JPH04356043A - Photograph recording material - Google Patents

Abstract

PURPOSE: To obtain a photographic recording material having improved photographic characteristics such as increased max. density by incorporating a mixture of a specified dye forming coupler compd. with dioctyl ester of sodium- sulfosuccinic acid. CONSTITUTION: This photographic recording material has a substrate and a silver halide emulsion layer and contains a dye forming coupler compd. dispersed in combination with dioctyl ester of sodium-sulfosuccinic acid. The amt. of the acid is 0.05-10 pts.wt. per 1 pt.wt. of the coupler compd. and the coupler compd. is represented by one of formulae I, II, etc. In the formula I each of R<1> and R<2> is 1-8C optionally substd. alkyl, part of a ballast group contg. O and S or <=30C optionally substd. aryl. In the formula II, R<3> is fluoro substd. alkyl, fluoro substd. aryl or an optionally substd. alkylamine or arylamine and the substituent is halo, alkyl, alkoxy, cyano or a ballast group.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to photographic recording materials, and more particularly to color photographic recording materials and emulsions for forming improved photographic images.

0002

BACKGROUND OF THE INVENTION Coupling agents are commonly used as dye-forming agents in color photographic applications. However, some coupling agents, or dyes obtained therefrom, have some drawbacks. These include relatively low maximum color density values and relatively slow speeds.

Various attempts have been made to improve the quality of couplers and the dyes derived therefrom. This is true, for example, for pyrazolotriazole couplers such as those described in Published Patent Publication No. 30895/1973. In this publication, 1H-pyrazolo (
A method for changing the structure of 3,2-c)-s-triazole magenta couplers is described. however,
The results of such structural modifications have not been entirely successful.

The use of bis-pyrazolotriazole magenta coupling compounds, such as those described in Published Patent Publication No. 16058/1974, provides some improvement in sensitivity as well as resistance to formaldehyde. However, these coupler compounds do not provide appreciable improvement in maximum color density.

[0005] Other attempts to improve dye properties are disclosed in Published Patent Publications Nos. 135841/1981 and 4204.
5/1983. These attempts to improve the quality of dyes derived from dye-forming couplers of the pyrazolotriazole type have not been entirely satisfactory.

More recently, US Pat. No. 4,581,
No. 326 describes couplers that are used in combination with certain phenolic compounds to increase color density and improve the sensitivity of the resulting magenta dye. The improvements attempted to be obtained with this combination have not proven satisfactory in terms of enhancing dye properties.

European Patent Application No. 284,239, published September 28, 1988, discloses couplers that form dyes with improved stability through the use of specific substituents. This application teaches the use of tricresyl phosphate as a coupler solvent.

The use of various agents to aid in the dispersion of photographic couplers is also known in the art. for example,
U.S. Pat. No. 2,835,579 describes the use of both alkyl- or acyl-phenolic compounds that may be used to disperse dyes formed from couplers without bleaching or discoloring the dye. has been done.

[0009]

All of these attempts to increase the Dmax, improve dispersibility, and increase speed values of dye-forming couplers or dyes derived therefrom have resulted in the desired type of improvement. It's not. As a result, efforts continue in the photographic industry to improve the quality of dyes derived from dye-forming couplers.

0010

SUMMARY OF THE INVENTION The present invention provides improved photographic properties in a photographic recording material comprising a support, a silver halide emulsion layer and a dye-forming coupler, wherein the coupler compound is sodium chloride. With dioctyl ester of sulfosuccinic acid, from 0.05 to 1 of said acid per part of coupler.
0 parts by weight, and the coupler compound has the following structural formula:

[0011]

[Case 2]

In the formula, R1 and R2 each have 1 carbon atom.
~8 optionally substituted alkyl groups, or substituted or unsubstituted aryl groups that may be part of a ballast group containing oxygen and sulfur atoms and have up to 30 carbon atoms;

R3 is a fluoro-substituted alkyl or fluoro-substituted aryl group; or an alkylamine or arylamine optionally substituted with a halo, alkyl, alkoxy, cyano or ballast group; (wherein the alkyl, aryl or ballast group is 1 ~30 carbon atoms);

R4 may be a straight or branched alkyl group or be part of a ballast group comprising oxygen and sulfur atoms and comprising up to 30 carbon atoms; a substituted or unsubstituted aryl group;

00
15] R5 is halogen, alkyl, halo-substituted alkyl, nitro, cyano, -COR, -CO2R, -SO
2R, -OR, -OCOR, 1 of sulfamoyl or carbamoyl (where R is an aliphatic group or an aromatic group)
species or more groups;

R6 is a straight or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms;

Y is one or more of halogen, alkyl, nitro, cyano or amino;

001
8] X is hydrogen or a coupling-off group; n is 1 to
3; and m is 1 or 2.

