JPS6333745A - Photographic material containing color coupler - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photographic recording material containing a phenolic cyan coupler having a 7-enyl ureido structure incorporated into the material by emulsification.

It is known to produce color photographic images by chromogenic development, i.e., developing an imagewise exposed silver halide emulsion layer with a suitable color-forming developer material in the presence of a suitable color coupler. . In this process, the oxidation products of the developer material produced in response to the silver image react with the color couplers to produce a dye image. The color couplers used are generally aromatic compounds containing 7 primary amide groups, particularly p-7 22-diamine-based compounds.

To generate a cyan partial image, a 7-tall or phenolic cyan coupler is generally used. For color photographic recording materials, 7-tall cyan couplers have generally been preferred over phenolic couplers in the past due to the more favorable absorption (at about 700 nm) of the image dyes produced from them when developing the chromogen. It is based on Phenolic cyan couplers generally provide dyes with maximum absorption in the shorter wavelength region.

Although the spectral properties of cabtol-based cyan couplers make them ideal, especially when used in color negative films, they have the serious disadvantage of providing dyes with insufficient stability, especially to moisture and heat. In this regard, 7E/-L cyan coupler is 7
Although they should be preferable to the toll-based cyan couplers, the dyes produced from them are too short (as mentioned above), and the wavelengths absorbed by them are too short so that an undesirable lateral density is produced in the green region of the spectrum. In terms of
It is unsatisfactory. This results in an unsaturated reproduction of the colors in the copy material, unless the excessively high lateral density in the green spectral region is offset in the color film by means such as the introduction of masking couplers. .

Phenolic cyan couplers in which a phenolureido group substituted in the benzene ring is present at the 2-position of the phenol ring are disclosed in European Patent Application No. 0028099 and European Patent Application No. 0028099.
No. 67689. Although the dyes obtained by color development from these couplers are stable and have a relatively long-wavelength absorption maximum, this absorption maximum is still generally clearly below 70 on-, so that in this respect the 7-tall cyanide It is not comparable to the dye obtained from the coupler and still has an unduly high lateral absorption in the green spectral region. A 2-phenylureidophenol cyan coupler containing a fluorosulfonyl group in the phenylureido group is disclosed in European Patent Application No. 0184.
It is described in No. 057. These color couplers are preferred with respect to the long wavelength absorption of the dyes produced from them (although under climatic conditions the fluorosulfonyl group clearly reacts with the uncrosslinked ami-7 groups of gelatin). It has the disadvantage that it results in flattening of the gradation.

It is an object of the present invention to provide a color photographic recording material containing a color coupler which upon chromogen development gives a stable cyan partial color image having a maximum absorption at about 700 nm and having little lateral density. That's true.

The present invention is sensitized to the red spectral region and
- a color photographic recording material having at least one silver halide emulsion layer associated with cyan couplers of the phenylureidophenolic type, which correspond to at least one cyan coupler corresponding to formula I and to formula II; Concerning a color photographic recording material in which at least one cyanide compound is associated with a silver halide emulsion layer sensitized to the red spectral region: In the above formula, R1 represents a ballast group. and X is H or a group other than hydrogen that can be released during the color coupling reaction, R2 and R3 are HSF, CI, CN, CF3 or S
O, + R' (where R4 is F, alkyl or alkylamino/) with the proviso that R2 and R' cannot both be H and cannot both be CN.

The releasable group represented by X can be, for example, a halogen atom, such as FlCl or Br, or an organic group bonded through an oxygen, sulfur or nitrogen atom.

The alkyl group contained in R2 or R3 can be straight-chain or branched and contain, for example, from 1 to 18 carbon atoms.

