JPS58189633A - Method for processing silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To speed up processing of a silver halide photosensitive material, by imagewise exposing said material contg. a silver halide emulsion layer contg. a specified phenol type cyan coupler, and color developing and bleach fixing it. CONSTITUTION:A phenolic cyan coupler has at the 2-position a substd.- or condensed-4-cyanophenylureido group, at the 4-position, H or a group releasable at the time of coupling with the oxidized product of a color developing agent, and at the 5-position an acyl amino group. A photosensitive material having on a support a silver halide emulsion layer contg. said coupler is imagewise exposed, and an subjectecd processing including a color developing process and a bleach fixing process. A preferable substd.-4-cyanophenylureido group has formula I in which Y is alkyl or the like and m is 1-4. A preferable condensed-4- cyanophenylureido group has formula II in which n is 0-4, and Z is a nonmetallic atomic group needed to form a 5- or 6-membered condensed ring toggether with a benzene ring.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for processing a silver halide photographic material having a silver halide emulsion layer containing a novel cyan dye-forming capsule. Normally, color images are produced by the reduction of exposed silver halide grains by an aromatic primary amine color developing agent. in a silver halide emulsion with a coupler forming
Formed by oxidative coupling.

Couplers typically used to form cyan dyes are phenols and naphthols. Considering the photographic performance of conventional couplers, especially for phenols, the basic properties required are that the dye should have good spectral absorption characteristics, that is, it should be sharp with no absorption in the edge region of the spectrum, and that the formed dye should be sensitive to light. It goes without saying that it has sufficient fastness against heat, moisture, etc., and good color development, that is, sufficient color development sensitivity and color development AM.However, on the other hand, conventional silver halide photographic SFT materials It has been a long-standing aspiration to speed up the process of imagewise exposure, development, and obtaining a bond. As one means for solving this demand, a technique is known in which a bleaching and fixing process is performed at the same time as the bleaching and fixing processes.

On the other hand, in recent years, it has become common to use aminopolycarboxylic acid Is complex #A (for example, EDT) in the bleach-fixing process because it is not toxic to pollution. There is a problem in that images are susceptible to loss of dye (especially cyan dye).

Therefore, there is a strong demand that, for example, a bleach-fixing bath containing EDTA as a main component does not cause loss of color even when fatigued by running.

Furthermore, from the standpoint of eliminating pollution, the removal of benzyl alcohol, which is added to color developing solutions, has been taken up as a major issue. However, what about benzyl alcohol in general? i
The current situation is that sufficient color development cannot be obtained unless T is added. Removal of benzyl alcohol reduces color development!
This is particularly noticeable in L7xL7x no-pla, and from this point of view as well, there is a demand for a phenol-supported anchor 1 color that has high coloring properties even without benzyl alcohol.

Research has been carried out to satisfy the above-mentioned Mi1, but to the best of the knowledge of the present inventors, a cyan coupler that satisfies all of the above-mentioned required properties has not yet been found.

For example, 6-[α-(2,4-di-t-amylphenoxy)butanamide')-2,4-dichloro-3-methylphenol described in U.S. Special Fraud No. 2.801,171 has light resistance. Although they are good, they have shortcomings in heat resistance, and in addition, it is difficult to remove dye loss in a tired bleach-fix solution. 2-Hebutafluoro as described in US@FF No. λ895,826. Butanamide-5-[α-(2,4-7-t
-amylphenoxy)hexanamide] Phenol is excellent in terms of heat resistance and dye loss in a fatigued bleach-fix bath, but inferior in terms of light resistance and color development. Further, the coupler described in JP-A-53-109630 also has problems in terms of benzyl alcohol removal and light resistance. Additionally, U.S. Patent No. 3,839,044
No., JP-A No. 47-37425, JP-A No. 48-36
Publication No. 894, Japanese Patent Application Publication No. 50-10135, 5G-
No. 117422, Patent No. 113,446,622, No. 3 in terms of heat resistance and removal of benzyl alcohol.
, No. 996,253, No. 3,758,308 and No. 3
, No. 880.661, etc., but the cyan dyes formed from these Kabutsu have a broad spectrum and the absorption maximum is in the relatively short wavelength range of 11 in the red region. al [region x has considerable absorption and is not favorable in terms of color reproduction. Although the JP-A-Sho has improved considerably, other characteristics are still lacking.

Therefore, an object of the present invention is to provide a processing method for silver halide photographic sensory materials that speeds up the processing of silver halide photographic sensory materials and that does not cause loss of cyan dye even when the processing solution is subjected to running processing. The purpose is to provide a method.

