JP2001337418A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material for a stable high quality color proof having improved white ground characteristics and superior dot quality in a wide dot gain range. SOLUTION: At least one of the silver halide emulsion layers of the silver halide color photographic sensitive material has >=100 nm difference between the wavelength at which spectral sensitivity in exposure is maximum and the wavelength at which a color forming dye has the absorption maximum and the sensitive material has a non-photosensitive hydrophilic colloidal layer between the base and a silver halide emulsion layer closest to the base, contains at least two white pigments different from each other in spectral reflection characteristics in the non-photosensitive hydrophilic colloidal layer and contains a hardening agent of the formula CH2=CHSO2-R0-SO2CH=CH2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material (hereinafter, also simply referred to as a "light-sensitive material"), and more particularly, to a silver halide photographic light-sensitive material which is exposed by an exposure device capable of forming a color image. In particular, the present invention relates to a silver halide color photographic light-sensitive material used for proofreading in accordance with halftone image information obtained by color separation and halftone image conversion in a color plate making and printing process.

[0002]

2. Description of the Related Art Silver halide light-sensitive materials are widely used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. Due to these characteristics, silver halide photosensitive materials are not only used in the field of photography,
Also in the field of printing, it has been widely used in the field of so-called proofing for checking the state of finished printed matter in the middle of printing.

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 light-sensitive material having a white support is used. A method of producing a color proof is disclosed in JP-A-56-113139 and JP-A-56-10.
No. 4335, No. 62-280746, No. 62-280
No. 747, No. 62-280748, No. 62-2807
Nos. 49 and 62-280750.

[0004] On the other hand, plate making methods for converting an image into a digital signal and editing the image on a computer without using the above-described halftone dot black and white film have come into wide use. By digitizing the image information, the image processing, the image can be quickly sent to a remote place, or the image in which the layout, the color tone, etc. of the image are changed can be quickly edited.

In recent years, this color proof has been increasingly used not only for plate inspection for confirming characters and pictures, but also for tone adjustment for confirming subtle shadows and colors. Further, in the color proof, various printing conditions, printing machines, and the like are used, and it is required that the color proof can be used over a wide range due to a difference in a picture pattern of a printed matter. However, in printing, halftone dots of a printed matter are larger than halftone dots of a document due to ink bleeding or the like. This ratio is called dot gain. This dot gain is equivalent to a gradation in a general photograph, and greatly affects the image quality. Therefore, in order to obtain a high-quality proof, it is necessary to adjust the dot gain so as to approximate a printed matter. In a method for producing a color proof using a photosensitive material, a method of adjusting a dot gain by adjusting an exposure amount is known. However, in this method, in the case of a negative type photosensitive material, if the exposure amount is changed, the density changes.Therefore, if the dot gain is adjusted, the density becomes out of the standard, and if the density is adjusted, the dot gain becomes out of the standard. In the case of the positive type, when the dot gain was to be increased, the white background was easily degraded, and the image quality was likely to be reduced. There is also known a method of adjusting the dot gain by changing the sharpness of a photosensitive material. In order to increase the dot gain, it is necessary to degrade the sharpness.However, since the reproducibility of large points and small points is significantly degraded by deteriorating the sharpness, adjustment of dot gain by this method is also required. There was a limit. Further, as a means for adjusting the dot gain, a method of adjusting the gradation of the photosensitive material to an appropriate range is also known, and in particular, a method of setting the gradation from a medium density to a low density to a certain softness is effective. . However, in the conventional image forming method, if the gradation from the middle density to the low density (leg gradation) is designed to be in an optimum range for adjusting the dot gain, the gradation from the middle density to the high density range (shoulder level). Tone) also tends to soften at the same time, and the exposure required to obtain the highest density increases. In addition, it has been found that a new problem that a white background deteriorates when a dot gain is largely changed is revealed, and the development of a color proof capable of realizing more stable finish quality has been demanded. .

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a stable and high-quality silver halide color photographic color proof having improved white background characteristics and excellent dot quality in a wide range of dot gain. Provided is a photosensitive material.

[0007]

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

[0008] 1. In a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, at least one of the silver halide emulsion layers The layer has a difference between the maximum wavelength of the spectral sensitivity at the time of exposure and the maximum wavelength of absorption of the coloring dye of 100 nm or more, and a non-photosensitive hydrophilic colloid layer is provided between the support and the silver halide emulsion layer closest to the support. Wherein the non-photosensitive hydrocolloid layer contains at least two kinds of white pigments having different spectral reflection characteristics and contains a hardener represented by the general formula (1). Silver color photographic light-sensitive material.

[0009] 2. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, represented by formula (2) above. A non-photosensitive hydrophilic colloid layer between the support and the silver halide emulsion layer closest to the support, wherein the non-photosensitive hydrophilic colloid layer has at least two types of spectral reflection characteristics. A silver halide color photographic light-sensitive material containing different white pigments.

[0010] 3. In the silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, the above-mentioned formula (3) or (4) Having a non-photosensitive hydrophilic colloid layer between the support and the silver halide emulsion layer closest to the support, wherein the non-photosensitive hydrophilic colloid layer contains at least two kinds of compounds. A silver halide color photographic material comprising a white pigment having a different spectral reflection characteristic.

4. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, represented by formula (5) above. A non-photosensitive hydrophilic colloid layer between the support and the silver halide emulsion layer closest to the support, wherein the non-photosensitive hydrophilic colloid layer has at least two types of spectral reflection characteristics. A silver halide color photographic light-sensitive material characterized by containing a white pigment having a different color.

5. In a silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, at least one of the silver halide emulsion layers The layer has a difference between the maximum wavelength of the spectral sensitivity at the time of exposure and the maximum wavelength of absorption of the coloring dye of 100 nm or more, and a non-photosensitive hydrophilic colloid layer is provided between the support and the silver halide emulsion layer closest to the support. Wherein the non-photosensitive hydrocolloid layer contains at least one white pigment and solid fine particles of the fluorescent whitening agent represented by the general formula (6) or (7), and the general formula (1) A silver halide color photographic material comprising a hardener represented by the formula:

6. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, represented by formula (2) above. A non-photosensitive hydrophilic colloid layer between the support and the silver halide emulsion layer closest to the support, wherein the non-photosensitive hydrophilic colloid layer contains at least one white pigment. A silver halide color photographic material comprising solid fine particles of a fluorescent whitening agent represented by the formula (6) or (7).

7. In the silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, the above-mentioned formula (3) or (4) Having a non-photosensitive hydrophilic colloid layer between the support and the silver halide emulsion layer closest to the support, wherein the non-photosensitive hydrophilic colloid layer contains at least one kind of compound. A silver halide color photographic light-sensitive material comprising a white pigment of the formula (1) and solid fine particles of a fluorescent whitening agent represented by the formula (6) or (7).

[8] A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, represented by formula (5) above. A non-photosensitive hydrophilic colloid layer between the support and the silver halide emulsion layer closest to the support, wherein the non-photosensitive hydrophilic colloid layer contains at least one white pigment. And a solid fine particle of a fluorescent whitening agent represented by the general formula (6) or (7).

Hereinafter, the present invention will be described in detail. In the invention according to claim 1, in the silver halide color photographic light-sensitive material, at least one of the silver halide emulsion layers has a difference between the maximum wavelength of the spectral sensitivity at the time of exposure and the maximum wavelength of absorption of the coloring dye of 100 nm or more. A non-photosensitive hydrophilic colloid layer between the support and the silver halide emulsion layer closest to the support, wherein the non-photosensitive hydrophilic colloid layer contains at least two white pigments having different spectral reflection characteristics. And a hardening agent represented by the general formula (1).

