JPH024239A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material having high degree of approximation of hue to the hue of printed picture by adding a Yellow or Magenta coupler dissolved and dispersed in a mixture of specified high boiling solvents to a silver halide color photographic sensitive material. CONSTITUTION:A Yellow or a Magenta coupler is dissolved and dispersed in a mixture of a first and a second high boiling solvent expressed by the formula I, wherein log P of the second high boiling solvent is 4.0-10.0. In the formula, each R1 to R3 is an alkyl group or an aryl group; each l, m, and n is zero or 1. Suitable alkyl group expressed by R1 to R3 may be any of a straight chain, branched chain, or cyclic one, and said alkyl group may be substituted. Thus, a photosensitive material having satisfactory hue suitable as photosensitive material for color proof and causing no decrease of the maximum density is obtd.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it is particularly suitable for producing color images for proofing in color plate making and printing processes, and The present invention relates to a silver halide color photographic material having improved color reproducibility even for general use.

[Background of the invention]

BACKGROUND ART Conventionally, in the process of color plate making and printing, a method using color paper is known as one method of obtaining a color image for proofing on a single sheet from color-separated black and white halftone dot images.

In this method, a color-separated black-and-white halftone image consisting of multiple sheets of color-separated and converted halftone images from a color original is sequentially printed onto sheets of color paper using a method such as contact printing, and subjected to color development processing. A color image formed with dye imagewise produced from the coupler by color development is used as a proofing image.

In such a method, the color paper used is required to have a hue of the color image generated from the coupler that is similar to the hue of the color image obtained by printing. , cannot be said to be fully satisfied.

[Purpose of the invention]

An object of the present invention is to provide a silver halide color photographic light-sensitive material that can be used in the above-mentioned color proof production method and can provide improved approximation in hue to a printed image.

A second object is to provide a silver halide photographic material for color proofing in which the maximum density does not decrease.

[Structure of the invention]

The object of the present invention is to provide a silver halide color photograph in which yellow coupler or magenta coupler is dissolved and dispersed in a mixture of a first high-boiling point solvent and a second high-boiling point solvent represented by the following general formula (1). A silver halide color photographic light-sensitive material, wherein the second high-boiling solvent has a LogP of 4.0 to 1010.

In the formula, Rr, Rx and R1 each represent an alkyl group or an aryl group, and Q, m and n each represent 0 or l, but Q
, m and n are never 1 at the same time. achieved by.

The silver halide color photographic light-sensitive material of the present invention is suitable not only for producing color proofs but also for other color uses such as general use, and is improved compared to conventional silver halide color photographic light-sensitive materials. This has the effect of obtaining high color purity.

The alkyl group represented by R1, R2, and R1 in the above general formula (I) may be linear, branched, or cyclic, and the alkyl group may have a substituent.

Examples of unsubstituted alkyl groups include alkyl groups having 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, such as ethyl group, butyl group, pentyl group, cyclohexyl group, octyl group, dodecyl group, heptadecyl group, octadecyl group, etc. .

Examples of the substituent of the substituted alkyl group include an aryl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group.

The aryl group represented by R, Rt and R3 in the above general formula [I] is a phenyl group or a naphthyl group, which may have a substituent, for example, up to 1 to 18 carbon atoms, preferably Alkyl group up to 1-12, carbon number 1-1
an alkoxy group having up to 2 carbon atoms, an amino group substituted with an alkyl group having up to 1 to 12 carbon atoms, an amino group substituted with an acyl group having up to 1 to 12 carbon atoms, a halogen atom, a hydroxy group, an amino group, etc. .

Specific examples of the compound represented by the general formula [I] used in the present invention are shown below, but the present invention is limited to these (I-2) (I-4) (I-6) (I-7) (I-8) I-10) (I-12) (I-14) (I-18) (I-31) Fl.

(I-11) (I-13) (I-15) (I-19) (■ -32) (■ (I -22) (I -26) (I -37) (I -38) (I - 40) (I-21) (I-23) I-25) (I-27) 12N2m (I-41) (I-42) (I-43) (■-51) (■ (I-54) I-55) and tl・ (I-47) (I-57) I-58) (I-59) (C!HsOCO(CHz) r.3TPOC4Hs(
I (I -71) (cansr-P=0 (Ca)Iste'P-0 CC1xlhs) rP-0 (CI4821u'P-0 (I -63) (I -64) CI-73) ( 1, -74) (i CaH*h''-P-0 (CsH+++rP-0 (I-65) (I -75) (I -76) (C6)113urp-.