As a result of extensive research into these conventional techniques, the present inventors have found that the present inventors have found that the present inventors have been able to solve these problems through intensive research on the support, substitution at the 2-position, and condensation condensation.
A silver halide photographic material vessel having a silver halide emulsion layer containing a 4-cyanophenylureido group, an elementary atom or the oxidation product of a color-developing crude drug at the 4-position and the 7-position. The purpose could be achieved by adopting a method for processing silver halide photographic materials that includes each step of the present processing step (2) bleaching, fixing, and grading.

The substituent of the τ-substituted -4-cyanophenylfreido group is of course located on the phenyl group, but preferably has the following general formula.

■] In the formula, Y is an alkyl group, preferably a C8 to C1 branched or IN# alkyl group, a group such as chlorine or bromine, a hydroxyl group, nitroft, c+ to C, f) aliphatic, 7siloxy group (preferably aromatic acyloxy group), alkoxy group (preferably C8-C1 alkoxy 1Ik), acyl group (aromatic acyl group, aliphatic acyl group),
m represents an integer from 1 to 4. Note that when m≧2, Y may be the same or different. 1 cup - 4
The -cyanophenylwaleido group may form a product at the 2- and 3-positions of the phenyl moiety, preferably the following (
YJn In the formula, Y is the same as defined above, and may be a phenyl moiety or a ZIIK moiety. n represents an integer from 0 to 4. 2 represents the nonmetal Fushiko's opinion that it forms a 5- or 6-member monomer with the benzene ring. Examples of condensed rings formed with 2 include naphthalene, quinoline,
Benzothiophene, benzofuran, ink! Hun etc. can stay here.

In the Kayapring reaction, the specific moiety that causes 1111111 is that the halogano atom (N is each baby of chlorine, bromine, fluorine, etc.) II compound atom or Densaku Foshi is an am car w
Aryl-o"?/ groups, carbamoyloxy groups, carbamoylmetho groups, acyloxy groups, sulfonamide groups, succinic acid indo groups, etc., which are attached to the 1-ring position, are mentioned, and as j!KJL-like Oka, is rice 1inWm 3
, 471, F) 63-%, 41INIIs47-3
No. 742fi, Special Publication No. 48-36894 JM Showa fsO
-101354, fiO-117422. No., same FS
O-130441-1. Same F) No. 1-108841, Same F) No. O-120334, Oka? )2-1831! S,
l! r153-F) No. 2423, No. 53-105226
The information listed in each publication such as No. 1 is useful.

In multilayer color photographic INK, the ballast of acylamino groups acts as a "weight" to stop the force in a specific layer and prevent it from spreading to other layers. 91 is a must for sufficient umbrella. Specific examples of the acylamino include aromatic acylamino and aliphatic acylamino, but in the case of aromatic acylamino, a substituent having an alkyl chain of 01 to C11 is required in the aromatic ring. Examples of substituents having a C, to C1 alkyl chain include an alkyl group, an acyloxy group, an acylamino group, a sulfonamido group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl 1, an alkylamino group, a dialkylamino group, etc. I can stay. In the case of aliphatic azila, the aliphatic group is typically a C, % C18 long chain alkyl group, and the aliphatic group is typically a phenoxyalkyl group or a 78-nylthioalkyl group.

In the case of a phenoxyalkyl group or a phenylthioalkyl group, there are cases in which a phenoxy-KcI to C4 alkyl-containing substituent is present, and cases in which the alkyl moiety itself deprives a C1 to C1. carbon. As the ballast-formed acylamino group of the present invention, a phenoxyalkyl group or a phenylthioalkyl group gives particularly preferable results when used as a ballast. Specific examples of the acylamino that ballasts the phenoxyalkyl group include the following targets.

α-(3-bentatecylphenoxy)butanamide α-(2,4-di-aryenoxy)hexaneamide r-(2,4-di-aryaenoxy)butanamide α-(2,4-di- t-forphenoxy)tet2tecanamide α-(4-butylsulfonylaminophenoxy)tetradecanamide α-(4-butylsulfamoylphenoxy)tetradecanamide α-(4-7cetoxyphenoxy)tetradecanamide α-(p- (α-(4-hydroxyphenyl)-α, α
-dimethyl]tolyloxy)toticanamide α-(4-carboxyphenoxy)toticanamide α-(2-1o a-4-)f-sulfonylaminophenoxy)tetradecanamide α-(4-dimethyl7minosulfonylaminophenoxy)tetradecanamide α-(3-dodecyloxyphenoxy)butanamide α-(4-dodecyloxyphenoxy)butanamide α-(4-hydroxyphenylthio)dodecane α-(4
-7cetylaminophenylthio) horse chestnut is shown below as KflJ, but is not limited thereto.

