JPS62275251A - Color image forming method - Google Patents

Abstract

PURPOSE:To form high color development density in a short time by processing a silver halide color photographic sensitive material provided with a silver halide emulsion layer containing a color coupler, after imagewise exposure, within a prescribed developing time with a color developing solution in the presence of a specified compound. CONSTITUTION:The silver halide color photographic sensitive material provided on a reflective support with at least one silver halide emulsion layer containing a color coupler is imagewise exposed and color developed with a color developing solution containing substantially no benzyl alcohol within a developing time of <=2min30sec in the presence of the compound represented by formula I in which Z is an atom or atomic group necessary to form a hetero ring; G is H or optionally substituted straight, branched chain, or cyclic alkyl or the like; R is optionally substituted alkyl or such aryl; X is an anion, and it may link to Z, G, or R to form an intramolecular betaine; and n is 1, 2, or 3.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a color image forming method, and more particularly to a color image forming method that causes less environmental pollution and allows rapid processing.

<Prior art> Conventionally, as a method for forming color photographic images, a so-called color coupler, which forms a dye through a coupling reaction with an oxidized product of an aromatic primary amine, is used in a silver halide photographic light-sensitive material (hereinafter referred to as "sensitive material"). The above-mentioned light-sensitive material, which has been imagewise exposed and incorporated into a lithium-ion film (called a chromophore), is immersed in a color developing solution containing an aromatic primary amine compound as a color developing agent, and the exposed silver halide grains are color-developed. The oxidized product of the aromatic primary amine compound produced by "development" (reduction of silver ions in silver halide) of the main agent is coupled with the above color coupler to form a dye and produce a color image. What you get is well known.

At this time, blue-sensitive,
using at least three layers having green sensitivity and red sensitivity,
If each photosensitive emulsion layer contains color couplers that develop colors as yellow, magenta and cyan dyes, it becomes possible to reproduce natural colors by the so-called subtractive color method.

A stable color photographic image can be obtained by removing the developed silver produced during the formation of the dye image and the silver halide remaining undeveloped by bleaching and fixing.

By the way, the color couplers incorporated into such photosensitive materials can be used in the form of being dissolved in a high boiling point solvent and dispersed in a hydrophilic colloid - the so-called oil protection method - for the purpose of increasing the stability of the resulting dye image. Preferably, most color sensitive materials currently used in the photographic industry are of this type.

In recent years, demands for improved productivity have been increasing in the photographic industry, and the problem of how to quickly process a large number of prints has always been the most important issue. In order to solve these problems, shortening the processing time for photosensitive materials, especially shortening the processing time for color photographic paper, is considered to be the most effective means.

In order to achieve such a reduction in development processing time, it is necessary to provide as high a color density as possible within a limited development time. The means to achieve this are to use color couplers with as high a coupling speed as possible, to use silver halide emulsions that are easily developed and have a large amount of developed silver per unit coated amount, or to use color development with a high development speed. Possible methods include using a liquid.

It is generally known that the coupling reaction rate depends on both the reactivity of the color coupler used and the permeability of an aromatic primary amine compound, which is a color developing agent, into oil droplets (including the coupler).

As mentioned above, it is very important to use a highly reactive color coupler, but on the other hand, when selecting a coupler to be used in a sensitive material, it is necessary to satisfy a number of performance requirements. It goes without saying that there is no adverse effect on the silver halide emulsion incorporated into the photosensitive material (such as increasing capri or decreasing sensitivity during storage).
Important properties include the fact that the hue of the coloring dye is favorable for color reproduction, and that the coloring dye and coupler themselves have high stability against heat and light. Therefore, when selecting a coupler with excellent overall performance, emphasis cannot necessarily be placed on coupling reaction activity.

For these reasons, various methods have been studied to increase the rate of penetration of color developing agents into oil droplets.

Among these methods, the method of increasing the development speed by adding benzyl alcohol to the color developing solution is currently widely used in the processing of color photographic paper because of its great effect of promoting color development.

When benzyl alcohol is used, diethylene glycol, triethylene glycol, almanolamine, or the like is required as a solvent due to its low water solubility. However, since these compounds, including benzyl alcohol, have high pollution load values such as BOD and COD, it is preferable to remove benzyl alcohol for the purpose of reducing the pollution load.

