JPH095914A - Silver halide color photographic sensitive material and color proof forming method - Google Patents

Abstract

PURPOSE: To provide a color photographic sensitive material capable of attaining a color proof good in tone and improved in approximation of image quality to an original print with stable dot image reproducibility from dot image information obtained by color separation and dot image conversion by using this photosensitive material and to provide a method for forming the color proof using the material mentioned above. CONSTITUTION: The silver halide color photographic sensitive material contains a compound represented by general formula I and its silver halide emulsion layer contains internal latent image type silver halide grains and the color proof is formed by using this photosensitive material. In general formula I, each of R1 -R3 is an H atom or a substituent; and A<-> is an anion. It is preferred to contain a compound represented by general formula II in which Z is a nonmetallic atomic group necessary to form an N-containing heterocyclic group; X is an H atom or a group to be released by reaction with the oxidation product of a color developing agent; and R is an H atom or a substituent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is suitable for producing a proof color image (color proof) from a plurality of black and white halftone images obtained by color separation and halftone image conversion in a color plate making / printing process. The present invention relates to a silver halide color photographic light-sensitive material (hereinafter also referred to as "color light-sensitive material" or simply "light-sensitive material") and a method for producing a color proof using the same.

[0002]

2. Description of the Related Art Conventionally, in a color plate making / printing process, a method for obtaining a color proof from a plurality of black and white halftone images obtained by color separation and halftone image conversion is to use a photopolymer or a diazo compound. An overlay method for forming a color image and a surprint method are known.

[0003] The overlay method is very simple, has a low production cost, and has the advantage that it can be used for calibration only by stacking four color (subtractive primary colors and black) film sheets. The drawback is that gloss is produced by the overlapping, which results in a texture different from that of the printed matter.

In the surprint method, a colored image is superposed on one support, and a method of obtaining a colored image by toner development utilizing the adhesiveness of a photopolymerizable material is disclosed in US Pat. No. 3,582,327. Nos. 3,607,264 and 3,620,726.

Further, a color proof is formed by transferring a photosensitive coloring sheet to a support, forming an image by exposure and development, laminating another coloring sheet thereon, and repeating the same process. The method of creating is 47
-27441 and JP-A-56-501217.

Further, a method is known in which a photosensitive colored sheet is used and each colored image obtained by exposing and developing the corresponding color separation film is transferred and formed on one support.
-Known as No. 97140. Since there is an advantage that a coloring material similar to the printing ink can be used as a toner for forming these images and a coloring agent for the coloring sheet, the color tone of the obtained color proof is close to that of a printed matter.

[0007] However, these methods have the drawback that images must be superimposed or transferred in the process of producing a color proof, which requires a long operation time and high production cost.

As a solution to these drawbacks, a method for producing a color proof using a silver salt color photographic light-sensitive material having a white support is disclosed in JP-A-56-113139 and JP-A-5-113139.
6-104335, 62-280746, 62-280747, 62-280
No. 748, No. 62-280749, No. 62-280750, No. 62-280849, etc.

In this method, a plurality of color-separated black and white halftone images converted from a color original into color-separated halftone images are sequentially printed on one sheet of color paper by a method such as close-contact printing to perform color development. The color image formed by the dye formed from the coupler imagewise by color development and color development is used as a proofing image.

However, further improvement is required to obtain a stable proof using this technique. For example, the magenta coupler described in JP-A-6-95283 has a good color tone, but there is room for improvement in stability with respect to processing conditions. That is, the pH of the developer
There are variations in gradation due to conditions such as running and fatigue,
Therefore, when used for proofing, there remains a problem in halftone dot reproducibility.

[0011]

Therefore, an object of the present invention is to produce a color proof from halftone image information obtained by color separation and halftone image conversion using a silver halide photographic light-sensitive material. It is to provide a color proof photosensitive material that can obtain a color proof having a good color tone and an improved degree of approximation of image quality with a printed material with stable halftone dot reproducibility, and a method for producing a color proof using the same. .

[0012]

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

(1) A silver halide color photographic light-sensitive material containing a compound selected from the following formula [T], and the silver halide emulsion layer containing internal latent image type silver halide grains.

[0014]

Embedded image

In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent, and A ⁻ represents an anion.

(2) A silver halide color photographic light-sensitive material containing a compound selected from the following general formula [MI] and a compound selected from the above general formula [T].

[0017]

Embedded image

In the formula, Z represents a group of non-metal atoms necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. R represents a hydrogen atom or a substituent.

(3) The silver halide color photographic light-sensitive material according to (2), wherein the silver halide emulsion layer containing a compound selected from the above-mentioned formula [MI] contains a yellow coupler.

(4) A layer containing a yellow image forming silver halide emulsion (referred to as Y emulsion), a layer containing a magenta image forming silver halide emulsion (referred to as M emulsion), a cyan image forming halogenated A layer containing a silver emulsion (referred to as C emulsion), and a fourth black image-forming silver halide emulsion (referred to as S emulsion), and said Y emulsion, M emulsion,
The spectral sensitivity distribution of any of the C emulsion and the S emulsion has a spectral sensitivity region having a sensitivity at least 6 times higher than those of the other three emulsions, (1), (2) or (3) Silver halide color photographic light-sensitive material.

(5) The method according to any one of (1) to (4) above, based on halftone dot image information composed of color-separated yellow image information, magenta image information, cyan image information and black image information. A method for producing a color proof by exposing a silver halide color photographic light-sensitive material of 1.

The present invention will be described in more detail below.

The light-sensitive material of the present invention contains a tetrazolium compound (Chemical Formula 1) represented by the above general formula [T].

In the general formula [T], a preferred example of the substituent represented by R _{1 to} R ₃ is an alkyl group (eg methyl,
Ethyl, cyclopropyl, propyl, i-propyl, cyclobutyl, butyl, i-butyl, pentyl, cyclohexyl, etc.), amino group, acylamino group (eg acetylamino), hydroxyl group, alkoxy group (eg methoxy, ethoxy, propoxy, butoxy) , Pentoxy etc.), acyloxy group (eg acetyloxy, benzoyloxy etc.), halogen atom (eg fluorine, chlorine, bromine etc.), carbamoyl group, acylthio group (eg acetylthio), alkoxycarbonyl group (eg ethoxycarbonyl), carboxyl group Groups such as an acyl group (eg, acetyl, benzoyl, etc.), a cyano group, a nitro group, a mercapto group, a sulfoxy group, and an aminosulfoxy group. Examples of the anion represented by A ⁻ include halogen ions such as chlorine ion, bromine ion and iodine ion, acid radicals of inorganic acids such as nitric acid, sulfuric acid and perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, and anions. -Based activators, specifically, lower alkylbenzene sulfonate anions such as p-toluene sulfonate anion, higher alkylbenzene sulfonate anions such as p-dodecylbenzene sulfonate anion, higher alkyl sulfate ester anions such as lauryl sulfate anion, tetra A boric acid anion such as phenylboron, a dialkylsulfosuccinate anion such as di-2-ethylhexylsulfosuccinate anion, a polyether alcohol sulfate anion such as cetyl polyethenoxysulfate anion, and a higher fatty acid anion such as stearic acid anion. On, polymers such as polyacrylic acid anion can be exemplified such as those with a acid radical.

Specific examples of the compound represented by the general formula [T] are shown below, but the invention is not limited thereto.

[0026]

Embedded image

Next, the magenta coupler preferably used in the present invention will be described.

