JP2006267212A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing method for a silver halide color photographic sensitive material by which stable images are obtained even under a condition of a small processing quantity. <P>SOLUTION: In the processing method for a silver halide color photographic sensitive material by color development with a color developer containing an aromatic primary amine developing agent, a processing quantity per day is ≤3 m<SP>2</SP>and following formulae (1)-(3) are satisfied; (1): W×Rc/T/1,000≤0.06 (where W represents the processing quantity (m<SP>2</SP>) per day; Rc represents a replenishment quantity (ml/m<SP>2</SP>) of the color developer; and T represents the capacity (l) of a color developer tank of an automatic developing machine), (2): Rc≥15×Ro (where Ro represents a replenishment quantity (ml/h) of the color developer, which is needed to restore the activation level of the developer changed due to oxidation of the developer by air), (3): Ro+10≤Rw≤Ro+50 (where Rw represents a quantity (ml/h) of water replenished per certain unit time). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for processing a silver halide color photographic light-sensitive material that develops color with a color developer containing an aromatic primary amine developing agent, and in particular, a silver halide capable of obtaining a stable image even when the amount of processing is small. The present invention relates to a method for processing a color photographic light-sensitive material.

  Conventionally, a silver halide color photographic light-sensitive material having a white support is used as a method for obtaining a proof from a plurality of black and white halftone images obtained by color separation and halftone image formation conversion in a color plate-making and printing process. A method for producing a color proof is described in JP-A Nos. 56-113139, 62-280746, 62-280747, 62-280748, 62-280747, 62-280750, and the like. .

  On the other hand, a method for converting an image into a digital signal and performing image editing on a computer without using the black and white film of the halftone dot has come to be widely used. By digitizing image information, image processing becomes easy, and it is possible to quickly send an image to a remote place, change the layout and color of the image, and edit the image quickly.

  As a method for outputting an image edited in this way as a color proof, a method of scanning and exposing color paper with LED light or laser light is known, but has various problems in practical use.

  Usually, a silver halide color photographic light-sensitive material is developed by an automatic processor (hereinafter abbreviated as a self-machine), and a replenisher is added according to the processed area.

However, reflecting the recent economic trends, there has been a downward trend in printed matter, and the output amount of the proof has decreased accordingly, and there has been a situation where the automatic processor is in operation but is almost undeveloped. It was. In order to compensate for the increase in pH due to air oxidation of the stopped color developer, it is known to determine the amount of the intrinsic replenisher per unit time and replenish it in an arbitrary manner within the unit time (for example, , See Patent Document 1). This replenishment method was effective when processing photographic light-sensitive materials close to 10 m ² per day, but was hardly effective when only a small amount of 3 m ² or less was used per day.

Further, improvement of the color developer was studied and various preservatives were examined, but sufficient effects were not obtained.
Japanese Patent Application Laid-Open No. H6-282049 (Claims)

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for processing a silver halide color photographic material capable of obtaining a stable image even when the amount of processing is small.

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

(Claim 1)
In the processing method of a silver halide color photographic light-sensitive material that develops color with a color developer containing an aromatic primary amine developing agent, the daily processing amount is 3 m ² or less, and the following formulas (1) to (3) And a method for processing a silver halide color photographic light-sensitive material.

Formula (1) W × Rc / T / 1000 ≦ 0.06
(Wherein, W represents the daily processing amount (m ² ), Rc represents the replenishment amount of the color developer (ml / m ² ), and T represents the color developer tank capacity (L) of the automatic processor. )
Formula (2) Rc ≧ 15 × Ro
(In the formula, Ro represents the amount of oxidation replenishment (ml / hr) of the color developer.)
Formula (3) Ro + 10 ≦ Rw ≦ Ro + 50
(Wherein, Rw represents the amount of water (ml / hr) replenished to the color developer in a fixed unit time.)
(Claim 2)
2. The method for processing a silver halide color photographic material according to claim 1, wherein the color developer contains hydroxylamine sulfate.

(Claim 3)
3. The method for processing a silver halide color photographic material according to claim 1, wherein the color developer contains 0.03 mol / L or less of sulfite ion.