The ballast group represented by R1 is preferably a group corresponding to the following formula (1): In the above formula, Z represents O* or S; R5 is a methylene group or has 2 to 20 carbon atoms and is a group corresponding to the formula R represents an alkylidene group corresponding to '-C-alkyl, where R7 is H* or alkyl which can be linear or branched: R6 is halogen, hydroxyl, carboxyl, alkyl, cycloalkyl , aryl, aralkyl, alkoxy, aryloxy, alkylsulfamoyl, arylsulfamoyl, alkylsulfonamide, arylsulfonamide, 7-rukylsulfonylbonyl or acyloxy, the alkyl group contains 1 to 20 carbon atoms and aryl The group is preferably a substituted or unsubstituted phenyl group; and furkyl, aryl and aralkyl can be optionally substituted with 0-furkyl, hydroxyl, carboxyl, alkoxycarbonyl or acyloxy; and 1 to 3 .

R1 can also represent a segment from a polymer obtained by polymerization of a monomeric coupler corresponding to one of the formulas I and 2, in which R1 is a group containing a polymerizable group. R' need not necessarily be the same in the two cyan couplers of a given combination of cyan couplers of formulas I and H.

Examples of cyan couplers corresponding to general formulas ① and H used as combination components according to the invention are shown below: - #
…#
#Co
++
B…
=1
...■-11 A coupler corresponding to general formula I can be prepared by a method known per se,
For example, it can be produced by reacting 3,4-dicyanophenyl isocyanate or phenyl-3,4-dicyanophenyl carbamate with a suitable 2-aminophenol. Methods of this type m are described, for example, in European Patent Application No. 0028099, European Patent Application No. 0067689, European Patent Application No. 017
No. 5573 and No. 0184057.

The 3,4-cisi7/phenylisocyanate required as an intermediate can be prepared, for example, by heating 143 g (1 mol) of 3,4-non7/aniline in 800 mf of niacetonitrile to 30-40°C. The resulting solution is introduced dropwise into 150 g of phosdene in 750 kg of toluene while cooling to 0-5°C. The initially formed 3,4-
Dicyanophenylcarbamide chloride is converted to 3,4-cisi7/phenylisocyanate by eliminating hydrogen chloride. After the evolution of hydrogen chloride has ceased, the toluene is distilled off under reduced pressure and replaced with anhydrous ethyl acetate 7501"C.

The yield is calculated from the NGO capacity test and is 93 to 93% of the theoretical yield.
It is 94%.

Couplers corresponding to general formula II can be used, for example, in European Patent Applications No. 0028099, European Patent Application No. 0067689, European Patent Application No. 01
No. 75573 and No. 0184057.

Couplers corresponding to general formulas I and II: 1:4 to 4:
Useful results are obtained when combined at a rate of 1.

To produce light-sensitive color photographic recording materials, the diffusion-resistant cyan coupler combinations of the invention can be combined with casting solutions of silver halide emulsion layers or other colloidal layers by known methods. For example, preferably oil-soluble or hydrophobic couplers can be added from solution in a suitable coupler solvent (oil former), optionally in the presence of wetting or dispersing agents. Hydrophilic casting solutions can, of course, contain the customary additives in addition to the binder. The solution of the coupler need not be directly dispersed in the casting solution of the silver dendenide emulsion layer or other water-permeable layer, but is advantageously first dispersed in a photosensitive aqueous solution of the hydrophilic colloid and obtained. The mixture is then mixed with a casting solution for a light-sensitive lambda silver halide emulsion layer or other water-permeable layer, optionally after removing the low-boiling organic solvent used before application of the casting solution. Can be mixed.

The light-sensitive silver halide emulsion used is an emulsion in one of the commonly used hydrophilic silver halide emulsions, containing silver chloride, silver bromide or mixtures thereof, optionally containing small amounts of silver iodide, up to 10 mol %. Something can happen. The binder used for the photographic layers is preferably gelatin, but this can also be partially or completely replaced by natural or synthetic binders.

The emulsions can be chemically or spectrally sensitized by conventional methods, and the emulsion layers as well as the non-light sensitive layers thereof can be further hardened by conventional methods using known hardeners.

Color photographic recording materials usually contain at least one silver halide to record light in each of the three spectral regions, red, red and blue. Contains an L agent layer.