In the above general formula [MI], the substituent represented by R is not particularly limited, and is typically alkyl,
Aryl, anilino, acylamino, sulfonamide,
Examples thereof include alkylthio, arylthio, alkenyl, and cycloalkyl groups, but in addition to these, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, Heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclicthio groups, and spiro A compound residue, a bridged hydrocarbon compound residue, etc. are also mentioned.

The substituent represented by R, the group represented by X which can be split off by the reaction with the oxidation product of the color developing agent, the nitrogen-containing heterocycle formed by Z and the ring formed by Z may have. The preferred range and specific examples of the substituents, and the preferred range of the magenta coupler represented by the general formula [MI] are the same as those described in EP 0327272, page 5, line 23 to page 8, line 52. .

Typical examples of the magenta coupler represented by the general formula [MI] are shown below.

[0031]

[Chemical 6]

[0032]

[Chemical 7]

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

Still another specific example is European Published Patent 0273.
Compounds M-1 to M-61 described in No. 712, pages 6 to 21
And compounds 1 to 2 described in No. 0235913, pages 36 to 92
There are other than the representative examples described above in 23.

Further, the coupler is a Journal of the Chemical Society.
ciety), Perkin I (1977), 2047-2052
Page, U.S. Pat.No. 3,725,067, JP-A-59-99437 and JP-A-58-42
045, 59-162548, 59-171956, 60-33552
No. 60, No. 60-43659, No. 60-172982, No. 60-190779, 62
-209457 and 63-307453, etc. can be referred to for synthesis.

The above-mentioned couplers can be used in combination with other types of magenta couplers, and usually 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-2 , per mol of silver halide in the silver halide emulsion layer. It can be used in the range of up to 8 × 10 ^-1 mol.

The color photographic light-sensitive material of the present invention preferably has a spectral absorption λ _L0.2 of a magenta image of ₅₈₀ to 635 nm.

Further, the silver halide color photographic light-sensitive material having λ _{L0.2 of 580} to 635 _nm has a λ of spectral absorption of magenta image.
It is preferable that max is 530 to 560 nm.

Here, λ _L0.2 and λ max of the spectral absorption of the magenta image of the silver halide color photographic light-sensitive material in the present invention are the amounts measured by the following method.

(Method of measuring λ _L0.2 and λ max) In the case of the positive type, the silver halide color photographic light-sensitive material is uniformly exposed with a minimum amount of red light which gives the minimum density of a cyan image, and After uniformly exposing with the minimum amount of blue light that gives the lowest density of the yellow image, applying white light through the ND filter and then developing, attach an integrating sphere to the spectrophotometer, and use a standard white plate of magnesium oxide. Make a magenta image by adjusting the density of the ND filter so that the maximum value of the absorbance is 1.0 when the spectral absorption at 500 to 700 nm is measured with zero correction.

In the case of the negative type, the density of the ND filter is adjusted so that the maximum absorbance similar to that of the above-mentioned positive can be obtained when a magenta image is formed by applying green light through the ND filter to develop the image. λ _L0.2 means a wavelength longer than the wavelength at which the maximum absorbance is 1.0 on the spectral absorbance curve of this magenta image and at which the absorbance is 0.2.

The magenta image forming layer of the silver halide photographic light-sensitive material according to the present invention contains a yellow coupler in addition to the magenta coupler. The pKa of these couplers
The difference between is preferably within 2 and more preferably 1.
Within 5

A preferred yellow coupler to be contained in the magenta image-forming layer of the present invention is a coupler represented by the following general formula [Y-I]. Of the couplers represented by the general formula [Y-I], particularly preferred ones are those represented by the general formula [M-I].
When combined with the magenta coupler represented by the formula (1), it is a coupler having a pKa value not lower than 3 by not lower than the pKa value of the coupler represented by [MI].

[0046]

Embedded image

In the formula, R ₁₁ represents a halogen atom or an alkoxy group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group which may have a substituent. R ₁₃ is an acylamino group which may have a substituent, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an arylsulfonamido group, an alkylureido group, an arylureido group, a succinimide group, an alkoxy group. Alternatively, it represents an aryloxy group.

X ₁₀ represents a hydrogen atom, a group capable of splitting off upon reaction with an oxidized product of a color developing agent, or a halogen atom.

Specific compounds include Y-I shown below.
-1, and Y-I-2, as well as JP-A-2-139542 (13) to (1
The compounds (Y-1) to (Y-58) described on page 7) can be preferably used, but of course the invention is not limited thereto.

[0050]

[Chemical 12]

The content ratio of the magenta coupler and the yellow coupler in the magenta image forming layer of the silver halide color photographic light-sensitive material of the present invention is determined by the spectral absorption of the dye image obtained by color development processing of the magenta image forming layer. May be determined so as to approximate the spectral absorption of the printed image by the magenta printing ink. Specifically, it is usually 0.02 mol of yellow coupler to 1 mol of magenta coupler.
A range of 0.5 mol is suitable.

In the silver halide photographic light-sensitive material used in the present invention, at least one layer containing a yellow image forming silver halide emulsion (referred to as Y emulsion) and at least one layer magenta image forming halogenated. Silver emulsion (M
And a layer containing at least one cyan image-forming silver halide emulsion (called C emulsion), and a fourth black image-forming silver halide emulsion (S emulsion). Called). Here, the fourth black image forming S emulsion may be any emulsion capable of forming a black image by imagewise exposure and development. In a preferred example, the S emulsion can also be used in combination with a black image layer containing a black coupler. In another preferred example, the S emulsion can also be used in combination with a black image layer containing a yellow coupler, a magenta coupler and a cyan coupler. Further, it is also a preferable example that the S emulsion contributes to image formation of a plurality of layers, and a black image is formed by a combination of a plurality of images resulting from the development of the S emulsion. As an example of forming a black image by combining a plurality of images, for example, a yellow image layer for forming a yellow image contains S emulsion, and a blue image (for example, a magenta image and a cyan image) which is a complementary color of the yellow image is separately formed. It becomes a blue image by being formed at the same time)
In some cases, the forming layer also contains an S emulsion and a black image is formed by developing the S emulsion. Further, the S emulsion may be contained in the magenta image forming layer and its complementary color image forming layer, or the S emulsion may contain the cyan image forming layer in its complementary color image forming layer.

Another preferable example is that the S emulsion is contained in any of the yellow image forming layer, the magenta image forming layer and the cyan image forming layer, and the S emulsion is developed to form a black image. In that case, the yellow image forming layer, the magenta image forming layer and the cyan image forming layer may or may not contain the Y emulsion, M emulsion and C emulsion of the present invention. Good.

One of the most preferred embodiments of the present invention is
Each of the yellow image forming silver halide emulsion layer, the magenta image forming silver halide and the cyan image forming silver halide emulsion layer in the present invention contains an S emulsion.

In another preferred embodiment of the present invention, the S emulsion is contained in the black image-forming silver halide emulsion layer.

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 of the present invention may be a single layer,
It may be composed of a plurality of layers. Further, the order of coating from the support can be arbitrarily selected.

The light-sensitive material used in the present invention is a Y emulsion,
Any of the M emulsion, the C emulsion, and the S emulsion is a light-sensitive material in which the spectral sensitivity region has at least a spectral sensitivity region having a sensitivity at least 6 times higher than those of the other three emulsions. That is, the sensitivity of Y emulsion is different from that of other M, C,
There is at least a spectral sensitivity region that is at least 6 times higher than the sensitivity of each S emulsion, and similarly for M emulsion, C emulsion, and S emulsion, a spectral sensitivity region that is at least 6 times higher than the other three emulsions. At least exist.