The present invention also provides a silver halide and a dye-forming coupler compound having one of the above structural formulas, wherein said coupler compound together with a dioctyl ester of sodium sulfosuccinic acid contains 0% of said acid per part of coupler.
．． An improved photographic emulsion comprising dye-forming couplers dispersed in a weight ratio of 0.05 to 10 parts is provided.

These dye-forming coupler compounds are known in the art from various publications. For example, for their synthesis, one or more of the following U.S. Pat.
, 622 and 4,581,326.

Typical examples of suitable coupling-off groups which can be represented by X include hydrogen, halogen atoms, especially chlorine, or:

[0022]

[Chemical formula 3]

[0023]

[C4]

[0024] Particularly preferred X groups are hydrogen,
halogen, alkylthio, arylthio, aryloxy or nitrogen-containing heterocycle, these groups may contain up to 20 carbon atoms.

Of the above coupler formulas, particularly preferred for the practice of the invention are the formulas:

[C5] This is a coupler.

Specific examples of coupler compounds within the above formula include:

[C6]

[0027]

[C7]

If less than 0.05 part of dioctyl ester of sodium sulfosuccinic acid is used per part of coupler, there is a risk that the dissolving or dispersing effect on the coupler will be insufficient. This, along with insolubilization of a portion of the coupler, causes ineffective utilization of the coupler compound, resulting in unsatisfactory imaging.

On the other hand, if more than 10 parts of the dioctyl ester dispersant of sodium sulfosuccinate is used per part of the coupler compound, there is a tendency to overdilute the coupler. This can result in an increase in the thickness of the coupler layer and a softening of the layer, thereby increasing its tendency to be easily scratched. Preferably, the dioctyl ester of the sodium sulfosuccinate compound is used in an amount of 0.2 parts to about 4 parts per part of coupler.

Dioctyl ester of sodium sulfosuccinic acid is one of the narrow range dye-forming couplers shown above.
The improved properties obtained when used with one can be obtained in the presence of other permanent type coupler solvents. For example, other commonly used coupler solvents such as dialkyl phthalates, mono- or di-alkyl substituted phenols, alkyl or aryl phosphates or mono- or di-alkyl substituted amide compounds can also be incorporated into the coupler dispersion. It can be present without any obvious adverse effect on the dispersion. Mixtures of one or more coupler solvents may be used as shown below. However, the presence of additional coupler solvent is not required as demonstrated below.

The amount of additional coupler solvent does not appear to be important in enhancing the dispersing and coupler effects derived from the use of dioctyl ester of sodium sulfosuccinate. At least 0.05 parts to 10 parts for each part of coupler
It is important to take into account that some sulfosuccinates are present.

Dioctyl ester of sodium sulfosuccinic acid has the structural formula:

[0033]

[Chemical formula 8] It is a commercially available substance.

Coupler solvents are divided into two general types. One type is “permanent”
This type of solvent has a relatively high boiling point and remains in the photographic layer when applied. This type has a relatively low boiling point and is used during various manufacturing or processing steps. These low-boiling solvents are sublimable and are considered non-permanent. Typical non-permanent solvents are ethyl acetate and butyl acetate. Such a solvent contains a dye-forming coupler component,
It is often used as an adjuvant with initial formulations and solutions of photographic elements. The coupler solvent, tricresyl phosphate, is a permanent solvent. Ethyl acetate is considered a non-permanent or sublimable solvent.

The photographic recording materials described herein may be monochromatic or multicolored. Multicolor photographic materials usually contain dye image-forming units sensitive to each of the three main regions of the spectrum. Each unit may be composed of a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum. The recording material layers, including the imageable unit layers, can be arranged in various orders known in the art.