  According to the present invention, it is possible to provide a method for processing a silver halide color photographic material capable of obtaining a stable image even when the amount of processing is small.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

As a result of diligent study, the present inventor has found that the processing amount per day in a processing method of a silver halide color photographic light-sensitive material (hereinafter also referred to as a light-sensitive material) developed with a color developer containing an aromatic primary amine developing agent. There is a 3m ² or less, and the method for processing a silver halide color photographic material which satisfies the following formulas (1) to (3), found that stable images can be obtained with the processing amount is small state, the present invention It is up to you to achieve that goal.

  Hereinafter, the present invention will be described in detail.

  Known compounds can be used as the aromatic primary amine developing agent used in the present invention. Examples of these compounds include the following compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4 : 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5: 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline CD-7: N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8: N, N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10: 4-amino-3-methyl-N- Til-N- (β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline In the present invention, the color developer is used in an arbitrary pH range. Although it can be used, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0 from the viewpoint of rapid processing.

  The processing temperature of the color developer according to the present invention is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature, the shorter the treatment 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.

  In general, the color development time is about 3 minutes 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.

  In addition to the above color developing agent, known developer component compounds can be added to the color developer. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ions and benzotriazoles, a preservative and a chelating agent are used.

In the present invention, the daily throughput of the silver halide color photographic light-sensitive material is characterized by 3 m ² or less, preferably 2 m ² or less.

  A feature of the present invention is that, in the development processing system having a small throughput of the silver halide color photographic light-sensitive material as described above, a color developer replenishment system that simultaneously satisfies the following formulas (1) to (3) is adopted. A stable image can be obtained even with a small amount of processing.

Formula (1) W × Rc / T / 1000 ≦ 0.06
(Wherein, W represents the daily processing amount (m ² ), Rc represents the replenishment amount of the color developer (ml / m ² ), and T represents the color developer tank capacity (L) of the automatic processor. )
As described above, W is characterized by being 3 m ² or less, and preferably 2 m ² or less.

As the amount of the replenisher of the color developing solution in the present invention (Rc), preferably in the range of 100~600ml / m ^2, more preferably in the range of 350~500ml / m ² is preferable in terms of stability of the image density.

  In formula (1), the value of W × Rc / T / 1000 represents the number of rounds per day in the running process, and being within 0.06 means a small amount of process.

Formula (2) Rc ≧ 15 × Ro
(In the formula, Ro represents the amount of oxidation replenishment (ml / hr) of the color developer.)
The oxidation replenishment amount of the color developer as referred to in the present invention means the amount of developer when the automatic developing machine is operated for a certain time (24 hours is desirable) or not operated (in the case of a holiday) without processing the photosensitive material. It can be easily determined by measuring the decrease in sulfite and the increase in pH value per 24 hours with the minimum replenishment amount required to restore the changed activity level due to air oxidation. The amount of oxidation replenishment varies depending on the type of automatic developing machine (difference in the opening area of the developing tank), the processing temperature, and the like, but can be easily obtained if these conditions are determined in advance.

  In addition, there are cases where the automatic processor is operated and not operated, but it is not always necessary to determine the amount of oxidation replenishment of both, and since the air oxidation is larger when it is operated, the oxidation replenishment only when it is operated Find the amount.

  In the present invention, the oxidation replenishment amount (Ro) of the color developer is preferably 1/15 or less of the replenishment amount (Rc) of the normal color developer from the viewpoint of stability of the white background, more preferably 1/20 or less. .

Formula (3) Ro + 10 ≦ Rw ≦ Ro + 50
(Wherein, Rw represents the amount of water (ml / hr) replenished to the color developer in a fixed unit time.)
The amount (Rw) of water replenished to the color developer in a certain unit time is preferably from 10 to 50 ml / hr or less from the viewpoint of image density stability, and more preferably +10 to +10 ml / hr. +30 ml / hr.

  The color developer of the present invention can use various preservatives, but preferably contains 3 to 10 g of hydroxylamine sulfate per liter of the color developer, and further contains 0.03 mol / L or less of sulfite ion. Preferably there is.