The maximum wavelength (λ _max1 ) of the spectral sensitivity referred to in the present invention refers to a silver halide color photographic material.
Exposure is performed with spectral light from 400 nm to 700 nm at intervals of several nm, and the reciprocal of the amount of exposure that gives a constant density at each wavelength is defined as the sensitivity at each wavelength, and a spectral sensitivity distribution curve is created using the sensitivity as a function of wavelength. The wavelength at which the highest sensitivity is shown. The maximum absorption wavelength (λ _max2 ) of the color-forming dye referred to in the present invention is defined as a spectrophotometer, such as a spectrophotometer U-3210 manufactured by Hitachi, Ltd. Where the horizontal axis-measurement wavelength and vertical axis-
A spectral absorption curve composed of the color density is created, and the wavelength at which the highest density is shown is indicated. In the present invention, at least one of the silver halide emulsion layers contains | λ _max1 −λ _max2
| ≧ 100 nm, preferably 100 to 700 nm, particularly preferably 100 to 60 nm.
0 nm. Further, λ of the blue-sensitive silver halide emulsion layer
The _max1, is preferably 430 to 480 nm, as lambda _max1 green-sensitive silver halide emulsion layer, 52
And λ _max1 of the red-sensitive silver halide emulsion layer is preferably 620 to 700 nm.
It is preferred that On the other hand, the λ _max2 of the silver halide emulsion layer containing the yellow coupler is 425 to 460 n
It is preferably m, as the lambda _max2 magenta coupler-containing silver halide emulsion layer, the lambda _max2 of preferably 530～560Nm, also the cyan coupler-containing silver halide emulsion layer, is 630~670nm Is preferred.

The setting of λ _max1 to the desired wavelength can be achieved by appropriately selecting known means such as the type and amount of the sensitizing dye and the halogen composition of the silver halide emulsion. of lambda _max2 it can be achieved yellow, magenta, and appropriately selecting the kind of cyan coupler, or by combining them to be used.

One of the characteristics of the present invention is that the non-photosensitive hydrocolloid layer contains at least two kinds of white pigments having different spectral reflection characteristics.

The difference in the spectral reflection characteristics according to the present invention means that
It means that the relative spectral reflectance differs in the main absorption wavelength region of the coloring dye or the main photosensitive wavelength region of the sensitizing dye. The spectral reflectance is determined by dissolving a dispersed white pigment in a gelatin solution, and then coating the dispersion on a support such as a TAC base so that the weight of the white pigment is 1.0 g / m ² .
Measured using a spectrophotometer (U-3210) manufactured by Hitachi, Ltd.
You can ask.

The white pigment which can be used in the present invention is
Examples of the inorganic material include rutile-type titanium dioxide, anatase-type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, and kaolin. One of the white pigments having different spectral reflection characteristics is preferably titanium dioxide because of the characteristics of the obtained photosensitive material. As the other white pigment, titanium dioxide having a different average primary particle size may be used, or rutile-type titanium dioxide and anatase-type titanium dioxide may be used in combination.

Further, in the invention according to claim 5, the non-photosensitive hydrocolloid layer contains, in addition to the white pigment, solid fine particles of a fluorescent whitening agent represented by the general formula (6) or (7). Is one of the features.

In the general formula (6), A represents a fluorescent brightener component having an anionic group such as a carboxyl group, B represents ammonium having a total of 15 or more carbon atoms,
Represents an organic cation compound such as pyridinium, wherein n is 1 to
Represents an integer of 9. Here, as the fluorescent whitening agent component having an anionic group, a substituted stilbene fluorescent whitening agent, a substituted coumarin fluorescent whitening agent, and a substituted thiophene fluorescent whitening agent having an anionic group are preferable.

In the general formula (7), C represents a fluorescent whitening agent component having a sulfonic acid group, D represents an ammonium or pyridinium organic cation compound having a total carbon number of 15 or more, and n represents an organic cation compound. Represents an integer of 1 to 9.
Here, as the fluorescent whitening agent component having a sulfonic acid group,
Preferred are a substituted stilbene-based fluorescent whitening agent having a sulfonic acid group, a substituted coumarin-based fluorescent whitening agent, and a substituted thiophene-based fluorescent whitening agent.

Examples of the optical brightener component corresponding to A in the general formula (6) and C in the general formula (7) used in the present invention include, for example, "Fluorescent Whitening Agent" edited by The Chemical Industry Association of Japan, British Patent No. 920,
No. 988, German Patent No. 1,065,838, U.S. Pat. No. 2,610,152 and the like.

The compounds having a fluorescent whitening effect used in the present invention include A of the general formula (6), a fluorescent whitening agent component corresponding to C of the general formula (7), B of the general formula (6), and a compound of the general formula (6). It can be synthesized by mixing each of the organic cation compounds such as ammonium and pyridinium having a total carbon number of 15 or more corresponding to D of 7).

As the organic cation compound, ammonium having a total carbon number of 15 or more is preferably used.

The ammonium organic cation compound having a total carbon number of 15 or more corresponding to B in the general formula (6) and D in the general formula (7) used in the present invention is represented by the following general formula (8). Compounds are preferred.

Formula (8) N ⁺ (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) wherein R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group or a phenyl group. As shown, the total number of carbon atoms of R ¹ , R ² , R ³ and R ⁴ is preferably 15 or more, more preferably 20 or more.

The pyridinium organic cation compound having a total carbon number of 15 or more corresponding to B in the general formula (6) and D in the general formula (7) used in the present invention is represented by the following general formula (9). Compounds are preferably used.

[0031]

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In the formula, R ₅ represents an alkyl group having 10 or more carbon atoms or a phenyl group, and the total number of carbon atoms of R ₅ is 15
It is preferable that it is above.

Next, specific examples of the fine particles having a fluorescent whitening effect substantially insoluble in water used in the present invention will be described, but the present invention is not limited thereto.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The white pigment or the fine particles having a fluorescent whitening effect according to the present invention (hereinafter referred to as the white pigment of the present invention) may be used as a fine particle dispersion in at least a support and a support constituting a silver halide photographic material. One of the features is that it is added to the non-photosensitive hydrophilic colloid layer between the silver halide emulsion layer closest to the silver halide emulsion layer.

The method for dispersing the fine particles of the white pigment of the present invention is a method of dispersing in water or an aqueous solution of hydrophilic colloid such as gelatin using a high-speed stirring type disperser, or an aqueous solution of hydrophilic colloid such as gelatin in a ball mill or a sand mill. Method of dispersing in water or aqueous solution of hydrophilic colloid such as gelatin using a disperser having high shear force such as Manton-Gauling disperser, dispersing using ultrasonic disperser Method and the like.

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

The spectral reflectance of the white pigment fine particles of the present invention is:
It is preferable to control by controlling the average particle size of the dispersion.

The average particle size of the dispersion of the white pigment of the present invention is:
0.05-5 μm, preferably 0.1-2 μm
And more preferably 0.2 to 1 μm.

The amount of the white pigment used in the present invention depends on the sensitivity of the present invention.
10 to 2000 mg / m in optical material ^TwoAttached to exist
, Preferably 50-1000 mg / m^TwoAddition
Is more preferable.

As the water-soluble binder used in the non-photosensitive hydrocolloid layer having a white pigment according to the present invention, gelatin is mainly used. If necessary, a gelatin derivative,
Hydrophilic colloids of gelatin and other macromolecules, such as graft polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers and copolymers, can also be used in combination with gelatin. .

The non-photosensitive hydrocolloid layer containing a white pigment of the present invention contains a colorant such as yellow, gray, blue and black colloidal silver, inorganic colored pigments, organic colored pigments and dyes in addition to the above white pigments. Can be added.

The colloidal silver that can be used in the present invention is not particularly limited, but black colloidal silver is preferably used in order to prevent irregular reflection on the support surface.

The coating 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.

In the present invention, various known filter dyes can be used. As such a light-absorbing substance, a substance that absorbs light in the entire spectral range of light to be exposed or a substance that selectively absorbs only light in a certain region can be used. Further, in order to obtain the desired absorption maximum wavelength (λ _max2 ) of the color forming dye referred to in the present invention, it can be used in an appropriate combination.

The water-soluble dye used in the present invention includes:
Oxonol, cyanine, merocyanine, azo, anthraquinone, arylidene, and other dyes.Examples include oxonol from the viewpoint of high resolution in a development processing bath and non-sensitization to a silver halide emulsion. Dyes and merocyanine dyes.

Examples of oxonol dyes include US Pat. Nos. 4,187,225, JP-A-48-42826, JP-A-49-5125, JP-A-49-99620, and JP-A-50-9.
No. 1627, No. 51-77327, No. 55-1206
No. 60, No. 58-24139, No. 58-143342
No. 59-38742, No. 59-11640,
Nos. 59-111641, 59-168438, 60-218641, 62-31916, and 62
-66275, 62-66276, 62-18
Nos. 5755, 62-273527 and 63-139
No. 949 and the like. Further, as a merocyanine dye, JP-A-50-14
No. 5124, No. 58-120245, No. 63-354
No. 37, 63-35438, 63-34539
And No. 63-58437.

