EP0296793A2 - Farbphotographische Silberhalogenidmaterialien und Verfahren - Google Patents

Farbphotographische Silberhalogenidmaterialien und Verfahren Download PDF

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Publication number
EP0296793A2
EP0296793A2 EP88305631A EP88305631A EP0296793A2 EP 0296793 A2 EP0296793 A2 EP 0296793A2 EP 88305631 A EP88305631 A EP 88305631A EP 88305631 A EP88305631 A EP 88305631A EP 0296793 A2 EP0296793 A2 EP 0296793A2
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EP
European Patent Office
Prior art keywords
group
silver halide
coupler
dye
photographic silver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88305631A
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English (en)
French (fr)
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EP0296793B1 (de
EP0296793A3 (en
Inventor
Bernard Arthur James Clark
Nigel Edgewick Milner
Paul Louis Reginald Stanley
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kodak Ltd
Eastman Kodak Co
Original Assignee
Kodak Ltd
Eastman Kodak Co
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Publication date
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Publication of EP0296793A2 publication Critical patent/EP0296793A2/de
Publication of EP0296793A3 publication Critical patent/EP0296793A3/en
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Publication of EP0296793B1 publication Critical patent/EP0296793B1/de
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Expired - Lifetime legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30535—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site not in rings of cyclic compounds