(CsH+ → “P-0 (I-67) (I-68) (r　-77) (I-78) (I-69) (I-70) (C, .112++r−P=0 (i-CH0H1lchi “P=0 ■ ((CaHs)zNco(CHz )3p-.

■ (■-82) I -89) (l-84) ■ Next, specific examples of compounds having a LogP of 4.0 to 1090, which are the second high boiling point solvents used in the present invention, are shown. The invention is not limited to this.

LogP LogP 4.56 5.58 6.11 ogp 4.81 The above LogP value is
; Chemical.

Pharm, Bull 24 (8) 1799-18
06 C1976).

The above-mentioned compounds I and H are easily available as commercial products, such as those available from Nihon Kagaku Kogyo Co., Ltd. under the trade name PoPo and others, and from Eastman Kodak Company under the trade name DELA.

Next, the silver halide emulsion used in the photosensitive layer of the silver halide color photographic light-sensitive material of the present invention will be described.

The silver halide emulsion used in the present invention includes any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, iodide, silver chloride, silver chlorobromide, and silver chloride. can be used.

The structure of the silver halide grain may be uniform from the inside to the outside of the grain, or the structure inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

There is no particular restriction on the particle size of the silver halide grains, but in consideration of other photographic performance such as rapid processability and sensitivity, it is preferably in the range of 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm. It is.

The particle size distribution of the silver halide grains may be polydisperse or monodisperse.

The silver halide emulsion used in the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or after forming seed particles,
You can let it grow. The method of creating and growing the seed particles may be the same or different.

Further, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof. Furthermore, as a type of simultaneous mixing method, pAg-
It is also possible to use the Chondrold-double jet method.

Furthermore, if necessary, a silver halide solvent such as thioether may be used.

Any shape of silver halide grains can be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide emulsion used in the present invention includes cadmium salt, zinc salt, lead salt, thallium salt, iridium salt,
Alternatively, metal ions can be added to the interior of the particles and/or on the surface of the particles by using complex salts, rhodium salts, complex salts, iron salts, or complex salts, and metal ions can be included inside the particles and/or on the particle surfaces by placing them in an appropriate reducing atmosphere. /Or reduction sensitizing nuclei can be provided on the particle surface.

In the silver halide emulsion used in the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, please refer to Research Disclosure 1764.
This can be carried out based on the method described in No. 3.

The silver halide grains used in the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

Particularly preferred are internal latent image type direct positive emulsion grains.

The silver halide emulsion used in the present invention is chemically sensitized by a conventional method. In other words, sulfur sensitization using compounds containing sulfur that can react with silver ions or active gelatin, selenium sensitization using selenium compounds, reduction sensitization using reducing substances, and noble metal sensitization using gold or other noble metal compounds. Sensitivity methods and the like can be used alone or in combination.

In the present invention, for example, a chalcogen sensitization method can be used as a chemical sensitizer. The chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. Patents 1,574,974 and 2,410.68
No. 9, No. 2,278.947, No. 2,728.668
No. 3,501.313, No. 3,656.955, OLS No. 1,422.869, JP-A No. 56-24937, No. 55-45016, etc. Sensitizers can also be used.

The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH 1 temperature and the size of silver halide grains, but as a guide, it is 1 mol per mole of silver halide.
-7 mol to about 10-1 mol is preferred.

Selenium sensitizers can be used instead of sulfur sensitizers, and examples of selenium sensitizers include aliphatic inselenocyanates such as allyl isoselenocyanate, selenoureas,
Selenides such as selenoketones, selenoamides, selenocarboxylic acid salts and esters, selenophosphates, diethylselenide, and diethylselenide can be used, and specific examples thereof include U.S. Pat.
No. 944, No. 1, No. 602, No. 592, No. 1,623
, No. 499.

Furthermore, reduction sensitization can also be used together. The reducing agent is not particularly limited, but examples include stannous chloride, thiourea dioxide, hydrazine, and polyamine.

Further, noble metal compounds other than the total, such as palladium compounds, etc. can also be used in combination.

When employing a direct positive image forming silver halide emulsion as the silver halide emulsion, for example, an internal latent image type silver halide emulsion can be used, for example, US Pat.
So-called conversion silver halide emulsions by the conversion method described in No. 50, or US Pat. No. 3,206.
No. 316, No. 3,317.322 and No. 3.367.
No. 778, silver halide emulsions with internally chemically sensitized silver halide grains, or U.S. Pat.
, 271.157, 3,447,927 and 3
, 531.291, or halogen containing dopants as described in U.S. Pat. No. 3,761.276. A silver halide emulsion in which the surface of silver grains is weakly chemically sensitized, or JP-A-1987
・No. 8524, No. 50-38525 and No. 53-24
The so-called core-shell type silver halide emulsion produced by the lamination method described in No. 08, and other JP-A-52-15661
No. 4, No. 55-127549 and No. 57-79940
The silver halide emulsions described in No. 3 can be used. In this case, it is particularly preferred that the internal latent image type silver halide emulsion be made of layered grains.

