EP0777151B1 - Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process - Google Patents
Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process Download PDFInfo
- Publication number
- EP0777151B1 EP0777151B1 EP19960203192 EP96203192A EP0777151B1 EP 0777151 B1 EP0777151 B1 EP 0777151B1 EP 19960203192 EP19960203192 EP 19960203192 EP 96203192 A EP96203192 A EP 96203192A EP 0777151 B1 EP0777151 B1 EP 0777151B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- ring
- coupler
- groups
- bonded
- 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
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 color photographic materials or elements comprising a yellow dye-forming coupler which forms a dye upon development which exhibits improved stability against dye fade upon exposure to light.
- a typical photographic element contains multiple layers of light-sensitive photographic silver halide emulsions with one or more of these layers being spectrally sensitized to blue light, green light, and red light, respectively.
- the blue, green, and red light sensitive layers will typically contain yellow, magenta or cyan dye forming couplers, respectively.
- image dyes are formed by the coupling reaction of these couplers with the oxidized product of the color developing agent.
- image couplers are selected to provide image dyes with good stability towards heat and light and which desirably have an absorption curve with a suitable peak absorption and low unwanted side absorptions in order to provide color photographic images with good color reproduction.
- the present invention is concerned with improving the light stability of yellow image dyes. Couplers that form yellow dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: U.S. Patent Nos. 2,298,443, 2,407,210, 2,875,057, 3,048,194, 3,265,506, 3,447,928, 4,022,620, 4,443,536, and "Farbkuppler-eine LiteratureUbersicht,” published in Agfa Mitannonen, Band III, pp. 112-126 (1961). Other examples of yellow dye-forming couplers are detailed in Research Disclosure No. 365, Item 36544, September 1994, Section X-B(6). Such couplers are typically open chain ketomethylene compounds.
- yellow image dyes to resist light fade is important to the longevity of color images, especially those which are destined to be subject to constant daylight exposure such as professional portraits and the like. Yellow images will fade and images formed with yellow dye as a component may change color if the rate of fade for the yellow dye is not sufficiently matched with the other dyes of the photographic element.
- U.S. Patent No. 4,248,962 relates to a pyrazolotriazole magenta dye-forming coupler designed to release a photographically useful group upon coupling.
- the patent proposes a timing group which will undergo an intramolecular nucleophilic displacement reaction to release a photographically useful group.
- coupler 44 which contains a ballast having an acetate substituent on a phenoxy group connected through a linking group to a phenyl ring in the ballast.
- Japanese published application 56-30126 discloses acylacetanilide yellow couplers containing a 2-chloro-5-carboxy anilino ring. There is no disclosure therein that couplers of this type can provide an improvement in dye light stability.
- a problem to be solved is to provide a yellow image dye-forming coupler which forms a dye upon development which exhibits improved stability upon exposure to light.
- the coupler is one for which the dye light stability may be further improved by the addition of a stabilizing addenda.
- the invention provides a photographic element comprising a light sensitive silver halide emulsion layer having associated therewith an open chain ⁇ -carbonyl acetanilide yellow dye-forming coupler having the formula: wherein
- Each R 2 is a substituent on the phenoxy ring "A", and there may be present up to four of these substituents.
- This substituent may be broadly selected from those substituents which have a Hammett's sigma value of 0 or less. Hammett's sigma values are provided in C. Hansch and A. J. Leo, "Substituent Constants for Correlation Analysis in Chemistry and Biology", Wiley, New York, N.Y., 1979. Generally, values less than 0 indicate that a substituent has an electron donating effect relative to hydrogen. Thus, R 2 is electron donating. It is further provided that at least one R 2 group is located ortho to the acyloxy group containing R 1 . This group desirably contains branching.
- R 2 is an alkyl, alkoxy or amino compound. Satisfactory compounds include thioalkyl, dialkylamino, and branched alkyl and alkoxy groups. Appropriate examples include t-butyl, t-pentyl, t-octyl, and isopropyl.