The layer containing the above dye or colloidal silver is not particularly limited, but, like the white pigment of the present invention, a non-photosensitive hydrophilic colloid layer between the support and the emulsion layer closest to the support. Is preferably contained.

One feature of the invention according to the first aspect is that the compound represented by the general formula (1) is used as a hardening agent.

The compound represented by the general formula (1) of the present invention is known as a hardener for gelatin, and the compound represented by the general formula (1) of the present invention will be described below.

In the above formula (1), R ₀ is a divalent linking group, which represents an alkylene group or an alkylene group substituted with a halogen atom, a hydroxyl group, a hydroxyalkyl group or an amino group as a substituent. Further, the linking group may have an amide linking moiety, an ether linking moiety or a thioether linking moiety.

Specific examples of the compound represented by formula (1) of the present invention are shown below, but the present invention is not limited thereto.

1-1 CH ₂ ＣＨCHSO ₂ —CH ₂ —SO ₂ CH ＝ CH ₂ 1-2 CH ₂ ＣＨCHSO ₂ — (CH ₂ ) ₂ —SO ₂ CH =
_{CH 2 1-3 CH 2 = CHSO 2} - (CH 2) 4 -SO 2 CH =
CH ₂ 1-4 CH ₂ ＣＨCHSO ₂ —CH ₂ OCH ₂ SO ₂ CH =
CH ₂ 1-5 CH ₂ ＣＨCHSO ₂ (CH ₂ ) ₂ O (CH ₂ ) ₂ SO
₂ CH = CH ₂ 1-6 CH ₂ = CHSO ₂ CH ₂ CH (OH) CH ₂ SO
_{2 CH = CH 2 1-7 CH 2} = CHSO 2 CH 2 CONH-CH 2 CH 2
_{-NHCOCH 2 SO 2 CH = CH 2} 1-8 CH 2 = CHSO 2 CH 2 CONH-CH 2 CH 2
CH ₂ —NHCOCH ₂ SO ₂ CH ＝ CH ₂ The hardener of the present invention may be used in combination with another vinyl sulfone hardener or chlorotriazine hardener. It is preferable to use a compound described in JP-A-61-249054 or JP-A-61-245153 as the specific compound to be used in combination. One feature is that at least one of the silver emulsion layers contains a yellow coupler represented by the general formula (2).

In the general formula (2), examples of the alkyl group represented by R ₁ include groups such as methyl, ethyl, i-propyl, t-butyl and dodecyl. R ₁
Examples of the cycloalkyl group represented by include cyclopropyl, cyclohexyl, and adamantyl. The aryl group represented by R ₁ has 6 to 6 carbon atoms.
And 14 aryl groups (phenyl, 1-naphthyl, 9-anthranyl, etc.). The aryl group can have a substituent. Examples of the substituent include a nitro group, a cyano group, an amino group (amino, ethylamino, dimethylamino, anilino and the like), an alkylthio group (methylthio and the like),
The alkyl group as defined for groups represented by R _1, or the like substituent group as defined represented as substituents for the alkyl group represented by R ₁ can be mentioned.

The heterocyclic group represented by R ₁ includes groups such as morpholino and indoline-1-yl.

R ₁ is preferably an alkyl group,
A branched alkyl group is more preferred, and a t-butyl group is particularly preferred.

The diffusion-resistant alkyl group represented by R ₄ is preferably a linear or branched alkyl group having 8 to 21 carbon atoms, for example, 2-ethylhexyl, i-tridecyl,
Examples include groups such as hexadecyl and octadecyl.
Further, the alkyl group of the non-diffusible represented by R _B is, for example, such as represented by the following formula (D), may have a structure through an intermediate functional group.

Formula (D) -JLR _{21 In the} formula, J is a linear or branched alkylene group having 1 to 20 carbon atoms, for example, methylene, 1,2-ethylene, 1,1-
Dimethylmethylene, represents 1-decyl methylene like, R ₂₁
Represents a linear or branched alkyl group having 1 to 20 carbon atoms, for example, a group having the same meaning as the alkyl group represented by R ₁ in the general formula (2).

L represents —O—, —OCO—, —OSO ₂ —,
-CO -, - COO -, - CON (R 22) -, - CON
_{(R 22) SO 2 -,} - N (R 22) -, - N (R 22) CO
_{-, - N (R 22)} SO 2 -, - N (R 22) CON
_{(R 23) -, - N} (R 22) COO -, - S (O) n -,
-S (O) _n N (R ₂₂ )-or -S (O) _n N (R ₂₂ ) C
Represents a bond such as O-. In the formula, R ₂₂ and R ₂₃ each represent a hydrogen atom or a group having the same meaning as the alkyl group and the aryl group represented by R ₁ in the general formula (2). n represents the integer of 0-2. R ₂₁ and J may be bonded to each other to form a cyclic structure.

The alkyl group represented by R ₄ may further have a substituent. Examples of the substituent include the aforementioned R ₁
And a group having the same meaning as the substituent of the alkyl group represented by

As the non-diffusible aryl group represented by R ₄ , for example, a group having the same meaning as the aryl group represented by R ₁ can be mentioned. The aryl group represented by R ₄ may further have a substituent. Examples of the substituent include the same groups as the substituents of the aryl group represented by R ₄ . Among these substituents of the aryl group represented by R ₄ , a linear or branched alkyl group having 4 to 10 carbon atoms is preferable.

R ₄ is preferably a diffusion-resistant alkyl group, particularly preferably a straight-chain alkyl group having 8 to 21 carbon atoms.

The halogen atom represented by R ₃ includes a chlorine atom or a bromine atom. R ₃ is preferably a chlorine atom.

[0068] X represents an oxygen atom, -NH, and -NR _D. R _D
Represents an alkyl group, an alkylene group, an aryl group or a benzyl group, and the alkyl group includes methyl, ethyl, i-
Each group such as propyl, t-butyl, dodecyl and the like,
Examples of the alkylene group include groups such as ethylene and propylene. Examples of the aryl group include groups having the same meaning as the aryl group represented by R ₁ .

The alkyl group represented by R ₂ is, for example, methyl, ethyl, propyl, i-propyl, butyl, t-
Each group such as butyl, hexyl, dodecyl and the like can be mentioned.

Preferably, one of R ₂ is a hydrogen atom and the other is a linear or branched alkyl group, more preferably a linear alkyl group having 3 or more carbon atoms.

Hereinafter, a yellow coupler represented by the general formula (2) (hereinafter also referred to as a yellow coupler of the present invention)
Are shown, but the present invention is not limited to these.

[0072]

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[0073] In the present invention, the total amount of yellow coupler to be contained in the photosensitive material is a photosensitive material 1 m ² per coating amount is 0.55～2.00G, preferably 0.5
5 to 1.80 g, most preferably 0.55 to 1.60 g
It is.

The invention according to claim 3 is one of the features of the silver halide color photographic light-sensitive material, which contains the compound represented by formula (3) or (4).

In the general formula (3), examples of the 5-membered heterocyclic ring formed by Q include an imidazole ring, a triazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring, a benzimidazole ring, a naphthimidazole ring and a benzoimidazole ring. Examples thereof include a thiazole ring, a naphthothiazole ring, a benzoselenazole ring, and a benzoxazole ring. Examples of the substituent of Q include a lower alkyl group, an alkoxy group, an aryl group, a sulfonyl group, a carbonyl group, a carboxyl group, a sulfonic acid group, an amino group, a carbamoyl group, a sulfonamide group, a carbamide group, and a heterocyclic group.

Preferred examples of the mercapto compound that can be used in the present invention are shown below, but the present invention is not limited to these.

[0077]

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[0078]

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Of the compounds represented by the general formulas (3) and (4), mercaptotetrazole compounds represented by ME-1 to ME-11 are particularly preferred.

The mercapto compound used in the present invention is
Preferably, 1 × 10 ⁻⁶ mol to 1 mol per mol of silver halide.
× 10 ⁻² mol, more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻³
It is used in a molar amount.

