JP2002122968A - Color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color image forming method for proofreading by which a white background is kept free from a change and unevenness and the color tone of black dots is kept stable in color plate making and printing steps. SOLUTION: In the color image forming method in which a silver halide photographic material with at least three silver halide emulsion layers whose spectral sensitivity regions do not overlap on the base is imagewise exposed with light in each of the spectral sensitivity regions and color-developed, the sensitive material is subjected to scanning exposure for 1×10-2 to 10.0 sec exposure time as expressed in expression: (E1×S1)/(E2×S2)<0.9, (E1×S1)/(E3×S3)<0.9 and developed with a color developing solution containing at least one compound of formula general: HO-N(R)-L-A and 0-2.0 g/l hydroxylamine to form a color image.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color image forming method (hereinafter, also simply referred to as "image forming method"), and more particularly, to an exposure developing device capable of forming a color image and a silver halide photographic material (hereinafter, simply referred to as "photosensitive material"). Material), especially in the color plate making / printing process, in which the exposure is performed on the silver halide photographic material in accordance with the halftone image information obtained by color separation and halftone image conversion. The present invention relates to a color image forming method used.

[0002]

2. Description of the Related Art Conventionally, as a method of obtaining a color proof from a plurality of black and white halftone images obtained by color separation and halftone image conversion in a color plate making and printing process, a silver halide color photographic material having a white support has been proposed. A method for producing a color proof using the method described in
6-104335, 62-280746, 62
-280747, 62-280748, 62-
No. 2,807,492 and No. 62-280750.

[0003] However, there are various problems in order to put it into practical use, for example, the following. The amount of light may fluctuate, for example, when the installation environment of the apparatus, for example, the temperature fluctuates, or the amount of light fluctuates partially in a large screen, and the quality of the image tends to fluctuate. In particular, there is a problem that the white background fluctuates inside the image and a problem that the image color tone fluctuates. Further, when the photographic material is stored for a long period of time, or when a processing solution that has been stored for a long period of time is used, a problem arises that a white background fluctuates and an image tone fluctuates. To solve these problems, various methods such as adding a stabilizer and an inhibitor to the emulsion and stabilizing the developing solution have been proposed, but no sufficient effect has been obtained.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a color image using a silver halide photographic light-sensitive material, in which the fluctuation of the white background is small and the color tone of the halftone dot of black is stable. An object of the present invention is to provide an image forming method.

Further, in a color plate making / printing process, a silver halide photographic light-sensitive material is exposed according to halftone image information obtained by color separation and halftone image conversion to obtain a color image. Another object of the present invention is to provide a color image forming method for calibration in which the color tone of black dots is stable.

[0006]

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

[0007] 1. In a color image forming method, a silver halide photographic light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivity regions from each other on a support is color-developed after image exposure with light in each of the spectral sensitivity regions. The silver halide photographic material contains at least one hardening agent selected from the formula (A),
Further, the sensitivity of the emulsion layer is set to S1,
S2 and S3, and when the maximum value of the exposure amount of the light source is set to E1, E2, and E3 in order of the wavelength, the image is exposed by the above-described formula (1) and then expressed by the above-described general formula (B). Image forming method comprising forming a color image by developing with a color developing solution containing at least one compound of the formula (1) and hydroxylamine in an amount of 0 to 2.0 g / l.

[0008] 2. In a color image forming method, a silver halide photographic light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivity regions from each other on a support is color-developed after image exposure with light in each of the spectral sensitivity regions. The sensitivity of the emulsion layer is determined by increasing the spectral sensitivity wavelength in the order of S
1, S2, and S3, and when the maximum value of the exposure amount of the light source is E1, E2, and E3 in order of wavelength, the image exposure is represented by the above equation (1) and the exposure time is 1 × 1
After a scanning exposure of 0 ^-2 seconds to 10.0 seconds, a color developer containing at least one compound represented by the above general formula (B) and containing 0 to 2.0 g / l of hydroxylamine Forming a color image by developing the color image.

3. A fourth support having at least three silver halide emulsion layers having different spectral sensitivity regions from each other and a spectral sensitivity region different from any of the silver halide emulsions on a support;
In a color image forming method of subjecting a silver halide photographic light-sensitive material having a silver halide emulsion to image development with light in each of the spectral sensitivity regions and then color developing the emulsion, the sensitivity of the emulsion layer is determined in the order of spectral sensitivity wavelength, S1, S2 and S3, and the maximum value of the exposure amount of the light source is set to E1 and E in order of wavelength.
2, E3, after the image exposure represented by the above formula (1), contains at least one compound represented by the above general formula (B),
A color image forming method, wherein a color image is formed by developing with a color developing solution containing g / l.

[0010] 4. In a color image forming method, a silver halide photographic light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivity regions from each other on a support is color-developed after image exposure with light in each of the spectral sensitivity regions. The silver halide photographic material contains at least one compound represented by the above general formula (C), and the sensitivity of the emulsion layer is determined by increasing the spectral sensitivity in ascending order of wavelength.
1, S2, and S3, and when the maximum value of the exposure amount of the light source is set to E1, E2, and E3 in the order of wavelength, after the image exposure represented by the above formula (1), the general formula (B) )
A color image forming method comprising forming a color image by developing with a color developing solution containing from 0 to 2.0 g / l of hydroxylamine, containing at least one compound represented by the formula:

5. In a color image forming method, a silver halide photographic light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivity regions from each other on a support is color-developed after image exposure with light in each of the spectral sensitivity regions. Among the photographic gradations of the emulsion layer, the photographic gradation of the emulsion layer having the longest spectral sensitivity wavelength is the largest, and the sensitivity of the emulsion layer is determined in order of S1, S2,.
S3, and when the maximum value of the exposure amount of the light source is E1, E2, and E3 in order of wavelength, after image exposure represented by the above formula (1), the exposure value is expressed by the above general formula (B). Image forming method comprising forming a color image by developing with a color developing solution containing at least one compound of the formula (1) and hydroxylamine in an amount of 0 to 2.0 g / l.

6. In a color image forming method, a silver halide photographic light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivity regions from each other on a support is color-developed after image exposure with light in each of the spectral sensitivity regions. The raw sample reflection density in the spectral sensitivity region having the longest wavelength in the emulsion layer is 0.8 or more, and the sensitivities of the emulsion layer are S1, S2, and S3 in ascending order of spectral sensitivity wavelength,
In addition, the maximum value of the exposure amount of the light source is set to E1, E1,
2, E3, after the image exposure represented by the above formula (1), contains at least one compound represented by the above general formula (B),
A color image forming method, wherein a color image is formed by developing with a color developing solution containing g / l.

Hereinafter, the present invention will be described in more detail. The silver halide light-sensitive material of the present invention has at least three silver halide emulsions having mutually different spectral sensitivity ranges. In the present invention, the spectral sensitivity region means a wavelength region in which the sensitivity of an emulsion layer is at least four times higher than the sensitivity of any other emulsion layer. In general, the design is often performed so that the spectral sensitivity of the emulsion layer is higher than the spectral sensitivity of the other emulsion layers at a wavelength near the spectral sensitivity maximum.

The three emulsion layers in the present invention are a yellow image forming layer, a magenta image forming layer, and a cyan image forming layer, and these emulsion layers have different spectral sensitivity regions. In the present invention, three light sources are used for the three emulsion layers, but have different wavelengths, and are used as a light source for forming a yellow image, a light source for forming a magenta image, and a light source for forming a cyan image, respectively.

As the light source used in the present invention, any light source conventionally known to be used for exposing a photosensitive material can be used. In a preferred embodiment of the present invention, a color image is obtained by exposing a silver halide photographic light-sensitive material according to halftone image information obtained by color separation and halftone image conversion, but according to the halftone image information decomposed, Exposure according to yellow image information, exposure according to magenta image information, and exposure according to cyan image information are performed. The light source performs exposure with light in the spectral sensitivity region of the yellow image forming emulsion layer, performs exposure with light in the spectral sensitivity region of the magenta image forming emulsion layer, and performs cyan exposure so that exposure is performed according to the respective image information. Exposure is performed in the spectral sensitivity region of the emulsion layer for image formation to form a color image. The light source wavelength used in the present invention may be light having a wavelength within the spectral sensitivity region to be exposed.

The silver halide photographic light-sensitive material used in the present invention is preferably a positive type silver halide photographic light-sensitive material, and includes a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a cyan coupler ( C) having a silver halide emulsion layer containing
A Y (yellow) halftone image, an M (magenta) halftone image, and a C (cyan) halftone image are formed. Further, in the present invention, the formation of the halftone dot image of black can be performed by the Y, M and C image forming layers, or an emulsion layer for forming a black image can be added.

The sensitivity of the emulsion layer of the light-sensitive material of the present invention is defined as S1, S2, S3 in the order of the wavelength of the spectral sensitivity, and the maximum value of the exposure amount of the light source is defined as E1, E2, E3 in the order of the wavelength.
Is expressed by the following equation (1).

Equation (1) (E1 × S1) / (E2 × S2) <0.9 (E1 × S1) / (E3 × S3) <0.9 where S1 is the longest wavelength in the spectral sensitivity region. When the sensitometry of the emulsion layer is carried out using an exposure light source corresponding to the emulsion layer, it is represented by the reciprocal of the exposure amount giving a density value of D = Dmin + 0.2.

Similarly, S2 can be determined similarly by using the exposure light source corresponding to the emulsion layer to determine the sensitometry of the emulsion layer having the second longest wavelength in the spectral sensitivity region.

Similarly, S3 can be obtained. In the case of a positive image, the image density decreases as the exposure amount increases, and an image is formed by changing the exposure amount to a white background portion, that is, the exposure amount that gives the smallest density in the image.
When a halftone image is exposed through a halftone image film, the exposure amount applied to the light-sensitive material surface that is transmitted through the lowest density portion of the original film is changed in the order of the wavelength, from E1 of the present invention to E1 of the present invention.
E2 and E3.

In the present invention, development is performed with a color developing solution after image exposure, and the color developing solution contains at least one compound represented by the above general formula (B).
And contains hydroxylamine at a concentration of less than 2.0 g / l.

The compound represented by formula (B) of the present invention will be described in detail. In the general formula (B), L represents 1 to 1 carbon atoms.
It represents 10 linear or branched alkylene groups which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, methylene, ethylene, trimethylene, and propylene are preferred examples. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a hydroxy group, and an amino group that may be alkyl-substituted, and preferred examples include a carboxy group, a sulfo group, and a hydroxy group. A represents a carboxy group, a sulfo group, a phosphono group, a hydroxy group, or an amino group which may be alkyl-substituted, and preferred examples thereof include a carboxy group, a sulfo group, and a hydroxy group. These may be salts of sodium, potassium, lithium and the like.