In the bleach-fixing process, as the bleach-fixing solution, at least one of the imidazole and derivatives thereof described in JP-A No. 64-295258 or the compounds represented by the general formulas [I] to [IX] described in the same specification and these exemplified compounds are used. It is preferable to contain one kind. In addition to the bleach-fixing accelerators described above, the exemplified compounds described on pages 51 to 115 of JP-A-62-123459 and the pages 22 to 25 of JP-A-63-17445. Exemplified compounds, compounds described in JP-A Nos. 53-95630 and 53-28426, and the like can be used in the same manner.

  In addition to the above, the bleach-fixing agent may contain halides such as ammonium bromide, potassium bromide, and sodium bromide, various optical brighteners, antifoaming agents, and surfactants.

  As a fixing main agent used for the bleach-fixing agent in the present invention, thiocyanate and thiosulfate are preferably used.

  In addition to these fixing agents, bleach-fixing agents include pH buffers, alkylamines, polyethylene oxides, and alkali halides or ammonium halides such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. It is desirable to contain a halogenating agent.

  To the bleach-fixing agent, it is preferable to add a compound represented by the general formula [FA] described in JP-A No. 64-295258, page 56 and this exemplified compound, and not only can the effects of the present invention be improved. Another advantage is that sludge generated in a processing solution having a fixing ability when a small amount of light-sensitive material is processed over a long period of time is extremely small.

  In the present invention, the pH of the bleach-fix solution is preferably from 3 to 5, more preferably from 3.5 to 5.0.

  Preferable compounds to be added to the stabilizer include, for example, ammonium compounds in addition to chelate compounds and fluorescent brighteners. The addition amount of the ammonium compound is preferably in the range of 0.001 to 1.0 mol, and more preferably in the range of 0.002 to 2.0 mol, per liter of the stabilizing solution.

The stabilizer preferably contains sulfite. The stabilizer preferably contains a metal salt in combination with a chelating agent. Examples of such metal salts include Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al, and Sr metal salts. Products, sulfates, carbonates, phosphates, acetates, and other inorganic salts or water-soluble chelating agents. The amount used is preferably in the range of 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, and more preferably in the range of 4 × 10 ⁻⁴ to 2 × 10 ⁻² mol, per liter of the stabilizing solution.

  The washing or stabilization treatment used in the present invention is preferably a multistage counter-current treatment tank, the treatment tank size is generally 3 to 7 L, and the circulation amount of the stable liquid is 2 to 6 L / min. Preferably there is. The time required for washing with water or stabilizing treatment is preferably 20 to 90 seconds for each tank.

  It is preferable that the processing temperature of washing with water or a stabilization process is 35 degreeC or more, More preferably, it is 35-38 degreeC. As the heating means of the water washing or stabilization tank according to the present invention, the stabilizer may be heated using an independent heater, or heated by following temperature control using a heater of a bleach-fixing tank or a developing tank. Also good.

The development processing apparatus used for the development processing of the silver halide photosensitive material of the present invention fixes the photosensitive material to the belt even if it is a roller transport type that conveys the photosensitive material between rollers arranged in a processing tank. The endless belt method may be used, but the processing tank is formed in a slit shape, the processing liquid is supplied to the processing tank, and the photosensitive material is transported and the processing liquid is sprayed. Also, a web system by contact with a carrier impregnated with a treatment liquid, a system by a viscous treatment liquid, or the like can be used. In the case of processing in large quantities, it is preferable that the running processing is performed using an automatic processor. At this time, it is preferable that the replenishment amount of the replenisher is small, and the most preferable processing form from the viewpoint of environmental suitability, etc. The method described in the published technical report 94-16935 is most preferable.

  Next, the silver halide color photographic light-sensitive material according to the present invention will be described.

  One of the preferred forms of the silver halide color photographic light-sensitive material according to the present invention is four kinds of light-sensitive emulsions of an infrared light-sensitive emulsion, a blue light-sensitive emulsion, a green light-sensitive emulsion and a red light-sensitive emulsion. A magenta image, a cyan image, and a black image are formed. The combination of the four types of photosensitive emulsion and the image to be formed can be arbitrarily selected.