In the present invention, a nitrogen-containing heterocyclic compound having a mercapto group is preferably contained in addition to the mercapto compound of the present invention. Preferred compounds are those represented by the general formula [XI] described in JP-A-6-95283, page 19, right column, lines 20 to 49, and particularly preferred in JP-A-6-95283, page 20, left column 5 lines to page 20, right column 2 lines. The general formula [XII], the general formula [XIII], and the general formula [XV]. Specific examples of the compound include, for example, JP-A-64-733.
No. 38, pages 11 to 15 for compounds (1) to
(39) can be mentioned.

The fourth aspect of the invention is characterized in that the silver halide color photographic light-sensitive material contains the thiosulfonic acid represented by the general formula (5).

In the formula, as the aliphatic group represented by R ₃₁ ,
An alkyl group having 1 to 22 carbon atoms or 2 carbon atoms
~ 22 alkenyl or alkynyl groups are preferred.
More preferably, an alkyl group having 1 to 8 carbon atoms, or an alkenyl group or an alkynyl group having 3 to 5 carbon atoms is preferable. These groups may have a substituent. Examples of the alkyl group include a methyl group, an ethyl group,
Propyl, iso-propyl, butyl, t-butyl, 2-ethylhexyl, decyl, dodecyl,
An octadecyl group, a cyclohexyl group and the like can be mentioned. Examples of the alkenyl group include an allyl group and a butenyl group. Examples of the alkynyl group include a propargyl group and a butynyl group.

The aromatic group represented by R ₃₁ is preferably an aromatic group having 6 to 20 carbon atoms, more preferably an aromatic group having 6 to 10 carbon atoms. These groups may have a substituent, and specific examples include, for example, a phenyl group, a p-tolyl group, and a naphthyl group.

The heterocyclic group represented by R ₃₁ is 3 to 1
A 5-membered ring is preferable, and a 5- to 6-membered ring containing a nitrogen atom is more preferable. Specific examples include a pyrrolidine ring, a piperidine ring, a pyridine ring, a tetrahydrofuran ring, a thiophene ring, an oxazole ring, an imidazole ring, a benzothiazole ring, a tellurazole ring, an oxadiazole ring, and a thiadiazole ring.

The group represented by R ₃₁ has a carbon number of 6 to
Most preferred are 10 substituted aromatic rings. Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, butyl group, pentyl group, etc.), an alkoxy group (eg, methoxy group, ethoxy group, etc.), an aryl group (eg, phenyl group, naphthyl group, etc.), hydroxyl group Group, halogen atom,
Aryloxy group (for example, phenoxy group, etc.), alkylthio group (for example, methylthio group, butylthio group, etc.), arylthio group (for example, phenylthio group, etc.), acyl group (for example, acetyl group, propionyl group, etc.), sulfonyl group (for example, methylsulfonyl group) Phenylsulfonyl, etc.), acylamino groups (eg, acetylamino groups, etc.),
Sulfonylamino group, acyloxy group, carboxy group,
Specific examples of the compound represented by the general formula (5) that can be used in the present invention, which include a cyano group, a sulfo group, an amino group, and the like, are shown below, but the present invention is not limited thereto.

[0087]

Embedded image

Next, other components of the image forming method and the silver halide photographic light-sensitive material of the present invention will be described.

In the present invention, color proofing is performed by exposing a silver halide color photographic light-sensitive material on the basis of halftone image information comprising color-separated yellow image information, magenta image information, cyan image information and black image information. In the step of producing a halftone image, at least a part of the halftone dot image information is 6.45 cm when the halftone dot area ratio is 40%.
The number of halftone dots per ² (1 inch ² ) is 200 × 10 ³
As described above, the halftone image converted is used. Preferably it is 300 × 10 ³ or more, more preferably 400 × 10 ³ or more, and still more preferably 400 × 10 ^{3 to} 2000 × 10 ³ .

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

The halftone image used in the present invention is particularly effective when it is a halftone image for high-definition printing in the AM screening method generally used conventionally. The present invention is most effective in the case of a dot image formed by a frequency-modulated screening method called the FM screen method.

In the present invention, the halftone image information is a halftone image recorded on a film, and it is preferable that the exposure is performed by scanning the light source with the film in close contact with the photosensitive material. For the adhesion, it is preferable to use a vacuum adhesion method.

In the present invention, the light from the exposure light source is
Exposure is preferably performed via optical means to improve parallelism. Means for improving the parallelism of the light emitted from the light source include, for example, an optical lens, a reflecting mirror, a honeycomb structure, or the like that absorbs components other than parallel light on a wall surface by passing through a linear tubular optical path. Is raised. The parallelism can also be improved by an aggregate of optical fibers.

Further, a method of performing exposure by laser scanning or the like based on halftone dot image information is one means that can be preferably used in the present invention.

In the present invention, the image forming exposure apparatus
The photosensitive material, which is preferably used for large-format color prints and color proofs, and is wound into a roll, is loaded into an exposure device in a form housed in a cartridge so that it can be handled in a bright room, and is pulled out to form an image. , And wound around a rotating drum. While rotating the drum, image exposure is performed by a laser exposure device or a light-emitting diode exposure device, followed by development processing to obtain a final color image. At that time, the exposure apparatus includes:
It is preferable to have a mechanism for reading information given to the light chamber cartridge and automatically identifying the type of photosensitive material and / or setting exposure conditions and / or developing processing conditions.

In the present invention, it is preferable that the silver halide photographic light-sensitive material is previously loaded in a cartridge that can be handled in a bright room in the form of 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 light chamber cartridges have been proposed, but all known light chamber cartridges can be used. Also, by covering the outer periphery of a roll-shaped 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 leader. In the image forming method of the present invention, a light-room cartridge includes a so-called easy-loading photosensitive material which does not require the image forming apparatus and can easily load the roll of the photosensitive material into the apparatus. In that case, the readable information can be given to the reader or to the flange or the like.

Next, the reflective support used in the present invention will be described. The reflection support used in the present invention is preferably a base material based on base paper and a laminate of a polyolefin resin on both sides thereof.

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 which are generally used in papermaking may be incorporated in the support. An agent, a surface strengthening agent, an antistatic agent and the like may be appropriately applied to the surface.

The reflective support has a mass per 50 m ² of 50.
A resin having a smooth surface of up to 300 g is used, and a resin for laminating both surfaces thereof is a homopolymer such as ethylene, α-olefins, for example, polypropylene, a copolymer of at least two kinds of the olefins, or a copolymer thereof. It can be selected from a mixture of at least two kinds of various polymers. Particularly preferred polyolefin resins are low density polyethylene, high density polyethylene or mixtures thereof.

The molecular weight of the polyolefin resin to be laminated on the reflective support is not particularly limited, but usually a molecular weight in the range of 20,000 to 200,000 is preferably used. The polyolefin resin coating layer on the side of the reflective support on which the photographic emulsion is coated is preferably 5 to 50 μm, more preferably 7 to 35 μm. As the polyolefin used for laminating the back side of the reflective support (the reflective side of the side on which the emulsion layer is provided), a mixture of low-density polyethylene and high-density polyethylene is usually melt-laminated. This layer is generally often matted. In forming the laminate on the front and back of the support, generally, in order to increase the flatness of the developed photographic paper in a normal environment, the density of the resin layer on the front side is slightly larger than that on the back side, or the amount of lamination on the back side is larger than that on the front side. For example, a means such as performing is used. Generally, the lamination on both the front and back surfaces of the reflective support can be formed by melt extrusion coating the polyolefin resin composition on the support. 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.
It is also preferable to provide a sub-coat layer on the surface of the surface laminate layer for improving the adhesion to the photographic emulsion, or a back coat layer on the back surface of the laminate layer for improving the printability and antistatic properties.

The polyolefin resin used for laminating the surface of the reflective support (the surface on which the emulsion layer is provided) preferably contains 13 to 20% by mass, more preferably 15 to 20% by mass of a white pigment dispersed therein. As the white pigment,
The above-mentioned inorganic and / or organic white pigments can be used, and are preferably inorganic white pigments. Among these, barium sulfate, calcium carbonate, and titanium oxide are preferred, and barium sulfate and titanium oxide are more preferred. The titanium oxide may be of a rutile type or an anatase type, and one whose surface is coated with a metal oxide such as hydrous alumina or hydrous ferrite is also used. Others
It is preferable to add a colored pigment and a fluorescent whitening agent for improving an antioxidant and whiteness.