Preferred examples of -LA include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group and a hydroxyethyl group. R is a hydrogen atom,
It represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a hydroxy group, and an amino group which may be alkyl-substituted, and preferred examples include a carboxy group, a sulfo group, and a hydroxy group. These substituents may be salts such as sodium, potassium and lithium. Next, specific examples of the compound represented by formula (B) of the present invention will be given, but the compound of the present invention is not limited thereto.

[0024]

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[0025]

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Among the above specific compounds, Exemplified Compound B-2, Exemplified Compound B-6 and Exemplified Compound B-16 are preferable, and Exemplified Compound B-6 is particularly preferable.

In the present invention, the compound of the general formula (B) is preferably contained in the color developing solution in an amount of 0.001 to 0.2 mol / l, particularly preferably 0.005 to 0.2 mol / l.
It is preferred that the content be 07 mol / l, more preferably 0.01 to 0.05 mol / l. Only one of the above compounds may be used in the color developing solution.
More than one type may be used in combination. When used in combination, it is preferable that the total concentration of the compounds of the general formula (B) be within the above range.

The color developing solution of the present invention contains hydroxylamine at a concentration of 0 to 2.0 g / l.

According to the first aspect of the present invention, the silver halide light-sensitive material contains at least one hardening agent represented by the above general formula (A).

The compound represented by formula (A) used in the present invention is known as a hardener for gelatin. Less than,
This compound will be described.

In the general formula (A), R ₁ is a divalent linking group, an alkylene group or a halogen atom as a substituent,
Represents an alkylene group substituted with a hydroxyl group, a hydroxyalkyl group, an amino group, or the like. Further, the linking group may have an amide linking moiety, an ether linking moiety or a thioether linking moiety.

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

A-1 CH ₂ = CHSO ₂ CH ₂ SO ₂ CH
_{= CH 2 A-2 CH 2} = CHSO 2 (CH 2) 2 SO 2 CH = CH 2 A-3 CH 2 = CHSO 2 (CH 2) 4 SO 2 CH = CH 2 A-4 CH 2 = CHSO 2 CH ₂ OCH ₂ SO ₂ CH = C
_{H 2 A-5 CH 2 =} CHSO 2 (CH 2) 2 O (CH 2) 2 SO
₂ CH = CH ₂ A-6 CH ₂ = CHSO ₂ CH ₂ CH (OH) CH ₂ SO
_{2 CH = CH 2 A-7} CH 2 = CHSO 2 CH 2 CONH (CH 2) 2 N
_{HCOCH 2 SO 2 CH = CH 2} A-8 CH 2 = CHSO 2 CH 2 CONH (CH 2) 3 N
HCOCH ₂ SO ₂ CH = CH ₂ According to the _{second aspect of the} present invention, image exposure is performed during an exposure time of 1 × 10 ^-2 seconds to 10 seconds. 1x
If the exposure is performed for a time shorter than 10 ^-2 seconds, the tone of the leg is softened, and the effect of the present invention is hardly obtained. On the other hand 10
If the exposure time is longer than seconds, the white background density increases and the image quality deteriorates. Exposure of the present invention is also a preferred example of being a scanning exposure light source. For example, it is preferable to use a long light source such as a fluorescent lamp to scan and expose the light source.

According to the invention of claim 3 of the present invention, the silver halide light-sensitive material of the present invention has, in addition to the three emulsion layers, a fourth region having a spectral sensitivity region different from that of any other silver halide. Contains silver halide emulsion. This emulsion becomes a fourth image forming layer different from the YMC image forming layer. Specifically, an image corresponding to a black image is to be formed using the fourth layer. In the fourth emulsion layer, for example, a black image may be formed, or a black image formed by forming a part of the black image and combining with the image of the other layer may be reproduced more faithfully.

According to the fourth aspect of the present invention, the silver halide light-sensitive material of the present invention contains at least one thiosulfonic acid compound represented by the general formula (C).

The thiosulfonic acid compound may be a free acid or a salt thereof. In the general formula (C),
As the aliphatic group represented by R ₁₁ , C 1 to C 22
And an alkenyl group or an alkynyl group having 2 to 22 carbon atoms is preferred. More preferably, an alkyl group having 1 to 8 carbon atoms or an alkenyl group or alkynyl group having 3 to 5 carbon atoms is preferable. These groups may have a substituent.

Examples of the alkyl group include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, 2-ethylhexyl, decyl, dodecyl, octadecyl, cyclohexyl and the like. Examples of the alkenyl group include groups such as allyl and butenyl. Alkynyl groups include groups such as propargyl and butynyl.

The aromatic group represented by R ₁₁ is preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group having 6 to 10 carbon atoms. These groups may have a substituent, and specific examples include phenyl and p-
Groups such as tolyl and naphthyl can be mentioned.

The heterocyclic group represented by R ₁₁ is 3 to 15
Member rings are preferred, and 5- to 6-membered rings containing a nitrogen atom are more preferred. Specific examples include pyrrolidine, piperidine, pyridine, tetrahydrofuran, thiophene, oxazole, imidazole, benzothiazole, tellurazole,
Each ring such as oxadiazole and thiadiazole can be exemplified.

The group represented by R ₁₁ has 6 carbon atoms.
Most preferred are from 10 to 10 substituted aromatic rings. Examples of the substituent include an alkyl group (eg, methyl, ethyl, butyl, pentyl), an alkoxy group (eg, methoxy, ethoxy),
Aryl group (phenyl, naphthyl, etc.), hydroxyl group, halogen atom, aryloxy group (phenoxy, etc.), alkylthio group (methylthio, butylthio, etc.),
Arylthio group (phenylthio etc.), acyl group (acetyl, propionyl etc.), sulfonyl group (methylsulfonyl, phenylsulfonyl etc.), acylamino group (acetylamino etc.), sulfonylamino group, acyloxy group,
Specific examples of the compound represented by the general formula (C) used in the present invention, which include a carboxy group, a cyano group, a sulfo group, an amino group and the like, are shown below, but the present invention is not limited thereto. .

[0041]

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According to claim 5 of the present invention, among the photographic gradations of the emulsion layers of the silver halide light-sensitive material of the present invention, the photographic gradation of the emulsion layer having the longest spectral sensitivity wavelength is the largest. The photographic gradation in the present invention is represented by the absolute value of the slope of a straight line connecting a point indicating D = Dmin + 0.3 to a point indicating D = Dmin + 0.8, where Dmin is the minimum density on the characteristic curve. The photographic gradation is preferably 2.5 or more, more preferably 3.0 or more. Although there is no particular upper limit, the photographic gradation is actually 20 or less.

According to the sixth aspect of the present invention, the reflection density of the raw sample in the spectral sensitivity region of the emulsion layer having the longest wavelength among the emulsion layers of the silver halide light-sensitive material of the present invention is 0.8.
That's it. It is known that sharpness is improved by increasing the reflection density of a raw sample, but it has been recognized that the reflection density of the raw sample in the spectral sensitivity region of the emulsion with the longest reflection density is important. Not particularly.

As a method for adjusting the reflection density to 0.8 or more before the development processing, a method of adding a water-soluble dye having absorption to at least a spectral sensitivity region of the silver halide emulsion and / or a method of adding the lowermost layer or other It is preferable to provide antihalation in the layer. Further, there is a method in which a dye is contained in the photosensitive material as solid fine powder to suppress diffusion of the dye in the photosensitive material.

The water-soluble dye used in the present invention includes:
Oxonol, cyanine, merocyanine, azo, anthraquinone, arylidene, etc., each of which may be mentioned.From the viewpoint of high resolution in a developing bath and non-sensitization to a silver halide emulsion, oxonol is particularly preferable. Dyes and merocyanine dyes.

As the oxonol dye, US Pat.
187, 225, JP-A-48-42826, and 49
No.-5125, No.49-99620, No.50-916
No. 27, No. 51-77327, No. 55-120660
No. 58-24139, No. 58-143342,
No. 59-38742, No. 59-111640, No. 5
Nos. 9-111641, 59-168438 and 60
-218641, 62-31916, 62-6
No. 6275, No. 62-66276, No. 62-1857
No. 55, No. 62-273527, No. 63-13994
No. 9, etc. Also, as merocyanine dyes, JP-A-50-145124 and JP-A-58-12012
No. 5, 63-35437 and 63-35438,
Nos. 63-34539 and 63-58437.

Representative specific examples of oxonol dyes and merocyanine dyes are water-soluble yellow dyes AIY-1 to AIY-14 described in JP-A-9-5954, and water-soluble magenta dyes AIM-1 to AIM-14. And water-soluble cyan dyes AIC-1 to AIC-14.

Next, typical examples of water-soluble dyes other than oxonol dyes and merocyanine dyes include the water-soluble yellow dyes AI described in JP-A-9-5954.
Y-15 to AIY-18, AIM-15 to AIM-1
8, AIC-15 to AIC-18.

Further, examples of the water-soluble dye used in the present invention include A-1 to A-4 described in JP-A-4-33037.
And 3 dyes.

The amount of the water-soluble dye to be used is selected and added so that the reflection density of the raw sample before development processing measured at the laser wavelength at which the photosensitive material is exposed becomes 0.8 or more.
The water-soluble dyes can be used alone or in combination of two or more.

In the present invention, an antihalation layer may be provided as the lowermost layer or another layer.

The antihalation layer contains a compound that absorbs light. Examples of the compound that absorbs light include various organic compounds and inorganic compounds having the action. As the inorganic compound, colloidal silver, colloidal manganese and the like are preferable, and colloidal silver is particularly preferable.
Since these colloidal metals have good decolorization properties, they are also effective when applied to the color light-sensitive material of the present invention.

The above colloidal silver, eg, gray colloidal silver, is reduced by keeping silver nitrate alkaline in gelatin in the presence of a reducing agent such as hydroquinone, phenidone, ascorbic acid, pyrogallol or dextrin, followed by neutralization. It is obtained by cooling and setting gelatin, and then removing the reducing agent and unnecessary salts by a noodle washing method. When the colloidal silver particles are formed in the presence of an azaindene compound or a mercapto compound during the reduction with an alkali, a colloidal silver dispersion of uniform particles can be obtained.

The coating weight of the colloidal silver is such that the reflection density of a raw sample before development processing, measured at least at one wavelength within the exposure region, of the silver halide emulsion having the spectral sensitivity region having the longest wavelength is 0.8 or more. It can be added in a selected amount.

The color light-sensitive material of the present invention has at least one of a carboxyl group, a sulfonamide group and a sulfamoyl group in any silver halide emulsion layer and / or other hydrophilic colloid photographic constituent layers. The dye may be contained as a solid dispersion dye in a solid state. Specific examples of the dye are described in JP-A-9-5954.
-1 to 8-7.

The carboxyl group, sulfonamide group,
The dye having at least one sulfamoyl group is a compound having a hydrophilic group which is substantially water-insoluble (with respect to water having a pH of 7 or less) and dissociates at a pH of 9 or more. Solid fine particle dispersion obtained by a method of dissolving in a solvent and dispersing in a gelatin solution (in the form of group particles having microscopic dimensions, the average particle diameter is preferably 10 μm or less, more preferably 1 μm or less;
m) or less in gelatin or a polymer binder, it can be contained in any photosensitive emulsion layer or non-photosensitive hydrophilic colloid layer in a photographic component layer.

