JPS62175744A - Color image forming method - Google Patents

Abstract

PURPOSE:To obtain the excellent color image for a short period by processing a photographic sensitive material contg. a specific compd. according to a prescribed operation, substantially without using benzyl alcohol. CONSTITUTION:The titled method lies in developing the silver halide color photographic sensitive material which forms a photographic layer contg. the compd. shown by the formula on a substrate, with a color developer which does not substantially contain benzyl alcohol for <=2.5min, after exposing it. In the formula, R2 and R3 are each 4-24C a hydrophobic group, L3 is a bivalent binding group, (m) is 0-5, X is a group contg. a quaternary nitrogen atom, L4 is a bivalent linking group. The surface active agent shown by the formula can be jointly used with a so-called anionic surface active agent and/or nonionic surface active agent. Thus, the load about a pollution is reduced, and the preparation of the developer is simplified by using substantially no benzyl alcohol. The lowering of the optical density of an image due to restricting a cyan coloring matter to leuco base is reduced.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a color image forming method using a silver halide color light-sensitive material, and in particular to a color image forming method that does not use benzyl alcohol and has a shortened processing time. Regarding.

<Prior Art> In order to form a color photographic image, photographic couplers of three colors, yellow, magenta and cyan, are contained in a photosensitive layer, and after exposure, the layer is processed with a color developing solution containing a color developing agent. In this process, the oxidized product of the aromatic primary amine undergoes a coupling reaction with the coupler to give a colored dye, but in this case, it is necessary to give as high a color density as possible within the limited development time. It is.

To obtain high color density, use couplers with as high a coupling rate as possible, or couplers that are easily developed and
This is usually achieved by using a silver halide emulsion with a large amount of developed silver per unit coating amount or by using a color developing solution with a high development speed.

(Problems to be Solved by the Present Invention) In order to speed up the development of a silver halide emulsion, it is easy to think of increasing the silver chloride content of the silver halide, but as the silver chloride content increases, the sensitivity decreases. It has the disadvantage that it tends to deteriorate and cause fogging. Further, in order to increase the amount of developed silver, it is possible to increase the above-mentioned silver chloride content or to strengthen chemical sensitization, but this also has the disadvantage that fog is likely to occur. Reducing the grain size of the silver halide emulsion is also a means of speeding up development, but it has the fatal drawback of decreasing sensitivity. A method using a silver chloride emulsion is described, for example, in JP-A-58-953.
No. 45, No. 59-232342 and No. 60-191
No. 40, however, the fog is high and it is not suitable for practical use.

On the other hand, various measures have been conventionally taken regarding color developing solutions to speed up development. Among them, various additives have been studied in order to accelerate the penetration of the color developing agent into the color coupler-dispersed oil droplets and promote color development.In particular, a method of adding benzyl alcohol to the color developer to accelerate color development has been proposed. Because of its great color development promoting effect, it is currently widely used in the processing of color photographic materials, especially color papers.

However, when benzyl alcohol is used, diethylene glycol, triethylene glycol, alkanolamine, etc. are 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, for the reasons mentioned above, it is preferable not to use benzyl alcohol. Conventionally, color development has generally been processed in 3 to 4 minutes, but recent advances have shortened the finishing delivery time and reduced laboratory work. There has been a desire to shorten 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.

Methods of incorporating 3-pyrazolidones (e.g., JP-A-60
No. -26338, No. 60-158444, No. 60-1
Even if the method described in No. 58446 is used, there are disadvantages in that the sensitivity decreases at the time of the main peak 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
No., JP-A-56-6235, JP-A No. 56-16133,
Even if the method described in Japanese Patent No. 57-97531, Japanese Patent No. 57-83565, etc. is used, it is not an appropriate method because it has drawbacks such as slow color development and fogging.

As described above, no method has been found for obtaining sufficient color images in a short time using a color developing solution that does not substantially contain benzyl alcohol.

(Means for solving the problem) The object of the present invention was achieved by the method described below.

After exposure, a silver halide color photographic light-sensitive material having a photographic layer containing a compound represented by the following general formula provided on a support is processed for up to 2 minutes and 30 seconds using a color developer that does not substantially contain benzyl alcohol. A color image forming method characterized by time-consuming development processing.