Preferably, any of the Y emulsion, the M emulsion, the C emulsion and the S emulsion has at least a spectral sensitivity region in which its sensitivity is at least 8 times higher than that of the other three emulsions.

In one preferred embodiment, the Y emulsion, the M emulsion, the C emulsion and the S emulsion each have a spectral maximum in a wavelength region different from each other. Y emulsion, M emulsion,
When exposed at a specific wavelength in the vicinity of the maximum value of the spectral sensitivity distribution of a certain emulsion among C emulsion and S emulsion, the sensitivity of that emulsion is at least 6 times higher than that of the other three emulsions. Exists. For all of Y emulsion, M emulsion, C emulsion and S emulsion, near the maximum value of the spectral sensitivity distribution,
At least such a wavelength range exists.

In another preferred embodiment, the spectral sensitivity distribution of one of the Y, M, C, and S emulsions is in the wavelength region where the spectral sensitivity distribution is at least 6 times more sensitive than the other three emulsions. In some cases, the spectral sensitivity of the emulsion is not near the maximum. Even in that case, if the sensitivity difference is at least 6 times, it can be used.

In a preferred embodiment, the Y emulsion, the M emulsion, the C emulsion and the S emulsion all have spectral wavelength regions different from each other, and their maximum sensitizing wavelengths are different from each other.
Preferably, the maximum sensitizing wavelengths differ by 20 nm or more from each other. More preferably, they differ by 30 nm or more.

The maximum light-sensing wavelength of the Y emulsion, M emulsion, C emulsion and S emulsion may be any wavelength as long as the above conditions are satisfied.
The maximum photosensitive wavelength of each emulsion can be arbitrarily selected from 350 nm to 900 nm. In one preferred embodiment, the Y emulsion is in the blue region,
The M emulsion is in the green region, the C emulsion is in the red region, and the S emulsion is in the infrared region. In another preferred embodiment, the Y emulsion is 400
± 30 nm, M emulsion is 460 ± 30 nm, C emulsion is 540 ± 30 nm, and S emulsion is 640 ± 30 nm, and it is also preferable to set so that the difference in maximum light-sensing wavelength of each emulsion is 20 nm or more. In yet another preferred example, the M emulsion can be set to 580 nm, the C emulsion to 660 nm, the Y emulsion to 750 nm, and the S emulsion to 850 nm. In yet another preferred embodiment, the Y emulsion is 540 nm, the M emulsion is 380 nm and the C emulsion is C.
The emulsion can be set to 460 nm and the S emulsion can be set to 630 nm. The examples given here are only examples, and the present invention is not limited thereto.

Any emulsion selected from the Y emulsion, the M emulsion, the C emulsion and the S emulsion is preferably at least 6 times higher than the sensitivity at the wavelength other than the emulsion in any wavelength region. Here, the sensitivity is the sensitivity represented by the reciprocal of the exposure amount required to bring the density of a certain image layer to the maximum density of -0.3. It is more preferably 8 times.

Y emulsion, M emulsion, C emulsion in the present invention,
The S emulsion can be realized by selecting from conventionally known spectral sensitizing dyes and sensitizing them.

The reflection support preferably used in the present invention is preferably a base paper which has a polyolefin resin laminated on both sides thereof.

The base paper can be selected from the raw materials generally used for photographic printing paper. For example, natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various types of raw materials for papermaking can be used. In general, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, etc. can be widely used.

Further, additives such as a sizing agent, a fixing agent, a toughening agent, a filler, an antistatic agent and a dye, which are generally used in papermaking, may be blended in the support, and the surface size may be An agent, a surface-strengthening agent, an antistatic agent, or the like may be appropriately applied to the surface.

A support having a smooth surface with a weight of 50 to 300 g / m ² is usually used, and the resin for laminating both surfaces is ethylene, polyethylene terephthalate, α-olefins such as polypropylene. Can be selected from the above homopolymers, copolymers of at least two kinds of the above olefins, and mixtures of at least two kinds of these various polymers. Particularly preferred polyolefin resins are low density polyethylene, high density polyethylene or mixtures thereof.

The molecular weight of the polyolefin resin is not particularly limited, but one having a molecular weight of 20,000 to 200,000 is usually used.

The polyolefin resin coating layer on the side of the reflective support on which the photographic emulsion is coated is preferably 25 to 50 μm,
More preferably, it is 25 to 35 μm.

The polyolefin used for laminating the back side of the support (the reflection side of the side on which the emulsion layer is provided) is usually a melt-laminated mixture of a low density polyethylene and a high density polyethylene. And this layer is often matted.

In forming the laminate on the front and back of the support,
Generally, in order to improve the flatness of the developed photographic paper in a normal environment, a means such as slightly increasing the density of the resin layer on the front side or increasing the laminating amount on the back side rather than the front side is used.

In general, the front and back surfaces of the support can be laminated by forming the polyolefin resin composition on the support by melt extrusion coating. In addition, it is preferable to perform corona discharge treatment, flame treatment, or the like on the surface of the support or on both the front and back surfaces as necessary. Also, a sub-coat layer for improving the adhesiveness with the photographic emulsion on the surface of the surface laminate layer,
Alternatively, it is preferable to provide a back coat layer on the back side of the laminate layer for improving the writing property and the antistatic property.

The polyolefin resin used for laminating the support surface (the surface on which the emulsion layer is provided) is preferably a polyolefin resin.
13 to 20% by weight, more preferably 15 to 20% by weight of white pigment is dispersed and mixed.

As the white pigment, inorganic and / or organic white pigments can be used, preferably inorganic white pigments. Examples of such white pigments include alkaline earth metal sulfates such as barium sulfate and carbonates. Examples thereof include carbonates of alkaline earth metals such as calcium, finely divided silicic acid, silicas of synthetic silicates, calcium silicate, alumina, hydrated alumina, titanium oxide, zinc oxide, talc and clay.

Of these, preferably barium sulfate,
Calcium carbonate and titanium oxide are preferable, and barium sulfate and titanium oxide are particularly preferable. Titanium oxide may be of rutile type or anatase type, and the one whose surface is coated with a metal oxide such as hydrous alumina oxide or hydrous ferrite is also used.

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

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

Further, as the reflective support, a synthetic resin film support such as polypropylene whose surface is further coated with polyolefin can be used.

The thickness of the reflective support is not particularly limited, but 80
~ 160μm thickness is preferably used, especially 90 ~ 130μm
Thick ones are more preferable.

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

In the present invention, a matting agent may be contained in the constituent layer on the image forming surface side of the light-sensitive material so that the surface roughness of the image forming surface is 0.30 to 3.0 μm. The layer to which the matting agent is added includes a silver halide emulsion layer, a protective film, an intermediate layer and an undercoat layer, which may be added to a plurality of layers and is preferably the uppermost layer of the light-sensitive material.

The surface gloss of the light-sensitive material on the image forming layer side 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 the treatment is measured by the method specified in JIS-Z 8741. It is preferable that (60 °) is 5 to 15. More preferably, it is 5-20.

In a preferred embodiment of the present invention, it is preferable to form a protective layer on the outermost surface of the light-sensitive material and add fine particle powder to the protective layer. As the fine particle powder (matting agent) and its use, it is preferable to use the technique described in JP-A-6-95283, page 4, left column, line 42 to right column, line 33.

The silver halide emulsion used in the light-sensitive material of the present invention is a surface latent image type silver halide emulsion which forms a latent image on the surface by imagewise exposure, and a silver halide which forms a negative image by development. An emulsion may be used. or,
Fog treatment (nucleation treatment) after image exposure using an internal latent image type silver halide emulsion in which the grain surface is not pre-fogged.
Those which can directly obtain a positive image are also preferably used by performing the surface development and then performing the surface development, or by performing the surface development while performing the fog treatment after the image exposure.

