JPS63128341A - Direct positive color image forming method - Google Patents

Abstract

PURPOSE:To improve color forming efficiency of a coupler and to decrease the amt. of the silver to be used by using a restoring agent for the oxidant of an arom. primary amine color developing agent and a color developing soln. of <=11.5pH provided with a capturing agent for the oxidant of the restoring agent for color development. CONSTITUTION:A photosensitive material having at least one photosensitive photographic emulsion layer contg. internal latent image type silver halide particles which are not previously fogged and a color coupler on a base is subjected to imagewise exposure then to the color development under the fogging exposure applied thereto prior to or during the development; further, said material is subjected to processing using bleach fixing and stabilizing or rinsing baths. The color development is processed by using the restoring agent for the oxidant of the arom. primary amine color developing agent and the color developing soln. of <=11.5pH provided with the capturing agent for said oxidant. Since the efficient use of the color developing agent is thereby permitted, the color forming efficiency of the coupler is high and the amt. of the silver to be used is decreased.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to an image forming method for directly obtaining a positive color image.

BACKGROUND OF THE INVENTION Photographic methods that provide direct positive images without the need for reversal processing steps or negative film are well known.

Conventionally, the methods used to create positive images using direct positive silver halide photographic light-sensitive materials can be divided into two main types, excluding special methods, considering their practical usefulness. I can do it.

The seven types use a silver halide emulsion that has been fogged in advance, and create a direct liquid positive image after development by destroying the fogging nuclei (latent image) in the exposed area using solarization or Burschel effect. It's something you get.

The other seven types use a non-fogged internal latent image type silver halide emulsion and directly obtain a positive result by performing full surface development after image exposure and fogging treatment, or while performing fogging treatment. be.

The above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion that has photosensitive nuclei mainly inside the silver halide grains and a latent image is mainly formed inside the grains upon exposure. Refers to emulsion.

This latter type of method generally has higher sensitivity than the former type of method and is suitable for applications requiring high sensitivity, and the present invention relates to this latter type of method.

Various techniques are known to date in this technical field. For example, US Patent No. ms+z92゜230, US Patent No. 2. ≠JJ, ri No. 17, same No. 2゜4 #7.17! issue,
Same No.-, JRR, No. 912, No. 3, 3/7, 322
No. J, 7J1. , 2JJ No. 3.7AI, 2
No.7A, samey, 3,7riA,! No. 77 and British Patent No. t,lz1.3z3, No. 1.1. ! 10. ! ! 3
No., same'av,.

/ / , as stated in each specification etc. of No. 062.
The main ones are:

By using these known methods, it is possible to produce direct positive type photographic materials with relatively high sensitivity.

For details of the direct positive image formation mechanism, for example,
The Theory of the Photographic Process by T. H. James
f The Photographic Process
) 7th edition, Chapter 7, pages 12 to 3, and U.S. Patent No. 3.7
t/, 27 is described in the issue etc. according to it,
produced inside the silver halide by the first imagewise exposure,
Due to the surface desensitization effect caused by the so-called internal latent image, fogging nuclei are selectively generated only on the surface of the silver halide grains in the unexposed areas, and then a normal so-called surface development treatment is performed to remove the unexposed grains. It is believed that a photographic image (direct positive image) is formed in the exposed area.

As mentioned above, as a means for selectively generating fogging nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called "photofogging method" (for example, British Patent No. 1./!1.
3t3) and a nucleating agent (n
A method using a nucleating agent is known. This latter method is discussed, for example, in Research Disclosure.
Closure) Magazine Volume 1!7, AI! /12(/9
7A/January issue), pages 7z to 7r.

To form a full positive color image directly, the internal latent image type silver halide photosensitive material is subjected to fogging treatment, or surface color development treatment is performed while fogging treatment is applied, and then bleaching and fixing (or bleach-fixing) are performed. can be achieved. After the bleaching and fixing treatments, washing and/or stabilizing treatments are usually performed.

[Problems to be solved by the present invention]

Various methods have been used to increase the development speed and coloring speed of color developers. Among these, in order for the color developing agent to finally couple with the coupler to form a dye, it is necessary for the color developing agent itself to be incorporated into the coupler-dispersed oil droplets. Various additives are known as additives that promote color development. Benzyl alcohol is known to have a particularly large effect of promoting color development, and has been used in the processing of various color photographic materials.

And it is still widely used today.

Although benzyl alcohol is soluble in water to some extent, its solubility is poor, and in order to increase solubility, diethylene glycol, triethylene glycol alcohol, or alkanolamines are widely used.

However, these compounds and benzyl alcohol itself have a large pollution load when treated as wastewater, resulting in high BOD and COD values, and despite the advantages of improved color development and solubility as mentioned above, figure,
From the point of view of wastewater treatment, it has been desired to reduce or eliminate benzyl alcohol.

Furthermore, even when a solvent such as the above-mentioned diethylene glycol is used, the solubility of benzyl alcohol is still insufficient, resulting in a burden of labor and time for preparing a developing solution.

In addition, if benzyl alcohol is carried into the subsequent bleach bath or bleach-fix bath with the developer and accumulates, leuco bodies may be formed depending on the type of cyan dye, causing a decrease in color density. . Furthermore, the accumulation of these substances makes it insufficient to wash out the developer components, especially the color developing agent, in the water washing process, resulting in deterioration of image storage properties due to their remaining (such as fading of color images and the occurrence of stains due to exposure to heat). ) was also seen to cause

From these various viewpoints, it is desired to reduce or eliminate benzyl alcohol from color developing solutions.

While the color laboratory industry is currently facing these problems, there is also a strong demand for shortening print finishing delivery times, and there is also a pressing need to shorten processing times.

However, it is clear that if benzyl alcohol is removed from the color developer and the development time is completely shortened, the developed r - color density will be significantly lowered by 1 degree, and these requirements cannot be met at the same time using conventional techniques. I'i
,do not have.

In particular, it is applicable to minilab systems that have recently been developed, and because photographs and copies can be obtained at low cost anytime and anywhere, the amount of drainage is small, and there is less concern about environmental pollution (as mentioned earlier). There is a need for the development of direct positive color imaging systems.

In addition, even if a color developing solution containing benzyl alcohol is required, the conventional direct positive color image forming method cannot achieve faithful color reproduction.Also, the finished quality of color images is poor due to large variations in development. Not only that, but the quick and easy processing time is faster than 3 minutes and 30 seconds.

Therefore, the first object of the present invention is to provide a method for forming direct positive color images with good finishing quality through rapid processing. Another object of the present invention is to provide a direct positive color image forming method that improves the coloring efficiency of the 21C coupler and reduces the amount of silver used.

A third object is to provide a direct positive color image forming method of the so-called 6 water-saving type, which has less concern about environmental pollution and requires less liquid waste.

As a result of extensive research, the present inventors have found that the above-mentioned objects include at least one light-sensitive photographic emulsion layer containing internal latent image type silver halide grains that have not been fogged in advance and a color coupler on a support. After the photosensitive material is imagewise exposed, it is subjected to color development by applying fogging exposure prior to or during development, and then subjected to bleach-fixing and processing using a stabilizing bath or a washing bath to directly form a positive color image. In the method, the color development is carried out at pH/1. j
Processing is performed using the following color developing solution, and more preferably, the bleach-fixing is performed using the following element B (B-1.B-co or B-3).
It has now been discovered that a pH of -10 having at least one of the following can be effectively achieved by a direct positive color imaging process featuring treatment with a PR bleach-fix solution.

-IO's λ- Element: Contains a restoring agent for the oxidized form of an aromatic primary amine color developing agent and a scavenging agent for the oxidized form of this restoring agent,
Preferably, it substantially contains hydroxylamine and benzyl alcohol.

Element B: B-/: Containing iron (DI) complex salt of ethylenediaminetetraacetic acid, B-J Iron (nl) of diethylenetriaminepentaacetic acid
containing complex salts, or B-3: iron (III) of cyclohexanediaminetetraacetic acids;
) Contains complex salts.

The above water washing bath contains the following elements C (C-1.C-2 or C-
It is preferable to have at least one of 3).

Element C: C-t: Contains no calcium or magnesium ions, or! C-2: Contains a chelating agent of calcium ions and/or magnesium-//- ions, or C-3: Contains at least one of inthiazolines. have

Next, the features of the present invention will be explained.

