EP0296793B1 - Matériaux photographiques couleurs à l'halogénure d'argent et procédé - Google Patents
Matériaux photographiques couleurs à l'halogénure d'argent et procédé Download PDFInfo
- Publication number
- EP0296793B1 EP0296793B1 EP19880305631 EP88305631A EP0296793B1 EP 0296793 B1 EP0296793 B1 EP 0296793B1 EP 19880305631 EP19880305631 EP 19880305631 EP 88305631 A EP88305631 A EP 88305631A EP 0296793 B1 EP0296793 B1 EP 0296793B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver halide
- group
- coupler
- photographic silver
- colour photographic
- 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.)
- Expired - Lifetime
Links
Images
Classifications
-
- 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 has a sulphonamido group on the anilide ring. Its properties are not reported.
- Japanese Kokai 59-174839 also discloses similar couplers.
- Compound 9 of this specification also has structural features in common with the couplers of the present invention but has an alkyl ester group on the anilide ring.
- 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) an aliphatic hydrocarbon group that is bonded to the anilide moiety directly or through a linking group that is carbamoyl (-CONH-), sulphonate (-O-SO2-), phosphate (-O-PO2) or alkylene, (ii) chlorine, and (iii) trifluoromethyl; said anilide moeity having no further substituents; wherein the coupler contains at least one bal
- Useful non-diffusible colour couplers have the formula: wherein R1 is an unsubstituted or substituted cyclic or non-cyclic aliphatic hydrocarbon group; Y is chloro or trifluoromethyl; Z is halogen, trifluoromethyl or -L-R2 wherein R2 is an unsubstituted or substituted aliphatic hydrocarbon group, L is a direct bond or a carbamoyl (-CONH-), sulphonate (-O-SO2-), phosphate (-O-PO2-), or alkylene group; and at least one of R1 and Z comprises a ballast group.
- 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, sulphonate, 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 may represent can be any of the groups given as examples of R1.
- Benzoylacetanilide couplers 1 to 5 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. Me herein means CH3-.
- the present couplers may be prepared by methods, in themselves, known.
- the following synthetic procedure for coupler 8 (a coupler outside the scope of the present invention but an analogous compound) 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 multicolour 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.
- Multicolour 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 sensitive 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 Section 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 Section XII
- antistatic agents see Research Disclosure Section XIII
- matting agents see Research Disclosure
- 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-vinyl-sulphonylmethane 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 (5) are as follows and are compared with comparative compound (6), a commercially used benzoylacetanilide which bears a hydantoin coupling-off group.
- Compound Dark/wet fade (6 weeks) (1) 0.06 (2) 0.04 (3) 0 (4) -0.03 (5) 0.01 (6) (Comparison) -0.16
- the structure of Coupler 6 is: Et herein means ethyl and Bz means benzyl.
- Table 1 containing examples of the invention (2) and (3), illustrates the superior Dmax and contrast consistently attained in dye images from couplers of the invention relative to a current commercial prior art pivaloylacetanilide coupler (7).
- the dark/wet fade data for this set illustrates the superiority of the couplers of the invention (2) and (3) containing a phenolic leaving group over a current commercial benzoylacetanilide (6) which bears a heterocyclic leaving group.
- contrast ratios of this set illustrate the superior activity exhibited by the present benzoylacetanilides relative to the commercial pivaloylacetanilide (7).