The above-mentioned fog treatment may be performed by exposing the entire surface, or may be chemically performed by using a fog agent,
Further, a strong developing solution may be used, and furthermore, a heat treatment or the like may be used.

The overall exposure is carried out by immersing or swelling the imagewise exposed light-sensitive material in a developing solution or other aqueous solution, and then uniformly exposing the entire surface. The light source used here may be any light source as long as it has light in the photosensitive wavelength region of the light-sensitive material, and can also be irradiated with high illuminance light such as flash light for a short time or weak light. May be applied for a long time. The whole surface exposure time can be varied over a wide range so that the best positive image can be finally obtained depending on the above-mentioned light-sensitive material, development processing conditions, type of light source used, and the like. In addition, it is most preferable that the exposure amount for the entire surface exposure be given in a certain fixed range in combination with the photosensitive material. Usually, an excessive exposure amount tends to raise the minimum density or desensitize, and the image quality tends to deteriorate.

The technology of the fogging agent that can be used in the light-sensitive material of the present invention is the technology described in JP-A-6-95283, page 18, right column, line 39 to page 19, left column, line 41. Is preferred.

The non-pre-fogged internal latent image type silver halide grains which can be used in the present invention form a latent image mainly inside the silver halide grains and have most of the photosensitive nuclei inside the grains. An emulsion having silver halide grains, comprising any silver halide such as silver bromide, silver chloride,
Silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide and the like are included.

Particularly preferably, the coated silver amount is about 1 to 3.5 g.
A portion of the sample coated on a transparent support to a range of / m ² was exposed to a light intensity scale for a defined period of time from about 0.1 second to about 1 second and was substantially halogenated. When only the surface image of a grain not containing a silver halide solvent is developed for 4 minutes at 20 ° C. using the following surface developer A, another part of the same emulsion sample is similarly exposed to give the inside of the grain. Is an emulsion showing a maximum density not greater than 1/5 of the maximum density obtained when developed with the following internal developer B for 4 minutes at 20 ° C. More preferably, the maximum density obtained with surface developer A is less than the maximum density obtained with internal developer B.
It is not larger than 1/10.

(Surface developer A) Metol 2.5 g L-ascorbic acid 10.0 g Sodium metaborate (tetrahydrate) 35.0 g Potassium bromide 1.0 g Water was added to 1000 cc (internal developer B) Metol 2.0 g Sodium sulfite ( Anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.5 g Potassium bromide 5.0 g Potassium iodide 0.5 g Water added 1000 cc Further, various internal latent image type silver halide emulsions preferably used in the present invention are available. Those prepared by the method of. For example, conversion type silver halide emulsions described in U.S. Pat.No. 2,592,250, or U.S. Pat.
Nos. 6,3,317,322 and 3,367,778, and silver halide emulsions having internally chemically sensitized silver halide grains, or described in U.S. Patents 3,271,157, 3,447,927 and 3,53,291. Emulsion having silver halide grains containing polyvalent metal ions, or silver halide grains containing the dopant described in U.S. Pat. No. 3,761,276, the surface of which is weakly chemically sensitized. Emulsion, or JP-A Nos. 50-8524, 50-38525 and 5
Examples thereof include silver halide emulsions composed of grains having a laminated structure described in JP-A No. 3-2408, and silver halide emulsions described in JP-A Nos. 52-156614 and 55-127549.

The internal latent image type silver halide grains preferably used in the present invention are silver halides having any halogen composition such as silver bromide, silver chloride, silver chlorobromide, silver chloroiodide and silver iodobromide. Any silver chloroiodobromide may be used. The grains containing silver chloride have excellent developability and are suitable for rapid processing.

The silver halide grains may have any shape such as cubic, octahedron, tetradecahedron composed of a mixture of (100) plane and (111) plane, shape having (110) plane, spherical shape, tabular shape and the like. Good.
An average particle size of 0.05 to 3 μm can be preferably used.
The grain size distribution may be a monodisperse emulsion having uniform grain size and crystal habit, or an emulsion having no uniform grain size or crystal habit, but a monodisperse silver halide emulsion having uniform grain size and crystal habit. Is preferred. What is a monodisperse silver halide emulsion?
The weight of silver halide contained in the grain size range of ± 20% around the average grain size rm is 60% or more of the total weight of silver halide grains, preferably 70% or more, more preferably 80% or more. % Or more. Here, the average particle size rm is the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is defined as the particle size ri when the maximum (three significant figures, the least significant digit Round off 4). The term "particle size" used herein means the diameter of spherical silver halide grains, or the diameter of a projected image converted into a circular image of the same area in the case of grains having a shape other than spherical. . The particle size is, for example, 1 with an electron microscope.
It can be obtained by enlarging the image from 10,000 to 50,000 times and measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is indiscriminately 1000 or more).

Particularly preferred highly monodisperse emulsions are those in which the breadth of distribution defined by (grain size standard deviation / mean grain diameter) × 100 = breadth of distribution (%) is 20% or less. Here, the average particle size and the particle size standard deviation are obtained from ri defined above.

The monodisperse emulsion is prepared by adding a water-soluble silver salt solution and a water-soluble halide solution to a gelatin solution containing seed grains at pAg and pH.
Under the control of the double jet method. In determining the addition rate, reference can be made to JP-A-54-48521 and JP-A-58-49938. As a method for obtaining a more advanced monodisperse emulsion, JP-A-60-122935 is known.
The growth method in the presence of the tetrazaindene compound disclosed in US Pat.

Further, it is preferable to add two or more kinds of the monodisperse emulsions to the same color-sensitive layer.

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

In one preferred embodiment of the present invention, the grain size of silver halide is 0.1 to 0.6 .mu.
m, green sensitive layer emulsion is 0.15 to 0.8 μm, and blue sensitive emulsion is 0.3 to 1.
A range of 2 μm can be preferably used.

The color light-sensitive material of the present invention preferably contains a nitrogen-containing heterocyclic compound having a mercapto group. Preferred compounds include JP-A-6-95283, page 19, right column, 2
General formula [XI] described in lines 0 to 49, particularly preferably the same number 20
General formula [XII], general formula [XIII], and general formula [XIV] described on page 5, left column, line 5 to page 20, right column, line 2 Specific examples of the compound include compounds (1) to (39) described in JP-A 64-73338, pages 11 to 15.

The addition amount of the mercapto compound may be appropriately changed depending on the kind of the compound used and the layer to be added, and when it is added to the silver halide emulsion layer, it is generally from 10 ^-8 to 10 ⁸ per mol of silver halide. The amount is in the range of 10 ^-2 mol, more preferably 10 ^-6 to 10 ^-3 mol.

The yellow image forming silver halide emulsion layer, the magenta image forming silver halide emulsion layer and the cyan image forming silver halide emulsion layer in the color light-sensitive material of the present invention have different spectral sensitivity wavelength regions from each other. At least one of the yellow, magenta, and cyan image-forming silver halide emulsion layers containing a silver halide emulsion and contained in the yellow, magenta, and cyan image-forming silver halide emulsion layers, respectively. It is preferable to contain a silver halide emulsion having a spectral sensitivity having a common part with any of the emulsions having different spectral sensitivity wavelength regions.