Furthermore, even if this solvent is used, it takes time to dissolve benzyl alcohol, so it is better not to use benzyl alcohol in order to reduce the preparation work.

Furthermore, if benzyl alcohol is brought into the bleaching bath or bleach-fixing bath, which is a post-bath, it causes the formation of a leuco dye, which is a cyan dye, and causes a decrease in color density. Furthermore, since the washing-out speed of the developer components is delayed, the image storage stability of the photosensitive material may be adversely affected.

Therefore, also for the above reasons, it is preferable not to use benzyl alcohol.

Conventionally, color development has generally been processed in 3 to 4 minutes, but with the recent shortening of finishing delivery times and the reduction of laboratory work, it has been desired to shorten the processing time.

However, if benzyl alcohol, which is a color development accelerator, is removed and the development time is shortened, it is inevitable that the color density will be significantly reduced.

In order to solve this problem, various color development accelerators (for example, U.S. Pat. No. 2,950,970, U.S. Pat. No. 2,515,1
No. 47, No. 2,496,903, No. 2,304,92
No. 5, No. 4,038,075, No. 4,119,462
British Patent No. 1,430°998, British Patent No. 1,455,4
No. 13, JP-A-53-15831, JP-A No. 55-6245
No. 0, No. 55-62451, No. 55-62452,
Even when used in combination with the compounds described in Japanese Patent Publication No. 55-62453, Japanese Patent Publication No. 51-12422, and Japanese Patent Publication No. 55-49728, sufficient color density could not be obtained.

In addition, methods of incorporating 3-pyrazolidones (for example, JP-A-60-26338, JP-A-60-158444, JP-A-6
Even if the method described in No. 0-158446 is used, there are disadvantages in that the sensitivity decreases over time and fog occurs.

Also, a method of incorporating a color developing agent (for example, U.S. Pat. No. 37
No. 19492, No. 3342559, No. 3342597
Even if the methods described in JP-A-56-62.35, JP-A-56-16133, JP-A-57-97531, JP-A-57-83565, etc. are used, color development is delayed,
This method has the drawback of generating fog, and is not an appropriate method.

On the other hand, in JP-A-50-137736, a benzothiazolium compound is used as an overdevelopment inhibitor in a color developing solution treatment containing benzyl alcohol.
It is described that the presence of phenyl-5-mercaptotetrazole gives high color density. However, there has been a desire for a development promotion method that is effective not only under the extremely limited conditions of coexistence of benzyl alcohol and 1-phenyl-5-mercaptotetrazole, but also under a wider range of development conditions.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a color image forming method that provides high color density in a short time even when using a color development processing liquid that does not substantially contain benzyl alcohol. be.

(Means for Solving the Problems) An object of the present invention is to imagewise expose a silver halide color photographic light-sensitive material in which at least one silver halide emulsion layer containing a color coupler is provided on a reflective support. After that, by a color image forming method characterized by processing in the presence of a compound represented by the following general formula (I) with a color developer substantially free of benzyl alcohol for a development time of 2 minutes 30 seconds or less. achieved.

General formula (I) %Formula% (In the formula, Z represents an atom or atomic group necessary to form a heterocycle.G represents a hydrogen atom, substituted or unsubstituted, linear, branched or cyclic Represents an alkyl group, or a substituted or unsubstituted aryl group.R represents a substituted or unsubstituted linear, branched, or cyclic alkyl group, or a substituted or unsubstituted aryl group.X is an anion and may be linked to a substituent represented by 21G or R to form intramolecular betaine. n is 1, 2 or 3
represents. However, at least one of the substituents represented by Z, G, or R is substituted with at least one sulfo group or carboxyl group. ) Among the compounds represented by general formula (I), the following are preferred.