  The emulsion for forming a black image may be an 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 image forming layer containing a black coupler, and a plurality of couplers having different maximum wavelengths can be used in place of the black coupler. In addition, a case where the emulsion contributes to image formation of a plurality of layers and a black image is formed by a combination of a plurality of images resulting from the development of the emulsion is also a preferred example. As an example of forming a black image by combining a plurality of images, for example, the emulsion is contained in a yellow image layer for forming a yellow image, and a blue image (for example, a magenta image and a cyan image are simultaneously complementary to the yellow image). Some of the forming layers (which form a blue image when formed) also contain the emulsion, and the emulsion is developed to form a black image. 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.

  In another preferred example, the emulsion is contained in any of the yellow image forming layer, the magenta image forming layer, and the 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 them.

  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. The order of coating from the support can be arbitrarily selected.

  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 from conventionally known spectral sensitizing dyes.

  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 when a silver produced in an image is bleached, 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, and after image exposure, fog processing (nucleation processing) is performed, followed by surface development, 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 by using a fogging agent, a strong developer, or by heat treatment.

  The entire surface exposure is performed by immersing the image-exposed photosensitive material in a developing solution or other aqueous solution or moistening it, 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 above-mentioned photosensitive material, and can be exposed to high illuminance light such as flash light for a short time, or weak light. 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 overall 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 second to about 1 second. When exposed to a light intensity scale for a given time and developed for 4 minutes at 20 ° C. using the following surface developer A that develops only the surface image of the grains that are substantially free of silver halide solvent: A maximum not greater than 1/5 of the maximum density obtained when another portion of the same 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 grain. It is an emulsion showing density. 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
The internal latent image type silver halide emulsion preferably used in the present invention includes those prepared by various methods. For example, a conversion type silver halide emulsion described in US Pat. No. 2,592,250, or an internal structure described in US Pat. Nos. 3,206,316, 3,317,322 and 3,367,778 Silver halide emulsion having chemically sensitized silver halide grains, or silver halide grains containing a polyvalent metal ion described in US Pat. Nos. 3,271,157 and 3,447,927 Or a silver halide emulsion in which the surface of silver halide grains containing a dopant described in U.S. Pat. No. 3,761,276 is chemically sensitized weakly, or JP-A-50-8524, 50-38525 and 53-2408, etc., silver halide emulsions composed of grains having a laminated structure, and others, JP-A 52-156614 and 55-127 , Etc. The silver halide emulsion as described in JP 49.

  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 monodisperse 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, enlarging and photographing the particles with an electron microscope 10,000 to 50,000 times and measuring the particle diameter on the print or the projected area (the number of measured particles is There are 1000 or more indiscriminately).

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.

  The 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 the 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 grain size of silver halide in 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. The 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 color 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 wavelengths. A silver halide emulsion having a region and at least one of the yellow, magenta and cyan image-forming silver halide emulsion layers contained in the yellow, magenta and cyan image-forming silver halide emulsion layers. It is preferable that a silver halide emulsion having a common spectral sensitivity portion is contained in any of the emulsions having different spectral sensitivity wavelength regions.

  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, as other specific examples, among compounds M-1 to M-61 described on pages 6 to 21 of European Patent Publication 0737712 and compounds 1 to 223 described on pages 36 to 92 of 0235913. 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. It can be used in the range.

The λ _max of spectral absorption of the magenta image formed in the photosensitive material according to the present invention is preferably ₅₃₀ to 560 nm, and λ _L0.2 is preferably ₅₈₀ to 635 nm.

Here, λ _L0.2 and λ _max of the 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. λ _L0.2 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, a particularly preferable one is 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 that is not 3 or lower than the pKa of the coupler.

  Specific examples of the yellow coupler 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 can be used usually 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 silver halide emulsion layer.

  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 of JP-A-3-209466. The 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 21 pages of Unexamined-Japanese-Patent No. 6-95283 can also be mentioned.