The first characteristic of the invention lies in the color developer. The color developing solution generally used in the development of color photosensitive materials is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, but p-phinidinediamine compounds are preferably used, and representative examples thereof include 3-methyl-guamino-N,N-diethylaniline, 3- Methyl-≠-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-guamino-
N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-μmamino-N-ethyl-N-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, and p-)luenesulfonates.

These diamines are generally more stable in their salt form than in their free form, and are therefore preferably used.

Furthermore, alkali metal carbonates, borates or -l 2
- It generally contains pH buffering agents such as phosphates, development inhibitors such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds, and antifoggants. be. Also, if necessary,
Preservatives such as sulfites, organic solvents such as triethanolamine, diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, color forming couplers, competitive couplers, sodium boron hydride, etc. Nucleating agent, l-phenyl-3-
Auxiliary developers such as pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, West German patent application ((JLS) No. 2. Antioxidants and the like described in No. 1 and 2. Rito are added to the color developing solution.

-l -? M 1-1 In the color development process according to the present invention, the l-electron oxidized product of the color developing agent oxidized by the development nuclei on the photosensitive silver halide grains formed in the photofogging step is oxidized by the coexisting color coupler. Coupling reaction occurs. The two-electron oxidized product of the color developing agent that is formed as a by-product or due to air oxidation is
The restoring agent restores the original color developing agent very efficiently. In this reaction, the oxidized restorative agent is returned to the original restorative agent by the coexisting scavenging agent. By the coexistence of the color developing agent, the restoring agent, and its scavenging agent, the color developing agent can be effectively linked to the formation of color pigments without being lost due to side reactions. Furthermore, since the restoring agent and its oxidized scavenger itself do not substantially react with the development nuclei, a small amount of silver halide is also required. The redox reaction system with the developing agent is, for example, hydroquinone,
It is observed in systems where l-phenyl-3-pyrazolidone and sulfite coexist. However, the reaction system of the present invention was not known for color development systems. The invention of this reaction system has the drawback that benzyl alcohol, which is a co-promoting agent in conventional development accelerators, and silver chlorides, especially silver chloride and silver chlorobromide, are reduced wastefully. Hydroxylamine could be substantially removed from the color developer. Here, "substantially removed" in the case of benzyl alcohol means 2 ml/or less, more preferably θ, rmi 7 or less, most preferably no alcohol at all.

In the case of hydroxylamine, /f/ means the following, preferably o, /f/L or less, most preferably not at all.

As described above, one of the features of the present invention is that a "restoring agent" that restores the oxidized form of the color developing agent and a "capturing agent" that captures the oxidized body sound of the restoring agent and returns it to the original state are allowed to coexist. It is in.

The color developing agent, restoring agent, and scavenging agent are defined by their mutual redox properties necessary to form the reaction system, and can be easily defined by certain tests.

Next, a method will be described using 3-methyl-guamino-N-ethyl-N-(β-methanesulfonamidoethyl)aniline as a representative example of a color developing agent. If the crude drug used changes, just measure the number of moles together.

Test method for restoring agent Prepare the following test solutions A, B, and C, mix equal amounts of test solutions A and B, and stir gently at room temperature for 70 minutes. After passing the mixed liquid through the mouth, the mixed liquid iD and D liquid and C
The absorbance of the liquid at 302 nm (C302 and D302) was measured.

Phosphoric acid/potassium 0.0jmol Sodium sulfite 0.2 73-Methyl-Hiro-amino-3,0f N-ethyl-N-(β-methanesulfonamide ether)-aniline silver oxide 1. Add t7g water
7000 g 1 pH is prepared with hydrochloric acid or potassium hydroxide.

l Potassium phosphate 0.0j mole Test compound 7 x lO mole pH 7,0 pH is adjusted with hydrochloric acid or potassium hydroxide.

Phosphoric acid/potassium 0.01 mol Sodium sulfite 0. / ? 3-Methyl-guamino 1. ! 2-N-Ethyl-N-(β-methanesulfonamide ether)-aniline pH 7.0 The pH is adjusted with hydrochloric acid or potassium hydroxide.

Regulation of restoring agent> D302/C302 is 00fO according to the above test method.
A test compound is defined as a "restorant" if:

[Regenerator J] of the color developing agent according to the present invention is a color developing agent (typically 3-methyl-≠-amino-N-
Ni7-ruN-(β-methanesulfonamidoethyl)
A compound that has the property of reducing the oxidized form of (aniline) and returning it to its original form. In addition, the restoring agent itself has the property of being difficult to be oxidized and decomposed in coexistence with the replenishing agent.

Hydroxylamine has the effect of lowering the color density, and because of its strong reducing property, it has the effect of fogging silver chlorobromide and silver chloride, so it is excluded from the scope of the restoring agent of the present invention. There is.

Test method for retrieval agents> The following test solutions E and F were prepared.

Test solution E K2CO323g Exemplary compound ■- (To) (Postscript μ, 22 restoring agent) Test compound 0.0! Add all of the molar water and add 1000 grams of test solution Established. The spectral intensity of solution E and the spectrum intensity of solution F are compared, and test compounds for which the spectral intensity (SE) of solution E is 0% or less compared to that of solution F (SF) are classified as "capture agents". ”.

The measurement conditions for the ESR spectrum were as follows.

(1) Central magnetic field 3371 G (Gauss) ±toG (2) Measured temperature Cos'C (3) Microwave output gmW (4) Modulation Modulation of o and t3G was applied to the frequency of 100kHz1.

(5) Response 0. / (6) Amplification rate 1000 times
ger) J refers to a compound that has the property of reacting with the /electron or two-electron oxidized form of the restoring agent in the alkaline aqueous solution used to return it to the original restoring agent.

The restoring agent is a hydroxylamine derivative (for example,
-/707jtt) and hydrazine derivatives (e.g., patent application Sho t/-/707!Δ, same Δ/-
/7/1r) issue, same! / -/7J4ZJ,! You can choose from among the compounds listed in No. ', etc.).

A restoring agent that can be preferably used for non-invention is the following general formula (1)
It is expressed as

General formula CI) In the formula, H, 1 and B2 represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, or an unsubstituted or substituted aryl group.

However, R and R are not hydrogen atoms at the same time.

It is preferable that RXR is an alkyl group or an alkenyl group, and it is more preferable that at least one of them has a substituent. Furthermore, R1 and R2 may be connected together with a nitrogen atom to form a heterocycle.

Alkyl groups and alkenyl groups may be linear, branched, or cyclic, and substituents include halogen atoms (F, α, Br
), aryl group (phenyl group, -+20-p-chlorophenyl group, etc.), alkoxy group (C) toxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group [phenoxy group, etc.], Sulfonyl group (methanesulfonyl group, I)-)luenesulfonyl group, etc.)
, sulfo/amide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group, unsubstituted sulfamoyl group, etc.),
Carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group, etc.), ureido group [methylureido group, phenylureido group, etc.], alkoxycarbonylamino group (methquincarnylamino group, etc.), Allyloxycarbonyl 7mino group (phenoxycarbonylamino group, etc.)
, alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, hydroxy group, carboxy group,
Sulfo group, nitro group, amino group, (unsubstituted amine group, diethylamino group), alkylthio group (methylthio-2l
- groups, etc.), arylthio groups (such as phenylthio groups), and heterocyclic groups (such as morpholyl groups, pyridyl groups, etc.). Here, 几1 and R2 may be the same or different, and the substituents of R1 and R2 may also be the same or different.

Further, the number of carbon atoms in R1 and B2 is preferably 1 to /θ, especially /
-7 is preferred. As the nitrogen-containing heterocycle formed by connecting R1 and R2, π is a lysyl group, a pyrolisilyl group,
Examples include N-alkylpiperazyl group, morpholyl group, indolinyl group, and benztriazolyl group.

Preferred substituents for Bl and R2 are a hydroxy group, an alkoxy group, a sulfonyl group, an amide group, a carboxy group, a cyano group, a sulfo group, a nitro group, and an amino group.

Specific examples of the compound represented by the general formula [■] used in the present invention are shown below, but the scope of the present invention is not limited to these compounds.

CH-N-C2H40CH3 CH-N-C2H40C2H5 l-44) CH nCH-N-C2H40CH3 I-(5) CH ■ CHQCH-N-C2H40CH3 CHQCHQCH-N-C2H4QC2H40Cf(3
C2H50C2H4N-C2H5 1-R9) CH CHQCHNCH-CH=CH2 -+2 ≠ - ■-〇■-α→ ■-4■- (to) CH ■ CH-N-C2H4S02C2H5 I-〇η CH ■-(to) In Moan I-(I) I-fl! 1) ■-(branch) -n ■-(c) ■-(i) -m H HOOC-CF(-N-CH2-Coon■-(i) H ■HOCH2CH2NCH2CH20H ■-(foundation) ■-Kan-Q The compound represented by the general formula CI) can be synthesized by the known method shown below.