The thickness of the reflective support used in the present invention is as follows:
Although there is no particular limitation, those having a thickness of 80 to 160 μm are preferably used. In particular, those having a thickness of 90 to 130 μm are more preferable. The shape of the surface of the reflective support used in the present invention may be smooth or may have an appropriate surface roughness, but it is preferable to select a reflective support having gloss close to that of printed matter. preferable. For example, JIS B 0
It is preferable to use a white support having an average surface roughness SRa specified in 601-1976 of 0.30 to 3.0 μm.

As the silver halide emulsion used for the light-sensitive material of the present invention, a surface latent image type silver halide emulsion which forms a latent image on the surface by image exposure is used, and a negative image is formed by performing development. Emulsions may be used. Also, using an internal latent image type silver halide emulsion in which the surface of the grains is not fogged in advance, fogging (nucleation) after image exposure and then surface development, or fogging after image exposure. Emulsions capable of directly obtaining a positive image by performing surface development while performing such development can also be preferably used. The emulsion containing the internal latent image type silver halide emulsion grains is defined as a silver halide grain having a photosensitive nucleus mainly inside silver halide crystal grains and forming a latent image inside the grains upon exposure. Containing emulsion.

The fogging treatment may be performed by exposing the entire surface, may be performed chemically using a fogging agent, a strong developing solution may be used, and heat treatment may be performed. The entire surface exposure is performed by immersing or moistening the image-exposed photosensitive material in a developing solution or other aqueous solution, and then performing uniform exposure over the entire surface.
Further, the time of the entire surface exposure can be varied over a wide range depending on the photosensitive material, the development processing conditions, the type of the 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. Normal,
If the exposure amount is excessively increased, the minimum density increases or desensitization occurs, and the image quality tends to decrease.

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

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

Particularly preferably, the coated silver amount is about 1 to 3.5.
A portion of the sample, coated on a transparent support in the range of g / m ² , is exposed to a light intensity scale for a defined period of time from about 0.1 seconds to about 1 second, and is substantially exposed to light. Containing no silver halide solvent, and developing at 20 ° C. for 4 minutes using the following surface developer A for developing only the surface image of the grains,
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 0.0g Sodium sulfite (anhydrous) 90.0g Hydroquinone 8.0g Sodium carbonate (monohydrate) 52.5g Potassium bromide 5.0g Potassium iodide 0.5g Add water 1000ml Internal latent image 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, U.S. Pat. No. 3,206,3.
No. 16, No. 3,317,322 and No. 3,36
Silver halide emulsion having internally chemically sensitized silver halide grains described in U.S. Pat.
No. 71,157 and 3,447,927, emulsions having silver halide grains containing polyvalent metal ions, and a dopant described in U.S. Pat. No. 3,761,276. A silver halide emulsion in which the surface of the silver halide grains contained is weakly chemically sensitized.
No. 24, No. 50-38525, No. 53-2408, etc., and silver halide emulsions composed of grains having a laminated structure, and others are described in JP-A Nos. 52-156614 and 55-127549. And a silver halide emulsion.

The shape of the silver halide grains used in the present invention may be cubic, octahedral, tetrahedral composed of a mixture of (100) and (111) planes, a shape having a (110) plane, a sphere, a flat plate 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 range of ± 20% of the average particle size rm as 60% of the total silver halide particle mass. The above is mentioned, preferably 70% or more, more preferably 80% or more. Here, the average particle diameter rm is the frequency ni of the particles having the particle diameter ri.
The product ni × ri ³ and ri ³ is defined as a grain size ri when the maximum (three significant figures, the minimum digit is ON 4 discard 5). The particle size referred to here is the diameter of spherical silver halide grains, or the diameter of a projected image converted to a circular image of the same area for grains having a shape other than spherical. . The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is 1000 or more indiscriminately).

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

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 of the preferred embodiments, the silver halide has a grain 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 according to the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

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

[0120] The addition amount of the sulfur sensitizer, it is preferable to change the size, etc. of the effect of the type of silver halide emulsions applied or expectations, per mol of silver halide 5 × 10 ^-10 to 5 × 10 ^-5 mol, more preferably a 5 × 10 ^-8 ~3 × 10 ^- is a ⁵ mols.

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

The light-sensitive material preferably contains the above-mentioned nitrogen-containing heterocyclic compound having a mercapto group. The amount of the mercapto compound varies depending on the kind of the compound to be used and the layer to be added. In general, when it is added to a silver halide emulsion layer, it is generally in the range of 10 ^-8 to 10 ^-2 mol, more preferably 10 ^-6 to 10 ^-3 mol, per mol of silver halide.

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

The silver halide emulsion can be optically sensitized by a commonly used sensitizing dye. The 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.

In the present invention, it is preferable to provide an infrared-sensitive silver halide emulsion layer. The infrared-sensitive silver halide emulsion layer has a spectral sensitivity maximum at a wavelength longer than 700 nm. As such a method of infrared spectral sensitization, a sensitization method using an infrared sensitizing dye is particularly preferably used.

The infrared sensitizing dye used in the present invention is not particularly limited.
Dicarbocyanine dyes containing a quinoline nucleus are preferred, and tricarbocyanine is particularly preferred.

The magenta coupler contained in the magenta image forming layer of the present invention includes a compound represented by the general formula [M-1] described in the right column of page 7 of JP-A-6-95283.
The coloring dye has good spectral absorption characteristics and is preferable. Preferred examples of the compound include compounds M-1 to 8 to 11 described in the same publication.
M-19 can be mentioned. Still other specific examples include compounds M-1 to M-61 and 235,9 described in EP-A-273,712, pp. 6-21.
No. 13, pages 36 to 92, compounds 1-223
Are other than the specific examples described above.

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 λ _max of the spectral absorption of the magenta image formed in the photosensitive material according to the present invention is 530 to 560 nm.
ΛL _0.2 is preferably 580 to 63
Preferably it is 5 nm.

Here, λL of the spectral absorption of the magenta image
_0.2 and λ _max are quantities measured by the following method.

[0131] When using a positive emulsion in the photosensitive material (method of measuring .lambda.L _0.2 and lambda _max), and uniformly exposed with red light minimal amount of light the color light-sensitive material a minimum density of the cyan images obtained, and yellow After uniformly exposing with the minimum amount of blue light to obtain the lowest density of the image, irradiating white light through an ND filter, and developing, attach an integrating sphere to the spectrophotometer and use a standard white plate of magnesium oxide The magenta image is produced by adjusting the density of the ND filter so that the maximum value of the absorbance when measuring the spectral absorption at 500 to 700 nm with the zero correction is 1.0. 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. λL _0.2 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 formula (1) are, when combined with the magenta coupler represented by the general formula [M-1], a pKa value not lower than the pKa of the coupler represented by the combination [M-1] by 3 or more. Is a coupler having

Specific examples of the yellow coupler include, in addition to the yellow coupler represented by the general formula (2), a compound represented by the formula (1) described in JP-A-6-95283, pp. 12-13.
1 and Y-2, JP-A-2-139542, 13-1
(Y-1) to (Y-58) described on page 7 can be preferably used, but are not limited thereto.

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, λ _max of the spectral absorption of the formed yellow image is preferably 425 to 460 nm, and λ L _0.2 is preferably 515 nm or less.

The yellow coupler is usually used in the silver halide emulsion layer in an amount of 1 × 10 ^-3 per mol of silver halide.
To 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol.

In the light-sensitive material according to the present invention, as the cyan coupler contained in the cyan image forming layer, a known phenol-based, naphthol-based or imidazole-based coupler can be used. For example, a phenol coupler substituted with an alkyl group, an acylamino group or a ureido group, a naphthol coupler formed from a 5-aminonaphthol skeleton, a bi-equivalent naphthol coupler having an oxygen atom introduced as a leaving group, and the like are representative. Is done.
Among them, preferred compounds are described in JP-A-6-9528.
General formula [C-I] [C-II] described on page 13 of JP-A No. 3
Is mentioned. The spectral absorption λ _max of the cyan image formed in the photosensitive material according to the present invention is 630 to 660 nm.
It is preferred that

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

An anti-fading agent can be used in combination with each of the magenta, yellow and cyan 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 a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be added.

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 [HBS-
Compounds represented by I] and [HBS-II], particularly preferably compounds represented by [HBS-II]. Specific compounds include, for example, compounds I-1 to II-95 described in JP-A-2-124568, pp. 53-68.

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-4-133,056, and the compounds II-1 to II-14 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.