Definitions

  • This invention relates to novel acylacetanilide photographic colour couplers and photographic elements containing them.
  • colour images may be obtained from imagewise exposed silver halide emulsions by developing them with a primary aromatic amine colour developing agent in the presence of a colour coupler.
  • the oxidized colour developing agent formed in the areas of silver halide development couples with the coupler to form a dye.
  • the coupler may be present in the developer solution but is normally incorporated in the sensitive photographic material.
  • image dye-forming couplers For image dye-forming couplers to be practically useful, they must react both efficiently and at a suitable rate with oxidized developer to produce the dye. In addition, the dyes thus formed must possess acceptable hue and exhibit adequate stability over a wide range of keeping conditions.
  • Benzoylacetanilides have been largely superseded by pivaloylacetanilides over the last thirty years owing to the superior dye characteristics imparted by the latter.
  • the present invention relates specifically to the use of benzoylacetanilides as yellow image dye-forming couplers.
  • European Patent Application 0126433 is largely concerned with pivaloylacetanilide couplers but three benzoylacetanilides (Compounds 4, 10 and 11) are disclosed; these compounds however do not fall within the claims of the present specification.
  • US Patent 4,587,207 in its general description covers both pivaloylacetanilide and benzoylacetanilide but its specific disclosure is restricted to pivaloylacetanilides.
  • Compound 17 of this patent has structural features in common with the couplers of the present invention but has the ballast group attached in a different position and its properties are not reported.
  • a colour photographic silver halide element comprising a support bearing at least one photographic silver halide emulsion layer and a non-diffusible yellow dye-forming para-R-oxybenzoylacetanilide coupler that has a combination of (a) a para-hydroxyphenylsulphonylphenoxy coupling-off group in the coupling-position, (b) a chloro or trifluoromethyl group in the ortho position on the anilide moiety, and (c) a group on the anilide moiety that is selected from (i) a sulphamoyl group, (ii) an aliphatic hydrocarbon group that is bonded to the anilide moiety directly or through a linking group that is a carbamoyl (-CONH-), oxycarbonyl (-CO-O-), carbonyloxy (-O-CO-), sulphonate (-O-SO2-), sulphamoyl (-SO2NH-), phosphat
  • Useful non-diffusible colour couplers have the formula: wherein R1 is an cyclic or non-cyclic aliphatic hydrocarbon group which may be substituted or unsubstituted and may comprise a ballast group, Y is chloro or trifluoromethyl, Z is -L-R2 or -SO2NR3R4, where R2 is an aliphatic hydrocarbon group which may be substituted or unsubstituted, R3 and R4 are each hydrogen or an aliphatic hydrocarbon group which may be substituted or unsubstituted, or R3 and R4 together form a ring, or, if R1 comprises a ballast group, Z may also be halogen or trifluoromethyl, and L is a direct bond or a carbamoyl (-CONH-), oxycarbonyl (-CO-O-), carbonyloxy (-O-CO-), sulphonate, (-O-SO2-), sulphamoyl (-SO2NH-),
  • the benzoylacetanilide image dye-forming couplers of the invention are readily soluble in common coupler solvents and, when incorporated into a color negative photographic material, exhibit excellent dye density and contrast characteristics. Furthermore, these couplers produce dyes of excellent hue and high extinction coefficient which are stable under a wide range of conditions, particularly dark keeping which is of fundamental importance for colour negative materials.
  • Examples of the groups which R1 may represent are alicyclic groups of 4 to 6 carbon atoms, and non-cyclic groups of 1-20 carbon atoms which may be substituted or unsubstituted, saturated or unsaturated, e.g. methyl, ethyl, n-butyl, n-dodecyl, n-hexadecyl, and n-undecyl.
  • the ballast group may form part of R1 in which case R1 may be an alkyl group of 10-16 carbon atoms.
  • the ballast can also be attached via substituent Z.
  • the group which links the ballast to the anilide ring has a strong influence on the solubility of the coupler in coupler solvent and also its propensity to crystallize in photographic coatings.
  • Linking groups or atoms which have been found to confer favorable solubility characteristics on the coupler include carbamoyl, oxycarbonyl, sulphonate, sulphamoyl, phosphate and alkyl. It is noted that linking groups or atoms which may give rise to coupler crystallinity problems include amide, sulphonamide and oxygen.
  • R1 preferably contains 1-4 carbon atoms.
  • the aliphatic hydrocarbon groups which R2, R3 and R4 may represent can be any of the groups given as examples of R1 or when R3 and R4 are taken together they may, for example, be the atoms required to complete a piperidine, pyrrolidine or morpholine ring.
  • Benzoylacetanilide couplers 1 to 11 specified below are examples of couplers of the invention whose derived dyes exhibit exceptional dark/wet stability. Furthermore, these compounds display all the other characteristics required of an image dye-forming coupler for use in color negative photographic materials.
  • coupler 6 may be prepared by methods, in themselves, known.
  • the following synthetic procedure for coupler 6 is illustrative for all the compounds of the invention.
  • Nitrogen gas was passed through a solution of methyl 4-chloro-3-[2-chloro-2-(4-dodecyloxybenzoyl) acetamido]benzoate (22g) and sulphonyldiphenol (40g) in DMF (300ml) for 30 minutes before adding triethylamine (12.12g) dropwise with stirring. The temperature was raised to 45-50°C and maintained for 2 hours. The reaction mixture was poured into stirred 5% hydrochloric acid (300ml) and the mixture was then stirred for 1 hour. The aqueous phase was decanted and the residual gum dissolved in ethyl acetate (300ml).