Z represents an atom or atomic group necessary to form a 5- or 6-membered heterocycle, especially an atom necessary to form a type of heterocycle commonly used in the production of cyanine dyes, as exemplified below. and represents an atomic group. For example, thiazoline, thiazole, benzothiazole, naphthothiazole,
Examples include oxazole, benzoxazole, naphthoxazole, indolenine, selenazole, benzoselenazole, imidazole, benzimidazole, pyridine, and quinoline, and these rings may be substituted. Examples of substituents include sulfo groups, carboxyl groups, hydroxy groups, halogen atoms, substituted or unsubstituted sulfamoyl groups, substituted or unsubstituted carbamoyl groups, substituted or unsubstituted sulfonamide groups, substituted or unsubstituted carboxyl groups. Amido group, substituted or unsubstituted acyl group, alkoxycarbonyl group, alkyl group, halogenated alkyl group, alkoxyalkyl group, aralkyl group, phenyl group, substituted phenyl group, alkoxy group, alkoxy-substituted alkoxy group, phenoxy group, substituted or Examples include an unsubstituted ureido group, hydroxyalkyl group, sulfoalkyl group, carboxyalkyl group, and sulfophenyl group, and the number of carbon atoms in these substituents is particularly preferably 30 or less.

R and G are each independently a substituted or unsubstituted linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted phenyl group having 6 to 30 carbon atoms; represents.

G may be a hydrogen atom. Examples of substituents include sulfo groups, carboxyl groups, hydroxy groups, halogen atoms, substituted or unsubstituted sulfamoyl groups, substituted or unsubstituted carbamoyl groups, substituted or unsubstituted sulfonamide groups, substituted or unsubstituted carboxyl groups. Amide group, substituted or unsubstituted ureido group, carboxylic acid ester group, alkyl group, hydroxyalkyl group, halogenated alkyl group, alkoxyalkyl group, aralkyl group, phenyl group, substituted phenyl group, alkoxy group, phenoxy group, sulfoalkyl group substituent groups, carboxyalkyl groups, sulfophenyl groups, etc., and the number of carbon atoms in these substituents is particularly preferably 20 or less.

X is an inorganic anion such as sulfate ion, nitrate ion, perchlorate ion, halide ion, or acetate ion,
Contains organic acid ions such as benzoate ion, methanesulfonate ion, and paratoluenesulfonate ion. However, these organic sulfonic acid ions or carboxylic acid ions are Z, C.

Alternatively, it may become part of the substituent represented by R to form intramolecular betaine. Preferably, n is 1 or 2.

Specific examples of the compound of general formula (I) of the present invention are listed below, but the present invention is not limited thereto.

Q SO□ ■-13 ■-14 ! -17 ■-19 ■-20 ■-23 ■-27 Ct Hs ■-29 In the present invention, color development can be carried out in the presence of at least one compound represented by general formula (I) as follows. Bye.

That is, it can be realized by making the compound represented by the general formula (I) exist in at least one of the photosensitive layer or non-photosensitive layer of the silver halide photographic light-sensitive material and/or in the color developing solution.

The amount of the compound represented by the general formula (r) used in the present invention varies depending on the composition of the sensitive material, but when it is added to the photosensitive layer or non-photosensitive layer of the sensitive material, 10-6 per mole of silver halide contained in
A range of mol to 10-1 mol is preferred. More preferably, the amount is in the range of 10-5 mol to 10-2 mol. Also,
When used by adding it to a color developing solution, 5 x 10
-9 mol/1 to 1.5X10-' mol/l, more preferably 5X10-' mol/j2 to 1
．． It is in the range of 5×10 −4 mol/l.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

The color developer used in the present invention does not substantially contain benzyl alcohol. Containing substantially no Hensyl alcohol means that its concentration is 2m 1/7! or less, preferably l ml / 1 or less, more preferably 0.5 mf/f or less.

Most preferably, it contains no benzyl alcohol at all.

Further, the color development time is 2 minutes 30 seconds or less, preferably 1 minute to 2 minutes 30 seconds, more preferably 1 minute 30 seconds to
It is 2 minutes and 10 seconds. The color development time herein refers to the time from when the photosensitive material comes into contact with the color developer until it comes into contact with the processing solution in the water bath, and includes the so-called transfer time.

The color developing solution used in the development process of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline, and 3-methyl-4-amino-N-ethyl-
N-β-hydroxylethylaniline, 3-methyl-4
-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p -toluenesulfonate, tetraphenylborate, p-(t-octyl)benzenesulfonate, and the like.

Examples of aminophenol derivatives include O-aminophenol, p-aminophenol, 4-amino-2-
These include methylphenol, 2-amino-3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene, and the like.

In addition, "Photographic Ink Processing Chemistry" by F. A. Meson, Focal Press (
I966) (L, F, A.

Mason, “Photographic Processes
sing Chemistry”.