General formula (13 Rz and Rx each represent a hydrophobic group having 4 to 24 carbon atoms; L3 represents a divalent linking group; m is O to 5; X is a group containing a quaternary nitrogen atom; Yes, L4 represents a divalent linking group.

Here, "containing substantially no benzyl alcohol" means that the concentration of benzyl alcohol in the developer is 0.5.
It means less than or equal to m 1 / It. Preferably, the developer does not contain benzyl alcohol.

Preferred specific examples of the compounds of the present invention are listed below.

X゛ Engineering = ○-0-be　　　　　　　0-○-00z −Engineer engineering ＾　　　D B 　　　　0 ′　　　　1 ″　　　　0 :el:! : 0-Q-be” engineering B .

1 Jinichiv The surfactant represented by the general formula (1) used in the present invention can be used not only alone but also in combination with other surfactants. In some cases, it may be preferable to use them in conjunction with certain other surfactants rather than using them alone.

The surfactant of general formula (I) used in the present invention can be used in combination with any anionic surfactant and/or nonionic surfactant.

The anionic surfactant has a hydrophobic group having 8 to 30 carbon atoms in one molecule and -3O, M or -03
It is preferable to use a compound having a 03M group (M has the same meaning as in (1) above). This type of compound is described in "Synthesis and Application of Surfactants" by Ryohei Oda and Hiroshi Teramura.
(Maki Shoten edition) and A, W. Perry, “Surface Active Agents (Surface A
active Agents)J(Interscie
nce Publications Inc., New
York).

As the above-mentioned nonionic surfactant, JP-A-48-30
It is preferable to use the nonionic surfactant and fatty acid ester surfactant of polyhydric alcohol described in No. 933. The fatty acid ester surfactant of polyhydric alcohol has at least two hydroxyl groups, preferably at least three hydroxyl groups. Preferably, the fatty acid has 6 to 25 carbon atoms. Specifically, a sorbitan fatty acid ester nonionic surfactant described in US Pat. No. 3,676,141 is advantageously used in the present invention.

Specific examples of the anionic surfactant include the following compounds.

(A I) C+ zllgsOsOJa(A
-2) C+ 5HtqO5O3Na (A-3)
Funnel oil (A 4) C+ JzsCONHCHzCH
zO5OJa(A 5 ) C+ zHz5sO
Ja(A 6 ) C+ 411zvsOJa(
A8) Na03S CHC00CJ l
? ■ C1h COOCsfltt In the present invention, at least one type of surfactant of the general formula (1) used in the present invention contains a hydrophobic group having 8 to 30 carbon atoms and a -3O, M or -3o1M group in one molecule. (M has the same meaning as in (I) above) and/or at least one type of sorbitan fatty acid ester nonionic surfactant are used in combination. This is especially preferable.

In the present invention, the coupler must be heated and melted or dissolved in an organic solvent to make it liquid before the emulsification operation. Compounds that can be directly emulsified by melting are limited to compounds with a melting point of about 90°C or less.

As the organic solvent (ie, so-called oil) used to finely disperse the coupler in the aqueous medium, it is useful to use one that is virtually insoluble in water and has a boiling point of 190° C. or higher at normal pressure. Organic solvents of this type can be selected from carboxylic esters, phosphoric esters, carboxylic amides, ethers, substituted hydrocarbons. Specific examples include di-n-butyl fucuric acid ester, di-isooctylfural ester, dimethoxyethylphthal ester, di-n-butyl adipate,
Diisooctyl azelenate, tri-n-butylphthalate, butyl laurate, di-
n-sebacic acid ester, tricresyl phosphate,
Tri-n-butyl phosphate, triisooctyl phosphate, N7・N-diethylcaprylic acid amide, N-
N-dimethylpalmitic acid amide, n-butyl-m-pentadecyl phenyl ether, ethyl-2.4-ter
Examples include t-butylphenyl ether and chlorinated paraffin.