In the present invention, an image is formed by exposing with a laser light source or a light emitting diode light source having a wavelength corresponding to the spectral wavelength region of each silver halide emulsion layer. At least one of the reflection densities of the undeveloped sample measured at the wavelength is 0.8 or more, more preferably 1.0 or more.

The reflection density of the undeveloped sample can be measured by a conventionally known method. For example, the value of the spectral reflection density measured using a color analyzer 607 manufactured by Hitachi, Ltd. can be used.

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 the spectral sensitivity region of the silver halide emulsion and / or the method of adding the lowermost layer or other It is preferable to provide antihalation in the layer. Further, there is a method in which the above-mentioned dye is contained in the photosensitive material in the form of fine solid particles to suppress the diffusion of the dye in the photosensitive material.

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, for example, gray colloidal silver, is reduced by keeping silver nitrate alkaline in gelatin in the presence of reducing agents 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 amount of the colloidal silver applied is selected so that the reflection density of the sample before development processing measured at at least one wavelength within the exposure area for cyan image-forming silver halide is 0.8 or more. Can be added.

In the light-sensitive material of the present invention, the reflection density of a raw sample at the maximum wavelength of the spectral sensitivity of the cyan image-forming silver halide emulsion layer is preferably 0.7 or more. The above-mentioned light-sensitive material can be obtained by including a dye having an absorption at the above-mentioned wavelength and a coloring material such as black colloidal silver in any of the photographic constituent layers.

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

It is preferable to add a compound for adjusting the foot tone 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 .

Gelatin is preferably used as a binder in the light-sensitive material. In particular, gelatin extract is subjected to hydrogen peroxide treatment to remove coloring components of gelatin,
Gelatin whose transmittance has been improved by extracting from raw material ossein that has been subjected to a hydrogen peroxide treatment or using ossein manufactured from uncolored raw bone 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 was 7 when a 10% solution was prepared and the transmittance was measured at 420 nm using a spectrophotometer.
It is preferably 0% or more.

Gelatin jelly strength (based on the Paggy method)
Is preferably 250 g or more, and particularly preferably 2 g or more.
70 g or more.

The ratio of gelatin to total coated gelatin is not particularly limited, but is preferably used in a large ratio, and more specifically, a preferable effect can be obtained by using at least 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 is determined by the method of measuring water described in the Paggy Method and converted to the mass of gelatin containing 11.0% of water.

Examples of the hardener of a binder represented by gelatin include, in addition to the hardener represented by the general formula (1) according to the present invention, a vinyl sulfone hardener and a chlorotriazine hardener. It can be used in combination. JP-A-61-
It is preferable to use the compounds described in Nos. 249054 and 61-245153. It is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of fungi and bacteria which adversely affect photographic performance and image storability.

In the present invention, the layer constitution is not particularly limited, but it is preferable that the emulsion layer having the longest spectral sensitivity wavelength be on the support side as compared with the other photosensitive emulsion layers.
In particular, when the emulsion having the longest spectral sensitivity wavelength is an emulsion having a spectral sensitivity in the infrared, the emulsion layer containing the infrared emulsion is preferably located closest to the support than the other emulsion layers.

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 the solid disperse dye and colloidal silver described above. 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 surface gloss of the image forming layer side of the photosensitive material preferably has a gloss close to that of a printed matter. For example, the glossiness GS of the surface of the image forming layer after treatment is measured by a method specified in JIS Z8741. (60 °) of 5 to 60 is preferred.

The light-sensitive material of the present invention preferably has a surface roughness of 0.30 to 3.0 μm on the image forming surface. An agent can be contained. The layers to which the matting agent is added include a silver halide emulsion layer, a protective film, an intermediate layer,
There is an undercoat layer and the like, which may be added to a plurality of layers, and is preferably the uppermost layer of the photosensitive material.

The light-sensitive material of the present invention may have a hydrophilic colloid layer having a dry film thickness of 3 to 15 μm containing fine powder 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 amount 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 that can be used on the front or back surface of the present invention include crystalline or non-crystalline silica, titanium dioxide, magnesium oxide, calcium carbonate, barium sulfate, strontium barium sulfate, alumina magnesium silicate, and magnesium halide. Silver, silicon dioxide, acrylic acid-ethyl acrylate copolymer, acrylic acid-
Methyl methacrylate copolymer, itaconic acid-styrene copolymer, maleic acid-methyl methacrylate copolymer, maleic acid-styrene copolymer, acrylic acid-phenyl acrylate copolymer, polymethyl methacrylate, acrylic acid-methacrylic acid- Examples include an ethyl methacrylate copolymer, polystyrene, starch, and cellulose acetate propionate. In addition, U.S. Pat. Nos. 1,221,980 and 2,992,101
And the like, 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 = Σniri / Σni 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.

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

In the light-sensitive material of the present invention, known photographic additives other than those described above can be used. Known photographic additives include RDNo. 17643 and the same No. 18716.

When developing the light-sensitive material of the present invention 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 and a replenishing bleaching. The developing process can be continuously performed while replenishing the fixing solution, the replenishing stabilizing solution and the like.

In the present invention, 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 light-sensitive material of the present invention include ordinary silver halide developers such as polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, and ascorbin. Acids and derivatives thereof, reductones, phenylenediamines and the like, 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 may be previously contained in the emulsion and act on silver halide during immersion in a high pH aqueous solution.

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

In order to form an image using the photosensitive material of the present invention, it is preferable to use an automatic developing machine of a light source section scanning exposure system. Specific examples of particularly preferable apparatuses and systems for image formation include Konsensus manufactured by Konica Corporation.
L, Konsensus 570, Konsensus II
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.

[0183]

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

Example 1 << Preparation of Silver Halide Emulsion >> (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 in molar ratio) and an aqueous solution containing them at the same time by a control double jet method.
A 30 μm cubic silver chlorobromide core emulsion was obtained. At that time, the pH and pAg were controlled so that a cube was obtained as the particle shape.

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

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

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

To the obtained core emulsion, an aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in molar ratio) were simultaneously added by a control double jet method. The shell was formed until the average particle size became 0.36 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-P2. The particle size distribution of this emulsion EM-P2 was 8%.

(Preparation of Blue-Sensitive Silver Halide Emulsion) Emulsion E
Optimum chemical sensitization was carried out at 55 ° C. using the following compound for M-P1, and then T-1 (4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene) was added per mole of silver. A blue-sensitive emulsion Em-1B was prepared by adding 600 mg.

Sodium thiosulfate 1.5 mg Chloroauric acid 1.0 mg Stabilizer STAB-1 4.5 × 10 ⁻⁴ mol Stabilizer STAB-2 1.5 × 10 ⁻⁴ mol Stabilizer STAB-3 2 × 10 ^{− 4} mol of sensitizing dye BS-1 4 × 10 ^-4 mol (Preparation of green-sensitive silver halide emulsion) The following compounds were used in emulsion EM-P1 for optimal chemical sensitization at 55 ° C., and then T-1 ( 4-hydroxy-6-methyl-1,3,3
a, 7-tetrazaindene) in an amount of 600 m
g was added to prepare a green sensitive emulsion Em-1G.

Sodium thiosulfate 1.5 mg Chloroauric acid 1.0 mg Stabilizer STAB-1 4.5 × 10 ⁻⁴ mol Stabilizer STAB-2 1.5 × 10 ⁻⁴ mol Stabilizer STAB-3 2 × 10 ^{− 4} mol of sensitizing dye GS-1 4 × 10 ^-4 mol (Preparation of red-sensitive silver halide emulsion) The following compounds were used for the emulsion EM-P2 to perform optimal chemical sensitization at 55 ° C. A red-sensitive emulsion Em-2R was prepared by adding 600 mg per mol of silver.

Sodium thiosulfate 1.8 mg Chloroauric acid 2.0 mg Stabilizer STAB-1 3 × 10 ⁻⁴ mol Stabilizer STAB-2 2.5 × 10 ⁻⁴ mol Stabilizer STAB-3 1.5 × 10 ^{− 4} mol Sensitizing dye RS-1 1 × 10 ^-4 mol Sensitizing dye RS-2 1 × 10 ^-4 mol (Preparation of infrared-sensitive silver halide emulsion) Emulsion EM-P2
An infrared-sensitive emulsion Em-2IFR was prepared in the same manner as the green-sensitive emulsion Em-1G, except that the following compounds were used and the chemical sensitization was optimally performed at 55 ° C.

