JPS62250434A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a rapidly processable multilayered silver halide color photographic sensitive material whose ground has superior whiteness by forming a green-sensitive silver halide emulsion layer contg. a specified amount of a specified photosensitive dye and silver halide particles made of silver chloride. CONSTITUTION:A green-sensitive silver halide emulsion layer contg. photosensitive dye represented by the formula by 1.51X10<-4>-0.57X10<-4>mol per 1 silver halide and silver halide particles made practically of silver chloride is formed. In the formula, Y1 is O or N-R4, Y2 is O or N-R5, each of Z1 and Z2 is a group of atoms required to form a benzene or naphthalene ring, each of R1-R5 is alkyl, R3 is H, alkyl or the like, X is an anion and n=1 or 2. The preferred amount of the photosensitive dye used is 1.13X10<-4>-0.76X10<-4>mol per 1mol silver halide. An excessively large amount of the dye deteriorates the whiteness of the ground and an excessively small amount of the dye reduces the green sensitivity.

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 capable of rapid development processing and has high image quality (sharpness,
The present invention relates to a silver halide color photographic material with improved color purity) and minimum density (white background).

[Prior art and its problems]

In general, silver halide color photographic light-sensitive materials have three types of photographic silver halide emulsion layers selectively sensitized to have sensitivity to blue light, green light, and red light, coated on a support. ing. For example, in silver halide photographic materials for color negatives, generally a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are coated in this order from the exposed side. A bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer to absorb the blue light that passes through the blue-sensitive silver halide emulsion layer. It is provided. Further, each emulsion layer is provided with other intermediate layers for various special purposes, and a protective layer as the outermost layer. For example, in a silver halide photographic light-sensitive material for color photographic paper, generally, from the side to be exposed, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer are arranged in this order. As with the silver halide photographic light-sensitive materials for color negatives, interlayers such as an ultraviolet absorbing layer, protective layers, etc. are provided for special purposes. It is also known that each of these silver halide emulsion layers is provided in a different arrangement from the above, and furthermore, each silver halide emulsion layer is sensitive to substantially the same wavelength range for each color light. It is also known to use a photosensitive silver halide emulsion layer consisting of two layers. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with a dye-forming coupler. In this method, cyan couplers, magenta couplers, and yellow couplers are typically used to form cyan, magenta, and yellow dye images, respectively.

In recent years, there has been a demand in the industry for silver halide color photographic materials that can be processed quickly, have high image quality, have excellent processing stability, and are low cost.
In particular, silver halide color photographic materials that can be rapidly processed are desired.

In other words, silver halide photographic materials are subjected to running processing in automatic processing machines installed at each processing laboratory, but as part of an effort to improve service to users, processing is carried out on the same day that the development is received. In recent years, it has even become necessary to return the product within a few hours of receiving it, and the development of silver halide color photographic materials that can be processed more quickly is becoming more and more important. It's urgent.

As mentioned above, in recent years, silver halide color photographic materials,
In particular, for color photographic paper, there is a strong desire for speedy processing, but on the other hand, color photographic paper is much more expensive than other color image forming methods that do not use silver halide, such as color electrophotography and color inkjet printers. High image quality,
The demands for high image quality such as color reproducibility, color purity, sharpness, whiteness (minimum density), and gradation are significantly stronger than in other image forming methods.

Therefore, color photographic paper is required to be simple and quick to process, as well as to have very strict image quality, and it has been a major technical challenge to satisfy both of these requirements at the same time.

Speeding up the processing of color photographic paper can be achieved by several improvements in photosensitive materials. One improvement method is to reduce the grain size of the silver halide grains contained in the blue-sensitive layer.

Due to the particularly high sensitivity requirements of blue-sensitive silver halide emulsions in conventional color photographic papers, considerably larger average grain sizes are used than for green- and red-sensitive silver halide emulsions. Therefore, the development speed of the silver halide grains in the blue-sensitive silver halide emulsion is slower than in the green- and red-sensitive silver halide emulsion layers, and this is the rate-limiting factor for the color development processing speed of silver halide color photographic light-sensitive materials. .

Therefore, speeding up of processing can be achieved by reducing the grain size of the silver halide grains in the blue-sensitive layer, but as is well known, the problem in this case is that the grain size of the silver halide grains If it is made smaller, the sensitivity will decrease, and the exposure time will become longer when exposing the color negative, which will significantly reduce the productivity of color prints in the photofinishing laboratory. This results in two drawbacks: the difference in sensitivity with respect to the photosensitivity becomes small, resulting in poor color separation and impaired color reproducibility. In order to overcome these drawbacks, it is necessary to develop a new sensitization method for silver halide grains so that even if the grain size is reduced, the sensitivity is equivalent to that of the conventional method. For this purpose, a technique is required to obtain sensitivity several times higher than conventional techniques. Such exacerbation methods include the sensitization method using SCN shown in Japanese Patent Application Laid-Open No. 58-30747, and the method of sensitization using SCN shown in Japanese Patent Application Laid-Open No. 58-111.
Technologies such as tabular silver chlorobromide grains shown in No. 936 are known. A sensitization method using a combination of a sulfur sensitizer and a gold sensitizer is also effective.