Such silver halide grains can be produced in the same manner as ordinary laminated silver halide grains. For example, JP-A-50-8524, JP-A-50-38525, JP-A-53-
No. 60222, No. 55-1524 and U.S. Patent No. 3,2
As described in No. 06.313, etc., silver chloride grains are formed, bromide is added to convert them to silver bromide grains, and halide is further added and laminated with silver nitrate, or iodobromide is carried out in a state with little excess halogen. Examples include a method of making silver particles and then sequentially stacking silver chloride and silver bromide.

When internal latent image type silver halide emulsions are used, the emulsions may contain stabilizers such as azaindene rings, which are commonly used, in order to keep the backside sensitivity as low as possible and to provide lower minimum density and more stable properties. and a heterocyclic compound having a mercapto group.

As the compound having an azaindene ring, for example, 4.hydroxy-6-methyl-1,3,3a,7-tetrazaindene is preferable. Among the heterocyclic compounds having a mercapto group, nitrogen-containing heterocyclic compounds include pyrazole ring, 1,2.4-triazole ring, 1.2.3-triazole ring, 1,3.4-thiadiazole ring, 1 .2.3
-thiadiazole ring, 1.2.4-thiadiazole ring,
l.

2.5-thiadiazole ring, 1.2.3.4-tetrazole ring, pyridazine ring, 1.2.3-triazine ring,
1.2.4-triazine ring, 1.3.5-triazine ring, etc., and a ring in which 2 to 3 of these rings are condensed, such as a triazolotriazole ring, diazaindene ring, triazaindene ring, tetrazaindene ring , a pentazaindene ring, a phthalazinone ring, an imidazole ring, etc., and particularly preferred is l-7enyl-5mercagutotetrazole.

In the silver halide color photographic light-sensitive material of the present invention, the following sensitizing dyes can be used to form at least three silver halide emulsion layers having different spectral sensitivities.

Examples of useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include West German Patent No. 929.080, US Pat. No. 2,231.658, US Pat. No. 2,519.001, No. 2
, No. 912, 329, No. 3,656゜959, No. 3,
No. 672.897, No. 3,694,217, No. 4.0
No. 25349, No. 4,046,572, British Patent No. 1,
No. 242,588, Special Publication No. 44-14030, No. 52
-24844 etc. can be mentioned. Further, useful sensitizing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Patent No. 1,939.201
No. 2,072.908, No. 2.739.149, No. 2,945.763, British Patent No. 505,979, etc. This can be cited as a representative example. Furthermore, useful sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 442.710, No. 2,454.629, No. 2776.280, and the like. Furthermore, U.S. Patent Nos. 2,213.995, 2,493.748, and 2
Cyanine dyes or composite cyanine dyes such as those described in German Pat.

These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization. Typical examples are Special Publications No. 43-4932, No. 43-4933, No. 4
No. 3-4936, No. 44-32753, No. 45-25
No. 831, No. 45-26474, No. 46-11627
No. 46-18107, No. 47-8741, No. 4
No. 7-11114, No. 47-25379, No. 47-3
No. 7443, No. 48-28293, No. 4g-3840
No. 6, No. 48-38407, No. 48-38408,
No. 48-41204, No. 48-41204, No. 49
-6207, 50-40662, 53-123
No. 75, No. 54-34535, No. 55-1569,
JP 50-33220, JP 50-33828, JP 50-38526, JP 51-107127, JP 51
-115820, 51-135528, 51-
No. 151527, No. 52-23931, No. 52-51
No. 932, No. 52-104916, No. 52-1049
No. 17, No. 52-109925, No. 52-11061
No. 8, No. 54-80118, No. 56-25728,
No. 57-1483, No. 58-10753, No. 58-
No. 91445, No. 58-153926, No. 59-11
No. 4533, No. 59-11645, No. 59-1166
No. 47, U.S. Patent No. 2,688,545, U.S. Patent No. 2,977
．． No. 229, No. 397.060, No. 3,522,
No. 052, No. 3,527.641, No. 3゜617.2
No. 93, No. 3,628,964, No. 3,666.48
No. 0, No. 3゜672.898, No. 3,679.428
No. 3,703.377, No. 3769.301, No. 3,814.609, No. 3,837.862,
It is described in No. 4°026.707.