U.S. Patent No. 3. Al1, No. 221, 3. Jt, 2°F
T/No., J, No. 293.0311, Tokuko Showa 4! Co. 2,72g, U.S. Patent No. 3. μri No. 1.111, same J
,t! ! , 7A≠ issue, PI3. ≠t7, 7// issue, same 3
．． Hiro 3! , No. 71, 3. Ko♂7. / Koj No. 3.
Col'7. /2≠, these compounds may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, and acetic acid. Other restoring agents can be selected from sugars, hydroxamic acids, α-hydroxyketones, and the like.

The amount of these compounds added to the color developer is preferably 0.it to 202, more preferably 0.1 to 20,000 per liter of color developer. If~iot.

- Kotter On the other hand, the retrieval agent is selected from compounds that satisfy the conditions defined above, but especially amine compounds represented by the following general formulas (n) and (1), and
Those selected from the aminocarboxylic acids described in No. 2 (specifically, compounds 1-(1) to (a) on pages 1 to 1.2 of the specification) are useful.

General formula (]l) In the formula, R3, R4, R5, R6 represent a hydrogen atom or an alkyl group, R, R,, R represent an unsubstituted alkylene group, and Xl, X2 are BIO -N-1-0 -1-S-1-CO-1-SO2-1-8
Represents a linking group composed of O- or a combination of these linking groups (B 10 represents a hydrogen atom or an alkyl group) m, n are 0. 1. , 2 or 3.

Here, the unsubstituted alkyl groups of R3, R4, R5, R6, and BIO preferably have carbon atoms of 1 to IO and may be linear, branched, or cyclic, and more preferably have carbon atoms/
~t. Specifically, methyl group, ethyl group, n
-propyl group, is.

-propyl group, n-butyl group, n-hexyl group, t-amyl group, cyclohexyl group, etc. These alkyl groups are B12, B, and 13 in the general formula (In) below.
, B14, and B15 may be substituted with those exemplified as substituents for the alkyl group.

The unsubstituted alkylene groups of R7, R8, and R9 preferably have a carbon number of 2, and may be either linear or branched, and specifically include a methylene group, a dimethylene group, a trimethylene group, a dimethyldimethylene group, a tetramethylene group, Examples include heptamethylene group.

As the linking group for BIO Xl and X2, -N-, -0-X-8-
are preferred, and -N- is particularly preferred.

Furthermore, R3, R4, R5, R6, and R10 may be the same or different, and R7, R8, and R9 may also be the same or different.

Specific examples of the compound represented by the general formula (II) of the present invention are shown below, but the invention is not limited thereto.

(n)-/ (n)-2 (II)-J (n)-1 (II)-7 (■)-r (n)-ta (n)-10 (n)-/ / (n)- /-2 (n)-/ 3 (II)-/≠ (II)-/1 (II)-# (n)-, /7 (n)-/ri(n)-λ/ (II)-22 (II)-23 (II)-λ≠ (II) -,2j 3 t- (II)-,2bu(II)-27 H2NCH2CH2NH2 (II)-j♂ H2NCH2CH2CH2CH2NH2 (]II-Kota H2NCH2CH2NCH2CH2NH2(II)- j
/ 37-(II)-3r (]II-jJ (II)-J4' CHNHCHCHNHCH2CH2NH2CH3NHC
H2CH2NHCH3 (II) --? J (n) -J 7 C2H5 CH2CH2NC2H3 HH (m) -J♂ (n) -jri(n) -HiroO CHNHCH2CH2NH2 The amount of the compound represented by the general formula (n) to be added is preferably per 1 liter of color developer. is 0.0!7 to 302, more preferably o, iy to /3? It is.

General formula (III) In the formula, R11 is a hydroxyl group, an alkoxyl group, an aryloxy group, an amine group, a sulfo group, a phosphonic acid group, a sulfonyl group, a ureido group, an acyl group, an alkylthio group,
Arylthio group, carbamoyl group, sulfamoyl group,
It represents a linear or branched alkylene group substituted with at least one of an acylamino group, a sulfonamide group, a halogen atom, a cyano group, and a nitro group (for example, a -monohydroxyalkylene group, l-methoxy represents an tylene group, etc.). In addition, B12, B13, 几14 and B, 15 may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. represent.

Substituents for this alkyl group, aryol group, and heterocyclic group include hydroxyl group, alkoxyl group, aryoloxy group, carboxyl group, amino group, sulfo group, phosphonic acid group, sulfonyl group, ureido group, Preferred are an acyl group, an alkylthio group, an arylthio group, a carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamide group, a halogen atom, a cyano group, and a nitro group. Two or more of these substituents or two or more types of substituents may be substituted on one alkyl group or aryl group. Note that among the functional groups included in the formula, carboxyl groups, phosphonic acid groups, and sulfo groups may be salts of alkali metals (eg, sodium, potassium, etc.).

In the general formula (III), preferred examples of 11 are hydroxy-substituted alkylene groups, alkoxy-substituted alkylene groups, amino-substituted alkylene groups, sulfo-substituted alkylene groups, and ureido-substituted alkylene groups. Also,
B 12 , B 13 , B 14 , and B 15 are preferably hydrogen atoms, unsubstituted alkyl groups (e.g., methyl, ethyl, isozolobyl, etc.), hydroxy-substituted alkyl groups, alkoxy-substituted alkyl groups, and carboxy-substituted alkyl groups. , and sulfo-substituted alkyl groups.

In addition, B, 11, B12, B13 in general formula 1),
The total number of carbon atoms in B14 and B15 is preferably 30 or less, more preferably 20 or less.

The addition amount of the compound represented by the general formula (iff) according to the present invention is preferably 1≠l per color developer/l.
- Is it O0/G~20? , more preferably 0.3 to iot
It is.

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

1] 1-1 H ■ H2N-CH2CH2H2-NH2 ■■λ 1[I-J ■-μ ■-O■ (HOCH2CH2)2NCH2CHCH2NmoCHC
H2CH20H)2+ [[-7 H ■ (HO2CCH2+2NCH2CHCH2NsoCH2C
0□H)2■-r H ■ HO□CCH2NHCH2CHCH2NHCH2CO□
H ■-ta H ■-IO jl-// (JR (Na03SCH2+2NCH2CHCH2N+CH2
503Na)2■-72■-73H (CH30CH2CH2CH2NCH2CHCH2N(C
H2CH20CH3)21[-/u -a μ - ■-/! [[-/7 ■-77 ill-/♂-gu! - ■-1ri1fi-20 ■-u/ ■-co2 ■-23 111-2μ ■-coj Among the restoring agents represented by the above general formula (I), preferable compounds are those represented by the following general formula ( IV).

General formula (fl/) (R170-Rls+rN-OH Also, among the capture agents represented by general formula (U) or (1), preferable compounds are, for example, the following general formula (V) or (V
l).

General Formula (V) [In the formula, R18 represents an unsubstituted alkylene group having carbon number/-j. t is l or O. ] General formula (Vl) (H2N-R19→, CH-OH -Guar2- [In the formula, R19 represents an alkylene group having 1 to ≠ carbon atoms.] The second feature of the present invention is that the selected This is true for certain bleach-fixing agents.In general, an obstacle to speeding up the development process of color photosensitive materials is bleach-fixing, especially speeding up bleaching.If development is accelerated, -≠7-3- Because the developed silver filament becomes concrete, it becomes increasingly difficult to bleach.In order to perform bleach-fixing quickly,
It is preferable to use a salt of iron 1) complex of ethylenediaminetetraacetic acid (EDTA) at a neutral to acidic pH range to fully enhance the oxidizing power. In particular, the iron(1111) complex salt of diethylenetriaminepentaacetic acid (DEPA), which has a strong oxidizing power, is used alone or in combination with the iron(III) complex salt of EDTA, or the iron(1111) complex salt of cyclohexanediaminetetraacetic acid (CyDATE), which has a strong oxidizing power, is used. I[[) complex salt alone or ED', rA iron(III) complex salt or/.

It is preferable to use the 3-diaminopro/e-nortetraacetic acid iron(III) complex salt.

In particular, the bleaching agent FiO is used to stabilize the bleaching action.