Focal Press), pages 226-229, U.S. Pat. No. 2,193,015, U.S. Pat.
Those described in JP-A No. 48-64933 may also be used. If necessary, two or more color developing agents can be used in combination.

The processing temperature of the color developer in the present invention is 30°C to 5°C.
0°C is preferred, and more preferably 33°C to 45°C.

Further, as the development accelerator, various compounds may be used, except that they do not substantially contain benzyl alcohol. For example, U.S. Patent No. 2,648,604, Japanese Patent Publication No. 44-95
Various birimidium compounds and other cationic compounds represented by No. 03 and U.S. Patent No. 3,171.247, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, and equity m44-93o.
・No. 4, U.S. Patent No. 2,533,990, U.S. Patent No. 2,531
．． No. 832, No. 2,950,970, No. 2゜577.
Polyethylene glycol and its derivatives described in No. 127,
Nonionic compounds such as polythioethers, thioether compounds described in U.S. Pat.
Examples include the compounds described in No.

In addition, in short-time development processing as in the present invention,
An important issue is not only a means to accelerate development, but also a technique to prevent development fog. Preferred antifoggants in the present invention include alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants.

Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and 1-phenyl-
Mercapto-substituted heterocyclic compounds such as 5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. Particularly preferred are halides. These antifoggants may be eluted from the color photochromic material during processing and may accumulate in the color developer.

In addition, the color developer according to the present invention includes a pH buffering agent such as an alkali metal carbonate, borate or phosphate; hydroxylamine, triethanolamine, a compound described in OLS No. 2622950; , preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; auxiliary development such as 1-phenyl-3-pyrazolidone. Drugs; viscosity imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and those described in JP-A-58-195845 Examples of compounds such as aminopolycarboxylic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, Research Disclo
sure) 11h18170 (May 1979), aminophosphonic acids such as aminotris (methylenephosphonic acid), ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, JP-A No. 52-102726 No. 53-4.2730, No. 54-121127, No. 55-4024, No. 55-
No. 4025, No. 55-126241, No. 55-65
No. 955, No. 55-65956, and Research Disclosure.
(sure) Th18170 (May 1979) chelating agents such as phosphocarboxylic acid can be contained.

In addition, the color developing bath can be divided into two or more parts as necessary.
Replenish color developer replenisher from the first bath or last bath,
The development time may be shortened or the amount of replenishment may be reduced.

After color development, the silver halide color photosensitive material is usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment (bleaching and fixing) or may be carried out separately. Examples of bleaching agents include compounds of polyvalent metals such as iron (I), cobalt (■), chromium (■), and copper (If), peracids,
Quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron (I) or cobalt (■), such as ethylenediaminetetraacetic acid,
Diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1.
Aminopolycarboxylic acids such as 3-diamino-2-propatoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid, and malic acid: pergates, manganates; nitrosophenols, etc. can be used. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (II[
) Sodium and iron hyethylenediaminetetraacetate (I[+
) ammonium, triethylenetetraminepentaacetate iron (I
[I) Ammonium and persulfates are particularly useful. Ethylenediaminetetraacetic acid iron(II[) complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

Further, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution, if necessary. For example, in addition to bromide ion and iodide ion, U.S. Pat.
No. 6, No. 49-26586, JP-A-53-32735
Thiourea-based compounds as shown in JP-A No. 53-36233 and JP-A No. 53-37016;
No. 3-57831, No. 53-32736, No. 53-6
No. 5732, No. 54-52534 and U.S. Patent No. 3,
Thiol compounds as shown in 893.858, etc., or JP-A-49-59644, JP-A-50-
No. 140129, No. 53-28426, No. 53-14
No. 1623, No. 53-104232, No. 54-357
Heterocyclic compounds described in JP-A No. 27, etc.; thioether compounds described in JP-A-52-20832, JP-A-55-25064, and JP-A-55-26506; Compounds such as quaternary amines described in JP-A-48-84440 or thiocarbamoyls described in JP-A-49-42349 may also be used.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides, but thiosulfates are generally used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing process and the fixing process, a washing process is usually performed. In the water washing process, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid to prevent precipitation, fungicides and anti-spiking agents to prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum salts. Typical hardeners, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Or L.E. West (L
, E, West), Photographic Science and Engineering (Photo.