Examples of dyes that do not themselves have a spectral sensitizing effect, or substances that do not substantially absorb visible light and exhibit supersensitization, are used with sensitizing dyes, such as aromatic organic acid formaldehyde condensates ( For example, U.S. Patent 3,
473.510), cadmium salts, azaindene compounds, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933.390,
3,635,721). The combinations described in US Pat. Nos. 3,615,613, 3,615,641, 3,617.295, and 3,635.721 are particularly useful.

In addition to those mentioned above, commonly used additives can be used in the silver halide color photographic material of the present invention.

Examples of wetting agents include dihydroxyalkanes, and examples of film property improving agents include copolymers of alkyl acrylates or alkyl methacrylates and acrylic acid or methacrylic acid, styrene-maleic acid copolymers, and styrene. Water-dispersible particulate polymeric substances obtained by emulsion polymerization such as maleic anhydride half-alkyl ester copolymers are suitable, and examples of coating aids include saponin, polyethylene glycol, lauryl ether, etc. . Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and development speed. The use of modifiers, matting agents, anti-irradiation dyes, etc. is optional.

In addition, in order to prevent fading of the dye image due to short wavelength actinic rays, ultraviolet absorbers can be used, such as thiazolidone, benzotriazole, acrylonitrile, benzophenone compounds, etc., and in particular Tinuvin PS,
120, 320, 326, 327, 328 (
Both products (manufactured by Ciba Geigy) are advantageous to use alone or in combination.

The image forming layer in the present invention can contain appropriate gelatin (including oxidized gelatin) and its derivatives depending on the purpose. Preferred gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin,
carbamylated gelatin, cyanethanolated gelatin,
Examples include esterified gelatin.

Further, in the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloid layer may contain other hydrophilic binders in addition to gelatin.

This hydrophilic binder can be added to photographic constituent layers such as an emulsion layer, an intermediate layer, a protective layer, a filter layer, and a backing layer depending on the purpose. It is possible to contain agents, lubricants, etc.

In addition, the silver halide color photographic light-sensitive material of the present invention may include, in addition to an emulsion layer forming an image-bearing layer on a support, a filter layer, an intermediate layer, a protective layer, a subbing layer, and a backing layer as necessary. ,
Various photographic constituent layers such as antihalation layers may be formed. As a coating method for each layer, dip coating, air doctor coating, extrusion coating, slide hopper coating, curtain flow coating, etc. can be used.

In the present invention, even when the image forming layer is composed of an internal latent image type silver halide color photographic light-sensitive material, any support can be used. Examples include subbed polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, baryta paper, polyolefin laminate paper such as polyethylene, and polyethylene terephthalate film kneaded with white pigment.

The silver halide photographic material according to the present invention contains a coupler that forms a color image with a color developer.

Main couplers include: As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

Examples of magenta dye-forming couplers include publicly known 5-pyrazolone couplers, pyrazolobenzimidazole couplers,
Pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, etc. can be used.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material of the present invention is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams,
Any known light source can be used, such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays, or the like.

The silver halide color photographic light-sensitive material of the present invention has a structure having each of the blue-sensitive, green-sensitive and red-sensitive color-sensitive layers that ordinary color paper has, and the filter (optical filter) is a three-color separation filter, such as Wratten No.
, 25. No. 29. No. 58. No, 61°No,
47B can be used.

The exposure time is 1 millisecond to 1 millisecond, which is normally used in printers.
Not only can exposure times be 0 seconds, but also exposures shorter than 1 millisecond, such as 100 microseconds or more using a cathode ray tube or xenon flash lamp.
Exposures of 1 millisecond can be used, or exposures longer than 10 seconds are possible.

The exposure may be performed continuously or intermittently.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes. These developing solutions contain aminophenol and p-phinidine diamine derivatives. Since these compounds are more stable in the free state, they are generally used in the form of salts, such as hydrochlorides or sulfates. Additionally, these compounds are generally used in concentrations of about 0.1 to about 309 for color developer IQ, and more preferably from about 1 g to about 159 for color developer Iff.

Examples of aminophenol-based developers include 0-aminophenol, p-aminophenol, and 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-oxy-3-amino-1,4-dimethylbenzene and the like.

A particularly useful primary aromatic amino color developer is N.

It is an N-dialkyl-p-phinidine diamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Examples of particularly useful compounds include N,N-diethyl-p-7 22-diamine hydrochloride, N-methyl-p-7 22-diamine hydrochloride, and N,N-dimethyl-p-phenylenediamine. hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate,
N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline- Examples include p-toluenesulfonate.

In addition to the first aromatic amino color developer, known developer component compounds can be added to the color developer applied to the processing of the silver halide photographic material of the present invention. For example, it may optionally contain alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, and thickening agents. can.