A second method for speeding up the processing of color photographic paper is to reduce the amount of bromide ions contained in the photosensitive material. The silver halide grains that form conventional color photographic paper are made of silver chlorobromide, and the average content of silver chloride and silver bromide is 60 mol% or more of silver bromide, but this halogen composition ratio is The so-called running process in which color photographic paper is continuously processed has a decisive effect on the bromide ion concentration in the developer. That is, when color photographic paper containing high silver chloride is subjected to running processing, the bromide ion concentration in the developer converges to a low concentration.

The bromide ion concentration in the developing solution has a large effect on silver halide grains, and by reducing the bromide content in the light-sensitive material and lowering the convergence concentration of bromide ions in the developing solution, processing speed can be achieved. be done.

When rapid processing is achieved using these methods, image quality deteriorates, which is not desirable for color photographic paper as a product.The biggest problem is an increase in the minimum density (hereinafter referred to as whiteness) of color photographic paper after processing. It is. This is a problem that inevitably arises as processing speeds up;
That is, unprocessed light-sensitive materials contain coloring substances such as dyes for preventing light scattering and so-called photosensitive dyes for making silver halide grains sensitive only to blue light sensitive to green light or red light. These colored substances are designed so that they do not affect the final image by decomposing or eluting during the development process. This shortens the time and remains until the final image, which undesirably colors the white parts of the image.

An object of the present invention is to provide a multilayer silver halide color photographic light-sensitive material that has excellent whiteness and can be rapidly processed.

As described below, means for improving speed and whiteness often have the disadvantage of impairing blue light sensitivity, green light sensitivity, and color reproducibility.

A second object of the present invention is to provide a silver halide color photographic material that can be rapidly processed without impairing blue light sensitivity, green light sensitivity, or color reproducibility and has excellent white background properties.

[Structure of the invention]

As a result of extensive research into methods to achieve the above objectives, the inventors of the present invention have found that the following method enables rapid processing with excellent whiteness without impairing blue light sensitivity, green light sensitivity, or color reproducibility. It has been found that a multilayer silver halide color photosensitive material can be obtained. That is, in a silver halide photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a reflective support, the green-sensitive halogenated The silver emulsion layer contains a photosensitive dye represented by the following general formula (I) of 1.51 x 10"4 to 0.57 x 1
The above object is achieved by a halogenated color photographic light-sensitive material characterized in that it contains silver halide grains containing 0-' (+1101 /11+01 AgX) and whose halide silver composition consists essentially of silver chloride. be done.

General formula % Formula % In the formula, Yl is selected from an oxygen atom or N-R4. Y2
is selected from an oxygen atom or N Rs.

ZI and Zz may be the same or different, and each represents an atomic group necessary to form an unsubstituted or substituted benzene ring or naphthalene ring.

R,,R,,R,,R,represents an unsubstituted or substituted alkyl group. However, at least one of R+, Rz, Ra, and Rs has an acid substituent.

R3 represents a hydrogen atom, an alkyl group or an aralkyl group.

X represents an anion, n represents 1 or 2, and is 1 when the dye forms an inner salt.

The present invention will be explained in more detail below.

The silver halide emulsion contained in the green light-sensitive layer according to the present invention consists essentially of silver chloride. Substantially silver chloride means that it may contain silver bromide and/or silver iodide within a range that does not impair the effects of the present invention, and the silver chloride content is 95 mol% or more, preferably 97% by mole. mol% or more, more preferably 9
It is 9 mol% or more.

The content of silver iodide is preferably 1 mol% or less. Accumulation of silver iodide in the processing solution is undesirable because it results in poor desilvering during bleaching, fixing, or bleach-fixing processing.

The light-sensitive layers above and outside the green light-sensitive layer are composed of silver halide, preferably silver chlorobromide or silver chloride emulsion, but from the viewpoint of rapid processing, the one with a higher silver chloride content is preferable. Since it contributes to rapid processing by reducing the bromide ion concentration in the processing solution during continuous processing of photographic paper, it contributes to the total amount of bromide ions in the blue-sensitive layer, green-sensitive layer, and red-sensitive layer.

The total silver bromide content of these three types of photosensitive layers is 15
It is preferably at most mol%, more preferably at most 10 mol%, even more preferably at most 5 mol%.

Most preferably, all the photosensitive layers, including the blue photosensitive layer, the green photosensitive layer, and the red photosensitive layer, are made of silver halide grains consisting essentially of silver chloride.