A typical multicolor photographic recording material comprises at least one cyan dye image-forming unit comprising at least one red-sensitive silver halide emulsion layer in combination with at least one cyan dye-forming coupler, at least one magenta dye image-forming unit. magenta image-forming units comprising at least one green-sensitive silver halide emulsion layer in combination with a dye-forming coupler and at least one blue-sensitive silver halide emulsion layer in combination with at least one yellow dye-forming coupler. The yellow dye-forming unit comprises a support supporting a yellow dye-forming unit. The recording material of the invention may contain additional layers such as filter layers, interlayers, overcoat layers and subbing layers.

The following discussion of materials suitable for use in elements of the invention is provided in Research Disclosure (
Research Disclosure), 198
December 9, Item 308119 (Kenneth
Mason Publications Ltd. Published by The Old Harbormaster's
, 8 North Street, Emswort
h, Hampshire P010 7DD, En
grand). This publication is
Hereinafter, it will be abbreviated as "Research Disclosure".

The silver halide emulsions used in the elements of this invention may be silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, silver chlorobromoiodide or mixtures thereof. can be. These emulsions can contain silver halide grains of any conventional shape or size. Specifically, these emulsions can contain coarse silver halide grains, medium silver halide grains or fine silver halide grains. High aspect ratio tabular grain emulsions are particularly contemplated and are described, for example, in Wilgus, U.S. Pat.
, 434, 226, Daubendiek et al. 4
, 414, 310, Wey, 4,399, 21.
No. 5, Solberg et al. No. 4,433,048, Mignot No. 4,386,156, Eva
No. 4,504,570 of Maskasky et al.
4,400,463, Wey et al. 4,4
No. 14,306, Maskasky No. 4,435,
No. 501 and No. 4,643,966 and Da
Ubendiek et al., 4,672,027 and 4,693,964. Also particularly contemplated are silver bromoiodide grains having a higher molar ratio of iodide in the core of the grain than in the periphery of the grain, such as those described in British Patent No. 1,027,146. , Japanese Patent Publication No. 54-48, 52
No. 1, U.S. Patent No. 4,379,837, U.S. Patent No. 4,4
No. 44,877, No. 4,665,012, No. 4,
No. 686,178, No. 4,565,778, No. 4
, No. 728,602, No. 4,668,614, No. 4,668,614, No.
No. 4,636,461 and European Patent No. 264
, No. 954 or the specification. These silver halide emulsions can be precipitated as either monodisperse or polydisperse. The grain size distribution of the emulsion can be adjusted by a silver halide grain separation method or by blending silver halide emulsions with various grain sizes.

Sensitizing compounds such as copper, thallium, lead, bismuth, cadmium and Group VIII noble metal compounds may be present during precipitation of the silver halide emulsion.

The emulsion can be either a surface-sensitive emulsion, ie, an emulsion that forms a latent image primarily on the surface of the silver halide grains, or an internal latent image-forming emulsion, ie, an emulsion that forms a latent image primarily within the silver halide grains. It can be an image-forming emulsion. These emulsions may be negative working emulsions, such as surface sensitive emulsions or unfogged internal latent image forming emulsions, or direct positive emulsions of the unfogged internal latent image forming type. As such, they operate positively when development is performed in the presence of uniform light exposure or nucleating agents.

These silver halide emulsions can be surface sensitized. Precious metals used individually or in combination (
Particularly contemplated are intermediate chalcogens (eg, sulfur, selenium or tellurium), and reduction sensitizers (eg, gold). Typical chemical sensitizers are the aforementioned Research Di
sclosure, Item 308119, No.
Listed in Section III.

These silver halide emulsions can be spectrally sensitized using dyes from various classes including polymethine dyes, including cyanine,
Included are merocyanine, complex cyanine and merocyanine (ie, trikaryotypic, tetrakaryotype and polynucleoid cyanine and merocyanine), oxonol, hemioxonol, styryl, merostyryl and streptocyanin. A specific spectral sensitizing dye is the aforementioned Resea
rch Disclosure, 308119, Section IV.

Suitable vehicles for the emulsion layer and other layers of the elements of this invention are found in the Research Disc
Losure, 308119, Section IX and the publications cited therein.

In addition to the couplers described herein, elements of the invention may be found in Research Disclosure,
Additional couplers may be included as described in Section VII, paragraphs D, E, F and G and the references cited therein. These additional couplers are Re
Search Disclosure, Section VII, Paragraph C and the documents cited therein.