  • the dye-forming couplers of this invention can be used in the ways and for the purposes that dye-forming couplers have been previously used in the photographic art.
  • the couplers are associated with a silver halide emulsion layer coated on a support to form a photographic element.
  • the term "associated with” signifies that the coupler is incorporated in the silver halide emulsion layer or in a layer adjacent thereto where, during processing, it is capable of reacting with silver halide development products.
  • the photographic elements can be single colour elements or multicolor elements.
  • the yellow dye-forming couplers of this invention would usually be associated with a blue-sensitive emulsion, although they could be associated with an emulsion sensitized to a different region of the spectrum, or with a panchromatically sensitized, orthochromatically sensitized or unsensitized emulsion.
  • Multicolor elements contain dye image-forming units sensitive to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sentive to a given region of the spectrum.
  • the layers of the element, including the layers of the image-forming units can be arranged in various orders as known in the art.
  • a typical multicolour photographic element comprises a support bearing a yellow dye image-forming unit comprised of at least one blue-sensitive silver halide emulsion layer having associated therewith at least one yellow dye-forming coupler, at least one of the yellow dye-forming couplers being a coupler of this invention, and magenta and cyan dye image-forming units comprising at least one green- or red-sensitive silver halide emulsion layer having associated therewith at least one magenta or cyan dye-forming coupler respectively.
  • the element can contain additional layers, such as filter layers.
  • the silver halide emulsion employed in the elements of this invention can be either negative-­working or positive-working. Suitable emulsions and their preparation are described in Research Disclosure Sections I and II and the publications cited therein. Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure Section IX and the publications cited therein.
  • the elements of the invention can include additional couplers as described in Research Disclosure Section VII, paragraphs D, E, F and G and the publications cited therein.
  • the couplers of this invention and any additional couplers can be incorporated in the elements and emulsions as described in Research Disclosures of Section VII, paragraph C and the publications cited therein.
  • the photographic elements of this invention or individual layers thereof can contain brighteners (see Research Disclosure Section V), antifoggants and stabilizers (see Research Disclosure Section VI), antistain agents and image dye stabilizer (see Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (see Research Disclosure Section VIII), hardeners (see Research Disclosure Section XI), plasticizers and lubricants (see Research Disclosure Secton XII), antistatic agents (see Research Disclosure Section XIII), matting agents (see Research Disclosure Section XVI) and development modifiers (see Research Disclosure Section XXI).
  • brighteners see Research Disclosure Section V
  • antifoggants and stabilizers see Research Disclosure Section VI
  • antistain agents and image dye stabilizer see Research Disclosure Section VII, paragraphs I and J
  • light absorbing and scattering materials see Research Disclosure Section VIII
  • hardeners see Research Disclosure Section XI
  • plasticizers and lubricants see Research Disclosure Secton XII
  • antistatic agents see Research Disclosure Section XIII
  • the photographic elements can be coated on a variety of supports as described in Research Disclosure Section XVII and the references described therein.
  • Photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX.
  • Processing to form a visible dye image includes the step of contacting the element with a colour developing agent to reduce developable silver halide and oxidize the colour developing agent. Oxidized colour developing agent in turn reacts with the coupler to yield a dye.
  • Preferred colour developing agents are p-phenylene diamines.
  • 4-amino-3-methyl-N,N-diethylaniline hydrochloride 4-amino-3-methyl-N-ethyl-N- ⁇ -(methanesulphonamido)-­ethylaniline sulphate hydrate, 4-amino-3-methyl-N-­ethyl-N- ⁇ -hydroxyethylaniline sulphate, 4-amino-­3- ⁇ -(methanesulphonamido)ethyl-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N-(2-methoxy­ethyl)-m-toluidine di-p-toluene sulphonate.
  • this processing step leads to a negative image.
  • this step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and then uniform fogging of the element to render unexposed silver halide developable.
  • a direct positive emulsion can be employed to obtain a positive image.
  • Each coupler of the invention was dissolved in half its weight of di-n-butyl phthalate, with one and a half times its weight of cyclohexanone as auxiliary solvent and dispersed in gelatin.
  • the auxiliary solvent was removed from the dispersion by continuous washing for 6 hours at 4°C and pH 6.0.
  • Experimental photographic coatings were prepared by coating a cellulose acetate film support with a photosensitive layer comprising a dispersion of the novel coupler as formulated above coated at a laydown of 1.93 mmol/m2, a silver bromoiodide emulsion at 0.81 Ag/m2 and gelatin at 2.42 g/m2. An overcoat containing gelatin at 0.89 g/m2 was applied to the photosensitive layer. Bis-vinyl­sulphonylmethane at 1.75% by weight of the total gelatin in the pack was also incorporated into the photosensitive layer. The dried experimental coating was then slit and chopped into 35mm x 12 inch test strips.