The average particle diameter of the silver halide grains of the present invention consisting essentially of silver chloride is not particularly limited, but is 0.1 μm to 2.0 μm.
Preferably it is 0.20 to 1.0 μm. In the case of cubic silver halide grains, the average grain size r here refers to the length of its side, or in the case of grains having a shape other than a cube, the length of one side when converted to a cube having the same volume. When the length and the individual particle diameter in this sense is ri, and the total number of measured particles is n, it is expressed as follows.

The silver halide grains may be a polydisperse emulsion in which the grain sizes are distributed over a wide range, or a monodisperse emulsion in which the grain size distribution is extremely narrow, but monodisperse emulsions are preferred.

In the present invention, the above-mentioned monodisperse silver halide grains are those in which most of the silver halide grains appear to have the same shape when the emulsion is observed using an electron microscope, have uniform grain sizes, and have the following formula: The defined coefficient of variation, ie, the value obtained by dividing the standard deviation S of the particle size distribution by the average particle size r, is 0.15 or less.

The photosensitive dye contained in the green photosensitive layer of the photosensitive material of the present invention is selected from those represented by the following general formula (I).

General formula (1) %Formula% In the formula, Yl is selected from an oxygen atom or N-R4. Y2
is selected from an oxygen atom or N-R.

ZI and Zz may be the same or different. □
represents an atomic group necessary to form an unsubstituted or substituted benzene ring or naphthalene ring.

RI+Rz, Ra, and Rs represent an unsubstituted or substituted alkyl group. However, at least one of R, R1, R, R5 has an acid substituent.

R1 represents a hydrogen atom, an alkyl group or an aralkyl group. The alkyl group and aralkyl group include those having a substituent.

X represents an anion, n represents 1 or 2, and is 1 when the dye forms an inner salt.

In the general formula (1) of the dye used in the present invention, Yl
, Y2. As Zl, Z2 and R1-R5, the following are preferably used.

Yl is selected from oxygen atoms and NR, with oxygen atoms being particularly preferred; Y2 is selected from oxygen atoms and NR, particularly oxygen atoms are preferred.

21.22 may be the same or different, respectively (and is an atomic group necessary to form an unsubstituted or substituted benzene ring or naphthalene ring).

Examples of substituents on the benzene ring or naphthalene ring include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 6 or less carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a vinyl-f-By5. 2-methylpropyl group, butyl group, hexyl group, etc.), alkoxy groups having 8 or less carbon atoms (e.g. methoxy group, ethoxy group, butyloxy group, benzyloxy group, phenethyloxy group, etc.), aryl groups having 8 or less carbon atoms ( For example, phenyl group, 4-methylphenyl group, 4-chlorophenyl group, etc.)
, an aryloxy group having 8 or less carbon atoms (e.g. phenoxy group, 4-methylphenoxy group, 4-chlorophenoxy group, etc.), an acyl □ group having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.) ), alkoxycarbonyl groups having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, butyloxycarbonyl group, benzyloxycarbonyl group, etc.), acyloxy groups having 3 or less carbon atoms (e.g. acetyloxy group,
propionyloxy group, etc.), a cyano group, a trifluoromethyl group, a carboxyl group, and a hydroxy group. In particular, as ZI- and Zt, the 5th position of the benzene ring is substituted with a phenyl group, a chlorine atom, or a methoxy group. Preferably.

R++Rz+Ra+Rs+ includes an alkyl group having 8 or less carbon atoms (e.g., methyl group, ethyl group, propyl group, vinylmethyl group, acyl group, pentyl group, hexyl group, heptyl group, octyl group, etc.), and a hydroxy group as a substituent, Carboxy group, sulfo group, cyano group, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.),
Alkoxycarbonyl groups having 8 or less carbon atoms (e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc.), alkoxy groups having 8 or less carbon atoms (
For example, methoxy group, ethoxy group, butyloxy group, benzyloxy group, phenethyloxy group), aryloxy group having 8 or less carbon atoms (e.g. phenoxy group, p-)lyloxy group, etc.), acyloxy group having 3 or less carbon atoms (e.g. acetyloxy group, propionyloxy group, etc.),
Acyl group having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, 4-fluorobenzoyl group, etc.) Acyl group having 8 or less carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, 4-fluorobenzoyl group, etc.) , a carbamoyl group having 6 or less carbon atoms (e.g. carbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), a sulfamoyl group having 6 or less carbon atoms (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group) , piperidinosulfonyl group, etc.), substituted with an aryl group having 10 or less carbon atoms (e.g., phenyl group, p-fluorophenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, etc.) An alkyl group having 6 or less carbon atoms is preferred. However, at least one of R+, Rz, Rn, and Rs has an acid substituent.

