphine oxide SO-2: Di-i-decylphthalate HQ-1: 2,5-di (t-butyl) hydroquinone HQ-2: 2,5-bis [(1,1-dimethyl- 4-hexyloxycarbonyl) butyl] hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone, 2,5-di-sec-tetradecylhydroquinone and 2-sec-dodecyl-5-sec-tetradecylhydroquinone Mixture of mass ratio 1: 1: 2 T-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole T-2: N-benzyladenine T-3: 2-mercaptobenzothiazole

  The obtained sample was subjected to a halftone dot test chart with the following laser scanning exposure apparatus, infrared laser light (semiconductor laser: GaAlAs, λmax; about 780 nm), red laser light (semiconductor laser: AlGaInAs, λmax; about 670 nm), green laser light. (Helium / neon laser, λmax; about 544 nm). Further, the sample was sucked and adhered to the exposure rotating drum, and the rotation was performed at 2000 sheets / minute, and an image was recorded by main scanning and sub scanning. However, at that time, 10 infrared semiconductor lasers were arranged, and the sample was simultaneously exposed as 10 beams of laser light through optical means.

  The exposure rotating drum was prepared as a semi-cylindrical aluminum member having a diameter of 375 mm and a length of 750 mm. In the circumferential direction of this aluminum drum, suction grooves having a width of 1.2 mm and a depth of 0.8 mm (suction holes having a diameter of 1 mm are provided in the grooves at intervals of 100 mm) are provided at intervals of 29 mm, from which blowers (220 V, 50 Hz, Suction was performed at an output of 0.24 kW. The sample was transported from a photosensitive material roll by combining a transport roller and a guide plate, loaded into the exposure rotary drum, and then sucked from the suction hole and brought into close contact with the drum with a squeeze roller. The sample was cut to a length of 850 mm and then sucked into the rotating drum and exposed. The exposure was performed under conditions of 23 ° C. and 20% RH.

The exposed sample was processed by the following processing steps to obtain an image.
(Processing step-1)
Processing Step Temperature Time Immersion (Developer) 37 ° C 12 seconds Fog exposure-12 seconds Development 37 ° C 95 seconds Bleaching fixation 35 ° C 45 seconds Stabilization 25-30 ° C 90 seconds Drying 60-85 ° C 40 seconds (Color developer composition) )
Benzyl alcohol 15.0ml
Ceric sulfate 0.015g
Ethylene glycol 8.0ml
Potassium sulfite 2.5g
Potassium bromide 0.6g
Sodium chloride 0.2g
Potassium carbonate 25.0g
T-1 0.1g
Hydroxylamine sulfate 5.0 g
Sodium diethylenetriaminepentaacetate 2.0g
4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate
4.5g
Optical brightener (4,4'-diaminostilbene disulfonic acid derivative)
1.0g
Potassium hydroxide 2.0g
Diethylene glycol 15.0ml
Add water to a total volume of 1000 ml and adjust to pH 10.15.
(Bleaching fixer composition)
Diethylenetriaminepentaacetic acid ferric ammonium 90.0g
Diethylenetriaminepentaacetic acid 3.0g
Ammonium thiosulfate (70% aqueous solution) 180.0ml
Ammonium sulfite (40% aqueous solution) 27.5 ml
3-mercapto-1,2,4-triazole 0.15 g
Adjust to pH 7.1 with potassium carbonate or glacial acetic acid and add water to bring the total volume to 1000 ml.
(Stabilizing liquid composition)
o-Phenylphenol 0.3g
Potassium sulfite (50% aqueous solution) 12.0ml
Ethylene glycol 10.0g
1-hydroxyethylidene-1,1-diphosphonic acid 2.5 g
Bismuth chloride 0.2g
Zinc sulfate heptahydrate 0.7g
Ammonium hydroxide (28% aqueous solution) 2.0 g
Polyvinylpyrrolidone (K-17) 0.2g
Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g
Add water to a total volume of 1000 ml and adjust to pH 7.5 with ammonium hydroxide or sulfuric acid.

  In addition, the stabilization process was made into the countercurrent system of 2 tank structure.

The prescription of the replenisher when performing the running process is shown below.
(Color development replenisher)
18.5 ml of benzyl alcohol
Ceric sulfate 0.015g
Ethylene glycol 10.0ml
Potassium sulfite 2.5g
Potassium bromide 0.3g
Sodium chloride 0.2g
Potassium carbonate 25.0g
T-1 0.1g
Hydroxylamine sulfate 5.0 g
Sodium diethylenetriaminepentaacetate 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 2.0g
Diethylene glycol 18.0ml
Add water to bring the total volume to 1 liter and adjust to pH 10.35.
(Bleach fixer replenisher)
Same as the bleach-fixing solution.
(Stabilizer replenisher)
Same as the stabilizing solution.

The replenishment amount is a development replenisher of 500 ml / m ²
Bleach fixer 350ml / m ²
Stabilizer 600ml / m ²
It was.

  The following evaluation was performed on the samples before and after the development treatment, and the results are shown in Table 2.

<Crack>
For each sample after coating, the coating quality (cracked state) on the back coat side was visually observed.

  ○: No cracks are observed.

Δ: 1 point to less than 4 points per 1 m ² (no problem in practical use)
×: Cracks 4 to 10 points per 1 m ² (practical problems)
-: Cracks generated on the entire surface (practical problem)
<Image unevenness>
Depending on the type of each sample, the state of close contact with the exposure drum changes, and image unevenness occurs due to floating from the exposure drum, uneven suction grooves due to excessive contact, and the like. About this image nonuniformity, the developed sample was evaluated visually according to the reference | standard shown below.

○: Image unevenness is not observed. Δ: Image unevenness is present, but there is no practical problem. ×: There are many image unevenness and practically problematic. −: Separation from the exposure drum and development processing is impossible.

  As is clear from Table 2, a sample having a hydrophilic colloid layer on the opposite side of the silver halide emulsion layer with the reflective support interposed therebetween, coated with the hydrophilic colloid layer, and cooled in 1 second or less was subjected to image unevenness. It turns out that there are few cracks and it is excellent. Furthermore, when the amount of the hydrophilic colloid and the matting agent applied satisfies the general formula (1), the quality was further improved.

Claims (4)

A silver halide photographic light-sensitive material having a hydrophilic colloid layer on the opposite side of a silver halide emulsion layer with a support interposed therebetween, wherein the time required for coating and cooling the hydrophilic colloid layer is 1 second or less. A silver halide photographic light-sensitive material. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the time from application of the hydrophilic colloid layer to cooling is 0.5 second or less. In a silver halide photographic light-sensitive material having a hydrophilic colloid layer on the side opposite to the silver halide emulsion layer with a support interposed therebetween, the hydrophilic colloid layer contains a matting agent, and the coating amount A ( The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the relationship between g / m ² ) and matting agent coating amount B (g / m ² ) satisfies the following general formula (1).
General formula (1)
0.05 ≦ B / A ≦ 0.15 4. The silver halide photographic light-sensitive material according to claim 1, wherein the support is a paper support coated with polyolefin.