Sci, and Eng,), Volume 9, No. 6, (I
965) and the like may be added.

Particularly effective is the addition of chelating agents and anti-piping agents.

It is also possible to save water by using a multistage (for example, 2 to 5 stages) countercurrent method in the water washing process.

Also, after or instead of the water washing process, JP-A-57-
A multi-stage countercurrent stabilization treatment process such as that described in No. 8543 may be performed. In the case of this step, a countercurrent column with 2 to 9 tanks is required. Various compounds are added to this stabilizing bath for the purpose of stabilizing the image.

For example, buffers for adjusting membrane pH (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, Polycarboxylic acids, etc.) and formalin can be given. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (proxel, isothiazolone, 4-thiazolylbenzimidazole, halogenated phenol benzotriazoles, etc.), a surfactant, a fluorescent brightener, a hardening agent, etc. may be added.

Also, the membrane pHtJ after treatment! Various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can also be added as conditioning agents.

The silver halide emulsion used in the present invention has an average grain size of 0.0000, expressed by the equivalent diameter of a circle in projection. 1
The range is preferably from μm to 2 μm, more preferably 0.5 μm. 2μ
m to 1.3 μm. Preferably, the emulsion is a monodisperse emulsion, and the grain size distribution representing the degree of monodispersion is expressed as the ratio of the statistical standard deviation (S) to the average grain size (di) =/
(variation rate) is preferably 0.2 or less, more preferably 0°15 or less.

The silver halide emulsion used in the present invention may have any halogen composition, but preferably consists of silver bromide and/or silver chlorobromide that does not substantially contain silver iodide, and more preferably contains silver chloride. The silver chlorobromide emulsion contains 2 mol% or more and 80 mol% or less, more preferably 2 mol% or more and less than 50 mol%.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), or may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more occupy 50% or more of the total projected area of the grains.

An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface, or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography J" by Glafkides.

Chimie et PhysiquePhoto
graphique (Pa, published by U1Monte1, 1967)], "Photographic Emulsion Chemistry J" by Duffin (
Photographic by G. F. Duff in
EmulsionChem'1try (Foca
V. L. Press, 1966), Zelikman et al., "Manufacture and Coating of Photographic Emulsions J"
Making and Coa by an etal
tingPhotographic Emulsio
(Focal Press, 1964)]. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which Ag in the liquid phase in which silver halide is produced is kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Furthermore, emulsions prepared by the so-called conversion method, which involves converting silver halide already formed into silver halide with a smaller solubility product before the completion of the silver halide grain formation process, and silver halide Emulsions which have undergone similar halogen exchange after the completion of the grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (for example, ammonia, Rodankali or U.S. Pat. No. 3,271,157, JP-A-5
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, JP-A-54-155828, etc.) by precipitation, physical Can be used in maturation and chemistry classes. In order to remove soluble root salts from the emulsion after physical ripening, Nordel water washing, flocculation sedimentation method, ultrafiltration method, etc. are used.

The silver halide emulsion used in the present invention contains active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfate,
Sulfur sensitization method using reducing substances (e.g. stannous salt amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal Compounds (e.g., gold complex salts, PtS Ir, Pd, Rh, Fe
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table, such as complex salts of metals in group 1 of the periodic table, etc., can be used alone or in combination.

Among the above chemical sensitizations, sulfur sensitization alone is more preferred.

In order to satisfy the target gradation of the color photographic window optical material of the present invention, two or more types of monodisperse silver halide emulsions (monodisperse (preferably those having the above-mentioned fluctuation rate) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention are spectrally sensitized with methine dyes and others so that they have color sensitivity. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes contain birapurin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic ring nucleus such as a rhodanine nucleus or a thiobarbyl nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is US Patent 2
, No. 688,545, No. 2゜977.229, No. 3,
No. 397,060, No. 3.522.052, No. 3.5
No. 27,641, No. 3,617,293, No. 3,62
No. 8,964, No. 3,666.480, No. 3. 67
2. No. 898, No. 3,679,428, No. 3,70
3゜377, 3,769,301, 3,814
．． No. 609, No. 3,837.862, No. 4°026.
707, British Patent No. 1,344,281, British Patent No. 1,50
No. 7,803, Special Publication No. 43-4936, No. 53-12
No. 375, JP-A-52-110618, JP-A No. 52-10
No. 9925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The sensitizing dye in the present invention may be added at any step up to coating the silver halide photographic emulsion on the support.