- R 3 and R 4 substituents bonded to each of the n carbon atoms may be independently selected.
- suitable R 3 and R 4 substituents may include alkyl, alkoxy (including polyalkoxy), aryl, aryloxy, heterocyclic, and amino groups. Alkyl or alkoxy groups of 1-18 carbon atoms and hydrogen are satisfactory substituents. If desired, R 3 or R 4 may form a ring with another R 3 or R 4 group.
- R 5 is a substituent which may or may not be present as indicated by the subscript "p".
- Each R 5 is a substituent which may be a halogen, an amino group, an alkyl group, or a group linked to the "B" ring by an provided that if L is other than wherein R is hydrogen or an alkyl group and R' is an alkylene group, then there is present at least one R 2 substituent on ring "A" ortho to the acyloxy group to which R1 is attached.
- the photographic element of the invention forms a yellow image dye which exhibits an improved stability to light degradation.
- R 1 is the substituent attached to the acyloxy group on the ring "A". It may be an alkyl, aryl, heterocyclic, or an amino group. Also, R 1 may form a ring bonded to another carbon atom which is a member of Ring "A". Desirably R 1 contains at least 4 carbon atom of oxygen or sulfur. Suitably, one or more of the R 5 substituents may occupy the 2-, 4-, or 6- position of the ring "B". Suitably, R 5 may be bonded to the ring "B” by an acyloxy, alkylthio, alkyl, amino, or oxy group.
- Particularly suitable groups are alkylacyloxy, arylacyloxy, trifluoromethyl, alkylthio, alkoxy, aryloxy, alkyl, or amino groups.
- the value of "p" may range from 0 to 3, suitably 1 to 3.
- R 6 is an amino group, an alkyl group or an aryl group. More suitably, R 6 may be a secondary or tertiary alkyl group, a phenyl group, a phenyl amino group, or an alkyl amino group. Typically, the secondary alkyl group may be an isopropyl group, the tertiary alkyl group may be t-butyl, t-pentyl, t-octyl, or 1-methyl-1-cyclopropyl.
- the phenyl group may be phenyl or phenyl substituted, for example, with alkoxy, alkyl or amido groups.
- the amino may be a phenylamino or alkylamino group.
- the group L is optionally present. As indicated by the value of q of up to three, there may be present as many as three L groups. Each of the L groups may be independently selected to provide a linkage between the ring "B" and the remainder of the coupler. In the broadest sense, L may be any divalent group linking the ballast directly or indirectly with a noncoupling position of the rest of the coupler. Each L may be represented, for example, by one of the groups: wherein R is hydrogen or an alkyl group and R' is an alkylene group. Specifically useful are: and
- the group Z represents a heterocyclic group containing, a nitrogen atom in a five or six membered ring, wherein the group Z is bonded to the remainder of the coupler through a nitrogen atom in the ring.
- a heterocyclic group contain one or more nitrogen atoms in the ring and possibly an oxygen atom.
- suitable groups are pyrazole, imidazole, hydantoin, urazole, and oxazole groups such as the following: wherein each R A , R B ,R C and R D is an independently selected group such as hydrogen, or an alkyl (e.g.
- group Z may represent a heterocyclic group containing in a five or six membered ring one or two nitrogen atoms and possibly an oxygen atom, where the group Z is bonded to the remainder of the coupler through a nitrogen atom in the ring.
- suitable groups are pyrazole, imidazole, hydantoin, succinimide, thiazole, thiazolidino, thiadiazole, saccharin, rhodanine, and oxazole groups such as the following: and wherein each R A , R B ,R C and R D is an independently selected group such as hydrogen, or an alkyl (e.g. methyl, ethyl ,propyl, phenylmethyl, sulfonamidoalkyl), aryl, or alkoxy (e.g. methoxy, ethoxy) group.