For this purpose, the photosensitive layer is spectrally sensitized in conventional manner using suitable sensitizing dyes. Blue-sensitive silver halide emulsion layers do not necessarily need to contain spectral sensitizers, since the inherent photosensitivity of silver halide is often sufficient to record previous light.

Each of the photosensitive layers described above can consist of a single layer;
Alternatively, it can consist of partial layers of two or more silver halide emulsion layers in a known manner, for example overlapping partial layers as in a so-called overlapping layer arrangement (DE 11 21 470). The red-sensitive silver halide emulsion layer is usually located closer to the layer support than the green-sensitive silver halide emulsion layer, the latter is located closer to the layer support than the blue-sensitive layer, and The green and blue sensitive layers are separated by a layer of non-light sensitive yellow filter, although other arrangements are commonly used as well. Iils of different spectral photosensitivity are generally separated by a non-photosensitive interlayer,
The latter can include agents that prevent accidental diffusion of developer oxidation products. If the material contains several silver halide emulsion layers of the same spectral sensitivity, these layers may be directly adjacent to each other or there may be light-sensitive layers of different spectral sensitivities arranged between them. (German Patent Application Publication IJI'! No. 1958709, German Patent Application No. 25
30645, 2622922).

Color photographic recording materials for producing multicolor images usually contain color-forming compounds, which in this case spatially and spectrally interact with the silver halide 7L agent layer to produce various partial color images, in particular cyan, magenta and yellow. It is a color coupler associated with

"Spatial association" refers to the interaction of the color coupler with the silver halide emulsion layer and the difference between the silver image produced during development and the color image produced from the color coupler. It means to be located in a spatial relationship such that an image match can be obtained. This is generally achieved by incorporating the color coupler into the silver halide emulsion itself or into an adjacent layer of buying which is optionally non-light sensitive.

"Spectral association" refers to the partial colors li! produced from color couplers that are spatially associated with the spectral sensitivity of each light-sensitive silver halide emulsion layer. ii images are mutually constitutive, meaning that each spectral sensitivity (red, green, blue) has associated with it a different color of the partial color image (eg cyan, magenta, yellow).

Each of the silver halide emulsion layers sensitized to different spectral regions can have one or more color couplers associated therewith. If there are several silver halide emulsion layers of the same spectrally sensitive nature, each of these layers may contain color couplers, and the various color couplers need not necessarily be identical, provided that they Development shall provide at least approximately the same color, usually a color complementary to the color of the light to which the particular halogenated L agent is primarily sensitive.

Therefore, in a preferred embodiment, the red-sensitive silver halide emulsion layer contains at least one non-diffusive color coupler, in the present case at least one of formula I, in association with it to produce a cyan partial color image. corresponding couplers and at least one coupler corresponding to formula II.

&) The light-sensitive silver halide emulsion layer contains at least one non-diffusive color coupler, generally a 5-pyrazolone, ingzolone or pyrazoloazole color coupler, associated therewith to produce a magenta partial color image. The blue-sensitive silver halide emulsion layer has at least one non-diffusive color coupler, generally a color coupler containing open-chain ketomethylene groups, associated therewith to produce a yellow color image. Color couplers (of
Mitte
Ilungen aus den Forsch
ungslaboratorien der Ag
fa + Leverkusen/Mtincben)
, Volume ■, 111* (1961), W. Pell (W.

PELZ) publication "7 Alpkupler"('Fa
rbkuρρler”), and “The Chemistry of Synthetic Guise” (The Chem
istry ofSynthetic Dyes''
) Volume 4, 341-387, Academic Press (Ac
ade+mic Press) (1971),
Penriki Taraman (K, VENKATA RAMA
See publication by N.

The color coupler can be a conventional 4-equivalent coupler or a 2-equivalent coupler which requires less silver herodenide for color production. , the 2-equivalent coupler is
As is known, 2-equivalent couplers are derived from 4-equivalent couplers in that they contain substituents in the coupling position that are removed during the coupling reaction. It includes both compounds that have a color that disappears upon color coupling or is replaced by the color of the ti image dye produced.