The photographic elements of this invention contain an optical brightener (Re
Search Disclosure, Section V), Antifoggants and Stabilizers (Research Disclosure, Section V)
Closure, Section VI), Stain Inhibitors and Image Dye Stabilizers (Research Disclosure, Section VI)
, Section VII, Paragraphs I and J), Light Absorbers and Scattering Materials (Research Disclosure
re, Section VIII), hardeners (Research Di
sclosure, Section XI), plasticizers and lubricants (
Research Disclosure, Chapter XII
Section I), antistatic agents (Research Discl.
osure, Section XIII), matting agents (Resear
ch Disclosure, Section XVI) and developer modifiers (Research Disclosure, Section XVI)
re, Section XXI).

These photographic elements are Research
It can be coated on a variety of supports, such as those described in Section XVII, Disclosure, and the references cited therein.

These photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, and are
h Disclosure, forming a latent image as described in Section XVIII and then processing and resetting.
A visible dye image can be formed as described in Arch Disclosure, Section XIX. The step of forming a visible dye image includes the steps of contacting the element with a color developing agent to reduce the developable silver halide and oxidize the color developing agent. The oxidized color developing agent reacts with the coupler in turn to form a dye.

Preferred color developing agents include p-phenylenediamines. Particularly preferred are
4-amino-3-methyl-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-β-
(methanesulfonamide) ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3-β-(
methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-
methoxyethyl)-m-toluidine di-p-toluenesulfonate.

Negative working silver halide emulsions yield negative images through the processing steps described above. To obtain a positive (or reversal) image, this step is first processed with a non-color developing agent to develop the exposed silver halide (no dye is produced), then the element is uniformly fogged and developed. Possible unexposed silver halide can be left behind. Alternatively, direct positive emulsions can be used to obtain positive images.

Development is followed by conventional bleaching, fixing or bleach-fixing steps to remove silver and silver halide, washing and drying.

[0051]

EXAMPLES The following examples specifically illustrate the invention.

Dispersions were prepared using various couplers and various solvents by first dissolving the couplers in a permanent solvent and then combining with an aqueous phase consisting of gelatin, surfactant, and water. The mixing of the oil and aqueous phases to obtain the dispersion was carried out using conventional means, such as a homogenizer or a colloid mill. In some cases, co-solvents were used to aid in dissolution of the couplers. If used, this co-solvent was later removed. In each example, the dioctyl ester of sodium sulfosuccinate (invention) was compared to a mixture of di- and tri-isopropylnaphthalene sulfonate (control) on an equimolar basis. The molar concentration levels used in each case are shown in the table.

Example 1 Pyrazolotriazole coupler compound no. The highest dye density of 7 was measured. For each part by weight of coupler, one half part by weight of a permanent coupler solvent as shown in Table 1 was used. The dispersed material was silver bromoiodide (6
%I) Coated with emulsion. After exposure, the film strip is
Developed with Kodak E-6® reversal process without formaldehyde stabilizer.

[0054]

[Table 1]

Table 1 shows the improved Dmax obtained using the dispersants of the present invention compared to art-recognized dispersants.

Example 2 Pyrazolotriazole coupler compound no. 2 in tricresyl phosphate. 1 (coupler:solvent ratio 1.0:0
．． A single layer coating containing the dispersion of 5) was prepared. The layer coated on transparent cellulose acetate is 1.18
g/m2 of silver (6% I as AgBrI), 2.1
It contained 5g/m2 of gelatin and 0.646g/m2 of coupler compound. An overcoat layer of hardened gelatin was used. Apply this coating to 0.2
4. Exposure to a 5500K light source for 2.5 minutes;
Developed with C-41® process with or without 0 g/liter citradinic acid (CZA).

Dispersion reactivity was determined from a dye-density plot in which the dye concentration was measured using Status M green densiometry. Developed silver was measured by X-ray fluorescence. Results are shown below using two separate dispersant concentrations, as shown in Table 2.

[0058]

[Table 2]

The increased dye concentration yields with and without citradinic acid in the processing phase are greater than 20% when using the dispersants described above with the selective dye-forming couplers of this invention. It seems that the improvement over the above can be obtained.