The λ _max of the spectral absorption of the yellow image formed by the light-sensitive material according to the present invention is preferably ₄₂₅ nm or more, and λ _L0.2 is preferably 515 nm or less. Here, λ _L0.2 is defined for the yellow image as in the case of the magenta image.

The yellow coupler can be used 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 the magenta color image, cyan color image, and 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 arranged as necessary.

  The magenta, cyan, and yellow couplers can be used in combination with an anti-fading agent in order to prevent fading of the formed dye image due to light, heat, humidity, and the like. Preferable compounds include phenyl ether compounds represented by general formulas I and II described in JP-A-2-66541, page 3, and phenol compounds represented by general formula IIIB described in JP-A-3-174150. An amine compound represented by the general formula A described in Japanese Utility Model Laid-Open No. 64-90445 and a metal complex represented by the general formulas XII, XIII, XIV, and XV described in Japanese Patent Laid-Open No. 62-182741 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 in combination with a boiling point and / or a water-soluble organic solvent, 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. High-boiling organic solvents that can be used to dissolve and disperse couplers and the like include phthalates such as dioctyl phthalate, diisodecyl phthalate, and dibutyl phthalate, and phosphate esters such as tricresyl phosphate and trioctyl phosphate. High boiling organic solvents such as phosphine oxides such as trioctylphosphine 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 point 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, including compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17 of the same specification. It is done.

  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. Representative 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 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 the carboxyl group, sulfamoyl group, and sulfonamide group include compounds represented by the 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. -7 can be mentioned, but is 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 with a commonly used sensitizing dye. The combination of sensitizing dyes used for supersensitization such as internal latent image type silver halide emulsions and negative type silver halide emulsions is also useful for the silver halide emulsions of the present invention. 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 the light-sensitive material, gelatin is preferably used as a binder. 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. The transmittance of the gelatin is preferably 70% or more when a 10% solution is prepared and the transmittance is measured at 420 nm with a spectrophotometer.

  The gelatin jelly strength (according to the Puggy method) is preferably 250 or more, particularly preferably 270 or more.

  The ratio of the gelatin to the total coated gelatin is not particularly limited, but it is preferably used in a large ratio, and specifically, a preferable effect can be obtained by using at a ratio of at least 20 to 100%.

The total amount of gelatin contained on the image forming surface side of the light-sensitive material is preferably less than 11 g / m ² . The lower limit is not particularly limited, but is generally preferably 3.0 g / m ² or more from the viewpoint of physical properties or photographic performance. The amount of gelatin is determined by converting to the mass of gelatin containing 11.0% of moisture by the moisture measurement method described in the Paggy method.

  As the hardener for these binders, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. It is preferable to use compounds described in JP-A-61-249054 and JP-A-61-245153. In order to prevent the growth of soot and bacteria that adversely affect photographic performance and image storage stability, it is preferable to add preservatives and antifungal agents as described in JP-A-3-157646 to the colloid layer.

  In the light-sensitive material according to the present invention, further known photographic additives can be used. Examples of the known photographic additive 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 Development accelerator 29 XXI 648 Upper right Antifoggant 24 VI 649 Lower right stabilizer 24 VI 649 Lower right color pollution 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 Brightening agent 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 Slipper 27 XII 650 Right Static inhibitor 27 XII 650 Right Matt 28 VII XVI 650 Right Binder 29 IX 651 Right The reflective support used in the light-sensitive material according to the present invention is preferably a base made of base paper and laminated with a polyolefin resin on both sides thereof.

  The base paper used as 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, and various types of combined paper materials can be mentioned. In general, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood and hardwood pulp, etc. can be widely used.

  Further, the support may contain additives such as a sizing agent, a fixing agent, a strength enhancing agent, a filler, an antistatic agent, and a dye that are generally used in papermaking. Agents, surface toughening agents, antistatic agents and the like may be appropriately applied to the surface.