It is preferable to contain it at a concentration of /~2 mol/l.

In particular, when the aforementioned B-/ is mixed with B-z and/or B-J, bleach-fixing can be carried out rapidly and stably at low cost.

As the iron(III) complex salt, one or more existing complex salts may be used, or iron(I[I) salts (e.g. ferrous sulfate, ferric chloride, ferric nitrate, ferrous sulfate) may be used. Ammonium, ferric phosphate, etc.) may be reacted with a chelating agent of the aminopolycarboxylic acid in a solution to form a ferric ion complex salt.

When forming a complex salt in a solution, one or both of the ferric salt and the chelating agent may be used in combination of two or more. In either case of forming a pre-formed complex salt or forming a complex salt, the chelating agent may be used in an amount greater than the stoichiometric amount. In addition, the bleach-fix solution containing the above-mentioned ferric ion complex includes aluminum, nickel, bismuth,
Metal ions such as zinc, tungsten, cobalt, and copper, complex salts thereof, or hydrogen peroxide may also be contained.

A persulfate salt may be added to the bleach-fixing solution used in the present invention as a bleach-fixing aid. Specific examples include alkali metal persulfates such as potassium persulfate and sodium persulfate, and ammonium persulfate.

Additionally, bleach-fix solutions contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride).
or an iodide (e.g. ammonium iodide) rehalogenating agent. If necessary, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, t# acid, phosphoric acid. sodium,
One or more types of inorganic acids having pH buffering capacity such as citric acid, sodium citrate, and tartaric acid, organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine, etc. can be added.

The fixing agents used for bleach-fixing are known fixing agents, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycol ff, J, J -Dithia-1. These are water-soluble silver halide dissolving agents such as thioether compounds such as ♂-octanediol and thioureas, and these can be used alone or in combination of more than one type.

jOichi The concentration of the fixing agent is preferably 0.2 to ≠ mol/l.

Further, the pH of the bleach-fix solution is usually ≠, or.

is preferable, and θ is preferably 7.0 for poetry.

In addition to the above-mentioned additives that can be added to the bleach-fix solution, preservatives such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites, hydrazine, and bisulfites of aldehyde compounds may be added to the bleach-fix solution. Additives (eg, acetaldehyde sodium bisulfite) and the like may be included. Furthermore, various fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone,
An organic solvent such as methanol can be contained.

A bleach accelerator can be used if necessary. Specific examples of useful bleach accelerators are described in U.S. Patent No. 3. 3.1! No. 1, West German Poetry License No. 1 and 2
Rio, ri2, same! , O, ty, tarlr issue, Akira Machikai J-,? -327Jt No., same Jrj-! 7♂3/issue, 3741/za issue, same j3--! /- No. 35732, No. 3-726.23, No. 3-726.23, No. 3-726.23, Jt3-ta! No. 430, same! 3-ta j63/issue, same! 3-10g 2
No. 32, same! 3-/21/111-day issue, same as 3-/1
．． t/A, No. 23, No. 33-211/-, No. 2, Research Disclosure JIG, / 7 / 22
Compounds having a mercapto group or a disulfide group described in No. (July 7, 1999) etc.; JP-A-ShojO-/IAO
Thiazolidine derivatives as described in /2 issue; λ-20,! Same as r32! 3-3.2733, U.S. Patent No. 3.70t,
Thiourea derivatives described in JTT No. 1; West German Patent No. 1. /
Iodide described in λ7,7/Evening issue, JP-A-Sho Sr-/123; West German Patent No. 9tt.

≠No. 10, same λ, 74! ♂, polyethylene oxides described in No. 4t30; polyamine compounds described in Japanese Patent Publication No. 4Jt-r♂3; other JP-A No. 4Jt-r♂3;
No., same≠ta, 2 Gugu No., same! 3-Tag No. 727, same ≠-33727, same! ! -21,! Ot issue and the same! I-/l! Compounds listed in Tag No. Q; other iodine and bromine ions can also be used.

Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of having a large promoting effect, and are disclosed in US Patent No. 3. ♂23, 1-2, West German patent No. 1, 2 O9♂/
λ issue, Tokukai Akira! The compounds described in No. 3-ta jt 30 are preferred. Additionally, U.S. Patent No. '/-,! Also preferred are the compounds described in No. 34L. These bleach accelerators may be added to the photosensitive material.

In the present invention, a commonly used stabilizing bath can be used after color development and bleach-fixing, but the above-mentioned requirement C2 according to the present invention! The water washing bath provided is effective in reducing the amount of processing liquid remaining in the film, especially chemicals such as color developing agent Yakuhiko, which cause discoloration, browning, and staining of the final color image.

Therefore, the water washing bath according to the present invention can be carried out for a short time (to seconds or less, preferably 30 seconds or less). Since the washing solution according to the present invention has a lower salt concentration than a commonly used stabilizing solution, it is advantageous in removing processing chemicals and their byproducts remaining in the membrane.

The washing bath according to the present invention is characterized by being water-saving. The amount may be about 2 to 30 times the amount brought in from the pre-bath per unit area of the photosensitive material to be processed. Normally, when this is done, the processing solution is replaced less often, so the residence time of the washing solution during processing becomes longer, and the growth of bacteria and algae becomes a problem. However, according to the present invention, the calcium ion and the 'magnesium ion each! In the washing liquid in which m9/ is removed below, the growth of bacteria and algae does not occur substantially. Furthermore, it is even more advantageous to include a chelating agent for calcium ions or magnesium ions.

Also, if you use all the disinfectants and anti-piping agents in the washing solution, the washing bath time can be further shortened. In the image forming method of the present invention, the following general formula [■]-! It is particularly advantageous for the above-mentioned purpose to add a compound represented by [2] to the washing solution.

General formula [■] -yo Goo general formula [■] In the formula, R2Q is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a halogenated alkyl group, -R, 3-0-R2
4, -CONHR25 or an alkyl group, RQ
1 and R22 each represent a hydrogen atom, a halogenated alkyl group or an alkyl group, R'2.3 represents an alkylene group, and R1 and R25 each represent a hydrogen atom, an alkyl group or an aralkyl group.

R26 is synonymous with R, o, R2+7, R23, R29,
R30 each represents a hydrogen atom, a hydroxy group, an alkyl group, an amine group, or a nitro group.

Specific examples of the compound will be given, but the invention is not limited thereto.

(■-l) 2-methyl-hiro-inthiazoline-3-one-! ! - (■-λ) j-chloro-λ-methyl-hiro-inteazolin-3-one (MTI-/) 1.2-benzisothiazoline-3
-On (■-λ)! -Chloro-1,2-benzisothiazolin-3-one These compounds are 0.0/? ~30'2
It is preferable to use the range of . These compounds are waiting for Shoj7-♂! It is written in the Hiroλ issue etc.

The amounts of calcium and magnesium compounds in the washing liquid tank can be adjusted to the above-mentioned values by various known methods. For example, ion exchange resins or reverse osmosis devices reduce the content of calcium and magnesium compounds in the washing solution (including replenisher) used.

Various cation exchange resins can be used as the above ion exchange resin, but CaJMgf:Na replacing Na
It is preferred to use a type of cation exchange resin. Further, an H-type cation exchange resin can also be used, but in this case, the pH of the treated water becomes acidic, so it is preferable to use it together with an OH-type anion exchange resin.

The ion exchange resin is preferably a strongly acidic cation exchange resin having a styrene-divinylbenzene copolymer as a base and having a sulfone group as an ion exchange group. Examples of such ion exchange resins include, for example, Mitsubishi Kasei Dia, Ion SK-/B, or Diaion PK-2.
/4 etc. The substrate for these ion exchange resins preferably contains divinylbenzene in an amount of ~/J% based on the total amount of monomers used during production. H
As an anion exchange resin that can be used in combination with a type cation exchange resin, a strongly basic anion exchange resin having a styrene-divinylbenzene copolymer as a base and having a tertiary amine or primary ammonium group as an exchange group is preferable. An example of such anion exchange resin is Diaion 5A-10K, also manufactured by Mitsubishi Kasei.
Alternatively, Diamondion PA-II/r can be mentioned.

All known methods can be used to remove calcium and magnesium from water using these ion exchange resins, but preferably the water is passed through a column filled with an ion exchange resin. The water flow rate is 7 to 100 times the resin volume per hour,
Preferably! ~! It is 0 times.

In the present invention, calcium ions and magnesium ions are completely removed as described above, or r mg/
is reduced to a concentration of
A chelating agent can be included in the washing water.