The carboxyl group, sulfonamide group,
The solid fine particle dispersion of a dye having at least one sulfamoyl group is insoluble in water and is stably present in the color photographic material. However, after the exposure, it is treated with a color developing solution (preferably at pH 9 or more). When the hydrophilic group in the dye compound is dissociated to become water-soluble or decolorized, most of the dye is lost from the color photographic material.

As the dye having at least one of a carboxyl group, a sulfonamide group, and a sulfamoyl group, two or more dyes may be used, or a water-soluble dye may be partially used depending on the purpose of use.

Carboxyl group, sulfonamide group, sulfone
Content of dye having at least one famoyl group
Is within the exposure area for cyan image-forming silver halide
Raw sample measured at least one wavelength before
Select the amount so that the reflection density is 0.8 or more and add
Wear. Specifically, generally 0.001 to 0.5 g / m
^TwoIt is preferably used so that

In the present invention, the difference between the highest dot gain and the lowest dot gain among the dot gains measured by BGR decomposition of the black halftone dot image portion composed of YMC halftone dots is within 6%. However, since the color tone of the black dot image is close to the color tone of the black dot image of the printed matter, if it exceeds 6%, the color tone of the black dot image will deviate significantly from the printing.

Here, the dot gain is a halftone dot area ratio (%) obtained by decomposing the reproduced black halftone image into BGR and measuring it when the halftone dot area ratio of the black dot image information of the document is 50%. ) Is subtracted from the value of 50). It is preferable that the difference between the maximum dot gain value and the minimum dot gain value among the obtained three dot gains is 6%. Note that the dot gain uses a value calculated using the color of Murray Davis.

In the present invention, at least one hydrophilic colloid layer colored with a diffusion-resistant compound is provided on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. Is preferred. The diffusion-resistant compound includes a solid disperse dye, colloidal silver, and the like. Further, it is preferable that an oil-soluble dye is dissolved in a high boiling point solvent and used as fine dispersed particles in the constituent layer of the silver halide photographic light-sensitive material.

The silver halide emulsion used in the present invention may be a surface latent image type silver halide emulsion which forms a latent image on the surface by image exposure, or an internal latent image having a grain surface which is not previously fogged. Using an image-type silver halide emulsion,
An internal latent image type halogenation that can directly obtain a positive image by performing fogging treatment (nucleation treatment) after image exposure and then performing surface development, or performing surface development while performing fogging processing after image exposure It may be a silver emulsion. The internal latent image type silver halide emulsion is an emulsion containing silver halide grains having a photosensitive nucleus mainly inside silver halide crystal grains and forming a latent image inside the grains upon exposure. Say.

The silver halide emulsion used in the present invention may have any conventionally known halogen composition. For example, silver chloride, silver bromide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide and the like are included. Among them, silver chlorobromide containing silver chloride, silver chloroiodide, silver chloroiodobromide, silver halide emulsion having a portion containing silver bromide in particular is preferably used, and in the vicinity of the surface, Silver chloroiodide containing 0.05 to 0.5 mol% of silver iodide is also preferably used. In the silver halide emulsion having a portion containing silver bromide at a high concentration, the portion containing silver bromide at a high concentration may be a so-called core-shell emulsion or may be simply formed without forming a complete layer. A so-called epitaxy region in which only a region having a partially different composition may exist may be formed. It is particularly preferable that the portion where silver bromide exists at a high concentration is formed at the top of crystal grains on the surface of silver halide grains. Further, the composition may change continuously or discontinuously.

One preferred form of the silver halide emulsion used in the present invention is an internal latent image type silver halide emulsion which has not been previously fogged. The internal latent image type silver halide grains have a large photosensitive nucleus. A silver halide grain having a portion inside the grain, wherein a latent image is mainly formed inside the grain. The composition of the silver halide grains includes any silver halide, for example, silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide and the like.

Particularly preferably, the coated silver amount is about 1 to 3.5.
A portion of the sample coated on the transparent support to a range of g / m ² is exposed to the light intensity scale for a defined period of time from about 0.1 seconds to about 1 second, and When developed at 20 ° C. for 4 minutes using the following surface developer A, which develops only the surface image of grains containing no silver halide solvent,
Another part of the same emulsion sample is also exposed to light and develops an image inside the grains. The maximum density not greater than 1/5 of the maximum density obtained when developed at 20 ° C. for 4 minutes with the following internal developing solution B This is an emulsion showing the density. More preferably, the maximum density obtained with the surface developer A is not greater than 1/10 of the maximum density obtained with the internal developer B. (Surface developer A) Methol 2.5 g L-ascorbic acid 10.0 g Sodium metaborate (tetrahydrate) 35.0 g Potassium bromide 1.0 g Add water 1000 ml (Internal developer B) Methol 2.0 g Sulfurous acid Sodium (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.5 g Potassium bromide 5.0 g Potassium iodide 0.5 g Add water 1000 ml Add an internal latent image type preferably used in the present invention Silver halide emulsions include those prepared by various methods. For example, a conversion type silver halide emulsion described in U.S. Pat. No. 2,592,250 or described in U.S. Pat. Nos. 3,206,316, 3,317,322 and 3,367,778. A silver halide emulsion having internally chemically sensitized silver halide grains, or an emulsion having silver halide grains containing polyvalent metal ions described in U.S. Pat. No. 3,271,157, or U.S. Pat. No. 3,761,276 discloses a silver halide emulsion containing a dopant which is obtained by weakly sensitizing the surface of silver halide grains containing a dopant.
Nos. 524, 50-38525 and 53-2408
And silver halide emulsions described in JP-A Nos. 52-156614 and 55-127549.

Such an internal latent image type silver halide emulsion which has not been previously fogged gives a positive image without performing reversal processing by performing surface fogging processing. Alternatively, the treatment may be performed chemically using a fogging agent, a strong developing solution may be used, and heat treatment may be performed.

The entire surface exposure is performed by immersing or wetting the image-exposed photosensitive material in a developing solution or other aqueous solution, and thereafter performing uniform exposure over the entire surface. As the light source used here, any light source may be used as long as it has light in the photosensitive wavelength region of the silver halide photosensitive material, and high-intensity light such as flash light can be applied for a short time. , Weak light may be applied for a long time. or,
The overall exposure time can be varied over a wide range depending on the silver halide photosensitive material, development processing conditions, type of light source used, and the like so that the best positive image is finally obtained.
In addition, it is most preferable that the exposure amount of the entire surface exposure be given in a certain fixed range in combination with the photosensitive material. Usually, when the exposure amount is excessively increased, the minimum density increases or desensitization occurs, and the image quality tends to be reduced.

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

In the present invention, a monodisperse silver halide emulsion is defined as having a silver halide content within a grain size range of ± 20% around an average grain size rm of not less than 60% of the total silver halide grain mass. And preferably 70% or more, more preferably 80% or more. here,
The average particle size rm is defined as the frequency ni and r of the particles having the particle size ri.
product ni × ri ³ and i ³ is defined as the particle size ri when the maximum (three significant figures, the minimum digit is ON 4 discard 5). In the case of spherical silver halide grains,
In the case of particles having a shape other than a spherical shape, the diameter is obtained by converting the projected image into a circular image having the same area. The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is 1000 or more indiscriminately).

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

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

It is also preferable to add two or more monodisperse emulsions to the same color-sensitive layer. The particle size of each emulsion layer used in the light-sensitive material of the present invention is determined from a wide range in consideration of the required properties, particularly various characteristics such as sensitivity, sensitivity balance, sharpness of color separation, and granularity. be able to.

In one preferred embodiment, the silver halide has a particle size of 0.1 to 0.6 μm for the red-sensitive layer emulsion.
The green-sensitive layer emulsion is 0.15 to 0.8 μm, and the blue-sensitive layer emulsion is 0.1 to 0.8 μm.
A range of 3 to 1.2 μm can be preferably used.

The silver halide emulsion can be optically sensitized by a commonly used sensitizing dye. Use of a combination of sensitizing dyes used for supersensitization, such as an internal latent image type silver halide emulsion and a negative type silver halide emulsion, is also useful for the silver halide emulsion in the present invention. Sensitizing dyes are described in Research Disclosure (hereinafter referred to as R).
D) 15162 and 17643 can be referred to.

It is preferable to add a compound for adjusting the toe gradation to the light-sensitive material. Preferred compounds include
The formula [AO-] described in JP-A-6-95283, page 17
Compounds represented by II] are preferred. Specific examples of the compound include compounds II-1 to II-8 described on page 18 of the publication. The addition amount of the compound [AO-II] is preferably 0.001 to 0.50 g / m ² , more preferably 0.005 to 0.20 g / m ² . The compounds may be used alone or in combination of two or more. Further, a quinone derivative having 5 or more carbon atoms can be used in combination with the compound of [AO-II]. However, in any of these cases, the amount used is 0.001 to 0.50 g as a whole.
/ M ² .

The light-sensitive material preferably contains a nitrogen-containing heterocyclic compound having a mercapto group. Preferred compounds are those represented by general formula [XI] described in JP-A-6-95283, page 19, right column, lines 20 to 49, and particularly preferably described in JP-A-6-95283, page 20, left column, lines 5 to page 20, right column, line 2. Of the general formula [XI
I] to [XIV]. In addition, as a specific example of the compound,
For example, compounds (1) to (39) described on pages 11 to 15 of JP-A-64-73338 can be exemplified.

[0078] The above mercapto compound may vary appropriately depending on the kind and layer the addition of compounds to be used as an additive amount, in general, when added to a silver halide emulsion layer, per mol of silver halide 10 ^{- It is in} the range of ⁸ to 10 ^-2 mol, more preferably 10 ^-6 to 10 ^-3 mol.

As the white pigment, for example, rutile-type titanium dioxide, anatase-type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used as inorganic materials. One of the white pigments having different spectral reflection characteristics is preferably titanium dioxide for various reasons. As the other white pigment, titanium dioxide having a different average primary particle size may be used. Rutile titanium dioxide and anatase titanium dioxide may be used in combination. It is also preferable to use solid fine particles having a fluorescent whitening effect.

The white pigment is added in a dispersed state to the layer of the present invention constituting the silver halide photographic light-sensitive material. The white pigment is dispersed in water or an aqueous solution of hydrophilic colloid such as gelatin using, for example, a high-speed stirring type dispersing group, a method of pulverizing and dispersing in water or an aqueous solution of hydrophilic colloid such as gelatin in a ball mill or a sand mill, It can be dispersed using a method of dispersing in a hydrophilic colloid aqueous solution such as water or gelatin using a disperser having a high shearing force such as a galling disperser, or a method of dispersing using an ultrasonic disperser. .