(1) ct(2) CIt'1l (3) (4) 1 (5) 1 (6) r (7) HHfl (8) (9) 0, H,? (10) C4 bird (11) 0 only υIl1%I (12) INJ (13) 1 (14) (intestine) 1-1 (16) (17) Bumu Xi W 7 enol of the present invention, substituted -p- Add cyanophenyl incyanate to a suitable aminophenol.
By reacting with 12-amino-5-nitrophenol or 2-amino-4-chloro-5-nitrophenol, 2
-(1111%-1)-cyanophenyl)waleidation product can be prepared from K by failure. The nitro group can then be reduced to a fin by conventional means and attached to the ballast group 7-one.

vinegar.

Synthesis Example 1 (Exemplary Coupler 2) (7) Synthesis of 2-(,-cyano-m-methoxyphenyl)ureido-5-ditrophenol 15.4N of 2-
Amino-5-nitrophenol is suspended in 300% toluene and refluxed. A solution of 1'1.4fi p-cyano-Otori-methoxyphenylinocyanate in 150-toluene KiIw4 was added dropwise to this while stirring. After the dropwise addition, the reaction solution was heated under reflux for 1 hour, and then cooled. Filter the precipitate and wash with hot toluene and alcohol.1.
22g of the target product was obtained.

(a) Synthesis of Exemplary Coupler 2 a, Using 2-(p-cyano-m-methoxyphenyl)ureido-5-nitrophenol of sII and a palladium-carbon catalyst, in 200-g alcohol at room temperature and normal pressure. A hydrogenation reaction was carried out. Next, the palladium-Kitake is filtered out,
The filtrate was concentrated and the residue was dissolved in 200 Km of acetonitrile. Add 1.6g of pyridine to this and continue to heat for 9 minutes.
, 5 g of 2-(4-butylsulfonylaminophenoxy)tetradecanoyl chloride were added with stirring. After stirring at room temperature for 5 hours, the mixture was extracted with water, fPl and ethyl acetate. Ethyl acetate was distilled off, and the residue was recrystallized from methanol and further from acetonitrile to obtain 7.2 g of the desired product. The target product was confirmed using mass spectra and nuclear magnetic resonance spectra.

Synthesis Example 2 (Exemplary Coupler 1) (7) Synthesis of 2-(0-juts-Shishif/phenyl)ureido-4-ria-5-nitrophenol 18.8 g of 2-amino-4-chloro-5- Nitrophenol, 2'1. 7-enyl 0-chloro-p-cyanophenyl carbamate of Sll and 0.68 g of imidazole were heated to reflux in 400-g of xylene for 5 hours. After cooling, the precipitate was filtered and washed with xylene and a small amount of alcohol to obtain 23.5IIf) desired product.

(a) Synthesis of Exemplary Coupler 1 11 2-(0-chloro-p-cyanophenyl) of Ii
Catalytic reduction with hydrogen was carried out in 300 Wlj of alcohol at normal temperature and pressure using Freid-4-chloro-5-2)c17X/-l and a palladium-carbon catalyst. After the reaction, the catalyst was filtered off, the filtrate was filtered, and 250117 setonidril was added to the residue. To this was added 2.411 g of pyridine, and 12.3 N of 2-(3-pentadecylphenococo)butanoyl chloride ta was added at room temperature with stirring. After stirring at room temperature for 6 hours, the mixture was poured into water and extracted with ethyl acetate. The residue obtained by distilling off ethyl acetate was subjected to chromatography using silica gel as a carrier and benzene-ethyl acetate as an eluent. The target product fractions were combined and the solvent was distilled off. The residue was further crystallized from methanol to obtain 5.8 g of the desired product. The target product was confirmed by mass spectrometry and nuclear magnetic resonance spectroscopy.

The cyan pigment forming power graph used in the present invention (hereinafter referred to as “
"Coupler according to the present invention". ), the method techniques used for conventional cyan dye-forming couplers are similarly applicable. Typically, the coupler is incorporated into a silver halide emulsion,
This emulsion is coated on a base to form a silver halide photographic material.