In the present invention, in addition to such a solvent, it is advantageous to use a low boiling point solvent (boiling point below 130° C. at room pressure) or a water soluble high boiling point solvent in order to dissolve the coupler. Sometimes. For example, propylene carbonate, ethyl acetate, butyl acetate, ethyl propionate,
5ec-butyl alcohol, tetrahydrofuran, cyclohexanone, dimethylformamide, diethyl sulfoxide, methyl cellosolve, etc.

As the emulsification device used to carry out the present invention, one that applies a large shearing force to the processing liquid or one that applies high-intensity ultrasonic energy is suitable. In particular, emulsifying devices having a colloid mill, a homogenizer, a capillary emulsifying device, a liquid siren, an electrostrictive ultrasonic generator, and a Pohlmann whistle can give good results.

The photographic layer containing the surfactant of general formula (1) used in the present invention is preferably a silver halide emulsion layer and/or a layer adjacent thereto, and particularly preferably a silver halide emulsion layer.

The amount of the surfactant of the general formula (I) used in the present invention depends on the type of coupler used, the type of other additives coexisting, the type and amount of the dispersion solvent, and in some cases, the amount of the surfactant used in combination with other surfactants. Although it varies depending on the type and amount of the activator, it is generally 0.2 to 50% by weight of the dispersion material (i.e., a solution of couplers and other oil-soluble photographic additives dissolved in a dispersion solvent).

As substances that coexist with the coupler, oil-soluble photographic additives such as anti-fading agents, ultraviolet absorbers, DIR couplers, and antioxidants can be included.

The "reflective support" used in the present invention refers to 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, polyethylene coated paper, polypropylene synthetic paper, transparent supports with reflective layers or reflective materials, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide There are films, polycarbonate films, polystyrene films, etc., and these supports can be appropriately selected depending on the purpose of use.

Next, a processing step (image forming step) in the present invention will be described.

The color development processing step in the present invention has a short processing time of 2 minutes and 30 seconds or less. The preferred treatment time is 1 to 2 minutes. The processing 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 next bath, and includes the transit 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 typical 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-toluene Examples include sulfonate, tetraphenylborate Lp-(t-octyl)benzenesulfonate, and the like.

Examples of aminophenol derivatives include 〇-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 Processing Chemistry" by F. A. Meson, Focal Press (
(1966) (L, F, A.

Mason, “Photographic Processes
sing Chemistry”.

Focal Press) pages 226-229, U.S. Patent 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 may be used in combination.

The processing temperature of the color developer in the present invention is 30°C to 5°C.
The temperature is preferably 0°C, 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
03, U.S. Pat. No. 3,171.247, various birimidium compounds and other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, and Japanese Patent Publication No. 1986-930.
No. 4, U.S. Patent No. 2,533.990, U.S. Patent No. 2,531.
No. 832, No. 2,950.970, No. 2.577.1
Nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in No. 27, US Patent No. 3
, 201.242, and other compounds described in JP-A-58-156934 and JP-A-60-220344.・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 photosensitive material during processing and may accumulate in the color developer.

In addition, the color developer in the present invention may contain pH buffering agents such as alkali metal carbonates, borates or phosphates; hydroxylamine, triethanolamine, as described in OLS No. 2622950; preservatives such as compounds, sulfites or bisulfites; organic solvents such as diethylene glycol; dye-forming couplers;
Competitive couplers; nucleating agents such as sodium boron hydride; auxiliary developers such as 1-phenyl-3-pyrazolidone; tackifiers; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxy Aminopolycarboxylic acids such as methylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and the compounds described in JP-A-58-195845, 1-hydroxyethylidene-1,1'-diphosphonic acid, research・Disclosure (Research Disclosure)
sure) 1'1h18170 (May 1979), organic phosphonic acid, aminotris (methylenephosphonic acid), ethylenediamine-N, N, N", N"
- aminophosphonic acids such as tetramethylenephosphonic acid,
JP-A-52-102726, JP-A No. 53-42730,
No. 54-121127, No. 55-4024, No. 55
-4025, 55-126241, 55-6
No. 5955, No. 55-L65956, and Research Disclosure (Research Disc.
losure) Na No. 18170 (May 1979)
It may contain a chelating agent such as the phosphonocarboxylic acid described in 1).