When dispersing the white pigment, a surfactant can be used for the purpose of increasing the dispersibility and improving the dispersion stability. Preferred surfactants include anionic surfactants, nonionic surfactants, and betaine amphoteric surfactants.

The spectral reflectance of the white pigment is preferably controlled by controlling the average particle size of the dispersion. The white pigment may be added to any of the layers constituting the silver halide photographic material, but is preferably added to the non-photosensitive hydrophilic colloid layer, and is preferably added to the silver halide emulsion layer closest to the support. More preferably, it is added to at least one non-photosensitive hydrocolloid layer provided between the body and the body.
The amount of the white pigment used in the present invention may be such that it is present in the silver halide photographic light-sensitive material of the present invention in an amount of 10 to 2000 mg / m ^2.
It is preferable to add ² .

Gelatin is mainly used as the water-soluble binder used in the non-photosensitive hydrocolloid layer having a white pigment. If necessary, gelatin derivatives, gelatin and other polymers, graft polymers, other than gelatin may be used. A hydrophilic colloid such as a protein, a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used in combination with gelatin.

The non-photosensitive hydrocolloid layer containing a white pigment preferably accounts for 5 to 30% by mass of the non-photosensitive hydrocolloid layer.

Coloring agents such as yellow, gray, blue and black colloidal silver, inorganic colored pigments, organic colored pigments and dyes can be added to the non-photosensitive hydrocolloid layer.

Various types of colloidal silver can be used, but black colloidal silver is preferably used in order to prevent irregular reflection on the surface of the support.

[0087] coated with the amount of black colloidal silver, preferably in the range of 0.01 to 1.0 g / m ^2, further preferably in the range of 0.03 to 0.8 g / m ^2.

The support preferably used in the present invention has both sides of a paper substrate coated with a resin containing a polyolefin resin as a main component, and continuously measures the unevenness of the support surface, and the measured signal is subjected to frequency analysis. It is preferable that the integrated value (PY value) of the power spectrum in the frequency range of 1 mm to 12.5 mm on the surface of the support is 2.9 μm or less.

To measure the PY value, the thickness unevenness of the polyolefin-coated support is continuously measured using a film thickness continuous measuring machine (for example, manufactured by Anritsu Corporation), and the obtained measurement signal is analyzed by a frequency analyzer. (For example, Hitachi Electronics: V
C-2403) to obtain a frequency analysis.

The substrate (base paper) of the support can be selected from raw materials generally used for photographic printing paper. For example, in addition to natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, various raw paper materials can be mentioned. In general, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, and the like can be widely used.

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

The reflection support is usually 50 g / m ² to 30 g / m ^2.
A smooth surface having a mass of 0 g / m ² is used, and the resin for laminating both surfaces is ethylene,
It can be selected from α-olefins, for example, homopolymers such as polypropylene, at least two kinds of copolymers of the above-mentioned olefins, and mixtures of at least two kinds 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 to be laminated on the reflective support is not particularly limited, but is usually in the range of 20,000 to 200,000.

The polyolefin resin coating layer on the side of the reflection support on which the photographic emulsion is coated is preferably 25 μm to 50 μm.
m, more preferably 25 μm to 35 μm.

The polyolefin used for laminating the back side (the side opposite to the side on which the emulsion layer is provided) of the reflective support is usually a mixture of low-density polyethylene and high-density polyethylene, which is itself melt-laminated. This layer is generally matted in many cases.

In forming the laminate on the front and back of the support,
In general, in order to improve the flatness of the developed photographic paper in a normal environment, a method of slightly increasing the density of the resin layer on the front side or increasing the amount of lamination on the back side compared to the front side is used.

In general, the laminate on both the front and back surfaces of the reflective support can be formed on the support of the polyolefin resin composition by a melt extrusion coating method. Further, it is preferable to apply a corona discharge treatment, a flame treatment or the like to the surface of the support or, if necessary, to the front and back surfaces. Further, it is preferable to provide a back coat layer on the surface of the surface laminate layer for improving the printing and writing properties and the antistatic property.

The polyolefin resin used for laminating the support surface (the surface on which the emulsion layer is provided) is preferably 13% by mass to 20% by mass, more preferably 15% by mass to
20% by mass of a white pigment is mixed and dispersed. As the white pigment, an inorganic and / or organic white pigment can be used, preferably an inorganic white pigment, and specifically,
Sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, finely divided silicic acid, silicas of synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc , Clay and the like.

Of these, barium sulfate is preferred.
Calcium carbonate and titanium oxide, more preferably barium sulfate and titanium oxide. The titanium oxide may be of a rutile type or an anatase type, and one whose surface is coated with a metal oxide such as hydrous alumina or hydrous ferrite is also used.

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

The surface shape of the reflective support may be smooth or may have an appropriate surface roughness, but is preferably a shape having a gloss close to that of a printed matter.
For example, it is preferable to use a white support having an average surface roughness specified in JIS B 0601-1976 of 0.30 μm to 3.0 μm. In order to adjust the surface roughness, a matting agent can be contained in the constituent layer on the image forming side of the photosensitive material. The layer to which the matting agent is added includes a silver halide emulsion layer, a protective layer, an intermediate layer, an undercoat layer, and the like, and may be added to a plurality of layers, and is preferably the uppermost layer of the photosensitive material.

In a preferred embodiment of the present invention, it is preferable to form a protective layer on the outermost surface of the light-sensitive material, and to add a matting agent to the protective layer. Matting agents and their use are described in JP-A-6-95283, page 4, left column, lines 42-4.
It is preferable to use the technique described in the right column of the page, line 33.

In the present invention, a support of a synthetic resin film such as polypropylene, the surface of which is further coated with polyolefin, can be used.

The thickness of the reflective support is not particularly limited.
Those having a thickness of 0 μm to 160 μm are preferably used. Particularly preferably, it is 90 μm to 130 μm.

In the light-sensitive material, gelatin is preferably used as a binder. In particular, gelatin extract was subjected to hydrogen peroxide treatment to remove coloring components of gelatin, or extracted from raw material ossein subjected to hydrogen peroxide treatment, or manufactured from uncolored bone. Gelatin whose transmittance is improved by using ossein is preferable. Gelatin may be any of alkali-treated ossein gelatin, acid-treated gelatin, gelatin derivative, and modified gelatin, and particularly preferably alkali-treated ossein gelatin.

The transmittance of gelatin is preferably 70% or more when a 10% solution is prepared and measured at 420 nm with a spectrophotometer.

Jelly strength of gelatin (by Paggy method)
Is preferably at least 250, particularly preferably 27
0 or more.

The ratio of gelatin to the total binder applied is not particularly limited, but is preferably used in a large ratio, specifically, preferably in a ratio of 20 to 100%.

The total amount of gelatin contained on the image forming side of the light-sensitive material of the present invention 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 can be determined by the method of measuring water described in the Paggy Method and converting it to the mass of gelatin containing 11% of water.

As a hardener of a binder represented by gelatin, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination.
It is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. In order to prevent the growth of fungi and bacteria which adversely affect photographic performance and image storability, it is preferable to add an antiseptic and an antifungal agent as described in JP-A-3-157646 to the colloid layer.

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

In a preferred embodiment of the present invention, it is preferable to form a protective layer on the outermost surface of the light-sensitive material, and to add fine particle powder to the protective layer. Japanese Patent Application Laid-Open No. 6-95283 describes fine particle powder (matting agent) and a method of using the same.
It is preferable to use the technique described in page 4, left column, line 42 to page 4, right column, line 33.

In the present invention, a support of a synthetic resin film such as polypropylene, the surface of which is further coated with polyolefin, can be used.

The thickness of the reflective support is not particularly limited.
Thicknesses of from 0 to 160 μm are preferred, especially from 90 to 130 μm.
More preferably, the thickness is μm.

The light-sensitive material of the present invention may have a hydrophilic colloid layer containing fine powder and having a dry film thickness of 3 to 15 μm on the surface of the reflection support opposite to the side having the silver halide emulsion layer. preferable. This fine particle powder is often referred to in the art as a matting agent, and hence is hereinafter referred to as a matting agent unless otherwise specified.

The light-sensitive material of the present invention has a hydrophilic binder on the emulsion layer side of the reflective support having a total weight of 5 g per unit area.
/ M ^{2 to} 10 g / m ² . Still more preferably ^{6g / m 2 ~9g / m 2} . Total with the amount per unit area of the hydrophilic binder viewed from support on the side opposite to the emulsion layer, it is preferable to provide a layer which is ^{3g / m 2 ~8g / m 2} .

Examples of the matting agent usable in the present invention include crystalline or non-crystalline silica, titanium dioxide, magnesium oxide, calcium carbonate, barium sulfate, strontium barium sulfate, alumina magnesium silicate, silver halide, silicon dioxide. , Acrylic acid-ethyl acrylate copolymer, acrylic acid-methyl methacrylate copolymer, itaconic acid-styrene copolymer, maleic acid-methyl methacrylate copolymer, maleic acid-
Examples include styrene copolymer, acrylic acid-phenyl acrylate copolymer, polymethyl methacrylate, acrylic acid-methacrylic acid-ethyl methacrylate copolymer, polystyrene, starch, and cellulose acetate propionate. Other US Patents 1,221,9
No. 80, No. 2,992, 101, etc., and these can be used alone or in combination of two or more. Colloidal silica may be used together with the matting agent.

The particle size of these matting agents is preferably 1 to 10 μm, more preferably 3 to 10 μm.
It is.

The average particle size (referred to as rm) here means
In the case of spherical particles, it is the diameter, and in the case of cubic or non-spherical particles, it is the average value of the diameter when the projected image is converted into a circular image of the same area, and the particle size of each particle Is ri
Where the number is ni, defined by the following equation: As a specific measuring method, a method described in JP-A-59-29243 can be applied.

Rm = Δniri / Δni In the present invention, the matting agent is dispersed and contained in the layer on the side opposite to the photosensitive layer. The method may be, if necessary, a nonionic, cationic or anionic interface. In a hydrophilic binder containing an activator, if necessary, other additives are added, and dispersed by an emulsification dispersion method using a shear stress by a high-speed rotation mixer, a homogenizer, an ultrasonic dispersion, a ball mill, or the like. It can be formed by coating.

[0121] The coating amount of the matting agent layer is contained 1 m ²
50 to 500 mg is preferable, more preferably 7
0 to 300 mg. Further, the content of the matting agent is preferably from 3 to 50% by mass, more preferably from 5 to 20% by mass, based on the hydrophilic binder.

The support used in the light-sensitive material of the present invention has a Taber stiffness.
ss) is preferably from 0.8 to 4.0. The Taber stiffness is a stiffness measuring instrument V-5 model 150B TaberV-5 Stiffness as a measuring instrument.
tester (TABER INSTRUMENT-
A TELEDYNE COMPANY). The support generally has different stiffness values in the vertical and horizontal directions, but it is sufficient that at least one of the stiffnesses falls within this range.