The silver halide photographic light-sensitive material (photographic element) is contained in a single agent, but may also be contained in a non-sensitized emulsion or a color*m* forming constituent unit that is sensitive to each of the three primary color regions of the spectrum. . Each structural unit can consist of a single emulsion II or a multilayer emulsion layer that is sensitive to a certain region of the spectrum. The layers, including the constituent layers of the 1Ije forming structure, can be arranged in various orders as is known in the art. A typical multicolor photographic element comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler (at least one green dye-forming coupler having at least one red-sensitive silver halide emulsion layer). At least one mazemme dye image-forming unit comprising a sensitive silver halide emulsion layer and at least one yellow dye-forming coupler.
It consists of two blue-sensitive silver halide emulsion layers supported on a base of a yellow dye image forming structural unit. The element may be provided with additional layers such as filter layers, intermediate layers, and protection according to conventional methods. For example, gelatin water containing a single surfactant, such as a high-boiling organic solvent with a boiling point of 175°C or higher, such as tricresyl phosphate or dibutyl 7-talate, or a low-boiling solvent, such as butyl acetate or butyl propionate.
ii, then emulsified in a high-speed 10-turn mixer or colloid mill, and then added to silver halide to form the emulsion used in the present invention, usually silver halide 1
About 0.07 to 0.7 mole per mole, preferably 0.1 mole.

The silver halide used in the silver halide emulsion of the present invention includes silver bromide, silver halide, silver iodobromide, silver chlorobromide, and those used in conventional silver halide emulsions dominated by Hanawa iodobromide. Anything is included.

The silver halide emulsion constituting the silver halide emulsion of the present invention can be produced by various manufacturing methods including the usual manufacturing method, such as the method described in Japanese Patent Publication No. 46-7772,
That is, forming an emulsion of at least some silver salt grains with a WI seismic intensity greater than that of silver bromide, and then converting at least a part of these grains to silver bromide or iodobromide chain. The manufacturing method of so-called con-sage emulsion such as
It can be produced by any production method such as the production method of Lippmann emulsion consisting of fine grain silver halide having an average grain size of μ or less.

Furthermore, the silver halide emulsion of the present invention may contain sulfur sensitizers such as ruthiocarbamide, 1,000 urea, cystine, etc., active or inactive selenium sensitizers, and reduction sensitizers such as tin III, Polyester, noble metal sensitizer,
For example, gold sensitizers, specifically potassium aurithiocyanate, potassium chromiolate, 2-oresulfopenzthiazole methyl chloride, etc., or hydrophobic sensitizers such as ruthenium, rhodium, iridium, etc.
Chemical sensitization can be achieved by using A-type KFi ammonium chloroparatate, potassium chloroplatinate, sodium chlorovaladide, etc. alone or in appropriate combinations.

Furthermore, the silver halide bill of the present invention can contain various known photographic additives. For example l*a@ar
eh Dii@l*awr*, 1978 month term @
17643 K is a photographic additive as described.

The silver halide of the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart sensitivity to the wavelength range required for red-sensitive emulsions. Various types of spectral sensitizing dyes can be used, and one or more of these #'i types can be used in combination.

Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat.
．． No. 270,378, Ii@$ No. 2,442,710, Ig No. 2,454,629, IQ Iris No. 2,776.
Typical examples include cyanine dyes, merocyanine dyes, and complex cyanine dyes as described in the specifications of No. 280.

This is the amount of time. Typical examples of this color-forming active ingredient include those based on UP-phenylenediamine, such as diethyl-p-phenylenediamine, monomethyl-p-7, dimethyl-p-7, and dimethyl-p-7. :c nylene diamine mound layer, 2-amino-5
-diethylaminotoluene salt, 2-amino-5-(
N-ethyl-N-dodecylamino)-toluene, 2-amino-5-(N-ethyl-N-β-methanesulfonamidoethyl)minotoluene sulfate, 4-(N-ethyl-
N-β-methanesulfonamidoethylamino)aniline, 4-(N-ethyl-N-β-hydroxyethylamino)aniline, 2-amino-5-(N-ethyl-N-β-
Methoxyethyl) a2notluene and the like.

After finishing the process, it is necessary to perform bleach-fixing to remove the chains and no-logenated chains! ! The usual steps of washing and drying are carried out accordingly.

Next, preferred modes of appeasement according to the present invention will be listed.

(1) A method for processing a silver chloride photographic alt material according to the claims, in which the 101-4-cyanophenylureido group has the following general formula.

((In the formula, Y is an alkyl group), rogene, hydroxyl group,
It represents a nitro group, an acyl group, an alkoxy group, or an acyl group, and m represents an integer of 1 to 4.