R1 is a hydrogen atom, an alkyl group having 4 or less carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, etc.) or an aralkyl group having 10 or less carbon atoms (for example, benzyl group,
phenethyl group, 3-phenylpropyl group, etc.) are preferred.

Examples of the photosensitive dye represented by the general formula (I) used in the present invention are shown below.

(Exemplary Compound 0-1) Hs (Exemplary Compound 0-2) (Exemplary Compound 0-3) (Exemplary Compound 0-4) (Exemplary Compound 0-5) (Exemplary Compound 0-6) (Exemplary Compound 0-7) (Exemplary Compound 0-8) (Exemplified Compound o-9) (Exemplified Compound 0-10) (Exemplified Compound 0-11) (Exemplified Compound 0-12) (Exemplified Compound 0-13) C, II % (Exemplified Compound 0 -14) C! HS The photosensitive dye used in the present invention may be one type of dye selected from general formula (1), or two or more types of dyes selected from general formula (1) may be used in combination.

The amount of the photosensitive dye used in the present invention has a great influence on the sensitivity and whiteness of the green photosensitive layer, and the object of the present invention can be achieved by selecting the optimum amount.

The amount of photosensitive dye used in the present invention is 1.51 x 10-4 to 0.57 x per mole of silver halide emulsion.
10-' mol, preferably 1.32XIO-4
~0.57 X 10-' moles, more preferably 1.13
X10-4 to 0.76 X10-' mol.

If the amount of the photosensitive dye is too large, the whiteness will deteriorate, and if it is too small, the green sensitivity will decrease, which is not preferable.

Each of the silver halide emulsion layers according to the present invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye.

In the present invention, conventionally known yellow couplers, magenta couplers, and cyan couplers can be used as the couplers.

These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these couplers, it is also possible to use diffusible dye-releasing type couplers.

The yellow couplers include conventionally used closed ketomethylene compounds, active point -〇-aryl-substituted couplers called so-called two-equivalent type couplers, active point -〇-acyl substituted couplers, and active point hydantoin compounds. Substituted couplers, active point urazole compound substituted couplers, active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -〇-sulfonyl substituted couplers, etc. can be used as effective yellow couplers. Can be done.

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

Examples of the magenta coupler include pyrazolone-based, pyrazolotriazole-ring pyrozoloazole-based, pyrazolinobenzimidazole-based, and indasilone-based compounds.

These magenta couplers are similar to the yellow couplers 4
Not only an equivalent type coupler but also a 2-equivalent type coupler may be used. A specific example of a magenta coupler is US Patent 2.
, No. 600,788, No. 2,983.608, No. 3.
No. 062.653, No. 3,127,269, No. 3,3
No. 11.476, No. 3,419.391, No. 3,51
No. 9,429, No. 3,558,319, No. 3.582
．． No. 322, No. 3,615.506, No. 3,834,
No. 908, No. 3,891,445, West German Patent No. 1,81
No. 0.464, West German Patent Application (OLS) 2,408
．． No. 665, No. 2,417.945, No. 2.418.
No. 959, No. 2,424.467, Special Publication No. 1977-1960
31, JP-A-51-20826, JP-A No. 52-58922
No. 49-129538, No. 49-74027,
No. 50-159336, No. 52-42121, No. 4
No. 9-74028, No. 50-60233, No. 51-2
No. 6541, No. 53-55'122, Patent Application No. 55-1
Examples include those described in No. 10943 and the like.

Examples of magenta couplers used in the present invention are shown below. In practicing the present invention, for example, the following exemplified compound M-1 can be used.

(Exemplary Compound M-1) In the present invention, the above magenta couplers can be selected as the magenta coupler, but the following general formulas (II) to (II
It is further preferred to select the compounds shown in I).

General formula (If) General formula (III) In general formulas (n) to (III), Z represents a group that reacts with the oxidized color developing agent and leaves, and R1 represents a sulfonyl group, an acylamino group, a diacylamino group, or a urethane group. It does not contain any dissociable groups such as phenolic hydroxyl group, sulfonamide group, or carboxyl group.

R? +RI represents an alkyl group.

X2 represents a hydrogen atom or a group that reacts with the oxidized product of the color developing agent and leaves it.

Examples of substituents that can be removed by reaction with oxidized color developing agents include halogen atoms (chlorine atoms, bromine atoms,
In addition to fluorine atom, etc.), examples include groups substituted via a carbon atom, an oxygen atom, a sulfur atom, or a nitrogen atom.

Examples of magenta couplers represented by general formulas (n) to (III) are shown below.

Shil Shi-11+tLtJ (Exemplary Compound M-8) (Exemplary Compound M-9) In the present invention, the following cyan couplers can be used.

Examples include phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers.