The last-mentioned couplers can be present as additional couplers in the light-sensitive silver halide emulsion layer and serve as masking couplers to offset undesirable lateral densities of image dyes. Also, among the 2-equivalent couplers,
Included are white couplers that do not yield dyes on reaction with color developer oxidation products; and also include development inhibitors that have a removable group in the coupling position that is diffusible on reaction with color developer oxidation products. Also included are known DIR couplers which are released as . Other photographically active compounds such as development accelerators or fogging agents may also be released from such couplers during the development process.

In addition to the components described above, the color photographic recording material according to the invention may contain other additives such as antioxidants, dye stabilizers and 8! It can include mechanically and electrostatically influencing substances. To reduce or prevent the adverse effects of U-rays on the color images produced by the color photographic recording materials of the invention, U-absorbers may be added to one or more layers of the recording material, preferably in the upper layers. It is advantageous to use it within one. Suitable U■ absorbers are described, for example, in U.S. Pat.
53921, German Patent No. 2036719 and European Patent No. 8810057160.

Conventional layer supports can be used for the materials of the invention; Research Disclosure
h Disclosure) No. 17643, Section X ■■.

As protective colloids or binders for the layers of the recording material, customary hydrophilic film-forming agents such as proteins, especially gelatin, can be used. Casting aids and softeners are also used; see the compounds described in Research Disclosure 17643, supra, Sections ■, XI and XII.

The layers of the photographic material can be hardened in conventional manner, for example using hardeners of the epoxide type, polycyclic ethyleneimine or acryloyl type.

The layer is also German Patent Application Publication IJI! fjS221800
It can also be cured according to No. 9 to produce a color photographic recording material suitable for high temperature processing. Additionally, the photographic layer can be hardened using diazine, tri7one or 1,2-dihydroxy/phosphorus based hardeners. Other suitable curing agents are German Patent Application No. 2439551, German Patent Application No. 2439551, tJIJ2
225230 and 2317672 and Research Disclosure 17643, Section Xl.
This is disclosed.

Other suitable additives are Research Disclosures 7
17643 and 1 “Product Licensing Index”
gIndex”), December 1971, 107-11
It is written on page 0.

To produce color photographic images, the color photographic recording material according to the invention is developed using color developer compounds.

As color developer compound, any developer compound capable of reacting in the form of its oxidation product with a color coupler to form an azomethine dye can be used. Suitable color developer compounds include at least one partial amino acid.
Aromatic compounds of the p-phenylenediamine type containing groups, such as NUN-noalkyl-p-phenylenecyamine, such as N,N-diethyl-+3-phenylenediamine, 1
-(N-ethyl-N-methyl-sulfonamidoethyl)
-3-methyl-p-phenylenenoamine, 1-(N-ethyl-N-hydroxyethyl)-3-methyl-p-7 22-diamine and 1-(N-ethyl-N-methoxyethyl)-3 -methyl-1)-7 2-2-diamine. .

Other suitable color developers are described, for example, in the Journal of the American Chemical Society (J.
Amer, Chew, Soc, )73.3100
(1951) and G. Heist, Modern Photographic Processing, 1979, John Riley.
and Sons, New York (G.

Haist+ Modern Photography
ic ProcessinHtl 9 7 9 e
John Wiley and 5ons+
New York) from page 545 onwards.

After color development, the material is bleached and fixed in conventional manner. Bleaching and fixing can be carried out separately or together. Common bleaching agents can be used, such as Fe'+ salts and VFc''+ complex salts, such as 7-erythyanide, dichromate, water-soluble cobalt complex salts, etc. In particular iron ([1 ) Complex salts are preferred, especially those of ethylenenoaminotetraacetic acid, N-hydroxyethyl-ethylene-noaminotriacetic acid, alkylim7nocarboxylic acids and the corresponding phosphonic acids.Persulfates are also suitable bleaching agents.