The pH value of the color developer is usually above 7, most commonly from about 10 to about 13.

Color development temperature is usually 15°C or higher, generally 2
It is in the range of 0°C to 50°C. 30 for quick processing
It is preferable to carry out the reaction at a temperature of 0.degree. C. or higher. Further, the color development time is generally preferably carried out within a range of 20 seconds to 60 seconds, more preferably 30 seconds to 50 seconds.

The silver halide photographic material according to the present invention may contain these color developing agents in the hydrophilic colloid layer either as the color developing agent itself or as its precursor, and may be processed in an alkaline activation bath. A color developing agent precursor is a compound that can generate a color developing agent under alkaline conditions, and includes a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, and a sugar amine reactant. Precursor Examples include urethane type precursors. The precursors of these aromatic primary amine color developing agents are:
For example, U.S. Pat. No. 3.342.599, U.S. Pat.
No. 114, No. 2,695.234, No. 3°719.4
No. 92, specifications of British Patent No. 803.783, Japanese Patent Application Laid-open Nos. 53-185628 and 54-79035,
Research Disclosure (Research D)
isclosure) No. 15159, No. 12146,
It is described in No. 13924.

It is necessary to add the aromatic primary amine color developing agent or its precursor in such an amount that sufficient color development can be obtained in the case of activation treatment. This amount varies depending on the type of photosensitive material, but is generally between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of silver halide. These color developing crude drugs or their precursors can be used alone or in combination.

When the image forming layer of the light-sensitive material of the present invention is an internal latent image type silver halide emulsion layer and a positive image is directly formed using this layer, the main process is to form an internal latent image type silver halide emulsion layer that has not been coupled in advance. It is common to carry out surface development of a silver photographic material after image exposure and after subjecting it to fogging treatment or while subjecting it to fogging treatment. The fogging treatment can be carried out by providing uniform exposure over the entire surface or by using a fogging agent. In this case, the entire surface uniform exposure is preferably carried out by immersing or moistening the image-exposed internal latent image type silver halide photographic material in a developer or other aqueous solution, and then uniformly exposing the entire surface. . The light source used here may be any light within the sensitive wavelength range of the internal latent image type silver halide photographic light-sensitive material, and it is also possible to irradiate with high-intensity light such as flash light for a short time, or with a weak Light may be irradiated for a long time. The time for uniform exposure over the entire surface can be varied over a wide range depending on the internal latent image type silver halide photographic light-sensitive material, the processing conditions, and the type of light source used so as to ultimately obtain the best positive image. Further, a wide variety of compounds can be used as the above-mentioned fogging agent, and this fogging agent only needs to be present during the development process, for example, in an internal latent image type silver halide photographic material such as a silver halide emulsion layer, or Although it may be contained in a developing solution or a processing solution prior to development processing, it is preferably contained in an internal latent image type silver halide photographic light-sensitive material (particularly preferably in a silver halide emulsion layer).

The amount used can vary widely depending on the purpose, and the preferable amount is 1 to 150 per mole of silver halide when added to a silver halide emulsion layer.
0a1g, particularly preferably 10-1000mg.

Further, when added to a processing solution such as a developer, the preferable amount is 0. O1 to 5g/a1, particularly preferably 0.08 to 0
．． It is 159/Q. Such fogging agents include, for example, US Pat. Nos. 2,563,785 and 2,588,982.
hydrazines described in No. 3 or U.S. Pat.
, US Pat. No. 3,615.615, US Pat. No. 3,718.470, US Pat. No. 3,719.494, US Pat.
, 734,738 and 3,759.901, etc., as well as U.S. Pat.
Examples include acylhydrazinophenylthioureas described in No. 30.925. Further, these fogging agents can also be used in combination. For example, Research Disclosure 1
No. 5162 describes the use of a non-adsorption type fogging agent in combination with an adsorption type fogging agent, which can also be applied to the present invention.

Specific examples of useful fogging agents include hydrazine hydrochloride,
Phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-(4-methylphenyl)hydrazine, l-acetyl-2-phenylhydrazine, l-acetyl-2-(4-acetamidophenyl)hydrazine, l-methylpurphonyl-2-phenylhydrazine, l-benzoyl-2-phenylhydrazine, l-
Examples include hydrazine compounds such as methylsulfonyl-amidophenyldophenylhydrazine.

When the light-sensitive material of the present invention is embodied as an internal latent image type silver halide photographic light-sensitive material, a positive image is directly formed by exposing the whole surface to light after image exposure or developing it in the presence of a fogging agent. However, any developing method may be employed as the developing method for the photosensitive material, preferably a surface developing method. This surface development processing method means processing with a developer substantially free of silver halide solvent.