- alkyl e.g. methyl, ethyl ,propyl, phenylmethyl, s
- a benzotriazole group is useful as Z.
- arylthio such as phenylthio groups and aryloxy such as phenoxy groups.
- substituent groups which may be substituted on molecules herein include any groups, whether substituted or unsubstituted, which do not destroy properties necessary for photographic utility.
- group When the term "group" is applied to the identification of a substituent containing a substitutable hydrogen, it is intended to encompass not only the substituent's unsubstituted form, but also its form further substituted with any group or groups as herein mentioned.
- the group may be halogen or may be bonded to the remainder of the molecule by an atom of carbon, silicon, oxygen, nitrogen, phosphorous, or sulfur.
- the substituent may be, for example, halogen, such as chlorine, bromine or fluorine; nitro; hydroxyl; cyano; carboxyl; or groups which may be further substituted, such as alkyl, including straight or branched chain alkyl, such as methyl, trifluoromethyl, ethyl, t-butyl, 3-(2,4-di- t -pentylphenoxy) propyl, and tetradecyl; alkenyl, such as ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di- t -pentylphenoxy)ethoxy, and 2-dodecyloxyethoxy; aryl such as phenyl, 4- t -butylphenyl
- substituents may themselves be further substituted one or more times with the described substituent groups.
- the particular substituents used may be selected by those skilled in the art to attain the desired photographic properties for a specific application and can include, for example, hydrophobic groups, solubilizing groups, blocking groups, releasing or releasable groups, etc.
- the above groups and substituents thereof may include those having up to 48 carbon atoms, typically 1 to 36 carbon atoms and usually less than 24 carbon atoms, but greater numbers are possible depending on the particular substituents selected.
- the photographic element can be used in conjunction with an applied magnetic layer as described in Research Disclosure , November 1992, Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire P010 7DQ, ENGLAND, and as described in Hatsumi Kyoukai Koukai Gihou No. 94-6023, published March 15, 1994, avaliable from the Japanese Patent Office, the contents of which are incorporated herein by reference.
- inventive materials in a small format film, Research Disclosure , June 1994, Item 36230, provides suitable embodiments.
- the silver halide emulsion containing elements employed in this invention can be either negative-working or positive-working as indicated by the type of processing instructions (i.e. color negative, reversal, or direct positive processing) provided with the element.
- Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I through V.
- Various additives such as UV dyes, brighteners, antifoggants, stabilizers, light absorbing and scattering materials, and physical property modifying addenda such as hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections II and VI through VIII. Color materials are described in Sections X through XIII.
- Scan facilitating is described in Section XIV.
- Supports, exposure, development systems, and processing methods and agents are described in Sections XV to XX.
- Desirable photographic elements and processing steps including other components suitable for use in photographic elements of the invention are also described in Research Disclosure , Item 37038, February 1995.
- the processing step described above provides a negative image.
- the described elements can be processed in the known Kodak C-41 color process as described in The British Journal of Photography Annual of 1988, pages 191-198. Where applicable, the element may be processed in accordance with color print processes such as the RA-4 process of Eastman Kodak Company as described in the British Journal of Photography Annual of 1988, Pp 198-199.
- Such negative working emulsions are typically sold with instructions to process using a color negative method such as the mentioned C-41 or RA-4 process.
- the color development step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and followed by uniformly fogging the element to render unexposed silver halide developable.
- a non-chromogenic developing agent to develop exposed silver halide, but not form dye
- uniformly fogging the element to render unexposed silver halide developable Such reversal emulsions are typically sold with instructions to process using a color reversal process such as E-6.
- a direct positive emulsion can be employed to obtain a positive image.
- Preferred color developing agents are p-phenylenediamines such as:
- Development is usually followed by the conventional steps of bleaching, fixing, or bleach-fixing, to remove silver or silver halide, washing, and drying.
- couplers of the invention are accomplished using conventional reactions.