The reflective support generally has a smooth surface having a mass of 50 to 300 g / m ² , and the resin for laminating both surfaces is ethylene, polyethylene terephthalate, α-olefins such as polypropylene, and the like. Can be selected from the above homopolymers, at least two copolymers of the olefins, or a mixture of at least two of these 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 usually a range of 20,000 to 200,000 is used.

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

  The polyolefin used for laminating the back side of the reflective support (the reflective side of the side on which the emulsion layer is provided) is usually a melt laminate of low density polyethylene and high density polyethylene itself. In general, this layer is often matted.

  In forming the front and back laminates of the support used in the light-sensitive material according to the present invention, the density of the resin layer on the front side is slightly larger than that on the back side in order to improve the flatness in the ordinary environment of developed photographic paper, or Means such as increasing the amount of lamination on the back side than on the front side are used.

  In general, the laminate on both the front and back surfaces of the reflective support can be formed by subjecting the polyolefin resin composition to a support by melt extrusion coating. 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. Further, it is preferable to provide a subcoat layer for improving the adhesiveness to the photographic emulsion on the surface laminate layer surface, or a backcoat layer for improving the printing writability and antistatic property on the backside laminate layer.

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

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

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

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

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

  In addition, it is preferable to apply a hydrophilic colloid layer containing a white pigment on the reflective support to improve sharpness. 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 whose surface is further coated with polyolefin can be used.

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

  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 by JIS-B0601-1976 of 0.30 to 3.0 μm.

  In the photosensitive material according to the present invention, the surface roughness of the image forming surface is preferably 0.30 to 3.0 μm. For this purpose, the matting agent is included in the constituent layer on the image forming surface side of the photosensitive material. Can be contained. 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, which 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 light-sensitive material according to the present invention preferably has a gloss close to that of a printed material. For example, the gloss measured by the method defined in JIS-Z8741 of the surface of the image forming layer after processing. G _S (60 °) preferably has from 5 to 60.

In the step of creating a color proof according to the present invention, the photosensitive material is exposed based on halftone dot image information that forms color-separated yellow image information, magenta image information, cyan image information, and black image information. In the step of creating a color proof, at least a part of the halftone dot image information indicates that when the halftone dot area ratio is 40%, the number of halftone dots per 1 inch ² (1 inch corresponds to 2.54 cm) is 200 ×. A dot image converted so that it is 10 ³ or more is used. Preferably, it is 300 × 10 ³ or more, more preferably 400 × 10 ^{3 to} 2000 × 10 ³ .

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

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

  The halftone dot image information used to create these halftone dot images is a halftone dot image recorded on a film, and exposure is performed by causing the film to adhere to the silver halide photographic light-sensitive material and scanning a light source. Is preferred. For the adhesion, a vacuum adhesion method can be preferably used.

  In these exposures, it is preferable to perform the exposure through optical means for improving the parallelism of the light from the light source. Examples of means for improving the parallelism of light emitted from a light source include a member that absorbs components other than parallel light by a wall surface through a linear tubular optical path such as an optical lens, a reflecting mirror, and a honeycomb structure. It is done. Further, parallel light can be improved by an assembly of optical fibers.

  It is also preferable to perform exposure by laser scanning based on the halftone dot image information.

  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 a particularly preferable system for forming an image include Konsensus 570, Konsensus 670, and Digital Konsensus manufactured by Konica Minolta.

  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 color proof photosensitive material can be mentioned.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

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 part 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 for 4 minutes at 20 ° C., and another part of the sample was 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 >>
A sensitizing dye (GS-1) was added to emulsion EM-P1 for optimal color sensitization, and then 100 mg of inhibitor (T-1) was added per mole of silver to prepare blue-sensitive emulsion Em-G1.
T-1: 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene << Preparation of red-sensitive silver halide emulsion >>
Red-sensitive emulsion Em-R1 was prepared in the same manner as green-sensitive emulsion Em-G1, except that sensitizing dyes (RS-1, RS-2) were added to emulsion EM-P2 for optimal color sensitization. .