Specific examples of cyan couplers include U.S. Pat.
No. 93, 2,521゜908, 2,895.82
No. 6, No. 3,034,892, No. 3,311゜476
No. 3,458.315, No. 3,476.563, No. 3,583゜971, No. 3,591,383,
No. 3,767.411, No. 4,004゜929, West German Patent Application (OL S) No. 2,414.830, No. 2
, No. 454.329, JP-A-48-59838, No. 5
No. 1-26034, No. 48-5055, No. 51-14
No. 6827, No. 52-69624, No. 52-9093
2, No. 58-95346, and the like.

In the present invention, the amount of these yellow, magenta and cyan couplers added is not limited, but is 2X10 per mole of silver halide in each light-sensitive silver halide emulsion layer.
""~5X10-' moles are preferred, more preferably l
Xl0-'' to 5X10-' moles.

In order to incorporate these couplers into the silver halide emulsion according to the present invention, if the couplers are alkali-soluble, they may be added as an alkaline solution; if they are oil-soluble, they may be added, for example, as described in US Pat. No. 2.322.0
No. 27, No. 2.801.170, No. 2,801.
No. 171, No. 2.272.191 and No. 2.3
-04.940 It is preferable to dissolve the coupler in a high boiling point solvent and, if necessary, in combination with a low boiling point solvent, disperse the coupler in the form of fine particles, and add it to the silver halide emulsion. . At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination. It is also possible to use a mixture of two or more couplers. Further, to explain in detail the preferred method of adding couplers in the present invention, one or more of the couplers are added to an organic acid amide along with other couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc. as necessary. , carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n
-butyl phthalate, triresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-pentadecyl phenylethyl ether, 2.5-di5ec-amyl phenyl butyl ether, monophenolic 0-chlorophenyl phosphate or fluorine paraffin, etc. high boiling point solvent, and/
Or low boiling point materials such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, etc. Anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate, and/or hydrophilic binders such as gelatin, dissolved in a solvent. The silver halide emulsion is mixed with an aqueous solution containing the compound, emulsified and dispersed using a high-speed rotating mixer, colloid mill, ultrasonic dispersion device, etc., and then added to a silver halide emulsion.

In addition, the above couplers may be dispersed using a latex dispersion method. The latex dispersion method and its effects are described in JP-A-49-74538, JP-A-51-59943, and JP-A-54.
-32552 Specification Publication and Research Disclosure August 1976, No. 14850, pages 77-79.

Suitable latexes include, for example, styrene, acrylate,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-(2-(2-methyl-4 -oxopentyl)]acrylamide, 2-acrylamide-2-
Homopolymers, copolymers and terpolymers of monomers such as methylpropanesulfonic acid and the like.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, such as anti-capri agents, stabilizers, ultraviolet absorbers, etc. described in Research Disclosure No. 17643, A color stain inhibitor, a fluorescent whitening agent, a color image fading inhibitor, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, etc. can be used.

In the silver halide color photographic light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, and cellulose acetate. , polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and these supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also, U.S. Patent No. 2.761.791;
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 941.898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer from the support side. .

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives can be included.

There are no particular limitations on the method of processing photographic materials using the silver halide emulsion according to the present invention, and any processing method can be applied. For example, a typical example is
After color development, a bleach-fixing treatment is carried out, and if necessary, washing and/or stabilization treatment is carried out; after color development, bleaching and fixing are carried out separately, and if necessary, further washing and/or stabilization treatment is carried out; or Pre-hardening, neutralization, color development, stop fixing, washing with water, bleaching, fixing, washing with water, post-hardening, washing with water in that order, color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water, stabilization Processing may be performed using any method, such as a method in which the developed silver produced by color development is subjected to 710 generation bleaching, and then color development is performed again to increase the amount of generated dye. .

The color developing solution used for processing the silver halide emulsion of the present invention is an alkaline aqueous solution containing a color developing agent and preferably having a pH of 8 or higher, more preferably a pH of 9 to 12. The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop silver halide exposed to light. Precursors that form such compounds may also be added.

The color developing agent mentioned above is typically p-phenyl diamine type, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-
N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N,N-dimethylaniline,
N-ethyl-N-β-[β-(β-methoxyethoxy)
ethoxy]ethyl-3-methyl-4-aminoaniline,
These include N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline and salts thereof such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, and the like.

Furthermore, for example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849, and Bent et al., Journal of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951).
The ones described above are also listed as representative ones.

The amount of these aromatic primary amino compounds to be used depends on where the activity of the developer is set, but in order to increase the activity, it is preferable to increase the amount used. The amount used ranges from 0.0002 mol/l to 0.7 mol/l. Moreover, two or more compounds can be used in appropriate combination depending on the purpose. For example, 3-methyl-4-amino-N,N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, etc. may be used in any combination depending on the purpose.

The color developer used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol,
A water softener, a thickening agent, a development accelerator, etc. can also be optionally included.

However, it is preferable that benzyl alcohol is not added to the color developing solution.