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Claims (8)
- Produit aux halogénures d'argent pour la photographie en couleurs comprenant un support avec, sur ce support, au moins une couche d'émulsion photographique aux halogénures d'argent, et un coupleur para-R-oxybenzoylacétanilide formateur de colorant jaune non-diffusible qui combine (a) un groupe parahydroxyphénylsulphonylphénoxy se séparant par couplage dans la position de couplage, (b) un groupe chloro ou trifluorométhyle en position ortho sur le radical anilide, et (c) sur le radical anilide, un groupe choisi parmi (i) les groupes hydrocarbonés aliphatiques liés au radical anilide directement ou par l'intermédiaire d'un groupe de liaison carbamoyle (-CONH-), sulfonate (-O-SO₂-), phosphate (-O-PO₂-) ou alkylène, (ii), le chlore et (iii) le radical trifluorométhyle ; ce radical anilide n'ayant aucun autre substituant ; le coupleur contenant au moins un groupe de lestage sur au moins l'un des radicaux anilide ou para-R-oxybenzoyle ; R étant un groupe hydrocarboné aliphatique cyclique ou non cyclique, substitué ou non substitué.
- Produit aux halogénures d'argent pour la photographie en couleurs selon la revendication 1, dans lequel le coupleur formateur de colorant jaune non diffusible est représenté par la formule :
R¹ est un groupe hydrocarboné aliphatique, cyclique ou non-cyclique, substitué ou non substitué ;
Y est chloro ou trifluorométhyle
Z est halogène, trifluorométhyle ou -L-R² dans lequel
R² est un groupe hydrocarboné aliphatique ou non substitué ;
L est une liaison directe ou un groupe carbamoyle (-CONH-), sulfonate (-O-SO₂-), phosphate (-O-PO₂) ou alkylène et,
au moins l'un des groupes R¹ et Z comprend un groupe de lestage. - Produit aux halogénures d'argent pour la photographie en couleurs selon la revendication 2, dans lequel Z comprend un groupe de lestage et R¹ est alkyl comprenant de 1 à 4 atomes de carbone.
- Produit aux halogénures d'argent pour la photographie en couleurs selon la revendication 2, dans lequel R¹ comprend un groupe de lestage.
- Produit aux halogénures d'argent pour la photographie en couleurs selon l'une des revendications 1 à 5 comprenant un support portant au moins une couche d'émulsion aux halogénures d'argent sensible au rouge associée à un coupleur formateur de colorant cyan, au moins une couche d'émulsion aux halogénures d'argent sensible au vert associée à un coupleur formateur de colorant magenta et au moins une couche d'émulsion aux halogénures d'argent sensible au bleu associée audit coupleur formateur de colorant jaune non diffusible.
- Procédé pour former une image de colorant dans un produit aux halogénures d'argent pour la photographie en couleur selon l'une des revendications 1 à 6, préalablement exposé, comprenant le développement de ce produit dans un révélateur pour la photographie en couleur.
- Coupleur benzoylacétanilide formateur de colorant jaune pour la photographie en couleur tel que défini dans l'une des revendications 1-5.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB878714866A GB8714866D0 (en) | 1987-06-25 | 1987-06-25 | Acylacetanilide photographic colour couplers |
GB8714866 | 1987-06-25 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0296793A2 EP0296793A2 (fr) | 1988-12-28 |
EP0296793A3 EP0296793A3 (en) | 1989-11-08 |
EP0296793B1 true EP0296793B1 (fr) | 1993-08-25 |
Family
ID=10619524
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19880305631 Expired - Lifetime EP0296793B1 (fr) | 1987-06-25 | 1988-06-22 | Matériaux photographiques couleurs à l'halogénure d'argent et procédé |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0296793B1 (fr) |
JP (1) | JPS6421448A (fr) |
DE (1) | DE3883446T2 (fr) |
GB (1) | GB8714866D0 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0574090A1 (fr) | 1992-06-12 | 1993-12-15 | Eastman Kodak Company | Copulants à un équivalent et colorants à pKa bas libérés |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0248098B2 (ja) * | 1983-03-24 | 1990-10-24 | Fuji Photo Film Co Ltd | Harogenkaginkaraashashinkankozairyo |
JPS6069653A (ja) * | 1983-09-27 | 1985-04-20 | Fuji Photo Film Co Ltd | カラ−画像形成方法 |
-
1987
- 1987-06-25 GB GB878714866A patent/GB8714866D0/en active Pending
-
1988
- 1988-06-22 DE DE19883883446 patent/DE3883446T2/de not_active Expired - Fee Related