As the magenta coupler used in the light-sensitive material of the present invention, a compound represented by the general formula [M-1] described in the right column of page 7 of JP-A-6-95283 is preferable because of its excellent spectral absorption characteristics of the coloring dye. . Preferred examples of the compound include compounds M-1 to M-19 described on pages 8 to 11 of the same publication. Still other specific examples include compounds M-1 to M-61 described in EP 0,273,712, pp. 6-21 and 0,235,913, pp. 36-92. Among the compounds 1 to 223, other than the above specific examples.

The above magenta couplers can be used in combination with other types of magenta couplers, and are usually 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻³ mol per mol of silver halide.
^-2 to 8 × 10 ^-1 mol can be used.

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

Here, λL of the spectral absorption of the magenta image
0.2 and λmax are values measured by the following method.

(Measurement Method of λL0.2 and λmax) When a positive emulsion is used for the light-sensitive material, the color light-sensitive material is
After uniformly exposing with the minimum amount of red light to obtain the minimum density of the cyan image and uniformly exposing with the minimum amount of blue light to obtain the minimum density of the yellow image, the white light is passed through the ND filter. After applying, when developed, an integrating sphere was attached to the spectrophotometer, and the maximum value of the absorbance when the spectral absorption of 500 to 700 nm was measured with zero correction with a standard white plate of magnesium oxide was 1.0. Then, the density of the ND filter is adjusted to produce a magenta image. When a magenta coupler or a negative emulsion is used for the light-sensitive material, the density of the ND filter is adjusted so that when the magenta image is formed by applying green light through an ND filter and developing to form a magenta image, the same maximum absorbance as the above positive is obtained. Adjust.
λL0.2 refers to a wavelength at which the absorbance of the magenta image is longer than the wavelength at which the maximum absorbance is 1.0 and the absorbance is 0.2 at the spectral absorbance curve.

The magenta image forming layer of the light-sensitive material of the present invention preferably contains a yellow coupler in addition to the magenta coupler. The difference in pKa between these couplers is preferably within 2 and more preferably 1.5.
Within. The preferred yellow coupler is represented by the general formula [Y-I] described in JP-A-6-95283, page 12, right column.
a). The general formula [Y-Ia]
Particularly preferred among the couplers represented by the general formula (M-1), when combined with the magenta coupler represented by the general formula [M-1],
It is a yellow coupler having a pKa value not lower than Ka by 3 or more.

Specific examples of the compound as the above-mentioned yellow coupler include Y-1 and Y-2 described on pages 12 to 13 of JP-A-6-95283 and JP-A-2-139542.
(Y-1) to (Y-58) described on pages 17 to 17 can be preferably used, but are not limited thereto.

As the cyan coupler contained in the cyan image forming layer, known phenol, naphthol or imidazole couplers can be used. For example, a phenol coupler substituted with an alkyl group, an acylamino group or a ureido group, a naphthol coupler formed from a 5-aminonaphthol skeleton, a bi-equivalent naphthol coupler having an oxygen atom introduced as a leaving group, and the like are typical examples. It is. Of these, preferred compounds are those represented by the general formula [C] described in JP-A-6-95283, page 13.
-I] and [C-II].

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

As the yellow coupler contained in the yellow image forming layer, known acylacetanilide couplers and the like can be preferably used. Specific examples of the yellow coupler include, for example, JP-A-3-24134.
Compounds represented by Y-I-1 to Y-I-55 described in No. 5, pages 5 to 9, or JP-A-3-209466 11-14.
Compounds represented by Y-1 to Y-30 on the page can also be preferably used. Furthermore, couplers represented by the general formula [Y-I] described in JP-A-6-95283, page 21, can also be mentioned.

In the present invention, λmax of the spectral absorption of the formed yellow image is preferably 425 nm or more, and λL0.2 is preferably 515 nm or less.

The λL0.2 of the spectral absorption of the yellow image is a value defined by the contents described in JP-A-6-95283, page 21, right column, lines 1 to 24. It is a spectral absorption characteristic showing the magnitude of absorption.

The yellow coupler is usually silver halide 1
1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² per mol
It can be used in a range of ８8 × 10 ⁻¹ mol.

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

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

An anti-fading agent can be used in combination with each of the magenta, cyan and yellow couplers 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 formulas I and II described in page 3 of JP-A-2-66541 and formula IIIB described in JP-A-3-174150.
A phenolic compound represented by
5, an amine compound represented by the general formula A described in JP-A-6-182741, a compound represented by the general formula XII, XIII, XIV,
The metal complex represented by XV is particularly preferred for magenta dyes. Further, the compounds represented by the general formula I 'described in JP-A-1-19649 and the compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

When an oil-in-water emulsion dispersion method is used to add a coupler or other organic compound used in a light-sensitive material, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher, if necessary. To dissolve in combination with a low boiling point and / or water-soluble organic solvent, and emulsify and disperse 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. After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be added.

Examples of the high-boiling organic solvent which can be used for dissolving and dispersing the coupler and the like include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate and dibutyl phthalate, tricresyl phosphate and trioctyl. Phosphate esters such as phosphates and phosphine oxides such as trioctylphosphine oxide are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Of course, two or more high-boiling organic solvents can be used in combination.

Particularly preferred compounds as high boiling organic solvents are those represented by the general formula [H] described in JP-A-6-95283, page 22.
Compounds represented by BS-I] and [HBS-II], particularly preferably compounds represented by [HBS-II]. Specific compounds include, for example, JP-A-2-124
No. 568, pp. 53-68.
95.

As a compound preferable as a surfactant used for dispersing a photographic additive used in a light-sensitive material or adjusting a surface tension at the time of coating, a compound having 8 to 3 carbon atoms in one molecule is preferable.
Those containing 0 hydrophobic groups and a sulfo group or a salt thereof are mentioned. Specific examples include A-1 to A-11 described in JP-A-64-26854. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used.
These dispersions are usually added to a coating solution containing a silver halide emulsion, but the shorter the time from dispersion to the time of addition to the coating solution, and the shorter the time from addition to the coating solution to coating. Often, both are preferably within 10 hours, more preferably within 3 hours and within 20 minutes.

In the light-sensitive material, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer to prevent fog. Is preferably improved. As the compound for this, a hydroquinone derivative is preferred, and more preferably
Dialkylhydroquinones such as 5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and the compounds II-1 to 11 described on pages 13 to 14 of the publication.
Compounds 1 described on pages II-14 and 17 are mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or to improve the light fastness of the dye image. Preferable examples of the ultraviolet absorber include benzotriazoles. Particularly preferable compounds are those represented by the general formula III described in JP-A-1-250944.
A compound represented by general formula III described in JP-A-64-66646;
No. 240, UV-1L to UV-27L;
Compounds represented by the general formula I described in JP-A-1633 and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

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

It is preferable to include a fluorescent whitening agent in the light-sensitive material and / or the processing solution in order to improve the white background.

When developing the light-sensitive material with a color developing solution, the developing solution, the bleach-fixing solution and the stabilizing solution are respectively a replenishing developer, a replenishing bleaching solution, a replenishing fixing solution, a replenishing bleach-fixing solution, Development processing can be continuously performed while replenishing a replenishing stabilizing solution or the like.

In the present invention, when the replenishment amount of the developer is
Material 1m^TwoMore effective if less than 700ml per
The effects of the present invention can be exhibited. More preferably 500 ml
It is as follows. The other processing solutions are the same as the developing solutions.
Yes, replenishment amount is 1m of photosensitive material ^Two700ml or less per
More preferably, the effect of the present invention is less than 500 ml.
Can be exhibited more effectively.

Examples of the developer which can be used in the developer used for developing the photosensitive material include ordinary silver halide developers, for example, polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, ascorbic acid and the like. Derivatives, reductones, phenylenediamines, etc., or mixtures thereof are included.

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,
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- (γ-hydroxypropyl) aniline and the like.

These developers can be incorporated in the emulsion in advance and act on silver halide during immersion in a high pH aqueous solution.

The developer may further contain a specific antifoggant and a development inhibitor, or these additives may be arbitrarily incorporated into the constituent layers of the light-sensitive material.

In the photographic material, known photographic additives can be further used. Examples of the known photographic additive include compounds described in RD17643, page 23, section III to page 29, section XXI and RD18716, page 648 to 651.

In order to form an image using the light-sensitive material of the present invention, it is preferable to use an automatic developing machine of a light-source scanning exposure system. Specific examples of particularly preferable devices and systems for image formation include Digital from Konica Corporation.
Konsensus and the like.

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

In the present invention, it is preferable that the silver halide photographic light-sensitive material is previously loaded in a cartridge which can be handled in a bright room by being wound in a roll. In a cartridge that can be handled in a light room, a light-sensitive material drawer that can be smoothly pulled out from the cartridge when it is mounted on an apparatus is provided with a light shielding unit that prevents the photosensitive material in the light room from receiving light in the light room. Yes,
Normally, when handled in a light room, the photosensitive material inside is not exposed to light.

In the present invention, a light-sensitive material wound in a roll shape is loaded in a light chamber cartridge in advance.
Moreover, it is preferable that the photosensitive material is wound so that the emulsion surface is arranged 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 leader, the photosensitive material can be handled in a bright room while being shielded from light, and after loading into an exposure apparatus, the leader is removed to remove the dark room. In the image forming method of the present invention, a bright room cartridge includes a so-called easy-loading photosensitive material which can be easily loaded with a roll of a silver halide photographic photosensitive material without requiring it.
In that case, the readable information can be given to the reader or to the flange or the like.

In the present invention, a silver halide color photographic light-sensitive material is exposed to light based on halftone image information comprising color-separated yellow image information, magenta image information, cyan image information and black image information, and In the step of producing a proof, when the halftone dot area ratio of at least a part of the halftone dot image information is 40%, 1 inch
^The number of halftone dots per ² (6.452 cm ² ) is 200 × 10
Use a dot image converted so that it is ³ or more.

In the present invention, the number of halftone dots can be measured by counting halftone images taken by an optical microscope or the like.

The dot image used in the present invention is particularly effective when it is a dot image for high-definition printing by the AM screening method. Further, the present invention is most effective when a halftone dot formed by the so-called FM screening method, which is frequency-modulated, is a layer.

In the present invention, it is preferable that the halftone image information is a halftone image recorded on a film, and the exposure is performed by bringing the film into close contact with the photosensitive material and scanning a light source. For the adhesion, a vacuum adhesion method can be preferably used.

In the present invention, it is preferable to perform exposure via an optical means for improving the parallelism of light from the light source. As a specific means, a means for absorbing components other than parallel light on a wall surface by passing through a linear tubular optical path such as an optical lens, a reflecting mirror, or a honeycomb structure may be used. In addition, parallelism can be improved by an aggregate of optical fibers.

