JPS5833250A - Cyan dye forming coupler - Google Patents

Abstract

PURPOSE:To obtain a novel phenolic cyan dye-forming coupler good in spectral absorption characteristics of the formed dye, high in resistance to light, heat, humidity, etc., good in color developability, sufficient in color developing sensitivity and density, small in loss of the dye even in an exhausted bleaching bath, and retained high in color developability even when benzyl alcohol is not added to a color developing soln. CONSTITUTION:A number of required characteristics are satisfied by a phenolic cyan coupler represented by general formulaeIand II in which R<1> and R<2> are alkyl, alkenyl, aryl, cycloalkyl, acyl, or heterocyclic, and they may link with each other to form a 5- or 6-membered ring; X stands for a hydrogen atom or a group releasable on reacting with the oxidized product of a color developing agent; and R<3> is a ballasting group.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a silver halide color photographic material containing the same. Normally, color images are produced by the aromatic primary amine thread color developing agent reducing the exposed silver halide grains, resulting in oxidation products of the color developing agent, yellow, and magenta.

It is formed by oxidative coupling between couplers forming each cyan dye in a silver halide emulsion.

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 has good spectral absorption characteristics, that is, there is no absorption in the edge region of the spectrum and that the formed dye is sharp. , have sufficient robustness against heat, moisture, etc. Good color development. That is, it must have sufficient color-forming electric shock and color-forming density. Furthermore, it is required that a bleaching bath or a bleach-fixing bath containing EDTA ferric salt as a main component undergoes no loss of elements even if it is fatigued by running.

Furthermore, from the viewpoint of depollution, the removal of benzyl alcohol added to color developing solutions has been taken up as a major problem. However, the current situation is that sufficient color development cannot generally be obtained unless benzyl alcohol is added.

The deterioration of color development upon removal of benzyl alcohol is particularly noticeable in phenolic cyan couplers, and from this point of view as well, there is a demand for phenolic cyan couplers that exhibit high color development even without benzyl alcohol.

Research has been conducted to satisfy the above requirements, but to the best of the present inventor's knowledge, a cyan coupler that satisfies all of the above required properties has not yet been found.

For example, Co[α-(Co,4t-di-t-amyl-3-methylphenol) described in U.S. Pat. In addition, there is a large loss of color in a tired bleach-fix solution.''!Next, the color development is highly dependent on benzyl alcohol, and it is difficult to remove benzyl alcohol from the color developer.U.S. Pat.

♂9! ,! Carp Hr [! Cohebutafluorobutaneamide! - [α-(2,4t-di-t-amylphenoxy)hexanamide] Phenol is excellent in terms of heat resistance and loss of dye in a tired, pale fixing bath, but has poor light resistance and color development. It's inferior. Manen Tokukaisho! J-109
The coupler described in Japanese Patent No. 630 also has problems in terms of removal of benzyl alcohol and light resistance. Furthermore, U.S. Patent No. 3,939.0 Dada, Japanese Patent Application Publication No. 1973
7-37 Octopus J Publication, Special Publication Shoda TR-3TY Tag Publication, Japanese Patent Publication ShojO-10/J! Same issue! 0-//7,41
No. 2-, No. 1O-130414t1, No. 2-/θ/
,! Da/No., same! The phenolic cyan coupler 4M described in θ-/, No. 2033, etc. is unsatisfactory in terms of thermal properties and removal of benzyl alcohol. Phenol couplers having a ureido group at the -position are disclosed in US patent gF, /,
0//, 9ri □ and U.S. Patent Nos. 3 and 4 trig, 22
No. 3. ? 6. λj No. 3, same J? ! ,! , 301
No. and J,! Although it is stated in No. 10, 44/etc.
The cyan 1 dye formed by these couplers has broad spectral absorption, and its absorption maximum is in the relatively short wavelength region of the red region, so it has a narrow absorption in the line region of the spectrum, which is difficult to reproduce in color. Undesirable. Tokukai Akira! Go 6! /3
Although the phenol coupler having a ureido group at the 2-position described in 2003 has been significantly improved in terms of green absorption in the low end of the spectrum, other properties are still unsatisfactory. As a result of intensive research into these conventional techniques, the present inventors have found that the couplers represented by the following general formulas c) and (11) sufficiently exhibit the characteristics required for the above-mentioned phenolic cyan couplers. I have found something that satisfies me.