- the following is a typical method for preparing coupler Y-2 of the invention which may be employed in an analogous manner to prepare other couplers of the invention.
- Methyl-4,4-dimethyl-3-oxovalerate (15.8 g, 0.1 mol) and 2-methoxy-5-nitroaniline (16.8 g, 0.01 mol) were taken up in toluene (150 mL) in a round bottomed flask fitted with a Dean-Stark trap. The mixture was heated to a vigorous reflux while the MeOH side-product was distilled off and removed. After 4 hours, the mixture was cooled and the toluene removed in vacuo. The residue was recrystallized from acetonitrile to yield 27 g of the desired condensation product.
- Dispersions of the couplers were prepared in the following manner, exemplified with representative coupler Y2.
- 1.55 g of the coupler, Y2, 0.72g of dibutyl phthalate, 0.6g of 2-(2-butoxyethoxy)ethyl acetate and 4.6g of ethylacetate were combined and warmed to 60°C to dissolve.
- 21.2g of 11.55% gelatin, 2.44g of Alkanol XCTM (surfactant and trademark of E. I. Dupont Co., USA) and 9.62g of water were combined and warmed to 40°C. The two mixtures were combined and passed three times through a Gaulin colloid mill.
- the photographic elements were prepared by coating the following layers in the order listed on a resin-coated paper support: 1st layer Gelatin 3.23 g/m 2 2nd layer Coupler dispersion 8.8 x 10 -4 mole coupling moieties/m 2 AgCl emulsion 0.28g Ag/m 2 and blue-sensitized 3rd layer Gelatin 1.4 g/m 2 Bis (vinylsulfonylmethyl)ether 0.14 g/m 2
- the photographic elements were subjected to stepwise exposure to blue light and processed as follows at 35° C: Color Developer 45 seconds Bleach-Fix 45 seconds Wash (running water) 90 seconds
- the developer and bleach-fix were of the following compositions: Developer Water 700 mL Triethanolamine 12.41 g Blankophor REU TM (Mobay Corp) 2.3 g Lithium polystyrene sulfonate (30%) 0.3 g N,N-diethylhydroxylamine (85%) 5.4 g Lithium sulfate 2.7 g N- ⁇ 2-[(4-amino-3-methylphenyl)ethylamino]-ethyl ⁇ -methanesulfonamide, sesquisulfate 5.0 g 1-hydroxyethyl-1,1-diphosphonic acid (60%) 0.81 g Potassium carbonate, anhydrous 21.16 g Potassium chloride 1.6 g Potassium bromide 7.0 g Water to make 1.0 L pH at 26.7°C adjusted to 10.2 Bleach-Fix Water 700 mL Solution of Ammonium thiosulfate(56.4% plus Ammonium sulfite (4%)
- Yellow dyes were formed upon processing of the photographic elements.
- the coatings were assessed sensitometrically for the following characteristics:
- the comparative couplers were as follows:
- Couplers C-1 and C-2 represent couplers actually in use in commercial photographic film. Couplers C-3 and C-4 are provides as additional comparisons.
- the coating strips were exposed to a high intensity Xenon light source at a luminous flux level of 50 Klux with a WRATTEN 2C filter interposed between the light source and sample. After 2 weeks and 4 weeks, the strips were removed and the decrease in density from initial densities of 1.7, 1.0 and 0.5 were measured. The data is recorded in Table 2 as a measure of the per cent dye retained for each sample dye.
- the couplers of the invention have superior light fastness as compared to couplers C-1 and C-2 typically used in the art and are advantageous over comparisons C-3 and C-4.
- the amount of dye remaining after exposure averages 82.6% for the inventive couplers compared to an average of 43.5% for the comparative couplers. At 14 days the corresponding values are 93.8 and 73.0, respectively.
- the inventive couplers are stable enough that they can be used without light stabilizing addenda when a neutral fade position with typical magenta and cyan dyes is desired.