As the cyan coupler contained in the cyan image forming layer, known phenol type, naphthol type or imidazole type couplers can be used. Typical examples include phenol-based couplers substituted with an alkyl group, an acylamino group or a ureido group, naphthol-based couplers formed from a 5-aminonaphthol skeleton, and 2 equivalent type naphthol-based couplers having an oxygen atom introduced as a leaving group. It Among them, preferred compounds include general formulas [CI] and [CI] described on page 13 of JP-A-6-95283.
I] can be mentioned.

These cyan couplers are usually used in a silver halide emulsion layer in an amount of 1 × 10 ^-3 per mol of silver halide.
It can be used in an amount of 1 to 1 mol, preferably 1 × 10 ^-2 to 8 × 10 ^-1 mol.

As the yellow dye forming coupler, known acylacetanilide type couplers can be preferably used, and among these, benzoylacetanilide type compounds and pivaloylacetanilide type compounds are advantageous.

Specific examples of the yellow coupler include compounds described in JP-A-3-241345, pages 5 to 9, Y-
Compounds represented by I-1 to Y-I-55, or JP-A-3-20
The compounds described on pages 11-14 of 9466, and the compounds represented by Y-1 to Y-30 are also preferable. Further, couplers represented by the general formula [Y-I] described in JP-A-6-95283, page 21 can be mentioned.

In the present invention, it is preferable that λmax of the spectral absorption of the yellow image is 425 nm or more.
_L0.2 is preferably 515 nm or less.

The spectral absorption λ _L0.2 of the yellow image is a value defined by the contents described in JP-A-6-95283, page 21, right column, lines 1 to 24, and the spectral absorption characteristic of the yellow dye image. Represents the magnitude of unwanted absorption on the long wave side.

These yellow couplers are generally used in a silver halide emulsion layer in an amount of 1 × 10 6 per mol of silver halide.
It can be used in the range of ^-3 to 1 mol, preferably 1 x 10 ^-2 to 8 x 10 ^-1 mol.

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

The yellow image forming layer, the magenta image forming layer, and the cyan image forming layer in the light-sensitive material of the present invention are laminated and coated on a support, but the order from the support is arbitrary. In one preferred embodiment, the cyan image forming layer, the magenta image forming layer, and the yellow image forming layer are provided from the side closer to the support. In addition to these, an intermediate layer, a filter layer, a protective layer and the like can be arranged as required.

An anti-fading agent may be used in combination with each of the above-mentioned couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Preferred compounds include phenyl ether compounds represented by the general formulas I and II described in JP-A-2-66541, page 3, phenolic compounds represented by the general formula IIIB described in JP-A-3-174150, and JP-A-64- 9044
Amine-based compounds represented by the general formula A described in JP-A No.
The metal complexes represented by the general formulas XII, XIII, XIV, and XV described in No. 2-182741 are particularly preferable for magenta dyes. or,
The compound represented by the general formula I ′ described in JP-A 1-196049 and the compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

When the oil-in-water type emulsion dispersion method is used to add the coupler or other organic compound used in the light-sensitive material, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, if necessary. A low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. 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 the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. Examples of the high boiling point organic solvent that can be used to dissolve and disperse the coupler and the like, dioctyl phthalate, diisodecyl phthalate,
Phthalic acid esters such as dibutyl phthalate; phosphoric acid esters such as tricresyl phosphate and trioctyl phosphate; phosphine oxides such as trioctyl phosphine oxide are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

A particularly preferable compound as the high-boiling point organic solvent is represented by the general formula [HBS-I] described in JP-A-6-95283, page 22.
And a compound represented by [HBS-II], and particularly preferably a compound represented by [HBS-II]. Specific compounds include, for example, compounds I-1 to II-95 described in JP-A-2-124568, pp. 53-68.

Preferred compounds as the surfactant used for dispersing the photographic additives and adjusting the surface tension at the time of coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. And the like. Specific examples thereof 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.
The time until addition to the coating solution and the time after coating to the coating solution are preferably short, 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 product of a developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or to a silver halide emulsion layer to fog. Is preferably improved. The compound for this is preferably a hydroquinone derivative, more preferably 2,5-
It is a dialkyl hydroquinone such as di-t-octyl hydroquinone. A particularly preferred compound is Kaihei 4-1330.
No. 56 is a compound represented by the general formula II, 13-
Compounds II-1 to II-14 described on page 14 and Compound 1 described on page 17 are mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or improve the light resistance of the dye image. Examples of preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds include compounds represented by the general formula III-3 described in JP-A-1-250944, and represented by general formula III described in JP-A-64-66646. Compound, UV-1L to UV-2 described in JP-A-63-187240
7L, a compound represented by the general formula I described in JP-A-4-1633,
Examples thereof include 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 the whiteness is improved. Typical examples of oil-soluble dyes include compounds 1 to 27 described on pages (8) to (9) of JP-A-2-842.

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

The transmittance of gelatin used in the light-sensitive material of the present invention is preferably 70% or more when a 10% solution is prepared and the transmittance is measured at 420 nm with a spectrophotometer.

Jelly strength of gelatin (by the Paggy method)
Is preferably 250 g or more, particularly preferably 270 g
That is all.

The ratio of the gelatin to the total coated gelatin is not particularly limited, but a higher ratio is preferable, and specifically a preferable result is obtained in the range of at least 20 to 100%.

The total amount of gelatin contained on the image forming surface side of the light-sensitive material according to the present invention is preferably less than 11 g / m ² . Although the lower limit is not particularly limited, it is generally preferably 3.0 g / m ² or more in view of physical properties or photographic performance. The amount of gelatin is determined by converting it to the weight of gelatin containing 11.0% of water by the water content measurement method described in the Paggy method.

As the hardener for these binders, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination. JP 61-249054
It is preferable to use the compounds described in JP-A No. 61-245153. Further, in order to prevent the growth of mold and bacteria, which adversely affect the photographic performance and the image storability, it is preferable to add an antiseptic and an antifungal agent as described in JP-A-3-157646 in the colloid layer.

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

The color light-sensitive material may contain a water-soluble dye in any silver halide emulsion layer and / or other hydrophilic colloid photographic constituent layers.
Further, a dye having at least one of a carboxyl group, a sulfonamide group and a sulfamoyl group may be solid-dispersed and contained in any silver halide emulsion layer and / or other hydrophilic colloid photographic constituent layers. it can.

As the dye having at least one of a carboxyl group, a sulfamoyl group and a sulfonamide group,
General formulas [I] to [IX] described on pages 14 to 16 of JP-A-6-95283
The compound shown by can be mentioned.

Specific examples of the dyes represented by the above formulas [I] to [VIII] include I-1 to VIII to 7 described in JP-A No. 4-18545, pages 13 to 35. However, it is not limited to this.

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

The silver halide can be optically sensitized by a commonly used sensitizing dye. The combined use of sensitizing dyes used for supersensitization such as internal latent image type silver halide emulsions and negative type silver halide emulsions is also useful for the silver halide emulsions of the present invention. Research Disclosure (ResearchDi)
Sclosure, abbreviated as RD hereinafter) Nos. 15162 and 17643 can be referred to.

It is preferable to add a compound for adjusting the gradation of the foot to the light-sensitive material according to the present invention. Preferred compounds include those represented by the general formula [AO-I described in JP-A-6-95283, page 17].
Compounds represented by I] are preferred. Examples of preferable compounds include compounds II-1 to II-8 described on page 18 of the same item. The amount of this [AO-II] compound added is 0.00
1 to 0.50 g / m ² is preferable, more preferably 0.005 to 0.20
g / m ² . The compounds may be used alone or in combination of two or more kinds. Further, a quinone derivative having 5 or more carbon atoms may be added to the compound [AO-II] for use. However, in any of these cases, the amount used is preferably in the range of 0.001 to 0.50 g / m ² as a whole.