- 1988-06-22 EP EP19880305631 patent/EP0296793B1/fr not_active Expired - Lifetime
- 1988-06-24 JP JP15507088A patent/JPS6421448A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
EP0296793A3 (en) | 1989-11-08 |
GB8714866D0 (en) | 1987-07-29 |
DE3883446T2 (de) | 1994-03-17 |
DE3883446D1 (de) | 1993-09-30 |
JPS6421448A (en) | 1989-01-24 |
EP0296793A2 (fr) | 1988-12-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4149886A (en) | Light-sensitive material with coupler containing triazole coupling-off group | |
EP0080355B1 (fr) | Eléments photographiques contenant des coupleurs photographiques substitués par aryloxy | |
EP0265196B1 (fr) | Stabilisation d'images de colorant produites dans des matériaux photographiques | |
EP0034951B1 (fr) | Emulsions et éléments photographiques contenant des coupleurs formateurs de colorant magenta du type 5-pyrazolone bloquée | |
US4758501A (en) | Photographic acetanilide couplers and photographic elements containing them | |
US4095984A (en) | Development inhibitor releasing coupler and photographic element containing same | |
EP0528930B1 (fr) | Utilisation de phenols substitues pour une stabilite accrue d'images a colorant magenta envers la lumiere | |
US4728599A (en) | Sterically hindered phenolic ester photographic coupler dispersion addenda and photographic elements employing same | |
US5143821A (en) | Color photographic material comprising a 2-alkoxy pyrazolo[1,5-a]benzimidazole color coupler | |
US5460927A (en) | Activated propenes as color couplers and a method for production of photographic elements therewith | |
US5021333A (en) | Color photographic element, compounds and process | |
US5250399A (en) | Photographic material and process comprising a universal coupler | |
EP0572422A1 (fr) | Propenes actives utilises comme agents de copulation de colorants et procede de production | |
US5443945A (en) | Activated propenes as colour couplers | |
EP0296793B1 (fr) | Matériaux photographiques couleurs à l'halogénure d'argent et procédé | |
US4978605A (en) | Benzoylacetanilide photographic yellow dye image-forming couplers and photographic elements containing them | |
US5021325A (en) | Photographic material and process comprising a pyrazolotriazole coupler | |
US4973545A (en) | Photographic couplers with aryloxysilyl groups | |
US5190848A (en) | Photographic β-ketoamide and photographic elements containing them | |
US5427898A (en) | Yellow couplers having an arloxy coupling-off group which contains an ortho polarizable functional group | |
US4824771A (en) | Photographic acetanilide couplers with novel ballast group and photographic elements containing them | |
US5215878A (en) | Benzoylacetanilide photographic yellow dye image-forming couplers and photographic elements containing them | |
EP0751427A1 (fr) | Coupleurs formant des colorants d'images et éléments photographiques les contenant | |
EP0379309B1 (fr) | Coupleurs photographiques de type benzoylacétanilide formateur d'images de colorant jaune et éléments photographiques les contenant | |
EP0443159B1 (fr) | Coupleurs formateurs de cyan et produits photographiques de reproduction les contenant |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): DE FR GB IT NL |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19900503 |
|
17Q | First examination report despatched |
Effective date: 19911104 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE FR GB IT NL |
|
REF | Corresponds to: |
Ref document number: 3883446 Country of ref document: DE Date of ref document: 19930930 |
|
ITF | It: translation for a ep patent filed |
Owner name: MODIANO & ASSOCIATI S.R |
|
ET | Fr: translation filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19940520 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19940608 Year of fee payment: 7 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19940630 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19940719 Year of fee payment: 7 |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19950622 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19960101 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19950622 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19960229 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19960101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19960301 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050622 |