- Neutral fade could also be achieved even if extremely stable magenta and cyan dyes were utilized by incorporating light stabilizing addenda along with the yellow couplers of this invention in an analogous photographic format to that described above with the following weight ratios:
- Yellow coupler coupler solvent such as dibutylphthalate : auxiliary solvent such as 2-(2-butoxyethoxy)ethylacetate : stabilizer addenda 54:15:18:13.
- the stabilizer addenda typically used are those exemplified by compounds 1-3 but are not limited to these.
- polymeric stabilizing addenda are also suitable.
- the polymers can be homopolymers or copolymers which are miscible with the coupler and coupler solvent which are present, for example, as a latex or as an organic solution.
- Table III describes 2-week and 4-week light fade data for dyes formed from representative couplers using compound 1 as stabilizing addenda. Coupler + Compound 1 Coupler Type Dye Retained from Initial Density 1.0 14 day 28 day Y-1 Inv 97% 90% Y-2 Inv 100% 93% Y-3 Inv 96% 86% Y-4 Inv 93% 84% Y-5 Inv 93% 90% Y-6 Inv 95% 85% C-1 Comp 88% 69% C-3 Comp 91% 71%
- the couplers of this invention yield dyes which show highly superior resistance to light fade when coated with stabilizing addenda.
- Coupler Y-2 was coated in a format similar to that described above with the weight ratio of coupler : dibutylphthalate : stabilizing addenda of 3:2:1.
- Emulsion addenda ADD-1 was present in the emulsion in the amount of 0.88 mg/ft 2 .
- Table IV thus show that coupler Y-2 is still quite stable even without stabilizing addenda and can be made even more stable in the presence of stabilizing addenda.
Description
- This invention relates to color photographic materials or elements comprising a yellow dye-forming coupler which forms a dye upon development which exhibits improved stability against dye fade upon exposure to light.
- A typical photographic element contains multiple layers of light-sensitive photographic silver halide emulsions with one or more of these layers being spectrally sensitized to blue light, green light, and red light, respectively. The blue, green, and red light sensitive layers will typically contain yellow, magenta or cyan dye forming couplers, respectively.
- For forming color photographic images, the color photographic material is exposed imagewise and processed in a color developer bath containing an aromatic primary amine color developing agent. Image dyes are formed by the coupling reaction of these couplers with the oxidized product of the color developing agent. Generally, image couplers are selected to provide image dyes with good stability towards heat and light and which desirably have an absorption curve with a suitable peak absorption and low unwanted side absorptions in order to provide color photographic images with good color reproduction.
- The present invention is concerned with improving the light stability of yellow image dyes. Couplers that form yellow dyes upon reaction with oxidized color developing agent are described in such representative patents and publications as: U.S. Patent Nos. 2,298,443, 2,407,210, 2,875,057, 3,048,194, 3,265,506, 3,447,928, 4,022,620, 4,443,536, and "Farbkuppler-eine LiteratureUbersicht," published in Agfa Mitteilungen, Band III, pp. 112-126 (1961). Other examples of yellow dye-forming couplers are detailed in Research Disclosure No. 365, Item 36544, September 1994, Section X-B(6). Such couplers are typically open chain ketomethylene compounds.
- The ability of yellow image dyes to resist light fade is important to the longevity of color images, especially those which are destined to be subject to constant daylight exposure such as professional portraits and the like. Yellow images will fade and images formed with yellow dye as a component may change color if the rate of fade for the yellow dye is not sufficiently matched with the other dyes of the photographic element.
- Heretofore, one method of improving the light stability of yellow image dyes has been to add one or more stabilizing addenda to the coupler dispersion. Compounds suitable for this purpose are described more fully in Research Disclosure No. 365, Item 36544, September 1994, Section X-D. Examples of suitable such compounds are shown as Compounds 1, 2, and 3 and P1 in conjunction with Table IV.