In other words, benzyl alcohol has a pollution load value of BOD.
Benzyl alcohol has a high BOD and low hydrophilicity, so diethylene glycol or triethylene glycol is required as a solvent, but glycols also have a BOD.

Since the COD is high, the processing liquid that is discarded due to overflow poses a problem of environmental pollution. In addition, benzyl alcohol has low solubility in developing solutions (it takes a long time to create a developing solution or a replenisher, creating a work problem. Also, if the amount of replenishment is large, the number of times a replenisher must be created is required). This also increases the workload.

Therefore, environmental pollution and operational problems can be eliminated by substantially not containing benzyl alcohol in the color developing solution, which is very preferable.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
In addition to compounds for quick processing solutions such as alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-methyl-benzotriazole, 1-phenyl-5-mercaptotetrazole, anti-stain agents, anti-sludge agents, preservatives, There are multilayer effect promoters, chelating agents, etc.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl ether diaminetetraacetic acidethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acid pentasodium saltnitrilotriacetic acid sodium saltBleaching solution contains various additives along with the above bleaching agents. It may also contain an agent. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. As in the case of the above-mentioned bleaching solution, various other additives such as pH11E buffer, optical brightener, antifoaming agent, surfactant, preservative, chelating agent, stabilizer, organic solvent, etc. It may be added or contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.

Color development of the silver halide color photographic light-sensitive material of the present invention,
The processing temperature of bleach-fixing (or bleaching, fixing), and various processing steps such as washing with water, stabilization, and drying, which are carried out as necessary, is preferably carried out at 30° C. or higher from the viewpoint of rapid processing.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 58-105145, 5B-1
No. 34634 and No. 58-18631 and patent application 1973
A stabilizing treatment as an alternative to washing may be performed as shown in Japanese Patent No. 8-2709 and Japanese Patent No. 59-89288.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited to these.

<Example 1> Emulsions commonly used in Examples will be described above.

- Preparation of seed emulsions Silver chloride and silver chlorobromide seed emulsions NE-1 to NE-3 as shown in Table 1 were prepared according to the method described in JP-A-50-45437. Each of the various emulsions contained 1.413 moles of silver halide per 11 parts.

Table-1 *Depends on the length of one side of the cube.

Next, silver halide emulsion EM- was prepared using the seed emulsion shown in Table 1.
1-EM-7 was created. According to the method described in JP-A-59-45437, the seed crystals shown in Table 1 were grown under neutral conditions by the Chondral double jet method to obtain a cubic monodisperse emulsion having the desired grain size. Created. The liquid that controls pAg during the growth of silver chloride emulsion is Na.
CA! A solution for controlling pAg during the growth of a silver chlorobromide emulsion as a comparative emulsion using an aqueous solution of
A mixed aqueous solution of chloride ions/bromide ions having the composition ratio shown in No. 437 was used. In the double jet method, the addition rate of the additive liquid was increased within a range in which new crystal nuclei other than seed particles contained in the seed emulsion were not generated.

After growing to a desired particle size, a desalting step was performed according to a conventional method to remove salts.

Table 2 shows the composition and particle size of EM-1 to EM-7.

Table 2 The emulsion prepared as described above was subjected to chemical sensitization and spectral enhancement.

Blue-sensitive emulsions The following four types of sensitized emulsions were prepared.

B-1: Conventional emulsion - Using the conventional sensitization method EM-1, the following Compound A and sodium thiosulfate were added as an enhancing dye to achieve optimal enhancement.

B-2=Silver chlorobromide emulsion that can be processed rapidly - Using the conventional sensitization method EM-2, optimal sensitization was carried out by adding the following compound A as a sensitizing dye and sodium thiosulfate.

B-3: Rapidly processable silver chlorobromide emulsion - JP-A-58-
Using the sensitizing method EM-2 shown in No. 30747, the following Compound A, sodium thiosulfate and ammonium thiocyanate were added as aggravating dyes to optimally aggravate the disease.

B-4=Silver chloride emulsion of the present invention- Use EM-7 as an exacerbation dye. Compound A, sodium thiosulfate In addition, it was optimally sensitized.

Compound A <Green-sensitive emulsion> The following nine types of enhanced emulsions were prepared. Each emulsion was optimally sensitized by adding Exemplified Compounds 0-8 and sodium thiosulfate as sensitizing dyes. (Table 3) M'-j Exemplary Compound 0-8 Red-sensitive Emulsion The following two types of sensitized emulsions were prepared.

R-1 = Conventional emulsion Using EM-3 as a sensitizing dye, Compound B, sodium thiosulfate In addition, it was optimally sensitized.

R-2 = Using emulsion EM-5 consisting essentially of silver chloride, the following Compound B and sodium thiosulfate were added as enhancing dyes to optimally sensitize the emulsion.