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

[0166]

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

Example 1 (Preparation of emulsion EM-P1) While controlling the aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (KBr: NaCl = 95: 5) was added simultaneously by a controlled double jet method to obtain a cubic silver chlorobromide core emulsion having a particle size of 0.30 μm. At this time, the pH and p are adjusted so that a cube is obtained as the particle shape.
Ag was controlled.

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

After washing with water to remove water-soluble salts, gelatin was added to obtain emulsion EM-P1. The width of the distribution of the emulsion EM-P1 was 8%.

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

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

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

(Preparation of Blue-Sensitive Silver Halide Emulsion) Emulsion E
After sensitizing dye BS-1 was added to MP-P1 for optimal color sensitization, 100 mg per mol of silver of stabilizer ST-1 was added to prepare blue-sensitive emulsion EM-B1.

(Preparation of Green-Sensitive Silver Halide Emulsion) Emulsion E
Green-sensitive emulsion EM was prepared in the same manner as blue-sensitive emulsion EM-B1, except that sensitizing dye GS-1 was added to M-P1 to optimize the color sensitization.
-G1 was produced.

(Preparation of Red-Sensitive Silver Halide Emulsion) Emulsion E
A red-sensitive emulsion EM-R1 was prepared in the same manner as the blue-sensitive emulsion EM-B1, except that sensitizing dyes RS-1 and RS-2 were added to MP-P2 to optimize the color sensitization.

(Preparation of Infrared-Sensitive Silver Halide Emulsion) The sensitizing dye IRS-1 was added to the emulsion EM-P2 for optimum color sensitization, and the blue-sensitive emulsion EM-B1 was used except that ST-1 was added. In the same manner as in the above, an infrared-sensitive emulsion EM-IR1 was prepared.

The structures of the additives used in preparing each emulsion are shown below. ST-1: 4-hydroxy-6-methyl-1,3,3
3a, 7-tetrazaindene

[0178]

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[0179]

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<Preparation of Multilayer Color Photosensitive Material Sample> A high-density polyethylene was laminated on one side and a molten polyethylene containing anatase-type titanium oxide dispersed at a content of 15% by mass was laminated on the other side. Mass 11
On a 5 g paper pulp reflective support, EM-B1, EM
Using each emulsion of -G1 and EM-R1, each layer having the following constitution was applied on the side of the polyethylene layer containing titanium oxide,
Further by coating gelatin 7.2 g / m ^2, a silica matting agent 0.65 g / m ² on the back side photosensitive material No. 11 was produced. In addition, H-1 and H-2 were added as hardening agents. Surfactants SU-1, S
U-2 and SU-3 were added.

SU-1: sodium sulfosuccinate di (2-ethylhexyl) ester SU-2: sulfosuccinate di (2,2,3,3,4,4,4)
5,5-octafluoropentyl) ester sodium SU-3: sodium tri-i-propylnaphthalenesulfonate H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium H-2: tetrakis (vinyl) (Sulfonylmethyl) methane The coating amount of the compound in each layer was represented by g / m ² .

Tenth layer (ultraviolet absorbing layer) Coating amount (g / m ² ) Gelatin 1.20 Ultraviolet absorbing agent (UV-1) 0.070 Ultraviolet absorbing agent (UV-2) 0.025 Ultraviolet absorbing agent (UV -3) 0.120 Silica matting agent 0.01 Ninth layer (blue-sensitive layer) Gelatin 0.92 Blue-sensitive emulsion Silver chlorobromide emulsion (EM-B1) 0.33 Magenta coupler (M-1) 0.20 Yellow coupler (Y-3) 0.05 Inhibitor (ST-1) 0.002 Inhibitor (ST-2, ST-3, ST-4) (Molar ratio 1: 1: 1) 0.0004 Stain inhibitor (HQ-1) 0.03 High boiling point solvent (SO-1) 0.31 Eighth layer (intermediate layer) Gelatin 0.40 Stain inhibitor (HQ-2) 0.02 Stain inhibitor (HQ-3) 0 .01 High boiling point solvent (SO-2) 0.005 7th layer ( Yellow colloid silver layer) Gelatin 0.08 Yellow colloid silver layer 0.09 Stain inhibitor (HQ-2) 0.02 Stain inhibitor (HQ-3) 0.005 Polyvinylpyrrolidone 0.004 6th layer (intermediate layer) Gelatin 0.04 Stain inhibitor (HQ-2) 0.02 Stain inhibitor (HQ-3) 0.01 High boiling solvent (SO-2) 0.005 Fifth layer (green sensitive layer) Gelatin 1.75 Green Sensitive silver chlorobromide emulsion (EM-G1) 0.24 Cyan coupler (CC-1) 0.35 Stain inhibitor (HQ-1) 0.035 High boiling solvent (SO-3) 0.33 High boiling solvent ( SO-4) 0.33 inhibitor (ST-1) 0.0015 inhibitor (ST-2, ST-3, ST-4) (molar ratio 1: 1: 1) 0.0004 4th layer (intermediate layer) ) Gelatin 0.70 stay Inhibitor (HQ-2) 0.04 Stain inhibitor (HQ-3) 0.02 High-boiling solvent (SO-2) 0.01 Anti-irradiation dye (AI-1) 0.02 Anti-irradiation dye (AI) -2) 0.02 Third layer (red-sensitive layer) Gelatin 1.10 Red-sensitive emulsion (EM-R1) 0.40 Yellow coupler (Y-1) 0.43 Yellow coupler (Y-2) 0.10 Stain Inhibitor (HQ-1) 0.05 High boiling organic solvent (SO-1) 0.43 Inhibitor (ST-1) 0.006 Inhibitor (ST-2, ST-3, ST-4) (molar ratio) 1: 1: 1) 0.0004 Second layer (intermediate layer) Gelatin 0.40 Stain inhibitor (HQ-2) 0.01 Stain inhibitor (HQ-3) 0.005 High boiling solvent (SO-2) 0.003 Optical brightener solid particles (F-10) .40 1st layer (antihalation layer) Gelatin 0.60 Latex (LA-1) 0.12 Black colloidal silver 0.03 Polyvinylpyrrolidone 0.10 Titanium oxide 1.00 Support: Polyethylene laminated paper (a trace amount of colorant Content) The amount of silver halide emulsion added was expressed in terms of silver.

The structure of each additive is as shown below. SO-1: tri (n-octyl) phosphine oxide SO-2: di (i-decyl) phthalate SO-3: tricresyl phosphate 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 and 2,5-di-sec-tetradecylhydroquinone A mixture of 2-sec-dodecyl-5-sec-tetradecylhydroquinone in a mass ratio of 1: 1: 2 ST-2: 1- (3-acetamidophenyl) -5-mercaptotetrazole ST-3: N-benzyladenine ST- 4: 2-mercaptobenzothiazole LA-1: Copolymer of ethyl acrylate and sodium acrylate

[0184]

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[0185]

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[0186]

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The light-sensitive material Nos. Samples were prepared in the same manner as in Sample No. 11, except that the compounds shown in Table 1 were used instead of H-2 as hardening agents. 12 and 13 were produced.

The spectral sensitivity peaks of the emulsion layers of the light-sensitive materials thus obtained were 460 nm for the blue-sensitive emulsion, 548 nm for the green-sensitive emulsion, and 670 nm for the red-sensitive emulsion.

Each of the above samples was cut to a width of 570 mm and a length of 55 m, wound around a core so that the emulsion surface was exposed, processed into a roll, and housed in a bright room type cartridge.

The sample obtained as described above is
Of the halftone dot original document, the yellow plate was brought into close contact with the material and exposed under the following exposure conditions -Y. Next, the magenta plate was brought into close contact with the sample and exposed under the following exposure conditions -M. Next, the cyan plate was brought into close contact with the sample and exposed under the following exposure condition-C. Next, the cyan plate was brought into close contact with the sample and exposed under the following exposure condition-C. In the above-mentioned halftone original document, an image having a halftone area of 175 lines / inch and a halftone area of 50% (hereinafter also referred to as a middle point) is incorporated in the yellow, magenta, cyan and black versions, respectively. It is possible to evaluate what kind of image the 50% halftone dot image is reproduced.
Separately, there is an image portion where the halftone dot area ratio of each plate is changed between 0% and 100% to evaluate the halftone dot reproducibility and halftone dot quality. At the same time, it has an image portion that can incorporate an optical wedge into a film original of each color so that gradation can be measured so that sensitometry can be performed.

(Exposure condition-Y) Each photosensitive material was exposed to light using a white light source (halogen lamp) through a red filter (Wratten No. 26), and further exposed to light by adjusting the ND filter density. (E1 × S1) / (E2 × S2) and (E1 × S
2) The value of / (E3 × S3) was adjusted as shown in Table 3.

(Exposure condition-M) Each photosensitive material was exposed to light using a white light source (halogen lamp) through a blue filter (Watten No. 47B), and further exposed to light by adjusting the ND filter density. As a result of the image evaluation, the value of (E1 × S1) / (E3 × S3) was adjusted as shown in Table 3.

(Exposure condition-C) Each photosensitive material was exposed to light using a white light source (halogen lamp) through a green filter (Ratten No. 58), and further exposed to light by adjusting the ND filter density. As a result of the image evaluation of
The value of (E1 × S1) / (E2 × S2) was adjusted as shown in Table 3.

The photosensitive material was fixed on an exposure table by a reduced-pressure suction contact method, the original film was brought into close contact with the light source, and the corresponding light source was made parallel light by a Fresnel lens.

Each exposed sample was processed in the following processing step-1 to obtain an image. (Processing step-1) Processing step Temperature time Immersion (developer) 37 ° C for 12 seconds Fog exposure -12 seconds Developing 37 ° C for 95 seconds Bleaching and fixing 35 ° C for 45 seconds Stabilizing treatment 25 to 30 ° C for 90 seconds Drying 60 to 85 40 ° C. (color developing solution composition) benzyl alcohol 15.0 ml ceric sulfate 0.015 g ethylene glycol 8.0 ml potassium sulfite 2.5 g potassium bromide 0.6 g sodium chloride 0.2 g potassium carbonate 25.0 g ST-1 0.1 g hydroxylamine sulfate 5.0 g pentasodium diethylenetriaminepentaacetate 2.0 g 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g fluorescent brightener (4,4′- Diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 1 Adjust the pH to 10.15 by adding 5.0 ml water to make the total volume 1000 ml.

(Composition of bleach-fixing solution) Ferric ammonium diethylenetriaminepentaacetate 90.0 g Diethylenetriaminepentaacetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution) 180.0 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-mercapto-1 , 2,4-triazole 0.15 g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to make the total volume 1 liter.

(Composition of stabilizing solution) o-phenylphenol 0.3 g potassium sulfite (50% aqueous solution) 12.0 ml ethylene glycol 10.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.5 g bismuth chloride 0.2 g Zinc sulfate heptahydrate 0.7 g Ammonium hydroxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g Water In addition, the total volume is made up to 1 liter and adjusted to pH 7.5 with ammonium hydroxide or sulfuric acid.