Sodium thiosulfate 1.8 mg Chloroauric acid 2.0 mg Stabilizer STAB-1 3 × 10 ⁻⁴ mol Stabilizer STAB-2 2.5 × 10 ⁻⁴ mol Stabilizer STAB-3 1.5 × 10 ^{− 4} mol sensitizing dye IRS-1 1 × 10 ^-4 mol sensitizing dye IRS-2 1 × 10 ^-4 mol STAB-1: 1- (3-acetamidophenol) -5-mercaptotetrazole STAB-2: 1- Phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0195]

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[0196]

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[0197]

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<< Multilayer silver halide color photosensitive material sample
Production >> High-density polyethylene on one side and A
Contains 15% Natase-type titanium oxide dispersed
115 g / weight laminated with molten polyethylene
m ^TwoOn a 100 μm thick paper pulp reflective support,
Em-1B, Em-1G, Em-2R and Em-2IF
Using R, each of the constituent layers shown in Tables 1 and 2
Sequentially on the side of the polyethylene layer containing
6.00 g / m2 gelatin on back side^Two, Silica matting agent
Is adjusted so that the Beck smoothness is 160 seconds.
Multi-layer silver halide color light-sensitive material by coating the back layer
Was prepared.

The maximum wavelength (λ _max1 ) of the spectral sensitivity of each silver halide emulsion layer of Sample 11 was 460 nm for the blue-sensitive layer, 548 nm for the green-sensitive layer, 670 nm for the red-sensitive layer, and 785 nm for the infrared-sensitive layer. there were.

However, the silver halide emulsion is shown in terms of metallic silver. H-1 and H-2 were added as hardeners. Surfactant SU as coating aid and dispersing aid
-1, SU-2 and SU-3 were added and prepared.

SU-1: di (2-ethylhexyl) sulfosuccinate sodium sodium SU-2: di (2,2,3,3,4,4, sulfosuccinate)
Sodium 5,5-octafluoropentyl) ester SU-3: Sodium tri-i-propylnaphthalenesulfonate H-1: Sodium 2,4-dichloro-6-hydroxy-S-triazine H-2: Tetrakis (vinylsulfonyl) Methyl) methane

[0202]

[Table 1]

[0203]

[Table 2]

The structures of the compounds shown in Tables 1 and 2 are shown below. SO-1: tri (n-octyl) phosphine oxide SO-2: di (i-decyl) phthalate SO-3: pt-octylphenol HQ-1: 2,5-di (t-butyl) hydroquinone HQ- 2: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5-di-sec-tetradecylhydroquinone And a mixture of 2-sec-dodecyl-5-sec-tetradecylhydroquinone at a mass ratio of 1: 1: 2 T-2: 1- (3-acetamidophenyl) -5-mercaptotetrazole T-3: N-benzyladenine T -4: 2-mercaptobenzothiazole TX: 1: 1: 1 by molar ratio of T-2, T-3, T-4
LA-1: Styrene / butyl methacrylate / 2-sulfomethyl methacrylate / sodium copolymer

[0205]

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[0206]

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[0207]

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[0208]

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(Preparation of Samples 12 to 18) As shown in Table 3, in Samples 15 to 18 in the above Sample 11, the hardener was changed to H-1 and H-2, and the general formula (1) of the present invention was used. Exemplified compound 1-7 which is a hardening agent according to
Samples 12 to 18 were prepared in the same manner except that the second layer was changed to white pigment or fluorescent whitening solid fine particles. The amount of the hardener was adjusted so that the degree of swelling in water was the same as that of Sample 11.

[0210]

[Table 3]

(Preparation of Samples 21 to 29) In the above Sample 11, as shown in Table 4, a white pigment or a fluorescent whitening agent solid fine particle was added to the second layer, and the general formula (I) of the present invention was added to the third layer. Samples 21 to 29 were prepared in the same manner except that the inhibitors according to 3) to (5) were used.

[0212]

[Table 4]

(Preparation of Samples 31 to 36) In Sample 11 described above, as shown in Table 5, a white pigment or a solid fluorescent fine particle was added to the second layer, and the yellow coupler Y-1 of the third layer was added to the second layer. Instead, samples 31 to 31 were prepared in the same manner except that the yellow coupler according to the general formula (2) of the present invention was used.
36 were produced.

[0214]

[Table 5]

(Preparation of Samples 41 to 48) In Sample 34 described above, as shown in Table 6, the inhibitors according to the general formulas (3) to (5) of the present invention were added to the third layer.
Samples 41 to 48 were produced in the same manner as in No. 48 except that the hardener according to the general formula (1) of the present invention was changed.

[0216]

[Table 6]

<< Exposure of Photosensitive Material Sample >> Each of the samples 11 to 48 produced above was cut into a width of 580 mm and a length of 55 m, wound around a core so that the silver halide photosensitive surface was exposed, and processed into a roll. And stored in a light room type cartridge.

Next, two copies of each sample stored in the cartridge were prepared, and a part was prepared at 40 ° C. and 50% relative humidity.
It was stored for a week and the other copy was stored in the refrigerator for the same period.

Each sample subjected to the above-mentioned treatment was subjected to image exposure under the following conditions. Image exposure was performed in combination with original films corresponding to green light, red light and infrared light. At the time of exposure, it corresponds to an infrared exposure corresponding to a yellow dot test chart image, a green exposure corresponding to a magenta dot test chart image, a red exposure corresponding to a cyan dot test chart image, and a black dot test chart image. Each of green, red and infrared exposures was prepared. The blue, green, and red exposures were performed by combining a three-wavelength fluorescent lamp with a filter that transmits blue, green, and red, respectively. The photosensitive material sample was fixed to an exposure table by a reduced-pressure suction contact method, a document film was brought into close contact, and scanning exposure was performed with a corresponding light source. The exposure amount is such that the dot gain of the halftone dot 50% portion of the refrigerated sample is 10% and 14% for each of yellow (Y), magenta (M), cyan (C) and black plate (K). , And the refrigerated sample and the high-temperature processed sample were exposed under the conditions. Here, the original halftone dot 50% dot gain is a halftone area measured by decomposing the reproduced black halftone image into BGR when the halftone dot area ratio of the black halftone image information of the original is 50%. It is represented by a numerical value obtained by subtracting 50 from the value of the ratio (%).

<< Development of Photosensitive Material Sample >> The sample exposed as described above was developed under the following conditions to obtain a color image.

(Processing Step) Processing Step Temperature Time Immersion (Developer) 37 ° C. for 12 seconds Fog exposure—12 seconds Development 37 ° C. 95 seconds Bleaching and fixing 35 ° C. 45 seconds Stabilization processing 25-30 ° C. 90 seconds Drying 60-85 ° C. 40 seconds (color developer 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 T-10 0.1 g hydroxylamine sulfate 5.0 g sodium diethylenetriaminepentaacetate 2.0 g 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g fluorescent whitening agent (4,4′-diaminostilbene) Disulfonic acid derivative) 1.0 g potassium hydroxide 2.0 g diethylene glycol Add 15.0 ml water to make the total volume 1000 ml and adjust to pH 10.15.

(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 1000 ml.

(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 Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g Water In addition, the total volume is made up to 1000 ml and the pH is adjusted to 7.5 with ammonium hydroxide or sulfuric acid.

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

(Color developing replenisher) Benzyl alcohol 18.5 ml Ceric sulfate 0.015 g Ethylene glycol 10.0 ml Potassium sulfite 2.5 g Potassium bromide 0.3 g Sodium chloride 0.2 g Potassium carbonate 25.0 g T-1 0.1 g hydroxylamine sulfate 5.0 g sodium diethylenetriaminepentaacetate 2.0 g 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 5.4 g fluorescent brightener (4,4′-diamino) (Stilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 18.0 ml Water is added to adjust the total volume to 1 liter, and the pH is adjusted to 10.35.

(Bleach-fixer replenisher) Same as the above-mentioned bleach-fixer.

(Stabilizer replenisher) Same as the above stabilizer.

The replenishing amounts of the developing replenisher, the bleach-fixer and the stabilizer were 320 ml per m ^{2 of} the photographic material.

The developing process was performed by an automatic developing machine Kon manufactured by Konica Corporation.
The processing was performed using a sensor 670. Further, the total amount of the replenished color developing replenisher is 3% of the amount of the color developing tank.
The running process was performed until the amount was doubled.