It is preferable to add a fluorescent brightening agent to the light-sensitive material and / or the processing solution of the present invention in order to improve the white background.

The developing solution, the bleach-fixing solution and the stabilizing solution for color-developing the light-sensitive material of the present invention are a replenishing developing solution and a replenishing developing solution, respectively.
The replenishing bleaching solution, the replenishing fixing solution, the replenishing bleach-fixing solution, the replenishing stabilizing solution and the like can be continuously developed while supplementing.

Examples of the developer that can be used in the developer include conventional silver halide developers such as polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, ascorbic acid and derivatives thereof.
It includes reductones, phenylenediamines, and the like, or mixtures thereof. Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, 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-
Examples thereof include hydroxyethyl) aniline and 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline. If these developers are included in the emulsion beforehand, the high p
It is also possible to act on the silver halide during the immersion in the H 2 aqueous solution.

The developer used may further contain a specific antifoggant and development inhibitor, or
It is also possible to optionally incorporate those developer additives into the constituent layers of the light-sensitive material.

Known photographic additives can be used in the light-sensitive material. Known photographic additives include, for example,
RD17643 (Dec. 1978) Page 23 III-29 XXI and RD18716
(November, 1979) Chemical sensitizers, sensitizing dyes, development accelerators, antifoggants, stabilizers, color stain inhibitors, image stabilizers, ultraviolet absorbers on pages 648, right column to 651, right column. , Filter dyes, brighteners, hardeners, coating aids, surfactants, plasticizers,
Examples include slip agents, antistatic agents, matting agents, and binders.

To form an image using the light-sensitive material of the present invention, it is preferable to use an automatic developing machine of the light source section scanning exposure system. Examples of particularly preferable image forming devices and systems include Konsensus L and Konsensu manufactured by Konica Corporation.
Examples include s570 and Konsensus II.

[0137]

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 Emulsion EM-P1) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (in molar ratio) were used.
An aqueous solution containing KBr: NaCl = 95: 5) was simultaneously added by the control double jet method to obtain a cubic silver chlorobromide core emulsion having an average grain size of 0.30 μm. At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in molar ratio) were simultaneously added to the obtained core emulsion by the control double jet method. To form an average particle diameter of 0.42 μm. At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-P1. The breadth of distribution of 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 (molar ratio KBr: NaCl = 95: 5). ) Is added simultaneously with the control double jet method to obtain an average particle size.
A 0.18 μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

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

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

(Preparation of Blue-Sensitive Silver Halide Emulsion) Emulsion E
A sensitizing dye BS-1 was added to M-P1 for optimum color sensitization, and then 600 mg of stabilizer T-1 was added per mol of silver to prepare a blue-sensitive emulsion Em-B.

(Preparation of Green-Sensitive Silver Halide Emulsion) Emulsion E
A green-sensitive emulsion Em-G was prepared in the same manner as the blue-sensitive emulsion Em-B except that the sensitizing dye GS-1 was added to M-P2 for optimum color sensitization.
Was prepared.

(Preparation of Red-Sensitive Silver Halide Emulsion) Emulsion E
A red-sensitive emulsion Em-R was prepared in the same manner as the blue-sensitive emulsion Em-B, except that the sensitizing dyes RS-1 and RS-2 were added to M-P2 for optimum color sensitization.

(Preparation of pan-sensitive silver halide emulsion) Emulsion E
Blue-sensitive emulsion Em except that optimum sensitization was performed by adding sensitizing dyes BS-1, GS-1, RS-1 and RS-2 to M-P1.
A pan-sensitive emulsion Em-K was prepared in the same manner as in -B.

T-1: 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene

[0149]

Embedded image

A high-density polyethylene was laminated on one side, and a molten polyethylene containing anatase type titanium oxide dispersed in a content of 15% by weight was laminated on the other side.
Em-B, Em- on the paper pulp reflective support of μm
G, Em-R and Em-K emulsions were used, each layer having the following constitution was coated on the side of the polyethylene layer containing titanium oxide, and on the back side, gelatin 6.00 g / m ² , A multilayer color light-sensitive material sample 1-1 coated with a silica matting agent 0.65 g / m ² was prepared. In addition, H-1 and H-2 were added as a hardening agent. Surfactants SU-1, SU-2, and SU-3 were added as coating aids and dispersing aids.

SU-1: Di (2-ethylhexyl) sulfosuccinate / sodium SU-2: Di (2-2,3,3,4,4,5,5-octafluoropentyl) sulfosuccinate / sodium SU -3: Sodium tri-i-propylnaphthalenesulfonate H-1: 2,4-dichloro-6-hydroxy-s-triazine / sodium H-2: Tetrakis (vinylsulfonylmethyl) methane layer composition coating amount (g / m ² ) 9th layer gelatin 1.60 (ultraviolet ray ultraviolet absorber (UV-1) 0.070 absorbing layer) ultraviolet absorber (UV-2) 0.025 ultraviolet absorber (UV-3) 0.120 silica matting agent 0.01 8th layer gelatin 1.10 ( Blue-sensitive layer) Pan-sensitive emulsion (Em-K) 0.04 Blue-sensitive emulsion (Em-B) 0.36 Yellow coupler (Y-1) 0.19 Yellow coupler (Y-2) 0.19 Inhibitor (T-1, T-2, T) -3; equimolar ratio) 0.004 Anti-staining agent (HQ-1) 0.004 Boiling point organic solvent (SO-1) 0.30 7th layer Gelatin 0.94 (Intermediate layer) Anti-staining agent (HQ-2, HQ-3 equivalent weight) 0.02 High boiling point organic solvent (SO-2) 0.05 Anti-irradiation dye (AI- 3) 0.03 6th layer Gelatin 0.45 (YC layer) Yellow colloidal silver 0.11 Anti-staining agent (HQ-1) 0.03 High boiling point organic solvent (SO-2) 0.008 Polyvinylpyrrolidone 0.04 5th layer Gelatin 0.45 (Intermediate layer) Antistaining agent (HQ-2) 0.014 Anti-staining agent (HQ-3) 0.014 High boiling point organic solvent (SO-2) 0.006 Fourth layer Gelatin 1.25 (Green sensitive layer) Pan-sensitive emulsion (Em-K) 0.05 Green sensitive silver chlorobromide Emulsion (Em-G) * 0.32 Magenta coupler (M-2) 0.25 Yellow coupler (Y-3) 0.06 Stain inhibitor (HQ-1) 0.035 Inhibitor (T-1, T-2, T-3; equimolar) Ratio) 0.0036 High boiling point organic solvent (SO- ) 0.38 3rd layer gelatin 0.80 (intermediate layer) anti-stain agent (HQ-2) 0.03 anti-stain agent (HQ-3) 0.01 anti-irradiation dye (AI-1) 0.04 2nd layer gelatin 0.90 (red sensitive layer) general Sensitive emulsion (Em-K) 0.075 Red-sensitive silver chlorobromide emulsion (Em-R) * 0.27 Cyan coupler (C-1) 0.35 Stain inhibitor (HQ-1) 0.02 Inhibitor (T-1, T-2, T3; equimolar ratio) 0.002 High boiling organic solvent (SO-1) 0.18 First layer Gelatin 1.20 (white pigment liquid paraffin 0.55 containing layer) Anti-irradiation dye (AI-2) 0.055 Titanium oxide
0.50 support Polyethylene laminated paper (containing a trace amount of colorant) * The amount of silver halide emulsion added is shown in terms of silver.