<< Preparation of infrared-sensitive silver halide emulsion >>
The emulsion EM-P2 was optimally sensitized by adding sensitizing dyes (IRS-1, IRS-2), and the inhibitor (AF-1) was added in the same manner as the green photosensitive emulsion Em-G1. Infrared photosensitive emulsion Em-IFR1 was prepared.
AF-1: Sodium ascorbate monohydrate

<Preparation of multilayer photosensitive material sample>
The Em-G1 is coated on a paper pulp reflective support having a thickness of 110 μm in which high-density polyethylene is laminated on one side and molten polyethylene containing 15% by mass of anatase-type titanium oxide is laminated on the other side. , Em-R1 and Em-IFR1 emulsions, each layer having the following layer structure was coated on the polyethylene layer side containing titanium oxide, and on the back side, gelatin 6.0 g / m ² , silica A multilayer photosensitive material sample coated with 0.65 g / m ^{2 of a} matting agent was prepared. The numerical value of each material indicates the coating amount (g / m ² ). The amount of each emulsion added is shown in terms of silver.

  In addition, H-1 and H-2 were added as a hardening agent. As coating aids and dispersion aids, surfactants SU-1, SU-2, SU-3 were added and prepared.

SU-1: Sulfosuccinic acid di (2-ethylhexyl) ester / sodium salt SU-2: Sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester / sodium salt SU-3: Sodium tri-i-propylnaphthalenesulfonate H-1: 2,4-dichloro-6-hydroxy-S-triazine sodium salt H-2: Tetrakis (vinylsulfonylmethyl) methane << Multilayer Photosensitive Material Sample Layer structure"
Eighth layer (ultraviolet absorption layer) Application amount (g / m ² )
Gelatin 1.60
Ultraviolet absorber (UV-1) 0.070
Ultraviolet absorber (UV-2) 0.025
Ultraviolet absorber (UV-3) 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 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) 0.050
Hardener (H-2) 0.012
5th layer (green-sensitive layer)
Gelatin 0.90
Green sensitive 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 0.80
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) 0.045
Hardener (H-2) 0.012
Third layer (infrared photosensitive layer)
Gelatin 1.10
Infrared photosensitive 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 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) 0.150
Irradiation preventing dye (AI-4) 0.010
Hardener (H-2) 0.017
1st layer gelatin 2.00
Styrene / n-butyl methacrylate / 2-sulfoethyl methacrylate sodium salt 0.12
Black colloidal silver 0.08
Polyvinylpyrrolidone 0.10
Surfactant (SU-2) 0.002

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-dodecyl hydroquinone, 2,5-di-sec tetradecyl hydroquinone and 2-sec-dodecyl-5-sec-tetradecyl hydroquinone Mixture of mass ratio 1: 1: 2 T-2: 1- (3-acetamidophenyl) -5-mercaptotetrazole T-3: N-benzyladenine The obtained multilayer photosensitive material sample was cut into a size of 570 mm × 850 mm The halftone dot test chart is converted into an infrared laser beam (semiconductor laser: G) using the laser scanning exposure apparatus described below. AlAs, .lambda.max; about 780 nm), red laser light (semiconductor laser: AlGaInAs, .lambda.max; was exposed at about 544 nm); about 670 nm), green laser beam (helium-neon laser, .lambda.max. Further, the sample was sucked and adhered to the rotating drum, and an image was recorded by performing main scanning and sub-scanning at a rotational speed of 2000 rotations / minute. However, at that time, twelve infrared semiconductor lasers were arranged, and the above-described silver halide photosensitive material was simultaneously exposed as 12 beams of laser light through optical means.

  Samples cut to the size and subjected to the above exposure were successively processed by the following processing steps one by one. The automatic developing machine was operated continuously for 24 hours, and the exposure processing was performed at equal intervals.