- U.S. Patent No. 4,248,962 relates to a pyrazolotriazole magenta dye-forming coupler designed to release a photographically useful group upon coupling. The patent proposes a timing group which will undergo an intramolecular nucleophilic displacement reaction to release a photographically useful group. Among the many proposed couplers is one (coupler 44) which contains a ballast having an acetate substituent on a phenoxy group connected through a linking group to a phenyl ring in the ballast. There is no indication that any dye light stability is inferred by the presence of the particular ballast employed in that example.
- Japanese published application 56-30126 discloses acylacetanilide yellow couplers containing a 2-chloro-5-carboxy anilino ring. There is no disclosure therein that couplers of this type can provide an improvement in dye light stability.
- A problem to be solved is to provide a yellow image dye-forming coupler which forms a dye upon development which exhibits improved stability upon exposure to light. Desirably, the coupler is one for which the dye light stability may be further improved by the addition of a stabilizing addenda.
-
- R1 is selected from the group consisting of alkyl, aryl, heterocyclic, and amino groups, provided that R1 may form a ring bonded to another carbon atom which is a member of Ring "A";
- each R2 is independently selected from the group consisting of those substituents having a Hammett's sigma value of 0 or less, and m is from 0 to 4;
- each R3 and R4 for each of the n carbon atoms is independently selected from the group consisting of hydrogen, alkoxy, aryl, heterocyclic, aryloxy, amino and alkyl groups, and n is 0 to 16;
- each R5 is independently selected from the group consisting of halogen, amino, alkyl groups, and groups linked to the "B" ring by oxygen or sulfur, and p is 0 to 3, provided that two R5 groups may join to form a ring;
- each L is independently a divalent linking group and q is 0 to 3; and
- Ring "A" is bonded indirectly to the 3-, 4-, or 5-position of Ring "B",
- R6 is selected from the group consisting of alkyl,
aryl, and amino groups; and
- (1) when an R5 is halogen, Z is hydrogen or a
coupling-off group selected from the group consisting
of:
- (a) an aryloxy or arylthio group;
- (b) a heterocyclic group containing, in a five or six membered ring, one or two nitrogen atoms, wherein the group Z is bonded to the remainder of the coupler through a nitrogen atom in the ring; and
- (c) a benzotriazole group wherein the group Z is bonded to the remainder of the coupler through a nitrogen atom in the triazole group; and
- (2) when no R5 is halogen, Z is hydrogen, or a group capable of coupling-off when the coupler reacts with an oxidized color developing agent, atoms. Particularly suitable are alkyl (including cycloalkyl and branched alkyl), amino, fused alkyl, and aryl groups. Particularly suitable are methyl, isopropyl, fused alkyl, t-butyl, dimethylamino, diethylamino, phenyl, and fused amino.
-
- Each R2 is a substituent on the phenoxy ring "A", and there may be present up to four of these substituents. This substituent may be broadly selected from those substituents which have a Hammett's sigma value of 0 or less. Hammett's sigma values are provided in C. Hansch and A. J. Leo, "Substituent Constants for Correlation Analysis in Chemistry and Biology", Wiley, New York, N.Y., 1979. Generally, values less than 0 indicate that a substituent has an electron donating effect relative to hydrogen. Thus, R2 is electron donating. It is further provided that at least one R2 group is located ortho to the acyloxy group containing R1. This group desirably contains branching. Suitably, R2 is an alkyl, alkoxy or amino compound. Satisfactory compounds include thioalkyl, dialkylamino, and branched alkyl and alkoxy groups. Appropriate examples include t-butyl, t-pentyl, t-octyl, and isopropyl.
- Where n>1 the R3 and R4 substituents bonded to each of the n carbon atoms may be independently selected. Besides hydrogen, suitable R3 and R4 substituents may include alkyl, alkoxy (including polyalkoxy), aryl, aryloxy, heterocyclic, and amino groups. Alkyl or alkoxy groups of 1-18 carbon atoms and hydrogen are satisfactory substituents. If desired, R3 or R4 may form a ring with another R3 or R4 group.