The structure of each compound is shown below.

SO-1: Trioctylphosphine oxide SO-2: Di-i-decylphthalate HQ-1: 2,5-di-t-butylhydroquinone HQ-2: 2,5-di [(1,1- Dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5-
Di-sec-tetradecyl hydroquinone and 2-sec-dodecyl-
A mixture of 5-sec-tetradecylhydroquinone in a weight ratio of 1: 1: 2 T-2: 1- (3-acetamidophenyl) -5-mercaptotetrazole T-3: N-benzyladenine

[0154]

Embedded image

[0155]

Embedded image

Next, in the same manner as in Sample 1-1, Sample 1-2.
1-7 were produced. However, Samples 1-2 to 1-7 were prepared in the same manner as Sample 1-1 except that the tetrazolium compound of the present invention was added to the fourth layer (green sensitive layer) as shown in Table 1.

To each of the samples thus obtained, a black plate and a cyan plate of a halftone original document were brought into close contact with the sample and exposed under the following exposure conditions-1. Then, the black plate and the magenta plate are brought into close contact with the sample and exposed under the following exposure conditions-2, and the black plate and the yellow plate are brought into close contact with the sample and exposed under the following exposure conditions-
Exposed at 3.

Another part of Samples 1-1 to 1-7 was exposed with a sensitometer through an ordinary optical wedge for sensitometry.

Each of the exposed samples was processed in the development processing step described later to obtain a dye image consisting of halftone dots and an image for sensitometry.

(Exposure condition-1) The ND filter density was adjusted when exposing the light-sensitive material sample to white light through a red filter (Ratten No. 26) and an ND filter so that the red density after development was minimized. With the minimum exposure amount of 0.5
Expose for 2 seconds.

(Exposure condition-2) When the light-sensitive material sample was exposed to white light through a green filter (Ratten No. 58) and an ND filter, the ND filter density was adjusted to minimize the green density after development processing. With the minimum exposure amount of 0.5
Expose for 2 seconds.

(Exposure condition-3) When the light-sensitive material sample was exposed to white light through a blue filter (Ratten No. 47B) and an ND filter, the ND filter density was adjusted to minimize the blue density after development. With the minimum exposure amount of 0.5
Expose for 2 seconds.

A daylight fluorescent lamp was used as a light source under each exposure condition.

Processing was carried out according to the following processing step-1 (new solution processing). However, the fog exposure was uniformly exposed on the entire surface of the light-sensitive material through the layer of the developing solution having a thickness of 3 mm while being immersed in the developing solution.

Another part of the sample was exposed under the same conditions as in the case of the new solution treatment and processed in the same manner as in the processing step-1, but the developing solution in the processing step-1 was replaced with the replenished developing replenisher. Was subjected to running processing in Sample 1-1 until the total amount thereof was three times as large as that in the developing tank, and then processing was carried out using the developing solution, the bleach-fixing solution and the stabilizing solution (running processing).

A part of another sample was exposed under the same conditions as in the case of the new solution treatment and was processed in the same manner as in the processing step-1, but the pH of the developing solution in the processing step-1 was reduced by 0.3. Processing was performed using a developing solution (low pH processing).

Process Step-1 Temperature Time Immersion (Developer) 37 ° C 12 seconds Fog exposure-12 seconds Color development 37 ° C 95 seconds Bleach-fix 35 ° C 45 seconds Stabilization 25-30 ° C 90 seconds Dry 60-85 ° C 40 seconds The composition of each treatment liquid is shown below.

Color developer Benzyl alcohol 15.0cc Cerium sulfate 0.015g Ethylene glycol 8.0cc Potassium sulfite 2.5g Potassium bromide 0.6g Sodium chloride 0.2g Potassium carbonate 25.0g T-1 0.1g Hydroxylamine sulfate 5.0g Diethylenetriamine penta Sodium acetate 2.0g 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Diethylene glycol 15.0 Add cc water to bring the total volume to 1 liter, and adjust to pH 10.15.

Bleach-fixing solution Diethylenetriaminepentaacetic acid ferric ammonium 90.0g Diethylenetriaminepentaacetic acid 3.0g Ammonium thiosulfate (70% aqueous solution) 180.0cc Ammonium sulfite (40% aqueous solution) 27.5cc 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 bring the total volume to 1 liter.

Stabilizing solution o-Phenylphenol 0.3 g Potassium sulfite (50% aqueous solution) 12.0 cc 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 Hydroxylation Ammonium (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g Add water to bring the total volume to 1 liter, and add ammonium hydroxide or sulfuric acid. Adjust to pH 7.5.

The stabilization treatment was a countercurrent system having a two-tank construction.

The formulation of the replenisher for the running process is shown below.

Color developing replenisher benzyl alcohol 18.5cc ceric sulfate 0.015g ethylene glycol 10.0cc potassium sulfite 2.5g potassium bromide 0.3g sodium chloride 0.2g potassium carbonate 25.0g T-1 0.1g hydroxylamine sulfate 5.0g diethylenetriamine Sodium pentaacetate 2.0g 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate) 5.4g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative 1.0g Potassium hydroxide 2.0g Diethylene glycol Add 18.0cc water to make the total volume 1 liter and adjust to pH 10.35.

Bleach-fixing solution replenishing solution Same as the above-mentioned bleach-fixing solution.

Stabilizer Replenisher Same as the above stabilizer.

The replenishing amount is the development replenishing solution, the bleach-fixing solution,
The stabilizing solution was 320 cc per 1 m ^{2 of the} light-sensitive material.

A color proof composed of halftone images was prepared using Konsensus 570 manufactured by Konica. The processing was continuously carried out until the total amount of the replenished color developing replenishing solution became three times the amount in the color developing tank. The density of the magenta image of the processed sample was measured with green light, and the sensitometry and the dot gain at the original dot area ratio of 50% were measured.
The results are shown in Table 1.

The gradation is represented by the absolute value of the slope of the straight line connecting the density point of the minimum density +0.30 and the density point of the minimum density +1.00, and the gradation variation is represented by the new liquid treatment. The gradation value is shown as a value obtained by subtracting the gradation value from the running solution and the low pH solution. The closer the variation is to 0, the better.

Similarly, the Dmax fluctuation shows the difference between the new solution, the running solution and the low pH solution with respect to the maximum concentration. Further, the dot gain fluctuation shows how the dot gain of the 50% halftone dot obtained by the new liquid treatment changes in the running liquid and the low pH liquid treatment, and it is desirable that there is no fluctuation.

[0180]

[Table 1]

From this result, it is understood that the sample of the present invention can obtain a stable gradation even when the condition of the treatment liquid is changed, and that the dot gain of the halftone dot image is not changed at all.

Example 2 The color tone of the solid portion (100%) of the magenta images obtained from Samples 1-1 to 1-7 in Example 1 was evaluated.

[0183]

[Outside 1]

It was measured by a color system.

Difference in color tone obtained by low pH treatment from color tone obtained by new liquid treatment (called color difference)

[0186]

[Outside 2]

The values of are shown below. Set the color difference of sample 1-1 to 10
It is a relative value with 0.

[0188] It can be seen that in the sample of the present invention, the variation in color tone due to the variation in processing conditions can be suppressed to a small level.

Example 3 (Preparation of infrared-sensitive silver halide emulsion) Blue-sensitive emulsion Em-B1 except that sensitizing dye IRS-1 was added to emulsion EM-P1 in Example 1 for optimum color sensitization. An infrared-sensitive emulsion Em-IR1 was prepared in the same manner as in.