That is, it can be added at any step such as during or after grain formation of a silver halide emulsion, before or after chemical sensitization, or during the step of adding additives for preparing a coating solution. .

Furthermore, it is also possible to add the aggravating dye separately in advance to each of the monodispersed emulsions that are mixed and used in the present invention, or it is also possible to add the dye after mixing the emulsions. The former example where it is added to is more preferred.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a two-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is US Patent No. 2. 4o
7:210, No. 2.875.057, and No. 3,265.506. The use of two-equivalent yellow couplers is preferred for the present invention, and U.S. Pat.
No. 3,933,501 and No. 4,022゜620, etc., as well as Japanese Patent Publication No. 58-10739 and U.S. Patent No. 4. ．． No. 401,752, No. 4,326.024,
RD18053 (April 1979), British Patent No. 1,
No. 425,020, West German Application No. 2.219,917
No. 2. 261. No. 361, No. 2.329,
Typical examples thereof include the nitrogen atom separation type yellow couplers described in No. 587 and No. 2,433.812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness.
On the other hand, α-henzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with a lylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. No. 2゜3
No. 43.703, No. 2,600,788, No. 2,
No. 908,573, same No. 3. 062. No. 653, No. 3,152,896 and No. 3936.015
It is written in the number etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Patent No. 4,310,619
or U.S. Pat. No. 4,3
The arylthio group described in No. 51,897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
Pyrazolobenzimidazoles as described in US Pat.
(June 1984) and Research Disclosure 24230 (I
Examples include pyrazolopyrazoles described in June 1984). The imidazo(I,2-b)pyrazoles described in European Patent No. 119.741 are preferable from the viewpoint of low yellow side absorption of coloring dyes and light fastness, and European Patent No. 1
Pyrazolo [1°5-b) described in No. 19,860 (
I,2,4) Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2,474°293, and preferably U.S. Pat.
, No. 212, No. 4゜146.396, No. 4,22
Typical examples include the oxygen atom elimination type two-equivalent naphthol couplers described in No. 8,233 and No. 4,296.20'O. Further, specific examples of phenolic couplers are given in U.S. Patent Nos. 2,369,929 and 2,
, No. 801,171, No. 2,772°162, No. 2,895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention and are typically described in U.S. Pat.
72,002, a phenolic cyan coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus; US Pat. No. 2,772,162;
No. 758,308, same No. 4. 126. No. 396, No. 4,334,011, No. 4.327.173,
West German patent publication cylinder 3. 329. 729 and Japanese Patent Application No. 58-42671, etc., and U.S. Pat.
No. 446,622, No. 4,333,999, No. 4
．． 451. No. 559 and No. 4,427,767
Examples include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers include magenta couplers in U.S. Pat. No. 4,366.237 and British Patent No. 2,125,570; , 234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,415.82.
No. 0 and No. 4,080°211. Specific examples of polymerized magenta couplers are described in British Patent No. 2. 102. No. 173 and U.S. Pat. No. 4,367
．． It is described in No. 282.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more different layers using the same compound. It can also be introduced into

The coupler used in the present invention can be introduced into the light-sensitive material by an oil-in-water dispersion method. In the oil droplet dispersion method in ice, the boiling point is 1
After dissolving in either a high boiling point organic solvent of 75°C or higher and a low boiling point so-called auxiliary solvent alone or in a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. . Examples of high boiling point organic solvents are described in U.S. Pat. No. 2,322,027 and others.

Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing or ultrafiltration before use in the fabric.

Specific examples of high-boiling organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-
ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate,
dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyl dodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol) ), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N
SN-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, those with a boiling point of about 30°C or higher,
Preferably, organic solvents having a temperature of 50'C to about 160C can be used, and typical examples include ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

The steps, effects, and specific examples of latex for impregnation of latex dispersion methods are described in U.S. Pat.
, No. 541, 230, etc.

Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.1 mole for yellow couplers.
5 mole, 0°003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The photosensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid FA conductors, colorless couplers, and sulfonamides as color capri-preventing agents or color-mixing preventive agents. It may also contain phenylene derivatives, l-ol derivatives, and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
6-hydroxychromans, 5-hydroxycoumarans, spirochroman Lp-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and each of these Typical examples include ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of a compound. Also, (bissalicylaldoximado) nickel complex and (bis-N,N-dialkyldithiocarbamide)
Metal complexes such as nickel complexes can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268.593,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent the deterioration of magenta dye images, especially the deterioration caused by light, the substitution of spiroindanes as described in JP-A-56-159644 and hydroquinone diether or monoether as described in JP-A-55-89835 is recommended. chromans give favorable results.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This UV absorber may be co-emulsified with the cyan coupler.

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is usually preferably 1X10-' mol/d to 2X10-' mol/d, especially 5X10-' mol/d.
It is set in the range of m-1,5X 10-' mol/, (.

In the conventional light-sensitive material layer structure of color paper, an ultraviolet absorber is contained in one of the layers on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

The present invention, as described above, is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Further, each emulsion layer in the first stage may be made up of two or more emulsion layers having different sensitivities, and a non-light-sensitive layer may exist between two or more emulsion layers having the same color sensitivity. .

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to provide an auxiliary layer such as a back layer as appropriate.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives;
Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, and Sci.

Phot, Japan, tm16.30 page (I966)
Enzyme-treated gelatin as described in may also be used;
Furthermore, gelatin hydrolysates and enzymatically decomposed products can also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developers or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, desensitizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are Research Disclosure 1764
3 (December 1978) and 18716 (I
(November 979).

(Example) The present invention will be explained in more detail below with reference to Examples.

Example 1 Table I was placed on a paper support laminated on both sides with polyethylene.
A multilayer color photographic paper with the layer structure shown below was created. The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (a) 19.1g and color image stabilizer (b)
) 4. 4g of ethyl acetate 27.2mJ and ? Container (
c) 7.9 mj! Calo et? Understood, this? 1 volume of liquid
The mixture was emulsified and dispersed in 185 mf of a 10% gelatin aqueous solution containing 8 ml of 0% sodium dodecylbenzenesulfonate.

On the other hand, silver chlorobromide emulsion (80 mo1% silver bromide, A g 70
g/kg) of the following venereal sensitizing dyes per mole of silver chlorobromide. 90 g of a blue-sensitive emulsion containing OX 10-'mo 1 was prepared. The emulsified dispersion and emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table 1 to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution.

The gelatin hardening agent for each layer is ■-oxy-3゜5-
Dichloro-5-) riazine sodium salt was used.

The following spectral enhancers were used for each emulsion.

Blue-sensitive emulsion layer (7.OX 10”m per 1mol of silver halide)
ol addition) 5OzHNCCtHs) 3 (per 1mol of silver halide 7.OX 10”m
ol addition) Red-sensitive emulsion layer (1.OX 10-' per mol of halogenated 111mol)
mol addition) The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer: Red-sensitive emulsion FJ: )υ38
The structural formulas of the compounds used in this example, such as the 3υ French coupler, are as follows.

(a) Yellow coupler (b) Color image stabilizer (e) Magenta coupler (f) Color image stabilizer (g) 2:1 mixture of solvent H3 (weight ratio) (h) Ultraviolet absorber (i) Color mixing inhibitor 0■ H (j) Solvent (iso CJtqO) TP=0 (k) Cyan coupler Cs
A 1=1 mixture (molar ratio) of H++ (t) (I) Ultraviolet absorber H (m) Solvent This was designated as Sample A. Compound 1-2 of the present invention was added to the coating solution for the first layer of sample A! Samples B, C, and D were prepared by adding -10 and ■-23 as shown in Table 2, respectively. In addition, samples prepared by adding the compound 1-22 of the present invention to the coating solution of the first layer to the sixth layer of sample A as shown in Table 2 were prepared as E.
It was set as F.

These samples A to F were exposed to light through an optical wedge and red, green, and blue filters, and the following color development treatments (a) to (d) were performed to obtain the results shown in Table 3.

The evaluation of photographic properties was based on the results of treatment (a). In other words, the sensitivity is defined as the reciprocal of the exposure amount required to give a density equal to the minimum density plus 0.5, the sensitivity in processing (a) of each layer of each sensitive material is set as 100, and the results in other processings are calculated as 100. Expressed as a relative value to In addition, in order to evaluate color development, treatment (a) was also used as a standard. That is, the exposure amount that gave a coloring density of 1.50 in processing (a) for each layer of each sensitive material was determined, and the coloring density in each processing at this exposure amount was used as a measure of coloring property.