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 that can be used include compounds of polyvalent metals such as iron (III), cobalt (■), chromium (■), and copper (n), peracids, quinones, and nitroso compounds. for example,
Ferricyanide, dichromate, organic complex salts of Fe(III) or Kobal) (III), amino acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propatoltetraacetic acid Complex salts of polycarboxylic acids or organic acids such as citric acid, tartaric acid, and malic acid; persulfates, manganates, and nitrosophenols can be used. Among these, potassium ferricyanide, sodium iron(III) ethylenediaminetetraacetate, ammonium iron(III) ethylenediaminetetraacetate, ammonium iron(III) triethylenetetraminepentaacetate, and persulfates are particularly useful. Ethylenediaminetetraacetic acid iron(III) complex salts are useful in both stand-alone bleach solutions and -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, (1
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.

Furthermore, various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can be added as membrane pH adjusting agents after treatment.

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 four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the coloring dye has adequate diffusivity, colorless couplers, or DfR 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 U.S. Patent No. 2.40
No. 7,210, No. 2,875.057 and No. 3
．． No. 265,506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
Same No. 3.933.501 and No. 4,022゜62
The oxygen atom separation type yellow coupler described in No. 0, Japanese Patent Publication No. 58-10739, and U.S. Patent No. 4.
No. 401.752, No. 4.326.024, RD1
8053 (April 1979), British Patent No. 1.425
, No. 020, West German Application No. 2,219,917, No. 2. 261. No. 361, No. 2,329.587
Typical examples thereof include the nitrogen atom separation type yellow couplers described in No. 1, No. 2, 433.812, and the like. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness;
- Benzoylacetanilide 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 an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and representative examples thereof include U.S. Pat. Same 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. Pat.
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, US Patent No. 3.
369.879, preferably pyrazolo(5,1-c)(1,2,4) l-lyazoles as described in U.S. Pat. 24220
(June 1984) and Research Disclosure 24230 (1)
Examples include pyrazolopyrazoles described in June 1984). Imidazo(1,2-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 (
1,2,4)) Riazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers. 474°293, preferably the naphthol couplers described in U.S. Patent No. 4,05
No. 2,212, No. 4゜146.396, No. 4.2
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 28,233 and No. 4.296.200. Further, specific examples of phenolic couplers are given in U.S. Pat.
, No. 801,171, No. 2,772°162, No. 2,895.826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. 3.7.
72,002, a phenolic cyan coupler having an alkyl group greater than or equal to an 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 No. 3. 329. 729 and Japanese Patent Application No. 58-42671, and the 2,5-diacylamino substituted phenolic couplers described in U.S. Patent No. 3.
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-diffusing couplers are 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 are used in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material.
The above may be used in combination, or the same compound may be introduced into two or more different layers.

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 light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamide phenols as color-fogging inhibitors or color-mixing inhibitors. It may also contain derivatives and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. As anti-fading agents, hydroquinones, 6-hydroxychroman 1,5-hydroxycoumarans, spirochroman'14, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex 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 deterioration of the agenta dye image, especially deterioration caused by light, the substitution of spiroindanes 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 set in the range of 1X10'' mol/d to 2X10-' mol/rd, particularly 5X10-' mol/rd-1, 5x 10-' mol/d.

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 of the first emulsion layers may be made up of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same 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 sulfate esters, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

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

Phot, Japan, N116.30 pages (1966)
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, plasticizers, 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 (1
(November 979).

The silver halide emulsion used in the present invention is silver bromide, silver chlorobromide, or silver chloride that does not substantially contain silver iodide, and the silver halide preferably used contains 2 to 80 mol% of silver chloride. Contains silver chlorobromide.

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.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or nearly spherical particles, the particle diameter is the particle size, and in the case of cubic particles, the particle size is the particle size, and the particle size is the average particle size based on the projected area) is preferably 2μ or less and 0.1μ or more, but it is particularly preferable. is 1μ or less 0.15μ
That's all. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is 20.
It is preferred to use so-called monodispersed silver halide emulsions within 15%, particularly preferably within 15%. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably one with a variable 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 shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), 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 in which tabular grains having a length/ff ratio of 5 or more, particularly 8 or more, account for 50% or more of the total projected area of the grains may be used.