Incidentally, the stabilizing treatment was of a countercurrent type having a three-tank configuration. A part of another sample is the same as the processing step-1.
An image was obtained by development processing of Nos. 2 to 5. However, the processing steps -2 to 5 are as shown in Table 2 below, and the amounts of hydroxylamine sulfate in the developing solution and the developing replenisher and the compounds of the general formula (B) of the present invention are shown in Table 2 below. Other than the addition, the image N
o. 1A to 1G were obtained.

[0199]

[Table 1]

[0200]

[Table 2]

The obtained image No. For 1A to 1G, the color tone of the image portion composed of each halftone dot of YMC in the chart was measured. For CIELab, the color tone difference between the center and the periphery of the screen was determined. The CIE, L ^* , a ^* , and CIE were measured using a Minolta colorimeter CM-2022.
b ^* was measured, and the color shift between the central portion and the peripheral portion was ΔE.
Was evaluated.

ΔE = (ΔL ^{* 2} + Δb ^{* 2} + Δa ^{* 2} ) 1/2 ΔL ^* , Δa ^* , and Δb ^* represent the differences between L ^* , a ^* , and b ^* between the central part and the peripheral part, respectively. .

The obtained ΔE is summarized in Table 3 below.

[0204]

[Table 3]

From the results shown in Table 3, it can be seen that the image obtained by the present invention has a stable black color tone and a small fluctuation in the color tone in the image plane (center and peripheral portions).

Example 2 The photosensitive material No. obtained in Example 1 was used. Using No. 11 an image was obtained as follows. Of the halftone dot originals, the yellow plate was brought into close contact with the sample and exposed under the following exposure conditions -Y2.
Next, the magenta plate was brought into close contact with the sample and exposed under the following exposure conditions -M2. Next, the cyan plate was brought into close contact with the sample and exposed under the following exposure condition-C2.

(Exposure condition-Y2) The photosensitive material is subjected to scanning exposure using a white light source (daylight fluorescent lamp) through a red filter (Ratten No. 26). At this time, the width of the slit and the scanning speed are adjusted. And (E1 × S1) / (E2 × S2) and (E1 ×
The value of (S1) / (E3 × S3) was adjusted as shown in Table 4.

(Exposure Condition-M2) The photosensitive material is subjected to scanning exposure using a white light source (daylight fluorescent lamp) through a blue filter (Ratten No. 47B). At this time, the width of the slit and the scanning speed are adjusted. Exposure was performed, and as a result of image evaluation after development, the value of (E1 × S1) / (E3 × S3) was adjusted to be as shown in Table 4.

(Exposure condition-C2) The photosensitive material was subjected to scanning exposure using a white light source (daylight fluorescent lamp) through a green filter (Ratten No. 58). At this time, the width of the slit and the scanning speed were adjusted. Table 4 shows the value of (E1 × S1) / (E2 × S2) as a result of image evaluation after development.
It was adjusted to be.

The photosensitive material was fixed to an exposure table by a reduced pressure suction contact method, and the exposure was performed by bringing the original films into close contact with each other and scanning the light sources. The exposure time was adjusted between 0.2 and 2 seconds.

Each of the exposed samples was subjected to development processing as shown in Table 4 in processing steps 1 and 4 similar to the processing steps in Example 1 to obtain images.

[0212]

[Table 4]

The obtained image No. 1A and 2A to 2C
For each sample, the color tone of the image portion composed of each halftone dot of YMC in the chart was measured. Measured in the same manner as in Example 1,
evaluated. From the results shown in Table 4, it can be seen that the image obtained in accordance with the second aspect of the present invention has a stable black color tone and a small fluctuation in the color tone in the image plane (central part and peripheral part).
Table 5 below shows the results of measurement of ΔE at the center and the periphery of a white background.

[0214]

[Table 5]

From the results shown in Table 5, it can be seen that the image obtained by the method of the present invention has a small variation in the white background in the screen.

Example 3 <Preparation of multilayer color light-sensitive material sample> One side was made of high-density polyethylene and the other side was made of anatase-type titanium oxide.
The above-mentioned EM-B1, EM-G1, and EM were placed on a paper pulp reflective support having a mass per square rice of 115 g laminated with a molten polyethylene dispersed and contained at a content of 5% by mass.
Using each emulsion of -R1 and EM-IR1, each layer having the following composition was coated on the side of the polyethylene layer containing titanium oxide, and on the back side, 7.2 g / m ² of gelatin and 0.65 g of silica matting agent were applied. / M ² coated with photosensitive material No. 31 were produced. In addition, H-1 and H-2 were added as hardening agents.
As a coating aid and a dispersing aid, a surfactant SU-
1, SU-2 and SU-3 were added.

The coating amount of the compound in each layer was represented by g / m ² . 12th layer (ultraviolet absorbing layer) Coating amount (g / m ² ) Gelatin 1.20 Ultraviolet absorbing agent (UV-1) 0.070 Ultraviolet absorbing agent (UV-2) 0.025 Ultraviolet absorbing agent (UV-3) 0.120 Silica matting agent 0.01 11th layer (blue-sensitive layer) Gelatin 0.92 Blue-sensitive emulsion Silver chlorobromide emulsion (EM-B1) 0.33 Magenta coupler (M-1) 0.20 Yellow coupler ( Y-3) 0.05 Inhibitor (ST-1) 0.002 Inhibitor (ST-2, ST-3, ST-4) (molar ratio 1: 1: 1) 0.0004 Stain inhibitor (HQ- 1) 0.03 High boiling solvent (SO-1) 0.31 10th layer (intermediate layer) Gelatin 0.40 Stain inhibitor (HQ-2) 0.02 Stain inhibitor (HQ-3) 0.01 High Boiling point solvent (SO-2) 0.005 9th layer (yellow Lloyd silver layer) Gelatin 0.08 Yellow colloidal silver layer 0.09 Stain inhibitor (HQ-2) 0.02 Stain inhibitor (HQ-3) 0.005 Polyvinylpyrrolidone 0.004 Eighth layer (intermediate layer) Gelatin 0.04 Stain inhibitor (HQ-2) 0.02 Stain inhibitor (HQ-3) 0.01 High boiling solvent (SO-2) 0.005 7th layer (green sensitive layer) Gelatin 1.20 green sensitivity Silver chlorobromide emulsion (EM-G1) 0.38 Yellow coupler (Y-1) 0.51 Magenta coupler (M-1) 0.11 Stain inhibitor (HQ-1) 0.06 High boiling organic solvent (SO -3) 0.31 inhibitor (ST-1) 0.004 inhibitor (ST-2, ST-3, ST-4) (molar ratio 1: 1: 1) 0.0002 6th layer (intermediate layer) Gelatin 0.50 Stain prevention (HQ-2) 0.04 Stain inhibitor (HQ-3) 0.02 High boiling solvent (SO-2) 0.01 Fifth layer (red-sensitive layer) Gelatin 1.75 Red-sensitive silver chlorobromide emulsion (EM-R1) 0.25 Green-sensitive silver chlorobromide emulsion (EM-G1) 0.24 Cyan coupler (CC-1) 0.35 Stain inhibitor (HQ-1) 0.035 High boiling solvent (SO- 4) 0.33 high boiling point solvent (SO-5) 0.33 inhibitor (ST-1) 0.0015 inhibitor (ST-2, ST-3, ST-4) (molar ratio 1: 1: 1) 0.0004 Fourth layer (intermediate layer) Gelatin 0.70 Stain inhibitor (HQ-2) 0.04 Stain inhibitor (HQ-3) 0.02 High boiling solvent (SO-2) 0.01 Irradiation prevention Dye (AI-1) 0.03 Anti-irradiation dye (AI-2) 0 03 Third layer (infrared-sensitive layer) Gelatin 1.10 Infrared-sensitive emulsion (EM-IR1) 0.40 Yellow coupler (Y-1) 0.43 Yellow coupler (Y-2) 0.10 Stain prevention Agent (HQ-1) 0.05 High boiling organic solvent (SO-1) 0.43 Inhibitor (ST-1) 0.006 Inhibitor (ST-2, ST-3, ST-4) (Molar ratio 1) : 1: 1) 0.0004 Second layer (intermediate layer) Gelatin 0.40 Stain inhibitor (HQ-2) 0.01 Stain inhibitor (HQ-3) 0.005 High boiling solvent (SO-2) 0 0.003 Anti-irradiation dye (AI-4) 0.05 Solid fluorescent brightener particles (F-10) 1.40 First layer (anti-halation layer) Gelatin 0.60 Latex (LA-1) 0.12 Black Colloidal silver 0.03 Polyvinyl pyro Lidone 0.10 Titanium oxide 1.00 Support: polyethylene laminated paper (containing a trace amount of colorant) The amount of silver halide emulsion added was expressed in terms of silver.

[0218]

Embedded image

The spectral sensitivity peaks of the emulsion layers of the light-sensitive materials thus obtained were 460 nm for the blue-sensitive emulsion, 548 nm for the green-sensitive emulsion, 670 nm for the red-sensitive emulsion, and 785 nm for the infrared-sensitive emulsion. Was.

Each of the above samples was cut to a width of 570 mm and a length of 55 m, wound around a core so that the emulsion surface was exposed, processed into a roll, and housed in a bright room type cartridge.

Using the obtained sample, an image was obtained as follows. Of the halftone dot originals, the yellow plate was brought into close contact with the sample and exposed under the following exposure conditions -Y3. Next, the magenta plate was brought into close contact with the sample, and the exposure conditions -M shown below were used.
3 was exposed. Next, the cyan plate was brought into close contact with the sample and exposed under the following exposure conditions-C3, and the black plate was brought into close contact with the sample and exposed under the following exposure conditions-K3.

(Exposure condition-Y3) Exposure is performed by using an infrared light source as the photosensitive material and passing through a filter that transmits infrared light (using LEE filters, 026 and 363 superimposed). Is adjusted, and exposure is performed. As a result of image evaluation after development, (E1 × S1) / (E2
× S2) and (E1 × S1) / (E3 × S3) were adjusted as shown in Table 6.

(Exposure condition-M3) Each photosensitive material was exposed to light using a white light source through a blue filter (Ratten No. 47B). At that time, the width of the slit and the scanning speed were adjusted to perform exposure. 50% of magenta after development
Each N is set so that the halftone dot area of the halftone
The exposure was adjusted with the D filter density.

(Exposure condition-C3) The photosensitive material was exposed to light using a white light source through a red filter (Ratten No. 26). At that time, the width of the slit and the scanning speed were adjusted, and the exposure was performed. As a result of the image evaluation of (E1 ×
The value of (S1) / (E2 × S2) was adjusted so as to be as shown in Table 6.