Here, the stability constant (KMA) is expressed by the following equation.

Here, [MA] is the molar concentration of the metal chelate, rr-[M] is the molar concentration of the metal ion, and [human] is the molar concentration of the chelating agent anion.

Chelating agents with such stability constants are available from Keihei Ueno's "Metal Chelate ■" (published by Nankodo), "Dotite Reagent General Catalog 73rd Edition" published by Isotope Kagaku Kenkyusho, and Shiley (L, G, Si 11enet al,)
“Stability constant of metal complexes (StabilityCon)”
stunt of Me, tal Complex
) J (published by Chemical Society).

Among these chelating agents, the following are specifically exemplified.

Stability constant (EDTA) cyclohexanediamine /λ, 01' 10.3
2-tetraacetic acid (GDTA) Diethylenetriamine 5 10.71A Ta, 3
Acetic acid (DTPA) -! trihydroxyethylidene r, l≠ 7.0 diamine triacetic acid (EDTA-OH) triethylenetetramine 10. Ot ♂, t7
Hexaacetic acid (TTHA) Diaminopropanol 4 t, to ♂, hexaacetic acid (DPTA-OH) 1.2-Diaminopropane /1. ≠7°io, s-tetraacetic acid (methyl-EDT A) Ethylenediamine tetramethyt, ri/2.7
0-lenephosphonic acid (ED TPO) Ethylenediamine-N, 10.7≠ Ta, ≠l
N'-diacetic acid-di(copropionic acid) 1.3-diaminopronoe 7. ．． 2/t,
O2-tetraacetic acid It is preferred to use seven or a mixture of two or more of the above-mentioned chelating agents and their soluble salts such as alkali metal salts and ammonium salts. Note that the content of the chelating agent is arbitrary, but if the water washing solution is 3x/θ-4~3x/
The amount is preferably θ-2 mol, preferably /xl0-3 to 1xlo-2 mol.

The rinsing liquid according to the invention may be combined with the above-mentioned compounds, such as, for example, Machikaisho! Compounds selected from the phosphonic acids described in No. 7 to J♂Hiro No. 3 can be used. For example /-hydroxyethylidene-1. /-diphosphonic acid, l
-Hydroxypropylidene-1. /-diphosphonic acid, /
-aminopropane, /-diphosphonic acid, etc. can be used in combination. This compound produces, for example, a sparingly soluble calcium phosphonate salt in ordinary water and produces scum when used for a long time, but this does not occur in the washing solution of the present invention because the concentration of calcium is low.

In the present invention, it is desirable that the water washing step be comprised of a large number of tanks or more, preferably λ~ tanks, more preferably 2~x tanks, and the amount of the washing replenisher preferably It is preferable to replenish the bath in a multi-stage countercurrent system in an amount 2 to 30 times the amount brought in from the pre-bath per unit area of the photosensitive material to be processed.

Furthermore, the content of calcium and magnesium compounds in the flushing solution (including replenisher) for toilet use can be lowered by using a reverse osmosis device.

As a reverse osmosis treatment device, any known device can be used without limitation, but the reverse osmosis membrane has an area of 3.2 or less, a working pressure of 30 to 9/m2 or less, particularly preferably 2m2 or less,
It is desirable to use an ultra-compact device of λOkg/712 or less. When such a small device is used, the workability is good and a sufficient water saving effect can be obtained. Furthermore, it is also possible to pass activated carbon or a magnetic field.

As the reverse osmosis membrane used in the reverse osmosis treatment device, cellulose acetate membrane, ethyl cellulose/polyacrylic acid membrane, polyacrylonitrile membrane, polyvinylene carbonate membrane, polyether sulfonate membrane, etc. can be used.

In addition, the liquid feeding pressure is usually t-tokg7α2, but in order to achieve the purpose of the present invention, it is 30 kg/crIL2.
The pressure below is sufficient; however, a so-called low-pressure reverse osmosis device having a pressure of 0 kg/cm 2 or less can also be used.

As the structure of the reverse osmosis membrane, any of the sno-irial type, tubular type, hollow fiber type, pleated type, and rod type can be used.

In the present invention, it is further preferable to irradiate the liquid in at least one tank selected from the washing tank and its auxiliary tank with ultraviolet rays, so that the growth of mold can be further suppressed.

The ultraviolet lamp used in the present invention has a wavelength of 253.7.
A low-pressure mercury vapor discharge tube is used that emits a nm line vapor. In the present invention, the germicidal radiation output o, rW~
7. ! W is preferably used.

The ultraviolet lamp may be installed outside the liquid and irradiated with it, or it may be installed inside the liquid and irradiated from within the liquid.

Although the present invention does not require the addition of an antibacterial agent or a fungicide as described above, it is optional to use an antibacterial agent or a fungicide depending on the purpose.

In addition, fungicides represented by the general formula (1) or (IT) described in, for example, Japanese Patent Application No. 1971 Tata Oto can also be used in the present invention.

The third aspect of the present invention lies in the color photosensitive material used. The color photosensitive material used in the present invention preferably has a silver halide photosensitive layer (BL) containing a yellow coupler on a support.
), a silver halide photosensitive layer containing a magenta coupler (G
L) and a silver halide photosensitive layer containing a cyan coupler (R
At least three layers of L) are provided, and a protective layer (PL) is provided.
, intermediate layer (ML), and if necessary antihalation layer (A
It is a photosensitive material that is provided with a single layer (HL), a single filter layer (FL), etc. The photosensitive silver halide used is an internal latent image type silver halide grain which is not prefogged, preferably a core/shell or even a multilayered grain. Although it is called core/shell, it is often predicted based on the method of addition of halogen salt in the prescription, and it is difficult to clearly distinguish the layer structure. It usually has a structure that changes continuously with .

In the color photosensitive material according to the present invention, the spectral sensitivity distribution of the cyan, magenta, yellow coloring photosensitive layer and other photosensitive layers can be changed depending on the use thereof.

In the case of full color printing, it is too~7yoOnm,
! ;000-5-AOOn, 1100~! It is preferable to perform spectral sensitization in the red-sensitive region, green-sensitive region, and blue-sensitive region within a range of 20 nm. Laser printer electronics are laser beams used for writing, such as helium-cadmium laser t+'-, fulgon ion laser, helium-neon ion laser-1 semiconductor, in the case of output hard copies for make-up systems and total scanners. Spectral sensitization is performed to match the wavelength of the laser beam used. The sensitizing dyes and dyes used have a hydroxyl group, a carboxylic acid, a sulfonic acid, a sulfamoyl group, or a hydroxyl group, a carboxyl group, or a sulfone group in the =N substituent so that they can be completely removed by the stabilizing bath or washing bath according to the present invention. It is preferable to introduce a hydrophilic group such as an acid group.

The photographic emulsion layer and other layers have surfaces that have specular reflection or second-type diffuse reflection by providing a plastic film, metal foil film, or a filling layer of metal powder particles, which are commonly used in photographic light-sensitive materials. Flexibility of supports (for example, described in Japanese Patent Application Sho J/-/lza♂00 and Sho &/-/6110/), baryta paper, paper coated with α~olefil polymer, cloth, etc. Applied to a support or rigid support such as glass, ceramic, metal, etc.

-2Δ1 The unfogged internal latent image type silver halide emulsion used in the present invention has silver halide grains whose surfaces are not prefogged and furthermore contains silver halide that forms latent images mainly inside the grains. It is an emulsion, and more specifically, 0.5 to 3 g of silver halide emulsion is prepared as silver on a transparent support.
1rd coating, exposed to light for a fixed time of 0.01 to 10 seconds, and developed for 5 minutes at 18°C in the following developer A (internal type developer). The maximum density obtained is at least the maximum density obtained when a silver halide emulsion coated in the same amount and exposed in the same manner as above is developed in the following developer B (surface type developer) at 20°C for 6 minutes. -5 times greater concentration, more preferably at least 1
It has a concentration 0 times greater.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Soda carbonate (-hydrate)
52.5gKBr
5 gKI
Add 0.5g water
11 Surface developer B Metol 2.5g1-ascorbic acid to gN a B O!・4
Hto 35gKBr
Add lg water
Specific examples of internal type emulsions include U.S. Patent No. 2,592,250 and Japanese Patent Publication No. 58-54379.
No. 58-3536, No. 60-5582, JP-A-52-156614, No. 57-79940, No. 58
Conversion type silver halide emulsion described in the specification of No.-70221 and an emulsion with a shell thereon, U.S. Pat. Nos. 3,761.276 and 3,850,6
No. 37, No. 3゜923.513, No. 4,035,18
No. 5, No. 4.395,478, No. 4,431.730
No. 4,504,570, JP-A-53-60222
No. 56-22681, No. 59-208540,
No. 60-107641 0. No. 61-3137, Patent Application No. 61-3642, Research Disclosure Magazine No. 23510 (published in November 1983) P236
, No. 18155 (published in May 1979) P26
Mention may be made of core/shell type silver halide emulsions in which a metal is doped inside, which are described in the patents disclosed in Nos. 5 to 268.