In the case of kvm 2, Y may be the same or may be different. ) +2) A method for processing a silver halogenide photographic material as claimed in the claims, wherein the 11-united 4-silonophenyl [/ide group has the following general formula.

(In the formula, Y is the same as the above definition, and may be present in the phenyl part or the 2 part. nViO represents an integer of 4. zii A 5- or 6-membered condensed ring together with the benzene ring (Represents a group of non-metallic atoms that form a group of non-metallic atoms.) The present invention will be specifically described below with reference to Examples, but the implementation of the present invention is not limited thereto.

Take 0.03 mol of each of the following comparative couplers (A), [:s], and (C:l) and add to a mixed solution with the same amount of 7-tal dibutyl and three times the amount of ethyl vinegar. In addition, ω
'CK was heated and completed 4 [11 times]. This iI can be treated with alkanol IB (alkylna-7talene sulfonate,
Bonn) and gelatin were emulsified in water using a colloid mill to prepare respective coupler dispersions. Next, a chlorobromide emulsion containing 0.1 mol of silver (20 mol of silver bromide) was added to this coupler dispersion, and
Six types of silver halide photographic sensory materials (sample numbers [1] to [6]) having stable coatings were obtained by coating on polyethylene laminated paper and drying.

Comparative coupler [M] (E Comparative coupler [ll] IIHII Hikusu coupler CC) These samples were subjected to wedge exposure according to a conventional method and then subjected to a fire treatment. However, the color development process was carried out for two types of compositions: one with benzyl alcohol added (color development [1]) and one without (color development [2]).

〔process〕

Processing process (30℃) Processing time Color development 3 minute fraction seconds Bleach fixing 1 minute addition Wash with water 2 minutes The composition of each treatment is shown below.

[Color development gII liquid composition 1] [Color developer composition 2] [Bleach-fix solution composition] The photographic properties of each of the obtained samples were measured.

JIII the result! Show IK. The relative sensitivity values in the table are expressed with the maximum sensitivity value when processed with color developer [1] as 100.

Sample t-S containing j111 front puller treated with white fixing:
/X) k7Ry: It can be seen that both the color development with ff-ru and the color development without benzyl alcohol are excellent in that good sensitivity and maximum density can be obtained.

It was found that the maximum absorption is in the long portion, and the absorption on the short wavelength side is small, indicating excellent color purity.

Example (2) Using a sample obtained in the same manner as in Example (1) above, the light resistance, heat resistance, and moisture resistance of the dye image were examined.

The results obtained are shown in Table 2.

~-゛, I-4 out of 1. In addition, the light resistance in the table is expressed by the residual am after exposing each obtained image to a xenon fade meter for 300 hours, with the 4 change before exposure being 100. In addition, the resistance is the remaining 11 molten strength after storage for 3 days under the condition of 77"C, and the concentration before the test is 10
It was expressed as O. (However, it can be seen that both samples with initial color development, developed with and without pendyl alcohol, had excellent results in subsequent light, heat, and moisture resistance tests. .

Example (3) Samples (1) to (6) obtained in Example (1) were subjected to wedge llft, and then subjected to color development (I) in Example (1). On the other hand, use the bleach-fix solution in the following set 5! Fatigue bleach-fixing 1 [The fading property of cyan dye due to K was investigated.

[Bleach-fix solution composition]

Ethylenediaminetetraacetate iron ammonium jig 50
1 Ammonium sulfite (40ch!11) 50
+J ammonium thiosulfate (70111111E)
140 mg ammonia water (28 ml solution) 20- Ethylene cyagine tetra vinegar 11 4 g hydrosulfide 5 g water added to 11
shall be.

The maximum amount of cyan dye in the sample obtained after processing was adjusted to 1. The results are shown in the 1m3 table.

Incidentally, the dye residual rate at the maximum 111f portion was determined as follows.

Table 3 *It is understood that the fading of the cyan dye in the RakuFaku bleach-fix solution is minimal even when treated with a fatigued bleach-fix solution.

Claims (1)

[Scope of Claims] A silver halide emulsion layer having a substituted or condensed 4-cyanophenylureido group at the 2-position and a hydrogen atom or a coupling with an oxidation product of a color developing agent at the 4-position is provided on a support. Silver halide photographic SFT, material that has, (1) *Process of 11f (-) Process of color development processing 0 button Each step of bleach-fixing process [Includes...Silver halide photograph II & processing method of original material .