  • Couplers of the invention have also been dispersed with ethyl acetate as auxiliary solvent (subsequently removed by evaporation under reduced pressure) and also in the complete absence of main coupler solvent (NS dispersions) and photographic coatings were prepared as above.
  • each coupler dispersion prepared for testing was investigated by spreading a few drops of dispersion on a microscope slide, placing a glass coverslip on top and viewing under a magnification of 1250x using Differential Interference Contrast to enhance the image.
  • In-film stability of the coupler was measured by incubating unexposed test strips for 24 hours at 21°C and 50% relative humidity followed by 1 week dry incubation at 49°C. The strips were then exposed and processed as below and sensitometry compared with that of fresh test strips of the same coupler.
  • the 35mm test strips were exposed through a 0-4.0 neutral density (ND) step-wedge (0.2 ND step increments) test object and Daylight V, Wratten 35 and 38A and 0.3 ND filters.
  • the strips were processed through a deep-tank sink line at 37.8°C using the following standard process: Colour Developer 2.5 minutes Bleach (FeIII/EDTA 4 minutes Wash 2 minutes Fix 4 minutes Wash 2 minutes in which the solutions are those described in the C41 process described in the British Journal of Photography Annual 1977 pages 204-5 in which the colour developing agent was 4-amino-3-methyl-N-ethyl-­N-2-hydroxyethylaniline sulphate.
  • the processed strips were then dried to give stepped yellow dye images.
  • test strips were developed in a competing process with the addition of 5.0 g/l citrazinic acid (CZA) to the colour developer solution and adjustment of the pH to 10.0 with sodium carbonate.
  • CZA citrazinic acid
  • step-wedge densities were measured using a Macbeth TD504/Hewlett Packard 85 automatic transmission densitometer. Measurements were made of minimum density (Dmin), maximum density (Dmax), contrast ( ⁇ ), and photographic speed (PS). The ratio of contrast in the CZA competing process to contrast in the standard process ( ⁇ CZA / ⁇ STD ) is quoted as an indication of in-film reactivity of the coupler.
  • 35mm Test strips were exposed as above through a 0-0.3 ND step-wedge (0.1 incremental steps) test object and Daylight V, Wratten 35 and 38A filters and the correct ND filters to give an optical density of about 1.0.
  • the strips were processed using the standard conditions described above and samples cut from the yellow dye image step with density closest to 1.0. Visible absorption spectra (normalized to 1.0 density) were obtained using a Pye Unicam SP8-100 Spectrophotometer. Dye hues are expressed in terms of the wavelength corresponding to the maximum absorption peak ( ⁇ max) and the half-bandwidth (HBW) calculated from the spectrophotometric curves.
  • Extinction coefficients of the yellow dyes were obtained from ethyl acetate solutions of the preformed dyes using a Varian DMS 90/Apple II automated uv/visible spectrophotometer.
  • Yellow dye sample patches of density circa 1.0 were prepared as for spectrophotometric testing and their absorption spectra measured as above.
  • the yellow dye samples were incubated in a dark oven for periods of 1, 3 and 6 weeks at a constant 60°C and 70% relative humidity.
  • the spectrophotometric curves of the samples were then remeasured and the degree of fade quoted as the fractional decrease in density at the absorption maximum ( ⁇ D) relative to the initial density prior to fading.
  • Couplers (1) to (11) are as follows and are compared with comparative compound (12), a commercially used benzoylacetanilide which bears a hydantoin coupling-off group.
  • the structure of Coupler 12 is:
  • Table 1 containing examples of the invention (4) and (7), illustrates the superior Dmax and contrast consistently attained in dye images from couplers of the invention relative to a current commercial pivaloylacetanilide coupler (13).
  • the dark/wet fade data for this set illustrates the superiority of the couplers of the invention (4) and (7) containing a phenolic leaving group over a current commercial benzoylacetanilide (12) which bears a heterocyclic leaving group.
  • the contrast ratios of this set illustrate the superior activity exhibited by the present benzoylacetanilides relative to the commercial pivaloylacetanilide (13).
  • Table 1 Compound Dmax Contrast Contrast Ratio D/W Fade 6 weeks (4) 2.52 2.04 0.69 +0.04 (4) + CZA 2.01 1.41 (7) 2.41 1.76 0.69 0.00 (7) + CZA 1.92 1.21 (12) 2.37 1.75 0.70 -0.16 (12) + CZA 1.83 1.22 (13) 2.04 1.36 0.60 +0.06 (13) + CZA 1.31 0.82 Footnotes 1) CZA denotes citrazinic acid. 2) A positive value for dye fade denotes an increase in dye density.
  • Couplers (4) and (7) have good fade and contrast ratio, that from coupler (12) shows acceptable Dmax, contrast and reactivity but poor dark/wet fade and the dye from coupler (13) shows acceptable dark/wet fade but low Dmax and contrast.
  • substituent Z in the general structure being a group or atom other than hydrogen in achieving excellent dark/wet fade data for a dye formed from coupler (6) compared against data for the dye from an analogous coupler (14) in which substituent Z is a hydrogen atom is illustrated in Table 2 below.
  • Table 2 X Y Z Dark/wet Fade (6 weeks) (6) OC12H25 Cl CO2Me 0.00 (14) OC12H25 Cl H -0.23
  • Table 4 X Y Z ⁇ max (2) OMe Cl CO2C12H25 449.5 (17) OMe OMe CO2C12H25 444.0
  • the extinction coefficients (measured in ethyl acetate solution) of the dyes (18) and (19) derived from benzoylacetanilide couplers of the invention have been shown to be significantly greater than the extinction coefficient of the dye (20) derived from a commercial pivaloylacetanilide coupler (Table 5).
  • Table 5 Dye Extinction Coefficient (EtOAc soln.)(lmol ⁇ 1cm ⁇ 1) (18) 2.01 x 104 (19) 2.30 x 104 (20) 1.73 x 104
  • the dyes have the following structures:

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  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19880305631 1987-06-25 1988-06-22 Farbphotographische Silberhalogenidmaterialien und Verfahren Expired - Lifetime EP0296793B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8714866 1987-06-25
GB878714866A GB8714866D0 (en) 1987-06-25 1987-06-25 Acylacetanilide photographic colour couplers

Publications (3)

Publication Number Publication Date
EP0296793A2 true EP0296793A2 (de) 1988-12-28
EP0296793A3 EP0296793A3 (en) 1989-11-08
EP0296793B1 EP0296793B1 (de) 1993-08-25

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EP19880305631 Expired - Lifetime EP0296793B1 (de) 1987-06-25 1988-06-22 Farbphotographische Silberhalogenidmaterialien und Verfahren

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EP (1) EP0296793B1 (de)
JP (1) JPS6421448A (de)
DE (1) DE3883446T2 (de)
GB (1) GB8714866D0 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0574090A1 (de) 1992-06-12 1993-12-15 Eastman Kodak Company 1-Äquivalentkuppler und freisetzbaren Farbstoffen mit niedrigem pKa

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59174839A (ja) * 1983-03-24 1984-10-03 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
US4587207A (en) * 1983-09-27 1986-05-06 Fuji Photo Film Co., Ltd. Color image-forming process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59174839A (ja) * 1983-03-24 1984-10-03 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
US4587207A (en) * 1983-09-27 1986-05-06 Fuji Photo Film Co., Ltd. Color image-forming process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 9, no. 30 (P-333)[1753], 8th February 1985; & JP-A-59 174 839 (FUJI SHASHIN FILM K.K.) 03-10-1984 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0574090A1 (de) 1992-06-12 1993-12-15 Eastman Kodak Company 1-Äquivalentkuppler und freisetzbaren Farbstoffen mit niedrigem pKa

Also Published As

Publication number Publication date
DE3883446D1 (de) 1993-09-30
DE3883446T2 (de) 1994-03-17
EP0296793B1 (de) 1993-08-25
JPS6421448A (en) 1989-01-24
EP0296793A3 (en) 1989-11-08
GB8714866D0 (en) 1987-07-29

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