0 animals
α Temple ID developer
38℃ 2.0 minutes bleach-fix solution
38℃ 1.0 minute water washing 28-
35°C 3.0 minutes Alpha developer formulation) Color developer (a) Diethylenetriamine pentaacetic acid 5Na salt
2.0g benzyl alcohol
15ml diethylene glycol
lQmlNag 5off
2. OgKB
r
1. Og hydroxylamine crushed salt
3.0g4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl2 p-phenylenediamine sulfate 5.0gNag CO
3 (Ishobutton 30.0g fluorescent whitening agent (stilbene type)
Add 1.0g water to total amount
1000ml (I00O, 2) Color developer (b) Diethylenetriamine 5 vinegar g 5 Na salt
2. OgNaz SO:+
2. OgKBr
1. 0g hydroxylamine sulfate 3.0g4
-Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl] -p-phenylenediamine/stone eyebrow salt 5. OgNaz c
oa+ (I long chain 30
．． 0g fluorescent brightener (stilbene type) 1. Add 0g water to make a total of 1000m
l(I00O,2) Color developer (C) Diethylenetriaminepentaacetic acid 5Na salt
2.0g benzyl alcohol
15ml diethylene glycol
10m1Naz 503
2. OgKBr
1. 0
gHydroxylamine sulfate
3.0g4-amino-3-methyl-N-ethyl-N
-[β-(methanesulfonamido)ethyl] -p-phenylenediamine 6Fa 5.
og compound I-60,O15g Naz CO:l
30-0g fluorescent brightener (stilbene type)
Add 1.0g water to total amount
1000ml (I00
O, 2) Color developer (d) Diethylenetriaminepentaacetic acid 5Na salt
2. OgNaz Sot
2. OgKBr
1. 0g hydroxylamine sulfate 3.0g4-
Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl] -p-phenylenediamine sulfate 5.0g Compound l-6
0,015g Naz CC) + (I-chain 30.Og fluorescent brightener (stilbene type) 1
．． Add 0g water to total amount
1000ml (I00O, 2) (bleach-fix solution formulation) Thiostone FJ + 12 ammonium (54wt%)
150m1Na Z S03
15 gNH, (Fe
(n[) (EDTA))
55gEDTA・2Na
Add 4g water to make the total amount
1000ml100O,9) As is clear from the results in Table 3, general formula (I) of the present invention
It can be seen that when color development processing is carried out in the presence of the compound represented by the formula, sufficient color development can be achieved after 2 minutes of development processing, even if a color development solution from which benzyl alcohol has been removed is used.

Example 2 Unlike Example 1, the compound (I-6) added to the treatment solutions (c) and (d) was changed to (I-18)', and the amount added was 0.
Exactly the same experiment was conducted except that the sample was changed to 02g, and the same results were obtained, confirming the effectiveness of the present invention.

<Effects of the present invention> By implementing the present invention, benzyl alcohol is substantially eliminated, thereby significantly reducing the pollution load, reducing liquid preparation work, and eliminating the decrease in concentration due to cyan dye remaining in the leuco form. Can be done. Furthermore, it is possible to quickly process large quantities of color prints and dramatically improve productivity. Furthermore, according to the present invention, color prints with good color development and high contrast can be obtained even when processing is performed for a short time of 2 minutes and 30 seconds using a color developer that does not substantially contain benzyl alcohol. .

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing a color coupler provided on a reflective support is subjected to imagewise exposure, and is then subjected to imagewise exposure. A color image forming method comprising processing in the presence of a compound with a color developer substantially free of benzyl alcohol for a development time of 2 minutes and 30 seconds or less. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z represents an atom or atomic group necessary to form a heterocycle. , represents a branched or cyclic alkyl group, or a substituted or unsubstituted aryl group.R is a substituted or unsubstituted linear, branched or cyclic alkyl group, or a substituted or unsubstituted aryl group represents an anion, and may be linked to a substituent represented by Z, G or R to form intramolecular betaine. n is 1, 2 or 3
represents. However, at least one of the substituents represented by Z, G, or R is substituted with at least one sulfo group or carboxyl group. )