An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be of 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 Grafkides.

Chimie et PhysiquePhoto
graphique (published by Pau1Monte1, 1
967)], Duffin, “Photographic Emulsion Chemistry J (G.
Photography by F. Duf in
c Emulsion Chemistry (Foc
al Press, 1966)], Zelikman et al. [Photographic Emulsion Production and Coating J (V, L, Zelik
Making and Co by man etal
atingPhotographic Emulsi
on (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 form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be 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 for ripening and chemical ripening. In order to remove soluble root salts from the emulsion after physical ripening, washing with water, flocculation sedimentation, ultrafiltration, etc. are performed.

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 salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal Compounds (for example, in addition to gold complex salts, P tl 1 rlPds Rh
A noble metal sensitization method using complex salts of metals of group (I) of the periodic table such as 5Fe can be used alone or in combination.

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

The blue-sensitive, green-sensitive and red-light emulsions of the present invention are spectrally sensitized with methine dyes and other dyes so as to 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, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus 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 Nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like 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,
397.060, 3.522.052, 3.5
No. 27,641, 3.617. -293 No. 3, 6
No. 28,964, No. 3,666.480, No. 3. 6
72. No. 898, No. 3,679,428, No. 3,7
03゜377, 3,769,301, 3,81
4.609, 3,837.862, 4゜026
．． 707, British Patent No. 1,344.281, 1,5
No. 07.803, Special Publication No. 43-4936, No. 53-1
No. 2375, JP-A-52-110618, JP-A No. 52-1
No. 09925.

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.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example I.

3 ethyl acetate to 24.0 g of yellow coupler (Y-1)
5 ml and 1 ml of diptyl phthalate as solvent
was added and dissolved, and using this solution as an emulsifying dispersant, a 12% gelatin aqueous solution containing the following comparative compound R-1 (dibutylnaphthalene sulfone solution I Qmf 160mj7
and emulsified and dispersed using a high-speed stirrer.

The entire amount of this emulsified dispersion was added to a silver chlorobromide emulsion (containing 70 g/kg of Ag) consisting of 80% Br, and paper laminated on both sides with polyethylene so that the amount of silver coated was 0.31 g/rrr. A comparative sample (A) was prepared by coating the sample on a support and providing a gelatin layer on top of this coated layer.

Next, samples (B) to (R) were prepared as follows.

Exemplary compound I of the present invention was used together with R-1 as an emulsifying dispersant for sample preparation.
The same sample as sample (A) except that 0.3 g of R-1 was used as an emulsifying and dispersing agent.
The same sample as sample (A) was used except that 0.3 g of -3 was further used.
The same sample as sample (A) was used except that 0.3 g of -4 was further used.
Example compound 1 of the present invention together with R-1 as an emulsifying dispersant and sample (A) except that 0.3 g of -5 was further used.
The same sample as sample (A) except that 0.3 g of -6 was further used, and yellow coupler (Y-1) of samples (A) to (F).
Instead, samples CG) to (L) and (M) to (R) were created using magenta coupler <M-1) and cyan coupler (C-1).

When a magenta coupler is used, the coating amount of the coupler is 0.37 g/rrr, and the coating amount of silver in a silver chlorobromide emulsion consisting of 75 mol% Br is 0.37 g/rrr. 20g/rrr,
The amount of cyan coupler applied was 0.33g/rrr.

The silver coating amount of the silver chlorobromide emulsion consisting of 1% B r 70mo was set to 0.28 g/rrr.

Y-1 SO3Na These samples were given a stepwise exposure for sensitometry. Thereafter, experiments of treatments A and B were conducted using color developing solutions (A) and (B) as shown below.

The contents of treatments A and B are distinguished by the difference in the contents of color developing solutions (A) and (B), and the contents of other treatment steps are the same for both A and B.