Compound B Example 2 On a paper support laminated with polyethylene, the following layers were sequentially coated from the support side to create 11 types of multilayer silver halide color photographic photonic materials.

Layer 1) 1.2g/r+? of gelatin, 0.32
g/m (in terms of Xm, the same applies hereinafter) blue-sensitive emulsion (the emulsion used is shown in Table 4), 0.80 g/rd yellow coupler (see below) dissolved in 0.50 g/rd dioctyl phthalate. layer containing compounds).

(Yellow coupler) Layer 2 > 0.7 g/rd (D Gelatin, 10+ag/rd (D Anti-irradiation dye (AI-1), 5 mg/rrf (AI-2)
The middle layer consists of

Layer 3 > 1.25 g/n (gelatin, 0.32
g/rd green light-sensitive emulsion (emulsions used are shown in Table 4)
'), 0.62 g/rd magenta coupler (
Layer containing exemplified compound M-3=the following compound).

(Magenta coupler) Layer 4) Intermediate layer consisting of 1.2 g/rrr of gelatin.

<ti5> 1.4 g/m (D gelatin, 0.20
g/rd red-sensitive emulsion (emulsions used are shown in Table 4)
), a layer containing 0.45 g/rd cyan coupler (exemplary compound) dissolved in 0.20 g/cd dioctyl phthalate.

layer 6) 1.0g, /n? of gelatin and 0.2
0, dissolved in 0 g/m dioctyl phthalate.
A layer containing 30 g/d of Tinuvin 328 (manufactured by Ciba Geigy).

How many layers? > Layer containing 0.5 g/m of gelatin.

Table 5 shows the contents of each color-sensitive emulsion contained in each sample.

Sample 1lkL12 was prepared in the same manner as sample Nn8 except that exemplified compound M-1 (the following compound) was used as the magenta coupler in layer 3 instead of exemplified compound M-3.

C+zHgs(n) (AI-2) These samples were then exposed to light through the front and then processed in the next step.

Treatment process temperature time! 1) Color development 35℃ 30 seconds, 40 seconds, 50
Seconds, 60 seconds.

6 types (90 seconds, 120 seconds) (2) Bleach fixing 35℃ 50 seconds (3) Stabilization bath
36-34°C 2 minutes (4) Drying 60-90°C - The composition of the treatment liquid used in each step is as follows.

Color developing solution (per IIt) [Pure water 8001 Bleach-fixing solution Stabilizing solution The amounts of MCI and KBr in the color developing solution are based on the average halogen composition in the light-sensitive material, assuming the convergence concentration when each light-sensitive material is continuously processed. It was changed according to the ratio.

(Table-4).

Table 4 Next, sensitometric evaluation was performed according to a conventional method. Sensitivity, white background properties, and rapid processing properties are shown in Table 5.

In the table, the sensitivity is the lowest density in 120 seconds development (Capri)
It is the reciprocal of the exposure amount that gives a density of +0.3, and it is the reciprocal of the exposure amount that gives a density of +0.3.
The relative sensitivity is shown when the sensitivity of Ll (conventional photosensitive material) is set to 100.

Rapid developability is indicated by the development time until the color density of the blue light-sensitive layer is saturated. That is, the smaller this value is, the better the rapid developability is.

Whiteness is achieved with a development time of 120 seconds and an accelerated development time of 5.
The spectral reflectance of the unexposed area of the uncoated paper support and the treated sample was measured using a spectrophotometer at 0 seconds.
Expressed as optical density difference at 0 nm. In other words, the smaller this value is, the better the whiteness is.

Next, the blue light sensitivity of the green-sensitive layer was determined as color reproducibility. This was exposed using an interference filter having a transmission maximum at 450 na+, and green light sensitivity was determined by sensitometry.

This value is expressed as a relative value with the sensitivity of sample number 1 being 100, and the larger this value is, the greater the turbidity of magenta with respect to yellow becomes, which is not preferable since pure yellow cannot be reproduced.

According to the results in Table 5, samples No. 3 to Arashi 5, in which the blue-sensitive layer was sensitized and the particle size was reduced by the sensitization method using SCN shown in JP-A No. 58-30747, were blue-light sensitive. However, even if the halogenated root nodule size and the amount of photosensitive dye in the green photosensitive layer are optimized, the green light sensitivity and reproducibility (blue light sensitivity of the green light sensitive layer) will not be compromised. , it is not possible to maintain the same level of whiteness during rapid development as with conventional printing materials.

This problem is present at a sufficient level even in these samples when the development time is long, and is a phenomenon that becomes more noticeable with rapid processing.

On the other hand, it can be seen that the sample of the present invention satisfies all the performances of blue light sensitivity, green light sensitivity, and whiteness, and can be rapidly processed.