In the present invention, a positive image (head image) corresponding to the original image is obtained by subjecting the exposed silver halide color photographic light-sensitive material to processing using a processing solution having development processing and fixing ability.
It can be made concrete by forming the following.

The above-mentioned development processing includes not only color development processing but also a combination of black and white development and color development such as in reversal color processing.

It also includes full-surface exposure or development in the presence of a fogging agent, such as in the processing of internal latent image type silver halide photographic materials.

The black-and-white developer used in the development process is a so-called black-and-white first developer used in the processing of color photographic light-sensitive materials, or a black-and-white developer used in the processing of black-and-white photographic materials; Various well-known additives added to developer solutions can be included.

Typical additives include l-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, etc. Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole,
Examples include water softeners such as polyphosphates, and surface overdevelopment inhibitors comprising trace amounts of iodides and mercapto compounds.

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be performed simultaneously with fixing treatment. Many compounds are used as bleaching agents, among them iron(III), cobal l-(I[[)
, polyvalent metal compounds such as copper (I[), especially complex salts of these polyvalent metal cations with organic acids, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, N-hydroxyethylethylenediaminediacetic acid,
Metal complex salts such as malonic acid, tartaric acid, malic acid, diglycolic acid, dithioglycolic acid, ferricyanates, dichromates, etc. may be used alone or in appropriate combinations.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate,
Examples include potassium thiocyanate, thiourea, and thioether.

After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination. The stabilizing liquid used in the stabilization treatment can contain a pH adjuster, a chelating agent, an anti-spill agent, and the like. These specific conditions are described in Japanese Unexamined Patent Publication No. 5
8-134636 etc. can be referred to.

To apply the present invention to a silver dye bleaching method, the difference in spectral absorption characteristics of the yellow dye used in the silver dye bleaching method to the printing ink is similar to the difference in the spectral absorption property of the dye produced from the yellow coupler by color development to the printing ink. Therefore, it can be easily carried out in the same manner as in the case of silver halide photographic materials using the color development method described above.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 Preparation of Emulsion S 750 mQ of a 2.0% inert gelatin solution was kept at 50°C, and while stirring, Solution AI and Solution B were added simultaneously and injected over 3 minutes. After aging for 25 minutes, excess salt was removed by precipitation and washing with water, followed by redispersion, and CI solution and DI solution were added. 10
After a few minutes, excess water-soluble salts were removed again, and gelatin emulsion was prepared. 750ml of 1.5% inert gelatin solution was kept at 60°C, and the following solutions A2 and B were simultaneously added while stirring, and injected over 15 minutes. . After aging for 40 minutes, excess salt was removed by precipitation and washing with water, followed by redispersion, 10 mg of hypo was added, and then liquid C2 and liquid D2 were added. After 10 minutes, excess water-soluble salt was removed again, and silver halide grains to which a small amount of gelatin had been added were dispersed.

Preparation of Emulsion M 750 mQ of 2.0% inert gelatin solution was kept at 50°C.
While stirring, the following solutions A3 and B were simultaneously added and injected over 5 minutes. After aging for 25 minutes, excess salt was removed by precipitation and water washing, followed by redispersion, and ct solution and D2 solution were added. l
After 0 minutes, the excess water-soluble salt was removed again, and silver halide grains to which a small amount of gelatin had been added were dispersed.

"Pure water 2000mff"'
A small amount of 35 g of NaCl2 was added to disperse the silver halide particles.

A sensitizing dye, coupler, etc. were added to these three emulsions as described below to prepare a multilayer color light-sensitive material.

Red-sensitive emulsion layer (layer 1) Sensitizing dyes (D-3), (D-4), stabilizers (T-1), (T-2), respectively, for a mixed emulsion of 12 mol of emulsion 5O and 08 mol of emulsion MO , surfactant (S-
2”), and a protected dispersed coupler solution containing dibutyl phthalate, ethyl acetate, surfactant (S-2), 2,5-dioctylhydroquinone, and cyan couplers (CC-2) and (CC-3) was added. .First intermediate layer (
Layer 2) A gelatin solution containing a protect-dispersed liquid containing dioctyl phthalate, 215-dioctylhydroquinone, the ultraviolet absorber Tinuvin 328 (manufactured by Ciba Geigy), and a surfactant (S-1) was prepared, and the coating amount of Tinuvin was 0. 15
The coating was applied so that the ratio was 1.9 g/In.