Example 3 Yellow dye-forming coupler compound No. 3 dispersed in di-n-butyl phthalate. 5 (coupler:solvent ratio 1.
0:0.5) to produce single layer coatings on a paper support. This coating layer contains 1.08 g/m2 of coupler,
It contained 0.335 g/m2 silver (as silver chloride) and 2.15 g/m2 gelatin. Dispersants as shown in the following table were used at a level of 1.7 x 10-2M. A gelatin overcoat was used. After curing, apply 0 to 3 step tablets and N
A 0.1 second exposure was given at 3000K using a P11 Kodak Wratten filter. Apply this application to 4
Developed with RA-4 Colenta processing for 5 seconds. (
The shoulder (of the characteristic curve) and the maximum density value are reported in Table 3.

[0061]

Table 3: Dye density values were increased by using dioctyl ester of sodium sulfosuccinic acid in combination with the dye-forming couplers of the present invention.

Example 4 Similar to that described in Example 3, but using magenta dye-forming coupler compound no. A coating was prepared using No. 2. Coupler No. 2 was dissolved in tricresyl phosphate at a coupler:solvent ratio of 1.0:0.5 and coated at 0.441 g/m2, at 2.15 g/m2.
gelatin, silver as silver chloride 0.279g/
It was applied in m2. Add 2.7 x 10 dispersants shown in the table below.
-2M was used. Exposure, development and processing were as described in Example 3. The results are shown in the table below.

[0063]

[Table 4]

Density values were enhanced by using the dispersants described above and selected coupler compounds of the invention.

Example 5 The effects on coupler reactivity when using various coupler dispersions are demonstrated by the results in Table 5. The above cyan dye-forming coupler compound No. A dispersion was prepared using the above dispersant and also di-n-butyl phthalate as the coupler solvent at a coupler:solvent ratio of 1.0:0.5. Coupling rate constants (Kc) were determined using an aqueous competition test with sulfite ions. The Kc values obtained are reported in Table 5 as dm3C-1x-1.

[0066]

[Table 5]

The above results show that the coupler reactivity was improved by the selected dispersants of the present invention. Example 6 Similar to Example 5, yellow dye-forming coupler compound No. The reactivity for No. 6 is shown in the following table.

[0068]

[Table 6]

An increase in coupler reactivity was observed at both concentrations of the preferred dispersant.

Example 7 Magenta dye-forming coupler compound No. 3, Example 5
and 6 were subjected to the same reactivity rate evaluation as described above. Using the same dispersant, the coupler was dissolved in tricresyl phosphate at a coupler solvent ratio of 1.0:0.5. The results are shown in Table 7 below.

[0071]

[Table 7] Dye-forming coupler compound No. For No. 3, the use of dioctyl ester of sodium sulfosuccinic acid as a dispersant clearly increases the coupling reactivity as shown in Table 7.

[0072]

The present invention is based on the use of specific dispersants with specific classes of dye-forming couplers to increase Dmax values without appreciably increasing Dmin. Speed values have also been improved.

Claims (1)

[Claims] 1. A photographic recording material comprising a support, a silver halide emulsion layer and a dye-forming coupler, wherein said coupler compound together with a dioctyl ester of sodium sulfosuccinic acid contains 0.0% of said acid per part of coupler. 0
The coupler compound is dispersed in a weight ratio of 5 to 10 parts, and the coupler compound has the following structural formula: [Image Omitted] In the formula, R1 and R2 are optionally substituted alkyl having 1 to 8 carbon atoms. or a substituted or unsubstituted aryl group having up to 30 carbon atoms, which may be part of a ballast group containing oxygen and sulfur atoms;
R3 is a fluoro-substituted alkyl or fluoro-substituted aryl group; or an alkylamine or arylamine optionally substituted with a halo, alkyl, alkoxy, cyano or ballast group; (wherein 1 to 30 alkyl, aryl or ballast groups carbon atoms)
R4 may be a straight-chain or branched alkyl group or be part of a ballast group comprising oxygen and sulfur atoms and comprises up to 30 carbon atoms; is a substituted or unsubstituted aryl group; R5 is
Halogen, alkyl, halo-substituted alkyl, nitro, cyano, -COR, -CO2R, -SO2R, -OR,
-OCOR, one or more groups of sulfamoyl or carbamoyl (wherein R is an aliphatic or aromatic group); R6 is a straight-chain or branched alkyl group having 1 to 8 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms; Y is one or more of halogen, alkyl, nitro, cyano or amino; X is hydrogen or a coupling-off group; a photographic recording material having one of the following: n is 1 to 3; and m is 1 or 2.