Procedural amendment July 21, 1988 Michibe Uga, Commissioner of the Patent Office1, Indication of the case 1988 Patent side No. 0935392, Title of invention Silver halide color photographic light-sensitive material 3, Person making the amendment Case Relationship with Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Subject of amendment Written amendment to the full text of the specification (voluntary) March 2, 1988 Commissioner of the Patent Office Kuro 1) Akio Tono 1, Indication of the case 1988 Year: Patent No. 093539 2, Name of the invention Silver halide color photographic light-sensitive material 3, Relationship to the amended person case Patent applicant address: 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent 6, Subject of amendment “Detailed description of the invention” in the specification
column.

7. Contents of amendment as per attached sheet Add the description.

[Effects of the Invention] According to the present invention, there is provided a silver halide color photographic light-sensitive material that can be rapidly processed without impairing the color reproducibility of blue light sensitivity and green light sensitivity and has excellent white background properties. be able to.

July 23, 1985 (1986) Patent side No. 093539 2. Name of the invention: Silver halide color photographic light-sensitive material. 3. Relationship with the person making the amendment. Address of the patent applicant. 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Konishiroku Photo Industry Co., Ltd. Dia Palace Niban-cho 506 FAX 03 (221) 1924 5, Date of amendment order Voluntary (1) In the specification (referring to the engraving specification submitted on July 21, 1985) ), on page 8, lines 8 to 9, amend "has a great influence on silver halide grains" to "has a great influence on silver halide grains."

(2) Insert the following sentence between page 41, line 18 and line 19.

``The color developing solution optionally contains N,N-diethylhydroxyamine tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone aromatic secondary alcohol, hydroxamic acid, pentose or hexose as an antioxidant, Pyrogallol-1,3-dimethyl ether, etc. may be contained.'' (3) The chemical formula of magenta coupler) on page 54 of the same is corrected as follows.

(Magenta coupler) ('1 (4) The chemical formula written under "Created" in line 9, line 100 on page 55 of the same is corrected as follows.

r# ShiL (5) rPH = 7 on page 58, lines 5 and 6. Correct OJ to rpH=6.2J.

(6) Table 4 on page 59 of the same is amended as follows.

Table-4 (7) Amend page 63 and subsequent pages as shown in the attached sheet.

Above is Example 3 In this example, the following steps were performed. All other procedures were the same as in Example 2.

As a result, the same results as in Example 2 were obtained.

Processing process (35℃) Color development 30 seconds, 40 seconds, 50 seconds, 60 seconds, 90
seconds.

6 types of 120 seconds Bleach fixing 45 seconds Wash with water for 90 seconds Drying 60-80℃ 2 minutes The composition of each treatment liquid is as follows.

Color developer B〉 Pure water 8
0〇-triethanolamine 10
gN,N-diethylhydroxylamine (8.5% aqueous solution) 5g Potassium chloride and potassium bromide varied according to average halogen composition (see Table 4) Potassium sulfite 0.2g Ethylenediaminetetraacetic acid 1g N-ethyl-N-β -Methanesulfonamidoethyl-3-methyl-
4-aminoaniline sulfate
5g1-hydroxyethylidene-1,1-diphosphonic acid 1
g Potassium carbonate 25 gW
hitex BB Conc (50% aqueous solution)
2- (Fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to adjust the pH to 11 and adjust the pH to 10.2.

Bleach-fix solution> Pure water 60〇-Iron(III)-ethylenediaminetetraacetate Ammonium 65 g Ethylenediaminetetraacetic acid-2-sodium salt g Ammonium 1000 sulfate 85 g Sodium hydrogen sulfite 10 g Sodium metasulfite 2 g Potassium chloride
10g color developer 8200
Add mZ pure water to bring the pH to 11 and adjust the pH to 6.2.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to provide a silver halide color photographic light-sensitive material that can be rapidly processed without impairing the color reproducibility of blue light sensitivity and green light sensitivity and has excellent whiteness.

Claims (1)

[Claims] (1) In a silver halide photographic material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a reflective support,
The green light-sensitive silver halide emulsion layer has the following general formula (I):
The photosensitive dye shown in 1.51 x 10^-^4~0.5
7×10^-^4 (mol/molAgX) (AgX represents silver halide), and contains silver halide grains whose silver halide composition consists essentially of silver chloride. Color photographic material. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Y1 is selected from an oxygen atom or N-R_4. Y
2 is selected from an oxygen atom or N-R_5. Z_1 and Z_2 may be the same or different, and each represents an atomic group necessary to form an unsubstituted or substituted benzene ring or naphthalene ring. R_1, R_2, R_4, and R_5 represent unsubstituted or substituted alkyl groups. However, R_1, R_2, R_4,
At least one of R_5 has an acid substituent. R_3 represents a hydrogen atom, an alkyl group or an aralkyl group. X represents an anion. n represents 1 or 2, and is 1 when the dye forms an intramolecular salt.