-! - General formula (Il p General formula (I [l lyl group, cycloalkyl group, sulfate group, acyl group (e.g. alkylcarbonyl group, arylcarbonyl group) t
-Represent. As substituents, for example, alkyl groups, aryl groups, halogen atoms (e.g. fluorine, chlorine or bromine)
, trifluoromethyl group, nitro group, cyano group, hydroxyl group, alkoxy group, acyloxy group, acylamino group, sulfonamide group, sulfonyl group, sulfonamide group, sulfa 6-moyl group, sulfo group, carboxylic acid group, etc. It's okay.

The orthogonal alkyl group may be straight or branched.

Further, R %R may be bonded to each other to form a j- or g-membered ring. Atoms constituting the ring can be selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. X represents hydrogen or a group that can be eliminated during the coupling reaction with the oxidation product of the color developing agent.Specific examples of groups that can be eliminated during the coupling reaction are:
For example, aryloxy groups, carbamoyloxy groups in which a halogen atom (e.g., chlorine, bromine fluorine, etc. atoms), an oxygen atom or a nitrogen atom is directly bonded to the coupling position,
Examples include carbamoylmethoxy group, acyloxy group, sulfonamide group, succinimide group, etc. More specific examples include US Patent No. 34t7/! No. 63, Japanese Patent Publication No. 4
t7-32guichi! issue, special public Sho 4try-, itt tag issue, special public Sho jO-/θ/3! Same issue! 0−//7 da, 2λ
No., JO-/3θ Kuda/No., J/-/071 G/No., No. 10-/20J34, No. J2-7? ! Ij
Same issue! ! -! 2da, No. 23, same j3-10j, 26
The information described in each publication such as No. 1 is useful. R3
Habarast group hail. (The last group acts as a "weight" in multilayer color photographic elements, trapping the coupler in a particular layer and essentially quadruple its diffusion to other layers.
For this purpose, sufficient ``bulkness'' is required oNH-
Specifically, aromatic acylamino groups and aliphatic acylamino groups are important as the acylamino group represented by Go-R. ff1ff with an alkyl chain of 05 to C18
Examples of the i substituent include an alkyl group, an alkoxy group, an acylamino group, a sulfonylamino group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylamino group, and a dialkylamino group. In the case of aliphatic acylamino, representative examples of the aliphatic group include a C to C long chain alkyl group, furthermore, a phenoxydialkyl group and a phenylthioalkyl group.

In the case of a phenoxyalkyl group or a phenylthioalkyl group, as for an acylamino group in which a 05 to C18 alkyl chain is pasted to the phenoxy moiety, particularly when a phenoxyalkyl group or a phenylthioalkyl group is used as the parast, favorable results are obtained. The following example φ! is an acylamino group whose parast is a phenoxyalkyl group. Can be mentioned.

α-(3-pentadecylphenoxy)butanamide α-(J,4t-di-t-amylphenoxy)hexanamide 7-(2,4t-di-t-amylphenoxycobutanamide α-(J,Q- di-t-amylphenoxy)tetradecanamide α-(terptylsulfonylaminophenoxy)tetradecanamide α-(cutylsulfonylaminophenoxy)tetradecanamide monoterα-(teracetoxyphenoxy)dodecaneamide α-(p-[α -(4t-hydroxyphenyl)-α,
α-dimethyl]tolyloxy)dodecanamide α-(glucoxyphenoxy)dodecanamide α-(,2-chloro-terphthylsulfonylaminophenoxy)tetradecanamide α-(4t-dimethylaminosulfonylaminophenoxy)tetradecanamide α-(3 -dodecyloxyphenoxy)butanamide α-(4t-dodecyloxyphenoxy)butanamide α-(4t-hydroxyphenylthio)dodecane azdo α-(guacetylaminophenylthio)dodecane abado Couplers within the scope of the present invention include: Examples are shown below, but the invention is not limited to these.

Compound Example H 17 ○ 73- -/4t- H3 23 Typical synthesis routes and synthesis examples of the couplers of the present invention are shown below. -pentamethylene)ureido-terchloro-! -Synthesis of (α-(3-butanesulfonylaminophenoxy)tetradecanamide)phenol - ditrophenol'fr dissolved in 20θml of ethyl acetate, /,0
Add pyridine of f. A 20 ml solution of piperidine carboxylic acid chloride in ethyl acetate was added under stirring at room temperature/jfl. After stirring at room temperature for 7 hours, it was cooled, the precipitated solid was collected, washed with water and then alcohol, and dried.
I got a companion item of 2F.