Example 1 One of the color couplers listed in Table 1, o, 0. i5 moles are dispersed with 16 g of dibutyl 7 tala) in 10% gelatin solution fi20 oioj and the dispersion is dispersed with A) HN
1 kg of a red sensitized silver iodobromide emulsion (5 mole % iodide) obtained from 0.3129 g and 45 g of gelatin. The mixture was then applied onto a film of cellulose triacetate at an application rate of 3°2 g of silver (A gN O3/11
2) It was cast. After curing the additional protection I with a carbamoyl bilinonium salt (CAS Registration No. 65411-60-1), the resulting material was exposed behind a gray wedge and published in the British Journal of
7 Otography (Brit, J., of
Photography), 1974, p. 597. Percentage magenta lateral density (green filter status M) and wavelength of absorption maximum D = 1
．． Measured at 0 (red filter status M) (
Table 1).

L 1-1' 708 10.51-
1. /n -1 (1:1) 699 11
．． 01-4/n-3 (3 near) 700
12.0:&1 shows that the combination according to the invention is not only able to bring lj3IIg to the desired absorption maximum at 700±2 nm fairly accurately, but also results in a considerably lower lateral density.

Example 2 Scraps were prepared as in Example 1, except that instead of the comparative couplers described therein, the comparative couplers described in Table 2 were used for comparison with the combinations according to the invention. A portion of the prepared material was stored for 7 days at 60° C. and 35% relative humidity. The remainder was stored at normal room temperature. The material was then exposed to light in stages and processed in the conventional manner. Table 2 shows that although the comparative couplers have the desired head-on absorption, after storage at elevated temperatures (which serves as a simulation for long-term storage at room temperature), they show less groove absorption than combinations according to the invention. This shows that it suffers a large maximum density loss.

L snoring Maximum density after 7 days storage 1 sentence 1-2/ll-9 (3 near) G98 2.2 2
．． 21-4/It-3 (3 near) 700 2.4
2.3 Example 3 A color photographic recording material for development was prepared by Carane by applying the following layers to a transparent cellulose triacetate layer support in the order listed. The amounts stated relate in each case to per II2. The applied amount of silver halide is the corresponding A gN
Denoted by O, i. All halogenated emulsions are AgN 0
0.0 per 3100 g. It was stabilized with 4-hydroxy-6-methyl-1,3,3a,7-titraazaindene of sg.

Layer 1 (antihalation layer) 0.32. Contains Ag and 2.2g gelatin,
Sodomy colloidal silver sol layer 2 (intermediate layer) Gelatin 0.38 Layer 3 (first red sensitized layer) 2.4 g AgNOs, 0, 9 mfaal cyan coupler (Table 3), 0.0
6. Red Mask MR-1, 0,025g DI R Coupler DC-1 and 1.
2 g gelatin, red sensitized silver chloride iodobromide emulsion (5 mol% iodide; 2 mol%
Chloride; average particle size 0.5μm) Layer 4 (red sensitized layer of fjS2) 2.9g A3N0:1 0.25a+mol cyan coupler 0.02g Red mask MR-1 0.04, DI R compound DC- Red sensitized silver iodobromide emulsion obtained from 2 (10 mol% iodide; average grain size 0.8 μm) M5 (intermediate layer) 0.98 Gelatin layer 6 (first green sensitized scrap) 2. 2g AgN0゜0.65g Magenta coupler M-10.04g D
IR coupler DC-30,02, yellow mask MY-1 1,4 g Green sensitized silver iodobromide emulsion obtained from gelatin (5 mol% iodide;
Average particle size: 0.4μ) Layer 7 (second green sensitized layer) 2.7g AgNO3 0.17g Magenta coupler M-10.04g
Yellow mask MY1 1.6 g Green sensitized silver iodobromide emulsion obtained from gelatin (10 mol% iodide; average grain size 0.8 μm) Layer 8 (yellow filter single layer) 0.07 g AgN0) 32g Yellow colloidal silver sol layer 9 containing gelatin (first blue sensitized layer) 0.95g AgN0) 0.96g M coupler Y-1 1.4g Silver iodobromide emulsion obtained from gelatin (3 mol% Iodide; average grain size 0.3 μm) N10 (second blue sensitization M) 1, Og N Oyo, 22 g Yellow coupler Y-1 1.6 g Silver iodobromide emulsion obtained from gelatin ( 8 mol% iodide; average particle size 0.8 μm) Layer 11 (protective layer) 1.1 g gelatin and o, sg UV absorber UV-1 Layer 12 (protection ii! layer) 0.8 g gelatin layer 13 (hardened layer) ) 0.3g gelatin and 0.9g hardening agent [CAS registration number 654.11-6
0-1] The formula of the compound used in Example 3 is shown below: UV-1 Various variants of the recording material with the above arrangement were prepared. They differ only in the cyan coupler introduced in layers 3 and 1//ω4.