(Processing process)
Processing Step Temperature Time Immersion (Developer) 37 ° C 12 seconds Fog exposure-12 seconds Color development 37 ° C 95 seconds Bleaching fixation 35 ° C 45 seconds Stabilization 25-30 ° C
1st tank 15 seconds 2nd tank 15 seconds 3rd tank 15 seconds Drying 60-85 ° C. 40 seconds (color developer)
Benzyl alcohol 15.0ml
Ceric sulfate 0.015g
Ethylene glycol 8.0ml
Potassium sulfite 0.6 g of potassium bromide shown in Tables 1 and 2
Sodium chloride 0.2g
Potassium carbonate 25.0g
T-1 0.1g
Hydroxylamine sulfate As shown in Tables 1 and 2, Diethylenetriaminepentaacetic acid sodium salt 2.0 g
4-Amino-N-ethyl-
N- (β-hydroxyethyl) aniline sulfate 4.5 g
Fluorescent whitening agent (FB-1) 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)
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)
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)
2.0g
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 multistage countercurrent system of 3 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 Potassium bromide 0.3g shown in Tables 1 and 2
Sodium chloride 0.2g
Potassium carbonate 25.0g
T-1 0.1g
Hydroxylamine sulfate As shown in Tables 1 and 2, Diethylenetriaminepentaacetic acid sodium salt 2.0 g
4-Amino-N-ethyl-N- (β-hydroxyethyl)
Aniline sulfate 5.4g
Fluorescent whitening agent (FB-1) 1.0g
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
Bleach fixer 300ml / m ²
Stabilization solution 500ml / m ² (Replenish to the third tank of stabilization treatment)
Tables 1 and 2 show the replenishment amount of the color developer, the oxidation replenishment amount of the color developer, the amount of water replenished in a certain unit time, and the daily processing amount.

  Development was performed using a digital Konsensus machine manufactured by Konica Minolta, and the tank capacity of the color developer tank was 20 L. Further, the processing was continued until the total amount of the replenished color developer reached an amount equivalent to twice the amount of the color developer tank.

<Evaluation of continuous processing>
For development samples that have been processed continuously by inputting halftone dot image information of the original, being exposed, and continuously processed until the total amount of the replenished color developer is equivalent to twice that of the color developer tank, yellow, magenta, Cyan and black densities were measured in mode T using X-Lite 528 manufactured by Nihon Hakusho Kaisha Co., Ltd., and Tables 1 and 2 show the density differences between the start of continuous processing and double equivalent processing.

For the white background, the Konica Minolta Co., Ltd. spectrophotometer CM-2022 was used at the start and end of development, and the photometric measurement was performed using a geometric condition d-0 for illumination and light reception and a xenon pulse light source. The values of L ^* , a ^* , and b ^* at light D50 were measured, and the color difference of the sample when processed at the start and end of continuous processing was determined. The color difference ΔE is obtained by the following formula.

ΔE = (ΔL ^{* 2} + Δa ^{* 2} + Δb ^{* 2} ) ^1/2
Note that ΔL ^* , Δa ^* , and Δb ^* represent the difference between processing at the start and end of continuous processing.

  As is apparent from the results, the color development processing sample according to the present invention has small variations in density and white background in the continuous processing. Further, when the color developer contains a hydroxylamine sulfate and a sulfite of 0.03 mol / L or less, the density and white background fluctuation are more preferable.

Claims (3)

In the processing method of a silver halide color photographic light-sensitive material that develops color with a color developer containing an aromatic primary amine developing agent, the daily processing amount is 3 m ² or less, and the following formulas (1) to (3) And a method for processing a silver halide color photographic light-sensitive material.
Formula (1) W × Rc / T / 1000 ≦ 0.06
(Wherein, W represents the daily processing amount (m ² ), Rc represents the replenishment amount of the color developer (ml / m ² ), and T represents the color developer tank capacity (L) of the automatic processor. )
Formula (2) Rc ≧ 15 × Ro
(In the formula, Ro represents the amount of oxidation replenishment (ml / hr) of the color developer.)
Formula (3) Ro + 10 ≦ Rw ≦ Ro + 50
(Wherein, Rw represents the amount of water (ml / hr) replenished to the color developer in a fixed unit time.) 2. The method for processing a silver halide color photographic material according to claim 1, wherein the color developer contains hydroxylamine sulfate. 3. The method for processing a silver halide color photographic material according to claim 1, wherein the color developer contains 0.03 mol / L or less of sulfite ion.