(Processing month / (warm)
@Ouu developer 38℃ 2.0 minutes Bleach-fix solution ・33℃ 1.5 minutes Washing with water 28-35℃ 3.0 minutes Alpha developer formulation) Color developer (A) Diethylenetriamine pentaacetic acid 5Na salt
2.0g benzyl alcohol
15m1 diethylene blade call
10m1 Nat SO32, Og KBr
O, 5g hydroxylamine sulfate
3.0g4-amino-3-methyl-N
-ethyl-N-[β-(methanesulfonamide)ethyl J
Ri-p-phenylenediamine sulfate
5. OgNag Cox (1 water tK)
30.0g fluorescent brightener (Stilbeth'iJ) Add 1.0g water to make a total of 1000m
l(plooO,1) Color developer (B) Diethylenetriaminepentaacetic acid 5Na salt
2. OgNap Sow
2. OgKBr
O, 5g hydroxylamine sulfate m 3.0g 4-amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-phenyl diamine sulfate 5. OgNag CO3 (17
) diD 30. 0
g Fluorescent brightener (stilbene type)
Add 1.0g water to total amount
1000ml (100O, 1) (bleach-fix solution Shinkoma ammonium thiosulfate (54wt%)
150m11'Jaz SO315g NH,rFe (III) (EDTA))
55gEDTA・2Na
Add 4g water to make a total volume of 1000ml10
0O, 9) The evaluation of photographic properties is based on the maximum density (Dmax) and the minimum density (Dmax).
This was done using two items: n+in). The results are shown in Table 1.

From the results in Table 1, it can be seen that regardless of whether yellow coupler, magenta coupler, or cyan coupler is used, the sample of the present invention has a higher maximum concentration than the comparative sample, and even treatment B, which does not contain benzyl alcohol, has almost the same color development as treatment A. It can be seen that this shows that

Example 2 Comparative multilayer color photographic paper (A) having the layer structure shown in Table 2 was prepared on a paper support laminated on both sides with polyethylene.

The coating liquid was prepared as follows.

-Amount of weight.

Yellow coupler (a) 19.1g and color image stabilizer (b)
) Ethyl acetate 27.2ffW to 4.4g! and solvent (c
)7.9rrl was added and dissolved, and this solution was used as an emulsifying dispersant to add 10% sodium dibutylnaphthalene sulfonate (
R-1) 12mj! 10% gelatin aqueous solution containing 1
85 mA' and emulsified and dispersed using a continuous stirrer to obtain an emulsified dispersion.

On the other hand, silver chlorobromide emulsion (silver bromide 80 mol%, silver 70 g/
kg gold-containing blue-sensitive sensitizing dye shown below in silver chlorobromide
Per mole? , 0.times.10-' mol was added to prepare a 90 gm blue-sensitive layer emulsion.

The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table 2 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 1-oxy-3゜5-
Dichloro-5-1-riazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer (per 1 sol of silver halide 7. OX 10-'s
ol addition) (per halogenated jllsol 7. OX
1. OX l O
-'mol addition) The following dyes were used as anti-irradiation dyes in each emulsion layer.

The structural formulas of the compounds used in this example, such as couplers, are as follows.

(a) Yellow coupler (b) Color image stabilizer (e) Magenta coupler (f) 2:1 mixture (weight ratio) of color image stabilizer (h) Ultraviolet absorber (i) Color mixing inhibitor (j) /8 Medium (iso C911190) TP=0 (k) Cyan coupler CsH
+ t (t) ff (1) Ultraviolet absorber H (m) Solvent Next, photosensitive materials (B) to (D) were prepared as follows.

Once in the 1st, 3rd and 5th layers of the photosensitive material (A), 0% of the exemplary compound I-1 of the present invention was added together with R-1 as an emulsifying and dispersing agent.
．． Exemplary compound 1 of the present invention was added to the photosensitive material (A) as an emulsifying dispersant together with R-1 in the 1st, 3.5th layer of the photosensitive material (A), except that 36g was further used. -3 to 0
．． 36g of the same photosensitive material as photosensitive material (A) except that 36 g of the same as photosensitive material (A) was added. 5 to 0
．． 36g of the same photosensitive material as photosensitive material (A) except that a photosensitive layer (Fuji Photo Film Co., Ltd. F
WH type, color temperature of light source 3,200°K)
Gradation exposure for sensitometry was provided through green and red filters. The exposure at this time was carried out so that the exposure time was 0.5 seconds and the exposure amount was 250 CMS.