General Method for Dispersing Cyan Coupler Coupler 100
g and dibutyl 7 thale) together with ethyl acetate 3
00mj! and at 50°C, also 5
1.7.5 g of gelatin preheated to 0° C. and containing 0 g of sodium dodecylbenzenesulfonate.
Emulsified in 3E. The low boiling solvent was then removed under reduced pressure and the dispersion left behind was solidified at 6°C. These various materials were added to
nseh-und Kino-T echnik)
1/1 9 7 9, U.S. in the middle of the 21st. Exposure to light reflected from the color chart described by Vielmuth (U., Viel@uth). After treating the material as in Example 1, the paper was coated with 7A color paper type 8 (7A color paper type 8).
Copied above technical data A81) of AgfaGevaeJtAG). The green reproduction and magenta reproduction were then colorimetrically measured in a CJELAB system 1976 according to DIN 6174. Table 3 shows that the green and magenta saturation is significantly higher in the combination according to the invention than in the comparative example.

Some of the combinations according to the invention are characterized in that the saturation of the seven tall yarn cyan coupler (corresponding to formula V-1 as a comparative coupler)
Although this coupler has ideal absorption properties, its stability against blackening is even higher than in experiments with very weak dyes.

l Old PuL ↓Pa.

Claims (1)

[Scope of Claims] 1. Color photographic recording material containing at least one silver halide emulsion sensitized to the red spectral region and associated therewith with a cyan coupler based on 2-phenylureidophenol. and at least one cyan coupler corresponding to formula I and at least one cyan coupler corresponding to formula II in the silver halide emulsion layer sensitized to the red spectral region: ▲ mathematical formula, chemical formula, There are tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^1 represents a ballast group, and X is H or a group other than hydrogen that can be released during the color coupling reaction. , R^2 and R^3 represent H, F, Cl, CN, CF_3 or SO_3-R^4 (where R^4 is F, alkyl or alkylamino), provided that R^2 and R
^3 cannot both be H and cannot both be CN). 2. In at least one cyan coupler corresponding to formulas I and II, R^1 is formula III ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, Z represents O or S; R^ 5 corresponds to a methylene group or the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ - alkyl (where R^7 represents H or alkyl, and the alkyl group can be linear or branched) Represents an alkylidene group having 2 to 20 carbon atoms; R^6 is halogen, hydroxyl, carboxyl, alkyl, cycloalkyl, aryl, aralkyl, alkoxy, aryloxy, alkylsulfamoyl, arylsulfamoyl, alkylsulfonamide, represents arylsulfonamide, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl or acyloxy, where the alkyl group contains 1 to 20 carbon atoms and the alkyl, aryl and aralkyl are optionally substituted with alkyl, hydroxyl, carboxyl, alkoxycarbonyl or acyloxy. 2. The recording material according to claim 1, wherein the recording material is a ballast group corresponding to m=1 to 3).