The above coarse crystal/! Dissolve f in alcohol of 3θθmt,
A palladium-carbon catalyst was added, and catalytic reduction with hydrogen was performed at room temperature and pressure.Then, the palladium-carbon catalyst was separated from each other, and after complete condensation of the Oki liquid, the residue was dissolved in 300 mt of acetonitrile. 0 for this
．． ! f pyridine was added, and a solution of 2+19 α-(3-butanesulfonylaminophenoxy)tetradecanoyl chloride in /θOml acetonitrile 5//− was added. After stirring at room temperature for 3 hours, it was poured into water and extracted with ethyl acetate. The Kasumi 0 extract was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was recrystallized with a mixed solvent of acetonitrile and methanol. Obtained the object 'f. The structure of the target product was confirmed by mass spectroscopy and proton NMR spectroscopy.

Synthesis Example λ (Example - Synthesis of Coupler 3), 1-(N, N
-diethyl azu)) ureido-cuchloro-! −(α−
(2, Kuji tert-pentylphenoxy)tetradecanamide) Synthesis of phenol/! The 2-amino-chloro-j-nitrophenol of rif was dissolved in ethyl acetate of θOmA, and pyridine of /, θf was added. While stirring at room temperature, a 3 omt solution of diethyl carbamyl chloride in ethyl acetate was added. 3
After stirring at room temperature for an hour, the mixture was cooled, and the precipitated solid was collected, washed with water and then alcohol, and dried to obtain crude crystals 2jrf.

The above crude crystal/4tII and palladium-carbon catalyst total 30θ
ml of alcohol and catalytic reduction with hydrogen at room temperature and pressure. Next, palladium-carbon probes were distributed from house to house, and the filtrate was concentrated, and the residue was dissolved in 11rjθθrnl of acetonitrile. Add pyridine θ and jf to this j!
A 700 mt acetonitrile solution of α-(2, tert-pentylphenoxy)tetradecanoyl chloride of f was added. After stirring at room temperature for 9 hours, the mixture was poured into water and extracted with ethyl acetate. Extraction fPIt - After concentration, silica gel column chromatography eluted with a mixed solvent of toluene and acetone, recrystallization from acetonitrile,
The target product 'f of ztH was obtained. The structural confirmation of the target product was carried out by mass spectroscopy and proton NMR spectroscopy.The method techniques used in conventional cyan dye-forming graphs are similarly applicable to the cyan dye-forming couplers used in the present invention. Typically, the coupler is incorporated into a silver halide emulsion and this emulsion is applied onto a base to form a photographic element. Form.

Photographic elements can be single color or multicolor elements. In multicolor elements, the cyan dye-forming couplers of this invention are normally incorporated into red-sensitive emulsions, but are not incorporated into unsensitized emulsions or color patch image-forming constituent potentials sensitive to each of the three primary regions of the spectrum. The layers of the element, including the image forming composition layer, can be composed of an emulsion layer or a multilayer emulsion layer, each structural unit having a sensitivity to a certain region of the spectrum. They can be arranged in various orders as known in the art. A typical multicolor photographic element comprises a cyan dye image-forming building block consisting of at least one red-sensitive silver halide emulsion Jv4 having at least seven cyan dye-forming couplers (at least seven of the cyan dye-forming couplers being couplers of the invention). ),
A yellow-forming image-forming building block consisting of at least seven blue-sensitive silver halide emulsion layers having at least seven magenta dye-forming couplers, intermixed with the overall pace.
The summary includes additional layers such as a filter layer, an intermediate layer, 49
- The coupler of the present invention may be incorporated into an emulsion by a conventionally known method. For example, the boiling point of tricresyl phosphate, diptylphthalate, etc./2! For high boiling point organic solvents at temperatures above ℃, use the coupler of the present invention alone or in combination with low boiling point solvents such as butyl acetate and butyl propionate, or in a mixture of n% of them as necessary. and gelatin water containing surfactant and dissolved in water, mixed with
Next, after emulsifying with a high-speed rotating ξ mixer or colloidal slurry, the coupler of the present invention can be added to silver halide to prepare the silver halide emulsion used in the present invention. When added to a silver halide emulsion, usually about θ, 07 to 0.7 mol per mol of silver halide,
Preferably, the coupler of the present invention is added in a range of θ,/mol - 0.1 mol.

The silver halide used in the silver halide emulsion of the present invention includes silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc., which are commonly used in silver 710 emulsions. Any of the above is included.