(Exposure condition-K3) Exposure was performed on the photosensitive material through a green filter (Ratten No. 58) using a white light source. At that time, the exposure was performed by adjusting the width of the slit and the scanning speed. As a result of the image evaluation of (E1 ×
The value of (S1) / (E3 × S3) was adjusted so as to be as shown in Table 6.

The photosensitive material was fixed on an exposure table by a reduced-pressure suction contact method, and the exposure was performed by bringing the original films into close contact with each other and scanning the light sources. The exposure time was adjusted between 0.2 and 10 seconds.

A part of another sample was subjected to the above-mentioned exposure condition-Y3
Exposure under the exposure conditions -Y4 to K4 was performed in the same manner as in the case of .about.K3. However, the exposure under the exposure conditions -Y3 to K3 was performed at a temperature of the environment where the equipment was installed at 25 ° C. and 55%, but the exposure under the exposure conditions -Y4 to K4 was performed only at 33 ° C. and 55%. I went different.

As a comparison, the image Nos.
In the same manner as in 1A, exposure conditions -Y to C were performed in a 25 ° C environment, and further, exposure was performed in a 33 ° C environment.

Each of the exposed samples was subjected to development processing in the same manner as the processing steps 1 and 4 in Example 1 with the contents shown in Table 6 to obtain an image.

For the obtained image, the Y
The color tone of the image portion composed of halftone dots of 50% of MC was measured, and the color difference ΔE between 25 ° C. and 33 ° C. was obtained.

[0231]

[Table 6]

From the results shown in Table 6, it can be seen that the image obtained according to the third aspect of the present invention has a stable black color tone even when the exposure temperature fluctuates, and a small color tone fluctuation.

Example 4 The photosensitive material No. prepared in Example 1 was used. No. 11 according to the photosensitive material No.
41 were produced. Sensitive material No. In 41 to 43, the third layer,
A sample in which the compound of the general formula (C) was added to the fifth and ninth layers according to the contents shown in Table 7 below. The addition amount was 0.5 × 10 ⁻³ mol per mol of silver. Sensitive material No. 11 and photosensitive material no. For 41-43, some of the samples were kept refrigerated, but some of the other samples were stored at 40 ° C and 55%
Stored for days.

Using the sample obtained above, the image No. obtained in Example 1 was used. An image sample was obtained in the same manner as in Example 1A, except that the sample stored in the refrigerator and the sample stored in the high temperature showed Y.
The color tone difference ΔE of an image composed of 50% halftone dots of MC was determined.

[0235]

[Table 7]

From the results shown in Table 7, it can be seen that the image obtained according to claim 4 of the present invention has a stable black color tone even when the raw sample is deteriorated by high-temperature storage, and has a small color tone variation.

Example 5 EM-E was prepared in the same manner as the emulsion EM-P2 prepared in Example 1.
P3 was prepared. EM-P3 was prepared by adding rhodium chloride at 1 × per mole of silver before forming a shell in the core emulsion.
It was prepared differently only by adding 10 ^-8 mol.

(Preparation of Red-Sensitive Silver Halide Emulsion) Emulsion E
A red-sensitive emulsion EM-R was prepared in exactly the same manner as the red-sensitive emulsion EM-R1 except that the emulsion EM-P3 was used instead of MP-P2.
2 was produced.

In the photosensitive material No. of Example 1, In the same way as 11,
Sensitive material No. The photosensitive material No. 51 was prepared. In No. 51, a sample was prepared except that EM-R2 was used instead of the red-sensitive emulsion EM-R1.

Sensitive material No. 11 and photosensitive material No. The sensitometric characteristics of each of the yellow layer, magenta layer, and cyan layer were obtained for 51, and the photographic gradations of the yellow image, magenta image, and cyan image were obtained.
The results are shown in Table 8 below.

[0241]

[Table 8]

From Table 8 above, it can be seen that the photosensitive material Nos. In No. 11, the photographic gradation of Y having the longest spectral sensitivity wavelength has other magenta layers,
Although smaller than the cyan layer, photosensitive material No. In 51, the photographic gradation of the yellow layer having the longest spectral sensitivity wavelength is larger than that of the magenta and cyan layers.

Sensitive material No. 11 and photosensitive material no. Regarding 51, a part of each sample was stored under refrigeration, while a part of another sample was stored at 40 ° C. for 10 days.

Using the sample obtained above, the image No. obtained in Example 1 was used. An image sample was obtained in the same manner as in Example 1A, except that the sample stored in the refrigerator and the sample stored in the high temperature showed Y.
A color tone difference ΔE of an image composed of 50% halftone dots of MC is obtained,
Table 9 shows the results.

[0245]

[Table 9]

From the results shown in Table 9, it can be seen that the image obtained according to claim 5 of the present invention has a stable black color tone even when the raw sample is deteriorated by high-temperature storage, and has a small color tone fluctuation.

Example 6 The photosensitive material No. 1 prepared in Example 1 was used. Sensitive material N in the same manner as 11
o. Nos. 61 to 64 were prepared. By changing the amount of the anti-irradiation dye (AI-2) added to the fourth layer of No. 11, the raw sample reflection density at 670 nm was added as shown in Table 10 below.

[0248]

[Table 10]

The photosensitive material No. obtained as described above was used. 61
From the photosensitive material No. A part of each sample of the sample No. 64 was stored in a refrigerator, while another part was stored in a 40 ° C. environment for 10 days.

Using the sample obtained above, the image No. obtained in Example 1 was used. An image sample was obtained in the same manner as in Example 1A, except that the sample stored in the refrigerator and the sample stored in the high temperature showed Y.
A color tone difference ΔE of an image composed of 50% halftone dots of MC is obtained,
Table 11 shows the results.

[0251]

[Table 11]

From the results shown in Table 11, it can be seen that the image obtained in accordance with the sixth aspect of the present invention has a stable black color tone even when the raw sample is deteriorated by high-temperature storage, and has a small color tone variation.

[0253]

According to the present invention, when a color image is obtained using a silver halide photographic light-sensitive material, it is possible to provide an image forming method in which the fluctuation of a white background is small and the color tone of black dots is stable. did it. Further, in the color plate making / printing process, a silver halide photographic light-sensitive material is exposed according to halftone image information obtained by color separation and halftone image conversion to obtain a color image. A color image forming method for calibration in which the color tone of black dots is stable can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 3/10 G03F 3/10 B

Claims (6)

[Claims] Claims: 1. A color for color developing a silver halide photographic light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivity regions on a support by image exposure with light in each of the spectral sensitivity regions. In the image forming method, the silver halide photographic material is represented by the following general formula (A)
And at least one hardening agent selected from the group consisting of: CH ₂ ＣＨCHSO ₂ —R ₁ —SO ₂ —CH =
CH ₂ [wherein, R ₁ represents an alkylene group or the like. And the sensitivity of the emulsion layer is set to S1,
When S2 and S3 are set, and the maximum value of the exposure amount of the light source is set to E1, E2, and E3 in order of wavelength, after image exposure represented by the following formula (1), the following formula (1) (E1 × S1) is obtained. /(E2×S2)<0.9 (E1 × S1) / (E3 × S3) <0.9 At least one compound represented by the following general formula (B) is contained, and hydroxylamine is contained in an amount of 0 to 2 A color image forming method, wherein a color image is formed by developing with a color developing solution containing 0.0 g / l. General formula (B) HO-N (R) -LA wherein L represents an alkylene group which may be substituted, and A represents a carboxyl group, a sulfo group, a phosphono group, a hydroxy group, an alkyl group, Represents an amino group which may be substituted, and R represents a hydrogen atom or an alkyl group which may be substituted. ] 2. A color in which a silver halide photographic light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivity regions on a support is image-exposed with light of each of the spectral sensitivity regions and then color-developed. In the image forming method, the sensitivity of the emulsion layer is set to S1,
S2 and S3, and when the maximum value of the exposure amount of the light source is E1, E2 and E3 in order of wavelength, the image exposure is represented by the above equation (1), and the exposure time is 1 × 10 ^{− 2} seconds ~
After scanning exposure for 10.0 seconds, color development is carried out using a color developer containing at least one compound represented by the above general formula (B) and containing 0 to 2.0 g / l of hydroxylamine. A color image forming method comprising forming an image. 3. A halide comprising, on a support, at least three silver halide emulsion layers having spectral sensitivity regions different from each other and a fourth silver halide emulsion having a spectral sensitivity region different from any of the silver halide emulsions. In a color image forming method in which a silver photographic photosensitive material is color-developed after image exposure with light in each of the spectral sensitivity regions, the sensitivities of the emulsion layers are set to S1, S2, and S3 in order of the spectral sensitivity wavelength, The maximum value of the exposure amount is determined by E1, E
2, E3, after the image exposure represented by the above formula (1), contains at least one compound represented by the above general formula (B),
A color image forming method, wherein a color image is formed by developing with a color developing solution containing g / l. 4. A color in which a silver halide photographic light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivity regions on a support is image-exposed with light in each of the spectral sensitivity regions and then color-developed. In the image forming method, the silver halide photographic material is represented by the following general formula (C)
And at least one of the compounds represented by S1 and S2 in order of spectral sensitivity wavelength.
2, S3, and when the maximum value of the exposure amount of the light source is E1, E2, and E3 in order of wavelength, after image exposure represented by the above formula (1), A color image forming method comprising forming a color image by developing with a color developing solution containing 0 to 2.0 g / l of hydroxylamine containing at least one of the compounds represented by formula (I). Formula (C) R ₁₁ in -SO ₂ -S-M [wherein, R ₁₁ represents an aliphatic group, an aromatic group or a heterocyclic group, M represents a hydrogen atom or a monovalent cation. ] 5. A color in which a silver halide photographic light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivity regions on a support is image-exposed with light in each of the spectral sensitivity regions and then color-developed. In the image forming method, among the photographic gradations of the emulsion layer, the photographic gradation of the emulsion layer having the longest spectral sensitivity wavelength is the largest, and the sensitivity of the emulsion layer is changed in the order of S1, S2, S
3, and when the maximum value of the exposure amount of the light source is set to E1, E2, and E3 in the order of the longest wavelength, after the image exposure represented by the above formula (1), the exposure is represented by the above general formula (B). At least one of the compounds
A color image forming method, wherein the color image is formed by developing with a color developing solution containing 0.1 to 2.0 g / l. 6. A color in which a silver halide photographic light-sensitive material having at least three silver halide emulsion layers having mutually different spectral sensitivity regions on a support is image-exposed to light in each of the spectral sensitivity regions and then color-developed. In the image forming method, the reflection density of the raw sample in the spectral sensitivity region having the longest wavelength in the emulsion layer is 0.8 or more, and the sensitivities of the emulsion layer are S1, S2, and S3 in ascending order of the spectral sensitivity wavelength; The maximum value of the exposure amount of the light source is determined by the order of E1, E
2, E3, after the image exposure represented by the above formula (1), contains at least one compound represented by the above general formula (B),
A color image forming method, wherein a color image is formed by developing with a color developing solution containing g / l.