The shapes of the silver halide grains used in the present invention include regular crystal shapes such as cubes, octahedrons, dodecahedrons, and tetradecahedrons, irregular crystal shapes such as spherical shapes, and length/ Tabular particles having a thickness ratio of 5 or more may be used. Further, an emulsion having a composite form of these various crystal forms or a mixture thereof may be used.

The composition of silver halide includes silver chloride and silver bromide mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide, or even if it contains it, it contains less than 3% mole of salt (
(iodine) silver bromide, (iodine) silver chloride or (iodine) silver bromide.

The average grain size of the silver halide grains is 2μ or less and 0.
1 μ or more is preferable, but 1 μ or less is preferable for samurai.
．． It is 15μ or more. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the number or weight of particles should be within ±40% of the average particle size, preferably within ±20% of the total particle size. % or more, so-called "monodisperse" silver halide emulsions having a narrow grain size distribution are preferably used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two emulsion layers having substantially the same color sensitivity have two different grain sizes.
More than one type of monodisperse silver halide emulsion or a plurality of grains of the same size but different in sensitivity 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 silver halide emulsion used in the present invention can be chemically sensitized inside or on the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. A detailed example can be found in the patent described in Research Disclosure Magazine No. 17643-I (Published December 1978, P23).

The photographic emulsions used in the present invention are spectrally sensitized with photographic sensitizing dyes in a conventional manner. Particularly useful dyes are those belonging to cyan dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, detailed specific examples of the use of the above-mentioned dyes and strong color enhancers in combination can be found in, for example, the patents described in Research Disclosure Magazine No. 17643 1V (published December 1978), pages 23-24.

The photographic emulsion used in the present invention may contain an anti-capri agent or a stabilizer for the purpose of preventing capri during the manufacturing process, storage or photographic processing of the light-sensitive material, or for stabilizing the photographic performance. For detailed examples, see Research Disclosure Magazine No. 17643-
Vl (published December 1978) pages 24-25 and
[! , J. Birr'5tabilization
of Photographic 5ilver Ha
rideEmulsions” (FocalPress
), published in 1974, etc.

A variety of color couplers can be used to form direct positive color images. Useful color couplers are
A compound that generates or releases a dye, preferably a substantially non-diffusible dye, by a coupling reaction with an oxidized form of an aromatic primary amine color developer, and which itself is substantially non-diffusible. It is a compound. Typical types of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazolone azole compounds, and open chain or heterocyclic ketomethylene compounds.

Specific examples of these cyan, magenta, and yellow couplers that can be used in the present invention can be found in Research Disclosure, 17643 (published December 1978), p.
25■-ri section, Kaimagai 18717 (issued November 1979) and Japanese Patent Application No. 61-32462 (pages 298 to 373)
Page) and the patents cited therein.

Among them, typical examples of yellow couplers that can be used in the present invention include oxygen atom elimination type and nitrogen atom elimination type Ely 3-Ero two-equivalent couplers. In particular, α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness;
-Benzoylacetanilide couplers are preferred because they provide high color density.

Furthermore, as the 5-pyrazolone magenta coupler that can be preferably used in the present invention, a 5-pyrazolone coupler in which the 3-position is substituted with a -ruamino group or an acylamino group (especially a sulfur atom-eliminating two-equivalent coupler) is preferred. be.

More preferred are pyrazoloazole couplers, and among them, pyrazolo(5,1-c) (1,2,4) triazoles described in U.S. Pat. No. 3,725,067 are preferred, but coloring dyes The imidazo[1°2-b]pyrazoles described in U.S. Pat. No. 4,500,630 are more preferred in terms of low yellow side absorption and light fastness; The pyrazolo(1,5-b)(1,2,4)) riazoles described are particularly preferred for lf, i-1.

Cyan couplers that can be preferably used in the present invention include:
U.S. Patent No. 2.474,293, U.S. Patent No. 4.052.21
Naphthol type and phenolic couplers described in US Pat. ,5
-Diacylamino-substituted phenolic couplers are also preferred from the viewpoint of color image fastness.

Specific examples of particularly preferred yellow, magenta and cyan couplers include Japanese Patent Application No. 61-169523 (Showa 6
No. 35 of Fuji Photo Film Co., Ltd. (filed on July 18, 2015)
These are the compounds listed on pages 1 to 51, and the following compounds can also be mentioned as preferred examples.

17 o'clock + 2-1-no (J
=≧− v 0 1#1#1 工 工≧ 0 工 〒の= and 17? - Colored couplers for correcting unnecessary short-wavelength absorption of the generated dyes, couplers whose coloring dyes have excessive diffusivity, non-coloring couplers, DIR couplers that release a development inhibitor along with the coupling reaction, or Couplers that release development accelerators and polymerized couplers can also be used.

Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitive silver halide;
Preferably 0, Ol to 0.5 for yellow couplers.
moles, for magenta couplers 0.003 moles to 0
．． 5 mol, and for cyan couplers 0.002 to 0
．． It is 5 moles.

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. Typical examples of color antifogging agents and color mixing prevention agents are patent applications filed in 1983.
-32462, pages 600 to 630.

Various 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.

Representative examples of these anti-fading agents are disclosed in Japanese Patent Application No. 32462/1986.
No. 401-440.

The purpose of these compounds can be achieved by co-emulsifying them with the couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the respective color couplers. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is effective to introduce an ultraviolet absorber into the layers on both sides adjacent to the cyan coloring layer. Further, an ultraviolet absorber can also be added to a hydrophilic colloid layer such as a protective layer. Representative examples of compounds are given in Japanese Patent Application No. 61-32462.
It is described on pages 391-400.

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.

The photosensitive material of the present invention includes dyes that prevent irradiation and λ-ration, ultraviolet absorbers, plasticizers, fluorescent brighteners, matting agents, air capping inhibitors, coating aids, hardeners,
Antistatic agents, slippery improvers, etc. can be added.

Representative examples of these additives are
Magazine No. 17643■-xm (published December 1978) p25-27, and 18716 (1979 January
Published in January), pages 647-651.

The invention is also 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. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Furthermore, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, or two or more emulsion layers having the same sensitivity.
A non-light sensitive layer may be present between the two or more emulsion layers. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the pre-malignant emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
It is preferable to provide auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an anti-nolation agent, a backing layer, and a white reflective layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are those described in Research Disclosure Magazine No. 001-7643 It is applied to the support described in Sho 61-97655. Also, Research Disclosure Magazine No. 17643XV
The coating method described in sections p.28 to 29 can be used.

Furthermore, when the photosensitive material of the present invention is used for color diffusion transfer, a dye developer can be used as a coloring material.
The coloring material itself is alkaline (in the developer) and non-diffusible (
It is advantageous to use a type of colorant that is non-migratory) but releases a diffusible dye (or its precursor) as a result of development. These diffusible dye-releasing coloring materials (DRR compounds) include couplers and redox compounds that release diffusible dyes, and these are applied using the color diffusion transfer method (wet method).
It is useful not only as a coloring material for heat-developable sensitive materials (dry method) as described in, for example, JP-A No. 58-58543.

The diffusible dye-releasing redox compound (hereinafter referred to as "DRR compound") can be represented by the following general formula.

(Ballast+-+redox cleavage group) In the formula D, for (Ballast) and the redox cleavage group, the compounds described on pages 12 to 22 of JP-A-58-163938 can be used.

Further, D represents a dye (or its precursor) moiety.

This dye moiety may be bonded to the redox cleavage atomic group via a linking group, and as for the dye moiety represented by D, those described in the following documents are effective.

Example of yellow dye U.S. Pat. No. 3,597,200, No. 3,309°199
No. 4,013,633, No. 4,245.028, No. 4,156,609, No. 4゜139.383,
No. 4,195.992, No. 4,145,641, No. 4,148,643, No. 4,336,322; JP-A-51-114977).