Green-sensitive emulsion layer (layer 3) Sensitizing dye (D-2), stabilizer (T-1), (T-2) for a mixed emulsion of 0.2 mol of emulsion S and 08 mol of emulsion MO
, surfactant (S-2), and a protect-dispersed liquid containing dibutyl phthalate, ethyl acetate, 2.5-dioctylhydroquinone, surfactant (S-1), and magenta coupler (M-1). .

Add gelatin and further add hardener (H-1) and apply.

Second intermediate layer (Layer 4) Same formulation as the first intermediate layer, coating amount of Chinbin 328 0.2
g/m".

Yellow filter layer (layer 5) Made by oxidation in an alkaline weak reducing agent; (weak reducing agent removed by noodle water washing method after neutralization) Yellow colloidal silver, dioctyl 7-talate, ethyl acetate, surfactant (S -1), 2,5-dioctylhydroquinone solution, surfactant (S-2') and hardener (H-1) are added to coat colloidal silver so that the amount of coated silver is 0.159/m2.

Third intermediate layer (layer 6) Same as the first middle layer.

Blue-sensitive emulsion layer (layer 7) Sensitizing dye (D-1), stabilizer (T-1),
(T-3), surfactant (S-2), dibutyl phthalate, ethyl acetate, 2,5-dioctylhydroquinone, surfactant (S-1) and yellow coupler (Y
-1) was added to the coupler solution in which the protectant was dispersed.

Add gelatin and further add hardener (H-1) and apply.

4th intermediate layer (layer 8) Same formulation as the 1st intermediate layer, coating amount of Chinbin 328 0-35
Coat so that it becomes 11" g/I.

Protective layer (layer 9) Colloidal silica, coating aid (S-2), hardener (H
A gelatin solution containing -2) and (H-3) is applied so that the gelatin coating amount is 1.0 g/m2.

Material CD-1'') (T-1) (T-2) (T-3) (D-2) The first to ninth layers were coated on surface-treated polyethylene laminated paper using a simultaneous coating method. (s-t) (S-2) (D-3) (H-1) (D-4) Cα (H-2) (H-3) (Y-1) (CC-2) SO□CH= C.I.

(CC-3) (M-1) ShiL Using the sample coated in multiple layers as described above as a reference sample,
For the seventh blue-sensitive layer, 10 types of multilayer coating samples were prepared in which only the high boiling point solvent was varied as shown in Table 1 below, and the other components were completely the same.

The resulting sample was exposed to the minimum amount of light necessary to obtain the lowest density of cyan and magenta images, and then wedge exposed with white light.

This sample was color developed according to the development process described below to obtain a yellow image.

The results obtained are shown in Table 1 below.

Note that the color suitability in the table is expressed in the following three-level evaluation of the extent to which the color tone matches the proof printed matter.

O Good color suitability as color proof △ /
/ //×〃〃 Processing process (processing temperature and processing time) (1) Immersion (color developer) 38°C (2) Fog exposure (3) Color development 38°C (4) Bleach-fixing 35°C (5 ) Stabilization treatment 25-30'0(6) Dry
Dry 75-80'C! Processing solution composition (color developing solution) Benzyl alcohol Ethylene glycol Potassium sulfite Potassium bromide Sodium chloride Potassium carbonate Hydroxylamine sulfate Polyphosphoric acid (TPPS) 3-Methyl/4-amino-N-ethyl Fairly good Poor 8 seconds l Lux: 10 seconds 2 minutes 60 seconds 1 minute 30 seconds 1 minute 0mff 511Q 2.0g 1.59 0.2g 30.0g 3.0g 2.59 -N-(β-methanesulfonamidoethyl)aniline sulfate 5.5g fluorescence enhancement Whitening agent (4
, 4'-diaminostilbenzsulfonic acid derivative)
1.09 potassium hydroxide
Add 2.0g water to bring the total volume to 1, and adjust the pH to 10.2.
Adjust to 0.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 609 Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100mQ Ammonium sulfite (40% solution) 27.5 mα potassium carbonate or glacial acetic acid p) (7,1 Add water and make the total volume IQ.

(Stabilizing liquid) 5-chloro2-methyl-4-inchazolin-3-one 1.09 Ethylene glycol 1091-hydroxyethylidene-1,1' ・diphosphonic acid 2.59 Bismuth chloride 0.2 g Magnesium chloride 0. 19 Ammonium hydroxide (28% aqueous solution) 2.09 Sodium nitrilotriacetate 1. Add Op water to bring the total amount to 1 g, and adjust to pH 7 with ammonium hydroxide or sulfuric acid.
, adjust to 0.

The stabilization treatment was carried out using a two-tank countercurrent method.