<< Evaluation of Developed Sample >> (Measurement of Absorption Maximum of Chromogenic Dye)
For the sample, use a spectrophotometer U-3210 manufactured by Hitachi, Ltd.
Then, the spectral absorption characteristics were measured. Each source in sample 11
Color dye absorption maximum (λ _max2) Indicates that the blue photosensitive layer is 545n
m, the green photosensitive layer is 440 nm, the red photosensitive layer is 645 nm and
The thickness of the infrared-sensitive layer was 440 nm. In addition, samples 31 to
Λ of the third layer at 36_max2Are described in Table 5 above.

(Evaluation of White Background and Halftone Image Quality) White background was measured when dot gains were set to 10% and 14% for all of Y, M, C and K. ΔR is the deviation of the color tone of the white background at the dot gain of 10% and 14%, and ΔR (10) and ΔR are the deviation of the white background between the sample stored in the refrigerator and the sample stored under high temperature conditions, respectively.
(14) was evaluated. ΔR, ΔR (10) and ΔR
It was determined that the smaller the value of (14) was, the smaller the change in white background under storage was and the better it was.

The black tint of the sample output under each condition was measured using a color meter CM-2022 manufactured by Minolta.

ΔR = (Δb * 2 + Δa * 2) 1/2 In the formula, Δa * and Δb * represent the difference between a * and b * between each sample.

Then, the dot image quality of each sample at 5% of the original was visually observed using a loupe, and evaluated according to the following criteria.

A: The outline is firm and clearly visible. B: The outline is slightly blurred, but clearly visible. C: The image is faint and somewhat problematic in practical use. Table 7 shows the results obtained as described above.

[0236]

[Table 7]

As is clear from Table 7, the sample according to the present invention has a very stable white background and excellent dot image quality even when the dot gain is changed or when it is stored for a long time under high temperature conditions. You can see that.

Example 2 Samples 111, 124, 129 and 147 were prepared in the same manner as in Samples 11, 24, 29 and 47 of Example 1, except that the structure of the fifth layer was changed to the contents shown in Table 8.
Was prepared, subjected to the same exposure and development treatments as in Example 1, and evaluated in the same manner. Table 9 shows the obtained results.

[0239]

[Table 8]

[0240]

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[0241]

[Table 9]

As is clear from Table 9, even when the cyan coupler of the fifth layer was changed to C-2, the samples 124, 129 and 147 according to the present invention changed the dot gain similarly to the first embodiment. It can be seen that the white background is extremely stable and the dot quality is excellent even when stored for a long time under high temperature conditions.

[0243]

According to the present invention, there is provided a stable and high quality silver halide color photographic light-sensitive material for color proof having an improved white background characteristic and excellent dot quality in a wide range of dot gain. Was completed.

Claims (8)

[Claims] 1. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support. At least one of the emulsion layers has a difference between the maximum wavelength of the spectral sensitivity at the time of exposure and the maximum wavelength of the absorption of the coloring dye of 100 nm or more, and is non-photosensitive between the support and the silver halide emulsion layer closest to the support. A non-photosensitive hydrophilic colloid layer, wherein the non-photosensitive hydrophilic colloid layer contains at least two types of white pigments having different spectral reflection characteristics, and a hardener represented by the following general formula (1). Characteristic silver halide color photographic material. General formula (1) CH ₂ ＣＨCHSO ₂ —R ₀ —SO ₂ CH ＝ CH ₂ [wherein, R ₀ represents a divalent linking group or an alkylene group or a substituted alkylene group, and an amide linking moiety in the linking group; It may have an ether linking moiety or a thioether linking moiety. ] 2. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, has the following general formula: Having a non-photosensitive hydrophilic colloid layer between the support and the silver halide emulsion layer closest to the support, wherein the non-photosensitive hydrophilic colloid layer contains at least two types of yellow couplers. A silver halide color photographic material comprising a white pigment having a different spectral reflection characteristic. Embedded image [In the formula, R ₁ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R ₂ represents a linear or branched unsubstituted alkyl group having 2 or more carbon atoms, and R ₃ represents a hydrogen atom or a halogen atom. Represents an atom. R ₄ represents a diffusion-resistant alkyl group or aryl group. ] 3. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler and a silver halide emulsion layer containing a cyan coupler on a support, wherein A non-photosensitive hydrophilic colloid layer containing the compound represented by (3) or (4) and between the support and the silver halide emulsion layer closest to the support; A silver halide color photographic light-sensitive material comprising at least two white pigments having different spectral reflection characteristics. Embedded image [In the formula, Q represents an atom group necessary for forming a 5-membered heterocyclic ring which may have a substituent or a 5-membered heterocyclic ring condensed with a benzene ring. M is a hydrogen atom, an alkali metal atom,
Or represents an ammonium group. [Chemical formula 3] [Wherein, Y represents a hydrogen atom, an amino group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, -CONHR
³² groups, -COR ³³ groups, -NHCOR ³⁴ groups or -HNS
Represents an O ₂ R ³⁴ group. Z represents a nitrogen atom, a sulfur atom, or an oxygen atom. n represents 1 when Z is a nitrogen atom, and represents 0 when Z is an oxygen atom or a sulfur atom.
R ³¹ represents a hydrogen atom, an amino group, an alkyl group, an alkenyl group, a hydroxyl group, a hydrazino group, an aryl group, a cycloalkyl group, a mercapto group, a —NHCOR ³⁵ group, —N
Represents an HSO ₂ R ³⁵ group or a —SR ³⁶ group. R ³² to R ³⁶
Represents an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, respectively. ] 4. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support, has the following general formula: A non-photosensitive hydrophilic colloid layer containing a thiosulfonic acid represented by the formula (5) and between the support and the silver halide emulsion layer closest to the support; A silver halide color photographic material comprising a white pigment having different spectral reflection characteristics. Formula (5): R ₃₁ —SO ₂ —S—M ₃₁ [wherein, R ₃₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, and M ₃₁ represents a hydrogen atom or a monovalent cation. ] 5. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler on a support. At least one of the emulsion layers has a difference between the maximum wavelength of the spectral sensitivity at the time of exposure and the maximum wavelength of the absorption of the coloring dye of 100 nm or more, and is non-photosensitive between the support and the silver halide emulsion layer closest to the support. A hydrophilic hydrophilic colloid layer, wherein the non-photosensitive hydrophilic colloid layer contains at least one white pigment and solid fine particles of a fluorescent whitening agent represented by the following general formula (6) or (7); A silver halide color photographic light-sensitive material comprising a hardener represented by the general formula (1). General formula (6) An ^- n [B ⁺ ] [wherein A represents a fluorescent brightener component having an anionic group such as a carboxyl group, and B represents ammonium, pyridinium or the like having a total carbon number of 15 or more. Wherein n represents an integer of 1 to 9. General formula (7): C ^n- n [D ⁺ ] [wherein C represents a fluorescent brightener component having a sulfonic acid group, and D represents ammonium having a total carbon number of 15 or more;
Represents an organic cationic compound of pyridinium, wherein n is 1 to 9
Represents an integer. ] 6. A silver halide color photographic light-sensitive material comprising a support having thereon a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler. A non-photosensitive hydrophilic colloid layer containing a yellow coupler represented by 2) between the support and the silver halide emulsion layer closest to the support; A silver halide color photographic light-sensitive material comprising: a white pigment of any kind; and solid fine particles of a fluorescent whitening agent represented by the formula (6) or (7). 7. A silver halide color photographic light-sensitive material comprising a support having thereon a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler. A non-photosensitive hydrophilic colloid layer containing the compound represented by (3) or (4) and between the support and the silver halide emulsion layer closest to the support; A silver halide color photographic light-sensitive material comprising at least one kind of white pigment and solid fine particles of a fluorescent whitening agent represented by formula (6) or (7). 8. A silver halide color photographic light-sensitive material comprising a support having thereon a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a silver halide emulsion layer containing a cyan coupler. 5) having a non-photosensitive hydrophilic colloid layer between the support and the silver halide emulsion layer closest to the support, wherein the non-photosensitive hydrophilic colloid layer contains the thiosulfonic acid represented by 5); A silver halide color photographic light-sensitive material comprising one type of white pigment and solid fine particles of a fluorescent whitening agent represented by the formula (6) or (7).