Example of magenta dye: U.S. Pat. No. 3,453,107, U.S. Pat. No. 3,544°545
No. 3,932,380, No. 3,931.144, No. 3,932,308, No. 3954.476,
4,233,237, 4.255,509, 4. 2so, No. 246, No. 4,142,891, No. 4,207,104, No. 4,287,292; JP-A-52-106.727, No. 52-106727,
No. 53-23,628, No. 5.5-36,804,
Those described in No. 56-73', No. 057, No. 56-71060, and No. 55-134.

Examples of cyan dyes: U.S. Pat. No. 3,482,972, 3. 929°76
No. 0, No. 4,013,635, No. 4,268.625
No. 4,171.220, No. 4242.435, No. 4,142,891, No. 4.195,994,
No. 4,147,544, No. 4,148,642; British Patent No. 1,551゜138; Japanese Unexamined Patent Publication No. 54-99431
No. 52-8827, No. 53-47823, No. 5
No. 3-143323, No. 54-99431, No. 56-
No. 71061; European Patent (RPC) 53°037
No. 53,040i Re5earch Disc
losure 17.630 (1978) and 1
6,475 (1977).

The application amount of these compounds is generally about lXl0-' to lXl
0-1 mol/rd is suitable, preferably 2XIO-
'~2X10-''mol/n?

In the present invention, the coloring material may be contained in the halogenated emulsion combined therewith, or may be contained in a layer adjacent to the emulsion layer on the exposed side or on the opposite side.

When the photosensitive material of the present invention is used in a color diffusion transfer method, the photographic material may be coated integrally on the same support on which the image-receiving layer is coated, or it may be coated on a separate support. may be coated on.

Further, the silver halide photographic emulsion layer (light-sensitive element) and the image-receiving layer (image-receiving element) may be provided in a combined form as a film unit, or may be provided as separate and independent photographic materials; The form of the film unit may be one that is integrated from start to finish through exposure, development, and inspection of the transferred image, or it may be a type that is peeled off after development, but the latter type is preferable for the present invention. more effective.

The present invention can be applied to various color photosensitive materials.

For example, typical examples include color reversal film for slides or television, color reversal paper, and instant color film. It can also be applied to full-color copying machines and color hard copies for storing images on CRTs. The present invention also applies to "Research Disclosure" magazine No. 1.
7123 (published in July 1978), etc., and which utilizes a mixture of three color couplers.

In the present invention, after imagewise exposure of the photosensitive material, a positive color image can be directly formed by developing, bleaching and fixing the photosensitive material with a surface developer containing an aromatic primary amine color developer in the presence of a nucleating agent. The invention will now be illustrated by way of examples. However, the invention is not limited to this.

Experimental Example 3 The following results were obtained according to the method described in the section on the specifications of the restoring agent.

Regarding the exemplary accessories of the present invention D 302 / C 302
showed a value of O1r or less.

Experimental example λ.

The following results were obtained according to the method described in the section regarding the scavenging agent for the one-electron oxidized form of the restoring agent.

The SE/SF value for the exemplary attachment of the present invention was less than 0. Here, regarding the SE value, since the measured value is obtained as a relative value without a unit, the 3E value of other compounds is shown as the measured value f1.00 for the -fi+ compound.

Example - Emulsion A An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution to which 0.37 of 32 μm dimethyl-7°3-thiazoline-corchion was added per 71 mole of A, and was heated to 70C with vigorous stirring. They were added simultaneously over a period of about 20 minutes to obtain an octahedral monodispersed silver bromide emulsion with an average grain size of O0≠μm. A chemical sensitization treatment was carried out by adding to this emulsion 7 moles of silver, respectively g + m9 of thiosulfate, and chloroauric acid (≠ hydrate) and heating at 750C for 10 minutes.

Using the silver bromide particles obtained in this way as a core, the particles were further grown by further treatment for 70 minutes in the same precipitation environment as the first time, and finally an octahedral monodisperse core/shell odor with an average particle size of 0.7 μm was obtained. A silver oxide emulsion was obtained. After washing with water and desalting, sodium thiosulfate and chloroauric acid (≠ hydrate) were added to this emulsion in amounts of 1 and 6 mg per mole of silver, respectively, and heated at t, o 0 c for to minutes to perform a chemical sensitization treatment. A latent image type silver halide emulsion A was obtained.

A full multilayer color photographic paper having the layer structure shown in Table 1 was prepared using a core/shell type internal latent image emulsion 8 on a paper support laminated on both sides with polyethylene.

The coating solution was prepared as follows.

Preparation of first layer coating solution Nidian coupler (2) tog and color image stabilizer (b), 2, j f and 10 ml of ethyl acetate
Add and dissolve solvent (C), and reduce this solution to 10%
Contains sodium dodecylbenzenesulfonate rm12/.

The gelatin was emulsified and dispersed in an aqueous gelatin solution. On the other hand, the silver halide emulsion A (A g 70 S' /
(containing Kg), add the following red-sensitive dye to silver halide 1
Mortoshi! , θ×10 mol was added to prepare a red-sensitive emulsion. Mix and dissolve the emulsified dispersion, the emulsion, and the development accelerator (d), adjust the concentration with gelatin so that it has the composition shown in Table 1, and add
A coating solution for the first layer was prepared.

The coating liquids for the λth layer to the seventh layer were also prepared in the same manner as the first layer coating liquid. As a gelatin hardening agent for each layer /-oxy-3
, j-dichloro-5-triazine sodium salt was used.

The following spectral sensitizers were used in each emulsion layer.

red-sensitive emulsion layer; Green-sensitive emulsion layer; (Cl-12) zsO3Na Blue-sensitive emulsion layer; The following dyes were used as anti-irradiation dyes.

The structural formulas of the compounds used in this example, including an anti-irradiation dye for the green-sensitive emulsion layer and an anti-irradiation dye coupler for the red-sensitive emulsion layer, are as follows.

○ ℃ Hammer ＼ J Koni-mai Parking τ (e) Color mixing inhibitor (g) Color image stabilizer n()H (h) Solvent 9q- /:1. ! Mixture (weight ratio) l: 2 = 2 mixture (weight ratio) /-1\ Engineering! Engraving of the specification (no change in content) The color photosensitive material prepared as described above was processed according to the following steps.

Time Temperature fogging exposure (0.2 lux with light source at j≠OO0) /j seconds color development
7 minutes hiro θ seconds 3r 0c bleach fixing
1 minute 3!0C water washing (or stable) ■
, 20 seconds! ■ 20 seconds l ■ 20 seconds I 3-methyl-≠-amino t, ootN-
Ethyl-N-(β-methanesulfonamide) Engraving of specification (no change in content) ethyl)-aniline potassium carbonate 30.0f Fluorescent brightener (stilbene type) 1. Add Og water
1000ml pHlo, λO pH was prepared with potassium hydroxide or hydrochloric acid.

1 oz- [Bleach-fix solution] Ammonium thiosulfate /10 g Sodium hydrogen sulfite 10 g Ferric ammonium ethylenediaminetetraacetic acid /water salt O0/2 mole Ethylenediaminetetraacetic acid disodium dihydrate jgpHg,t pH is ammonia water or hydrochloric acid Adjusted with.

/-Hydroxyethylidene-/, /'-diphosphonic acid (to%) 1. A gBismuth chloride 0.33g Polyvinylpyrrolidone 0.23g Aqueous ammonia
Co, rml nitrilotriacetic acid/JNa
1. Og! - Chloroko Methyl - Hiro - Inchiazoline - 3 one on ro mri! -Octyl-guinthiazolin-3-one jtO ■Fluorescent brightener (≠, add gou'-di water, loooml pH 7
,s pH is adjusted with potassium hydroxide or hydrochloric acid.

Table 3 shows the maximum and minimum concentrations of the samples obtained through the above treatments. In addition, the chemical oxygen demand (BOD') of the color developing solution used in the experiment was measured according to the method specified in the JIS standard. The results obtained are shown in Table 3.

As is clear from Table 3, when processed with the color developer of the present invention, a desirable image with a high maximum density and a low minimum density can be obtained.
We were able to provide a treatment liquid with low pollution load.

Example 2 In the processing steps of Example 2, the stabilizing solutions (1) to (2) were replaced with the following washing solutions (6) to (3).