12- The halogen anchor emulsion constituting the silver halide emulsion of the present invention can be prepared by various manufacturing methods such as λ
The method described in Japanese Patent Publication No. t4-777.2 is to form an emulsion of silver salt grains consisting of at least a part of a complex salt whose solubility is greater than that of a bromide complex, and then at least one part of the grains is Silver silver or iodobromide fl
11 of requested conversion emulsions such as conversion to I salt! l
! The Lippmann emulsion can be prepared by any manufacturing method.

The silver halide emulsions of the present invention may further contain sulfur sensitizers such as allylthiocarbide, thiourea, cystine sensitizers, active or inactive selenium sensitizers, and reduction sensitizers such as stannous salts. , polyamines, etc., ■ Metal sensitizers, such as gold sensitizers, specifically ['11IIium aurithiocyanate, potassium chloroaurate, λ-aurosulfobenztheazole mether chloride, etc., or, for example, ruthenium, rhodium, iridium, etc. It can be chemically sensitized using water-soluble salt sensitizers such as ammonium chlorobaratate, potassium chlorooleate, and sodium chloroparadite alone or in a negative manner as appropriate. .

Further, the silver halide emulsion of the present invention can be used in various known 4JJ emulsions. The world's first lambda
5earch Disclosure (Research History) / 1997r / -February item / 76ri 3
Photographic additives such as those described in .

The silver halide of the present invention is spectral sensitized by selecting an appropriate sensitizing dye in order to impart photosensitivity to the wavelength range necessary for red-sensitive emulsions. Various types of spectral sensitizing dyes are used, and seven types or two or more types of these can be used in combination.

Spectral sensitizing dyes advantageously used in the present invention include, for example, U.S. Pat. Ko 3rd issue, 2nd issue. Core 0.37♂ No. 2. &@+2,710 No. 2
．． Da! Gu, No. 629, No. 2,774. Ko! Between each of the θ passes, cyan dyes such as those described in [F etc., merocyanine dyes, and Fi composite cyanine color charts as representative ones include #0, which can be used in the present invention. The cleaning solution preferably has an aromatic 11G primary amine coloring agent as its main component. Specific examples of these color-forming and brightening herbal medicines include Fip-phenylenediamine-based drugs, such as Diebru p-phenylenecyamine salt 2+=, monomethyl-p-phenylenecyamine 4feli, Dimethyl-p-phenylenediamine tower acid salt, λ-amino-!-diethylaminotoluene dioate, 2-amino-!-(N-ethyl-N-dodecylamino)-toluene, no-amino-j-(N-ethyl-N- β-methanesulfonamidoethyl)aminotoluene krc NRFm, "-(N-ethel-N
-β-methanesulfonamidoethylamino)aniline t
”-(N-ethyl-N-β-hydroxyethylamino)
Aniline, λ-abanoj-(N-ether-N-β-methquinether)abanotoluene calculation is my idea.

After one use, bleach, fix or bleach-fix, wash and dry to remove silver and silver chlorides. - ■ Normal steps are carried out. The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example (1) Take 0.03 mole each of the coupler of the present invention and the liquid comparison couplers (A), rB), and [C) shown in the table below, and add an amount equal to their weight. Diptyl phthalate and 3 times the amount of ethyl acetate were added to remove VC and heated to 60°C to completely dissolve this solution. A chlorobromide emulsion containing 0.1 mol as this coupler dispersion f# was prepared by emulsifying each coupler dispersion by adding λ and using a colloidal bar.
Silver halide color photographic material H (sample number [/] ~
[t]) got it.

161 Comparative coupler rA) Comparative coupler [B) H These samples were wedge exposed according to the conventional method? After that, the following process was performed. However, in the color development process, pendel alcohol is added ([Color development solution composition/])
Two types of compositions were tested: one without additives ([Color forming plastic composition composition]).

〔process〕

Processing process (30'Q) Processing time Color development 3 minutes 3 o seconds Retsuichi established 7 minutes 30 seconds Washing with water The composition of each treatment is shown below.

[Color developer composition/]

[Color forming plastic composition 2] [Determined composition along M] 29- The maximum dark value when processed with [Color development % IJ liquid enrichment/] was expressed as 100.

30- As is clear from the above Table 7, the samples obtained with Coupler 7 related to Komei VC had good separation and excellent strength regardless of the presence or absence of benzyl alcohol. I understand.

Also, the coloring spectrum f! : As a result of measurement, using the coupler of the present invention (Q7?), the dye has a large absorption strength in the I+P region of the red region, and has a small but excellent absorption strength in the shortwave I11+1 region, and also has a high color purity. It was found that it shows.