[0190]

Embedded image

On the same support as used in Example 1, each of the emulsions of Em-B1, Em-G1, Em-R1 and Em-IR1 prepared in Example 1 was used, and each layer having the constitution shown below was used. Is applied to the side of the polyethylene layer containing titanium oxide, and the backside layer is made of gelatin 6.00 g / m ² and silica matting agent 0.65.
A multilayer color light-sensitive material sample 3-1 coated with g / m ² was prepared. The same compounds as in Example 1 were used for the hardener and the surfactant.

Layer composition Coating amount (g / m ² ) Eleventh layer Gelatin 1.60 (UV / UV absorber (UV-1) 0.070 absorption layer) UV absorber (UV-2) 0.025 UV absorber (UV-3) 0.120 Silica matting agent 0.01 Tenth layer Gelatin 1.10 (Blue sensitive layer) Blue sensitive emulsion (Em-B1) 0.36 Yellow coupler (Y-1) 0.19 Yellow coupler (Y-2) 0.19 Inhibitors (T-1, T-2) , T-3; equimolar ratio) 0.004 Anti-staining agent (HQ-1) 0.04 High boiling point organic solvent (SO-1) 0.30 9th layer gelatin 0.94 (intermediate layer) Anti-staining agent (HQ-2, HQ-3 etc.) Weight) 0.02 High boiling organic solvent (SO-2) 0.05 Irradiation preventing dye (AI-3) 0.03 Eighth layer Gelatin 0.45 (YC layer) Yellow colloidal silver 0.11 Stain inhibitor (HQ-1) 0.03 High boiling organic solvent ( SO-2) 0.008 Polyvinylpyrrolidone 0.04 Layer Gelatin 0.45 (Intermediate layer) Anti-staining agent (HQ-2, HQ-3 etc. weight) 0.03 High boiling point organic solvent (SO-2) 0.006 6th layer Gelatin 1.25 (Green sensitive layer) Green sensitive silver chlorobromide emulsion ( Em-G1) * 0.32 Magenta coupler (MA) Table 2 Yellow coupler (Y-3) 0.06 Stain inhibitor (HQ-1) 0.035 Inhibitor (T-1, T-2, T-3; equimolar ratio) ) 0.004 High boiling organic solvent (SO-1) 0.38 Fifth layer Gelatin 0.80 (Intermediate layer) Anti-stain agent (HQ-2) 0.03 Anti-stain agent (HQ-3) 0.01 Anti-irradiation dye (AI-1) 0.04 High Boiling point organic solvent (SO-2) 0.06 4th layer Gelatin 0.90 (red-sensitive layer) Red-sensitive silver chlorobromide emulsion (Em-R1) * 0.27 Cyan coupler (C-1) 0.35 Stain inhibitor (HQ-1) 0.35 Inhibitor (T-1, T-2, T-3; equimolar ratio) 0.002 High boiling organic solvent ( O-1) 0.18 Third layer Gelatin 0.80 (Intermediate layer) Anti-stain agent (HQ-2) 0.03 Anti-stain agent (HQ-3) 0.01 Anti-irradiation dye (AI-1) 0.04 High boiling organic solvent (SO-2) ) 0.06 Second layer Gelatin 1.00 (Infrared sensitive infrared sensitive silver chlorobromide emulsion (Em-IR1) 1.00 functional layer) Yellow coupler (Y-1) 0.50 Magenta coupler (M-1) 0.20 Cyan coupler (C-1) ) 0.35 Anti-staining agent (HQ-1) 0.04 Inhibitor (T-1, T-2, T-3; equimolar ratio) 0.005 High boiling organic solvent (SO-1) 2.00 1st layer gelatin 1.20 (white pigment flow Paraffin 0.55-containing layer) Irradiation preventing dye (AI-2) 0.055 Titanium oxide 0.50 support Polyethylene laminated paper (containing a trace amount of colorant) * The amount of silver halide emulsion added is shown in terms of silver.

[0193]

Embedded image

Sample similar to Sample 3-1, except that the magenta coupler in the sixth layer was changed as shown in Table 2 and the compounds of the present invention shown in Table 2 were added to the fourth to sixth layers. Three
-2-3-7 were produced.

A cyan plate of a halftone original document was brought into close contact with each sample thus obtained and exposed under the following exposure condition-1. Then, the magenta plate was brought into close contact with the sample and exposed under the following exposure condition-2. Then, the yellow plate was brought into close contact with the sample and exposed under the following exposure condition-3. Further, the black plate was brought into close contact with the sample and exposed under the following exposure condition-4.

Each of the exposed samples was processed by the above-mentioned development processing step to obtain a dye image consisting of halftone dots.

(Exposure Condition-1) Exposure Condition-1 of Example 1
Same as.

(Exposure Condition-2) Exposure Condition-2 of Example 1
Same as.

(Exposure Condition-3) Exposure Condition-2 of Example 1
Same as.

(Exposure condition-4) The density of the ND filter was adjusted when exposing the light-sensitive material sample to white light through an infrared transmission filter and an ND filter so that the black density after development was minimized. The exposure amount is 0.5 seconds.

A daylight fluorescent lamp was used as the light source for exposure conditions-1 to 3, and a xenon lamp was used as the light source for exposure condition-4.

Processing was carried out in the same manner as the fresh solution treatment and running treatment of the treatment step-1 of Example 1. About the obtained image, yellow plate, magenta plate, cyan plate and black plate are respectively
The image density of a portion having a halftone dot ratio of 50% was measured with a densitometer, and the ratio D _B / D _G of the density (D _G ) measured with green light and the density (D _B ) measured with blue light was obtained. .

Table 2 shows the values (relative values) of D _B / D _G in the running liquid when D _B / D _G in the fresh liquid of each sample was 100.

[0204]

[Table 2]

As is clear from Table 2, the sample of the present invention has little color tone variation even when there is a process variation, and a stable color proof consisting of a halftone dot image can be obtained.

[0206]

According to the present invention, it is possible to stably obtain a color proof having good color tone and close to the image quality of an original document (printed matter) by using a color photosensitive material from halftone image information, even if there is a process variation. You can

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material containing a compound selected from the following formula [T], and the silver halide emulsion layer containing internal latent image type silver halide grains. Embedded image [In the formula, R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent, and A ⁻ represents an anion. ] 2. A silver halide color photographic light-sensitive material comprising a compound selected from the following general formula [MI] and a compound selected from the above general formula [T]. Embedded image [In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. R represents a hydrogen atom or a substituent. ] 3. A silver halide color photographic light-sensitive material according to claim 2, wherein the silver halide emulsion layer containing a compound selected from the general formula [MI] contains a yellow coupler. 4. A layer containing a yellow image-forming silver halide emulsion (referred to as Y emulsion), a layer containing a magenta image-forming silver halide emulsion (referred to as M emulsion), and a cyan image-forming silver halide. A layer containing an emulsion (referred to as C emulsion) and a fourth black image-forming silver halide emulsion (referred to as S emulsion), and said Y emulsion, M emulsion, C
2. The spectral sensitivity distribution of either emulsion or S emulsion has a spectral sensitivity region at least 6 times higher in sensitivity than the other three emulsions.
2. A silver halide color photographic light-sensitive material as described in 2 or 3. 5. The halogenation according to claim 1, based on halftone dot image information consisting of color-separated yellow image information, magenta image information, cyan image information and black image information. A method for producing a color proof, which comprises exposing a silver color photographic light-sensitive material to light.