- R5 is a substituent which may or may not be present as indicated by the subscript "p". Each R5 is a substituent which may be a halogen, an amino group, an alkyl group, or a group linked to the "B" ring by an provided that if L is other than wherein R is hydrogen or an alkyl group and R' is an alkylene group, then there is present at least one R2 substituent on ring "A" ortho to the acyloxy group to which R1 is attached.
- The photographic element of the invention forms a yellow image dye which exhibits an improved stability to light degradation.
- R1 is the substituent attached to the acyloxy group on the ring "A". It may be an alkyl, aryl, heterocyclic, or an amino group. Also, R1 may form a ring bonded to another carbon atom which is a member of Ring "A". Desirably R1 contains at least 4 carbon atom of oxygen or sulfur. Suitably, one or more of the R5 substituents may occupy the 2-, 4-, or 6- position of the ring "B". Suitably, R5 may be bonded to the ring "B" by an acyloxy, alkylthio, alkyl, amino, or oxy group. Particularly suitable groups are alkylacyloxy, arylacyloxy, trifluoromethyl, alkylthio, alkoxy, aryloxy, alkyl, or amino groups. The value of "p" may range from 0 to 3, suitably 1 to 3.
- R6 is an amino group, an alkyl group or an aryl group. More suitably, R6 may be a secondary or tertiary alkyl group, a phenyl group, a phenyl amino group, or an alkyl amino group. Typically, the secondary alkyl group may be an isopropyl group, the tertiary alkyl group may be t-butyl, t-pentyl, t-octyl, or 1-methyl-1-cyclopropyl. The phenyl group may be phenyl or phenyl substituted, for example, with alkoxy, alkyl or amido groups. The amino may be a phenylamino or alkylamino group.
- The group L is optionally present. As indicated by the value of q of up to three, there may be present as many as three L groups. Each of the L groups may be independently selected to provide a linkage between the ring "B" and the remainder of the coupler. In the broadest sense, L may be any divalent group linking the ballast directly or indirectly with a noncoupling position of the rest of the coupler. Each L may be represented, for example, by one of the groups: wherein R is hydrogen or an alkyl group and R' is an alkylene group. Specifically useful are: and
- With regard to Z,
- (1) when an R5 is halogen,
Z is hydrogen or a coupling-off group selected from the
group consisting of:
- (a) an aryloxy or arylthio group;
- (b) a heterocyclic group containing, in a five or six membered ring, one or two nitrogen atoms, wherein the group Z is bonded to the remainder of the coupler through a nitrogen atom in the ring; and
- (c) a benzotriazole group wherein the group Z is bonded to the remainder of the coupler through a nitrogen atom in the triazole group; and
- (2) when no R5 is halogen, Z is hydrogen, or a group capable of coupling-off when the coupler reacts with an oxidized color developing agent. In the latter case, any suitable coupling-off group of the art may be employed as described more fully hereafter. Typical such group include aryloxy, arylthio and nitrogen heterocyclic groups. If desired, the coupling-off group may include a so-called timing group together with a photographically useful group ("PUG") which can permit the PUG to diffuse away from the coupler's initial location to perform a function such as inhibiting development, assisting bleaching etc. Such groups are more fully described hereafter.