After this, use color developing solutions (A) and (B) as shown below.
Experiments for treatments A and B were conducted using the following.

The processing consisted of the steps of color development, bleach-fixing, and washing with water, and the photographic properties were evaluated by changing the development time to 1 minute, 2 minutes, and 3 minutes. The contents of treatments A and B represent the differences between the color developing solutions A and B, and the other treatment contents are the same for both A and B.

Photographic properties are evaluated based on relative sensitivity, gradation, maximum density (Dmax
), minimum concentration (Dmin).

The relative sensitivity is a relative value based on 100, which is the sensitivity when the color development time in Process A of each photosensitive layer of each photosensitive material is 2 minutes. Sensitivity was expressed as a relative value of the reciprocal of the exposure amount required to provide the minimum density plus 0.5. The gradation was expressed as the density difference from the sensitivity point to the point where the logarithm of the exposure amount (6 layers gE) increased by 0.5.

The results are shown in Table 3.

(1 fetus treated (temperature
(Time r1H developer 38℃ 1.0~3.0
Bleach-fix solution 33℃
1.5 minutes water washing 28-35℃ 3.0
Color developer (A) Diethylenetriaminepentaacetic acid 5Na salt
'1. Qg benzyl alcohol
15ml diethylene glycol
10mINaz SO32, Og KBr
O, 5g hydroxylamine sulfate
3.0g4-amino-3-methyl-N-
Ethyl-N-[β-(methanesulfonamido)ethyl]
-p-phenylenediamine sulfate 5. OgNazCO
z (monohydrate salt) 30
．． 0g fluorescent brightener (stilbene type)
Add 1.0g water to total amount
1000ml color developer (B) diethylenetriaminepentaacetic acid 5Na salt
2. OgNaz so:l
2. OgKBr
0. 5g hydroxylamine sulfate 3.0g4-
Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]-p-phenylenediamine sulfate5. OgNat CO3 (monohydrate)
30.0g fluorescent brightener (stilbene type) Add 1.0g water to make a total of 1000m
l (100O, 1) (Bleach-fix solution formulation) Ammonium 1000 sulfate (54wt%)
150m1 NatSOs
15gNHa (F e (II
I) (EDTA) ) 5
5gEDTA・2Na
Add 4g water and chop with fins.
As is clear from Table 3, the photosensitive materials (B) to (D) of the present invention are different from the comparative photosensitive material (A).
), it can be seen that the difference in photographic properties in Process B is small in terms of relative sensitivity, gradation, and maximum density, and Process B, which does not contain benzyl alcohol, shows performance comparable to Process A.

Further, the light-sensitive materials (B) to (D) of the present invention exhibited good photographic properties even in Process B, which did not contain benzyl alcohol, with a developing time of 2 minutes.

Effects of the present invention> By implementing the present invention, benzyl alcohol is substantially eliminated, reducing the pollution load and reducing liquid preparation work.
It has the effect of eliminating the decrease in density caused by cyan dye remaining as a leuco body. Further, by using the silver halide emulsion of the present invention, even if benzyl alcohol is eliminated, Dyaax is high, Dmin is low, and photographic properties with little change in sensitivity and gradation can be obtained.

1. Indication of work by jS Patent Application No. 18484 of 1988 2. Name of the invention Color image forming method 3. Person making the amendment 4. Agent 6. Number of inventions increased by the amendment 2 07. Amendment Target: Particulars Old procedure amendment letter Z 9, 1986

Claims (1)

[Scope of Claims] After exposure, a silver halide color photographic light-sensitive material having a photographic layer containing a compound represented by the following general formula provided on a support is processed using a color developer substantially free of benzyl alcohol. A color image forming method characterized by developing in a time of 2 minutes and 30 seconds or less. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ R_2 and R_3 each represent a hydrophobic group having 4 to 24 carbon atoms. L_3 represents a divalent linking group, m is 0 to 5
It is. X is a group containing a quaternary nitrogen atom. L_4 is 2
represents a valent linking group.