Washing liquid ■〜■ Tap water is converted into H-type strong acidic cation conversion resin (manufactured by Mitsubishi Kasei■).
Water was passed through a mixed bed column packed with Diaion SK-/B) and OH-type strong basic anion exchange resin (Diaion SA-/oA) to obtain the following water quality, and then treated with dichloride as a disinfectant. Sodium isocyanurate m9#' was added.

Calcium ion 1.1 m9/1 Magnesium ion 0.3 m9/1 pI-1,4,2 The results obtained were similar to Example/.

Example 3 The color photosensitive material prepared in Example 1 was processed using the color developing solution (f) in the processing steps of Example 1 and with the following bleach-fix solution.

Bleach ↑ Listed in Table μ Ammonium thiosulfate / 10 g Sodium bisulfite 10 g Bleach accelerator
! ×/Q Add molar water
loooomlpH'
a, J'pn were prepared with aqueous ammonia or acetic acid.

The amount of residual silver in the maximum density portion of the sample obtained by the treatment was examined.

As is clear from the Puffer Table, when processed with the bleach-fix solution of the present invention, favorable images with clearly low amounts of residual silver were obtained.

Example ≠.

The color light-sensitive material prepared in Example 1 was continuously processed for 60 days using an automatic processor consisting of the following processing steps.

Time Temperature Replenishment amount processing process (Photosensitive material/m2
per) Color development 1 minute po seconds 3♂00 3rO
ml bleach fixing 7 minutes 3j0C200ml water washing ■ 20 seconds 33°C-■ 20 seconds
33°(C - ■, 20 seconds 33°c
, 2oome The replenishment method for the washing bath is to replenish the washing bath ■, lead the overflow liquid of the washing bath ■ to the washing bath ■, and guide the overflow liquid of the washing bath ■ to the washing bath ■, so-called countercurrent replenishment. method.

The composition of the treatment liquid used was as follows.

Color developer diethylenetriamine λ, Q g λ, og
Pentaacetic acid exemplary compound I-(3ta 0.03 mol 0.
0 hmol II −+11 0.0 rmol 0.
05mol Sodium Bromide 0.26g
- Sodium chloride 3.20g -
3-Methyl-7-amine A, 00 g 7.
5Og-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline potassium carbonate 23 g, 30
g Fluorescent brightener (stilbene type) 1. (17g 1.
Add 5g water / 000ml
/ 000ml pHto, 2r io, g0 Bleach-fix solution Mother solution Replenisher Sodium sulfite aqueous 10 g Ethylenediaminetetraacetic acid 110 g Ferric ammonium l-hydrate Ethylenediaminetetraacetic acid jg Co-sodium l-hydrate pHA, s Washing solution■ -■: Both the mother liquor and the replenisher have the same composition as shown in Table 5.

Here, the treatment using Washing Ronin was treated as Processing A1, and the following treatments were carried out in the same manner as Processing B1 and Processing C'f using washing liquids B and C, respectively. The generation of floating substances in the washing bath during continuous processing and the presence or absence of adducts on the surface of the photosensitive material after processing were investigated.

Washing liquid A　■〜■ 6 well water was used.

The concentrations of calcium ions and magnesium ions in the well water were as follows.

[Calcium ion 10m971 washing liquid B ■～■ Tap water f, H-type strong acidic cation exchange resin Diaion SK-/B manufactured by Ryo Kasei), O1J type strong basic anion exchange resin (Diaion 5A- manufactured by Ryo Kasei ■) After passing water through a mixed bed column packed with loA) f to obtain the following water quality, sodium incyanurate dichloride m9/l was added as a disinfectant.
'x added.

Calcium ion 1.1m9/1 Magnesium ion 0. jtm9/1pH/:, Washing liquid C■~■/-Hydroxyethythene 1. 1. A gl'
-Diphosphonic acid (30%) Bismuth chloride 0.3rg Polyvinylpyrrolidone 0125g Aqueous ammonia
Co, jml nitrilotriacetic acid/JN
a1. Ogj-Chlorokomethyl-≠-
zomg isothiazolin-3-one λ-octyl-guinthiazo 50m9 phosphorus-3-
On fluorescent brightener (11,μ'-diami 1.Og nostilbene type) Add water 1000m100O
7.j pI-1 is adjusted with potassium hydroxide or hydrochloric acid.

The concentrations of calcium ions and magnesium ions in the washing solution were as follows.

-//l1. − Example-Yo.

Fully multilayer color photographic paper was prepared in the same manner as in Example 1, except that the chemical compounds listed in Table 6 below and their added amounts were changed.

(f, z) Magenta coupler (g-2) Color image stabilizer (h-2) Solvent (1-2) Yellow coupler Example-t, Magenta coupler (f) of the third layer according to Example-/ ) was replaced with (f-J) below, and a sample was prepared in the same manner except for the following.

This sample was developed under the conditions of the composition of the color developing solution in Examples A, C, and C. I got the following result.

/7 (comparative example) I co, j0 0.
/71 r(z) mouth
1. ri r O,/A' ri (present invention)
Ha J, 4! , 2 0. //(f-J
) ≠ Equivalent magenta coupler - l + 20/- (Effect of the invention) Direct positive color with high maximum color density (Dmax) and low minimum color density (Dmin) even with rapid processing in which the total processing time including drying process is within 4 minutes. An image is obtained. Further, the above-mentioned effects can be obtained even if a color developer having a low BOD[ or COD value and a low pollution load (particularly a developer that does not substantially contain benzyl alcohol) is used. Furthermore, by substantially not containing benzyl alcohol, the problem of generation of leuco bodies of cyan dye and the problem of deterioration of image storage stability due to residual color developing agent are also solved. Further, according to the present invention, since the color developing agent can be used efficiently, the coloring efficiency of the coupler can be improved, and the amount of silver used can be reduced.

Further, according to the present invention, even if the above-mentioned rapid treatment is performed, there is little problem of insufficient desilvering, and furthermore, even if water-saving treatment is performed, there is no problem of floating matter being generated in the washing bath.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment (formality) Showa A, March 2nd, 2015

Claims (7)

[Claims] (1) After imagewise exposure of a light-sensitive material having at least one light-sensitive photographic emulsion layer containing internal latent image type silver halide grains and a color coupler on a support, which are not pre-fogged, and before development or development. In a method of directly forming a positive color image by applying fogging exposure to color development, followed by bleach-fixing and processing using a stabilizing bath or water washing bath, the color development comprises the following element A. pH
A direct positive color image forming method characterized by processing using a color developing solution of /1.5 or less. A: Contains a restoring agent for the oxidized form of an aromatic primary amine color developing agent and a scavenging agent for the oxidized form of this restoring agent. (2) The direct positive color image forming method according to claim 1, wherein the bleach-fixing process is performed using a bleach-fixing solution having a pH of 4 to 8 and containing at least one of the following elements B. Element B: B-1: Contains an iron (III) complex salt of ethylenediaminetetraacetic acids, B-2: Contains an iron (III) complex salt of diethylenetriaminepentaacetic acids, or B-3: Contains an iron (III) complex salt of cyclohexanediaminetetraacetic acids. Iron (III)
Contains complex salts. (3) The direct positive color image forming method according to claims 1 and 2, wherein the washing bath comprises at least one of the following elements C. Element C: C-1: Does not contain calcium or magnesium ions or contains them at a concentration of 5 mg/l or less, C-2: Contains a chelating agent for calcium or magnesium ions, or C-3: Isothiazoline Contains at least one of the following. (4) The color developing solution is benzyl alcohol and/or
The direct positive color image forming method according to claim 1, characterized in that the direct positive color image forming method does not substantially contain hydroxylamine. (5) The direct positive color image forming method according to claim 1, 2 or 3, wherein the total development processing time including the drying step is within 6 minutes. (6) The direct positive color image forming method according to claim 1, wherein the total amount of silver halide in the photosensitive layer of the photosensitive material is 1.30 g/m^2 or less in terms of silver. . (7) The above color coupler has the following general formula [M- I
] or [M-II], the direct positive color image forming method according to claim 1, characterized in that it is a magenta coupler represented by [M-II]. General formula [M-I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [M-II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, G_1 and G_3 represent substituted or unsubstituted phenyl groups, G_2 represents a hydrogen atom, an aliphatic or aromatic acyl group, or an aliphatic or aromatic sulfonyl group. G_4 represents a hydrogen atom or a substituent. Za and Zb represent a methine group, a substituted methine group or a =N- group. Y_1 and Y_2 represent a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized developing agent. Furthermore, G_1, G_2, G_3 or Y_1; or G_4
, Za, Zb or Y_2 may form a dimer or more multimer.