Example 2) Previous Kr! Using samples obtained in the same manner as in Example (1), the light resistance, heat resistance, and moisture resistance of the dye images were investigated.

The obtained results are shown in the table.

33- In addition, the light resistance in the table is expressed by the residual density after 300 hours of atomization using each obtained image and a xenon fade meter, and the # change before exposure is expressed as /θO. For humidity resistance, we tested the residual # degree after storage for 3 weeks under the conditions of a θ℃ and relative humidity f7θ.
jI! The density of the song is expressed as 10θ, and the heat resistance is the residual If after storage at 27°C for 3 weeks.
The m degree before the test is expressed as ioo (however, the initial concentration is 1.
θ〕.

As is clear from Table 1, the comparative coupler (A) has excellent light resistance, but has a problem with heat and humidity resistance, and comparative couplers rB) and [C) #-j have superior heat and humidity resistance. However, there are some differences in light resistance with [color developer composition].

On the other hand, it can be seen that the exemplary couplers [/], [3] and [) according to the present invention have excellent performance in all respects.

Example (3) Couplers of the present invention as shown in Table 3, former 81" comparative couplers (A), ["B) and comparative Cub 5-CD below.
``J'fr each took 01 mole of Q, and its weight was 34 tons.
- It was added to a mixture of the same amount of tricresyl phosphate and 3 times the amount of ethyl acetate and heated to 30°C to completely dissolve. This solution was added to an aqueous solution of Alkanol B and gelatin, and the mixture was milked using a colloidal bar to prepare each coupler dispersion.

Next, this coupler dispersion 'fr#' was added to a silver iodobromide emulsion containing 0.7 mole (g mole is an iodide bale), coated on a cellulose acetate film base, and dried to form a stable coating #. We obtained silver halogenide color photographic light-sensitive materials (sample numbers [/3] to [/l]) of the following types.

Comparative coupler [D) H These samples were subjected to wedge exposure according to the conventional method and then subjected to fire treatment. Composition] 37- [Stabilizing liquid composition]
The results are shown in Table 3.

As is clear from Table 3-3 and Table 3, it can be seen that the samples using the coupler according to the present invention are excellent in sensitivity and inventiveness.

Moreover, as a result of measuring the spectroscopic spectrum, the sample according to the present invention has a maximum absorption wavelength in the long wavelength region of the red candy region, and has a sharp cutoff wavelength in the ship wavelength region. It was found that the color reproducibility of green areas and the dye image quality were excellent compared to the comparative couplers.

Example (4) After performing wet filling light on the samples [/] to [”=G] obtained in Example (1), the samples were developed with [color developer composition/] of Example (1). On the other hand, the white-fixing solution was developed with the following GI by WE substitute, and the fading of the cyan dye due to fatigue bleaching was investigated.

[Bleach-fixing M composition]

Ethylenediaminetetraacetic acid iron ammonium salt 502 Ammonium sulfate (4t0 solution) jOm 1 Ammonium thiosulfate (70% t?i W)/aomt39- The reflection'a degree was measured.The P' result f4 is shown below.

Incidentally, the dye residual rate in the large conductivity part was determined as described by Shunshita.

Table 9: ψBF = White mark: N liquid - θ - From Table 9, it can be seen that the sample using the coupler according to the present invention shows less fading of the cyan dye when treated with a fatigue bleach-fix solution.

Agent Yoshikazu Kuwahara/- Procedural amendment affixed N1-September 1611 Commissioner of the Japan Patent Office Kazuo Wakasugi 1 Indication of the case 1982 Patent Application No. 13130-2 Name of the invention Cyan dye Formative coupler 3 Relationship with the case of the person making the amendment Patent applicant address Konishi Rokushasei, 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo, 1 Incorporated Company 5 Date of amendment order Voluntary 6, Subject of amendment Section 7 of the "Claims" of the specification: Contents of amendment The claims are amended as shown in the appendix 〇Claims General cyan dye-forming couplers for silver halide photography represented by the following general formulas CD and ■ Formula CD General formula■

Claims (1)

[Scope of Claims] Cyan dye-forming coupler for silver halide photography represented by the following general formula (11 and (Wl) general formula (It nth general formula (Kl H aryl group, cycloalkyl group, acyl group, heterocyclic group) , and by combining R %R#'' with each other!Also, Fi
A d-membered term may be formed, where X represents a hydrogen atom or a group that separates color development by reacting with an oxidized form of a drug, and R5 represents a pallast group. )