[Comparison/A] 0=P(OC+zH2i)i
LogP-16, 23 As is clear from Table 1 above, the combination of high boiling point solvents of the present invention can produce color proofs with a color tone that matches well with that of the proof without reducing the maximum density. On the other hand, in the comparative samples, the color suitability was poor, or even though the color suitability was good, the maximum density decreased.

Example 2 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a negative silver halide color photographic light-sensitive material sample No. 1 (for comparison).

Layer 1 - 1.29/I11'' gelatin, 0.329/
A blue-sensitive AgCffBr emulsion (average grain size 0.8 μna) of 0.80 g/m' yellow coupler (Y-1) dissolved in dioctyl phthalate of 0.509/m' (in terms of silver, same hereinafter) was used. Containing layer.

Layer 2...0.709/m" gelatin, 8 g/m" irradiation dye (Al-1') and 4 mg/m
” (AI-2).

Layer 3 - 1.259/IQ" gelatin, 0.20 g/m
green-sensitive AgCl2Br emulsion (A9Br content 70 mol%), 0,629/11'' magenta cobra (MC-
A layer containing 1).

Layer 4: Intermediate layer consisting of 1.20 g/m'' gelatin.

Layer 5...1.209/I11" gelatin, 0.30
g/m'' red-sensitive AgCffBr emulsion (AgBr content 70 mol%), 0.45 g/m'' cyan Kabra (CC-
A layer containing 1).

Layer 6-1.009/1112 (7) Gelatin layer 0.
20g/l 112 Nodioctyl phthalate dissolved in 0
, 309/I11'' layer containing an ultraviolet absorber (UV-1).

Layer 7: A layer containing gelatin 0-509/I11'.

(AI-1) (AI-2) As a hardening agent, 2.4-dichloro-6-hydroxy-5-sodium triazine was added in layer 29, layer 4, and layer 7 at a concentration of 0.0179 per 1 g of gelatin, respectively. Added so that

Using the thus obtained multilayer color photosensitive material as a standard comparative sample, tests were conducted as in Example 1 by varying only the high boiling point solvent of layer 1. As a result, the obtained multilayer color photosensitive material After wedge exposure with blue light, color development was performed according to the processing steps described below.

As a result, the combination of high boiling point solvents according to the present invention had a high maximum concentration and excellent color suitability.

Processing steps (35°C) Color development 1 minute and 1 minute 30 seconds Bleach-fixing 1 minute Water Washing 1 minute Drying 60-80°C 2 minutes The composition of each processing solution is as follows.

(Color developer A) Pure water
800m+2 sulfuric hydroxylamine
2.09 potassium bromide
1.5g sodium chloride
1.0g potassium sulfite 2.0
g Triethanolamine 2.0g
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 8.0g1
-Hydroxyethylidene-1,1'-diphosphonic acid (60% aqueous solution) l
, 5+aff potassium carbonate
329Whitex B B (50% aqueous solution)
2+Q (fluorescent brightener, manufactured by Sumima Kagaku Kogyo Co., Ltd.) Add pure water to make the pH 112, and adjust the pH to -11.2 with 20% potassium hydroxide and 10% dilute sulfuric acid.

(Bleach-fix solution) Pure water 550mm Iron ethylenediaminetetraacetic acid (I
-Sodium 209 Sodium Bromide
Add 109 pure water to make H, and adjust the pH to 7.0 with ammonia water or lt dilute sulfuric acid.

Example 3 The procedure was carried out in exactly the same manner as in Example 2, except that the magenta cobra in layer 3 of Example 2 was replaced with M-2 below, and the high boiling point solvents shown in Table 2 below were used. A color photosensitive material was created.

The obtained sample was wedge exposed to green light and then developed in the same manner to obtain Table 2 below.

As is clear from Table 2, sample No. 14.15 of the present invention
It can be seen that Samples No. 1 and No. 16 are superior in both color suitability and maximum density compared to the comparative samples.

〔Effect of the invention〕

As explained in the above embodiments, the present invention makes it possible to provide a color silver halide photographic light-sensitive material that has good tone properties as a light-sensitive material for color proofing and exhibits little decrease in maximum density.

Claims (1)

[Claims] Yellow coupler or magenta coupler is expressed by the following general formula [I
] In the silver halide color photographic light-sensitive material which is dissolved and dispersed in a mixture of a first high-boiling point solvent and a second high-boiling point solvent, the LogP of the second high-boiling point solvent is
4.0 to 10.0. General formula [I] [In the formula, R_1, R_2 and R_3 each represent an alkyl group or an aryl group, and l, m and n each represent 0 or 1, but l, m and n may not be 1 at the same time. do not have. ]