-
- It is suitable that the group Z represents a heterocyclic group containing, a nitrogen atom in a five or six membered ring, wherein the group Z is bonded to the remainder of the coupler through a nitrogen atom in the ring. Examples of such a heterocyclic group contain one or more nitrogen atoms in the ring and possibly an oxygen atom. The use of dione formulas is convenient. Examples of suitable groups are pyrazole, imidazole, hydantoin, urazole, and oxazole groups such as the following: wherein each RA, RB,RC and RD is an independently selected group such as hydrogen, or an alkyl (e.g. methyl, ethyl ,propyl, phenylmethyl, sulfonamidoalkyl), aryl, or alkoxy (e.g. methoxy, ethoxy) group. Particularly useful as Z are the following:
- When an R5 is halogen, group Z may represent a heterocyclic group containing in a five or six membered ring one or two nitrogen atoms and possibly an oxygen atom, where the group Z is bonded to the remainder of the coupler through a nitrogen atom in the ring. The use of dione formulas is convenient. Examples of suitable groups are pyrazole, imidazole, hydantoin, succinimide, thiazole, thiazolidino, thiadiazole, saccharin, rhodanine, and oxazole groups such as the following: and wherein each RA, RB,RC and RD is an independently selected group such as hydrogen, or an alkyl (e.g. methyl, ethyl ,propyl, phenylmethyl, sulfonamidoalkyl), aryl, or alkoxy (e.g. methoxy, ethoxy) group.
- When it is desired to release a development inhibitor group, a benzotriazole group is useful as Z.
- Other useful coupling-off groups are arylthio such as phenylthio groups and aryloxy such as phenoxy groups.
-
- Unless otherwise specifically stated, substituent groups which may be substituted on molecules herein include any groups, whether substituted or unsubstituted, which do not destroy properties necessary for photographic utility. When the term "group" is applied to the identification of a substituent containing a substitutable hydrogen, it is intended to encompass not only the substituent's unsubstituted form, but also its form further substituted with any group or groups as herein mentioned. Suitably, the group may be halogen or may be bonded to the remainder of the molecule by an atom of carbon, silicon, oxygen, nitrogen, phosphorous, or sulfur. The substituent may be, for example, halogen, such as chlorine, bromine or fluorine; nitro; hydroxyl; cyano; carboxyl; or groups which may be further substituted, such as alkyl, including straight or branched chain alkyl, such as methyl, trifluoromethyl, ethyl, t-butyl, 3-(2,4-di-t-pentylphenoxy) propyl, and tetradecyl; alkenyl, such as ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di-t-pentylphenoxy)ethoxy, and 2-dodecyloxyethoxy; aryl such as phenyl, 4-t-butylphenyl, 2,4,6-trimethylphenyl, naphthyl; aryloxy, such as phenoxy, 2-methylphenoxy, alpha- or beta-naphthyloxy, and 4-tolyloxy; carbonamido, such as acetamido, benzamido, butyramido, tetradecanamido, alpha-(2,4-di-t-pentyl-phenoxy)acetamido, alpha-(2,4-di-t-pentylphenoxy)butyramido, alpha-(3-pentadecylphenoxy)-hexanamido, alpha-(4-hydroxy-3-t-butylphenoxy)-tetradecanamido, 2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolin-1-yl, N-methyltetradecanamido, N-succinimido, N-phthalimido, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, and N-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino, 2,5-(di-t-pentylphenyl)carbonylamino, p-dodecyl-phenylcarbonylamino, p-toluylcarbonylamino, N-methylureido, N,N-dimethylureido, N-methyl-N-dodecylureido, N-hexadecylureido, N,N-dioctadecylureido, N,N-dioctyl-N'-ethylureido, N-phenylureido, N,N-diphenylureido, N-phenyl-N-p-toluylureido, N-(m-hexadecylphenyl)ureido, N,N-(2,5-di-t-pentylphenyl)-N'-ethylureido, and t-butylcarbonamido; sulfonamido, such as methylsulfonamido, benzenesulfonamido, p-toluylsulfonamido, p-dodecylbenzenesulfonamido, N-methyltetradecylsulfonamido, N,N-dipropyl-sulfamoylamino, and hexadecylsulfonamido; sulfamoyl, such as N-methylsulfamoyl, N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-hexadecylsulfamoyl, N,N-dimethylsulfamoyl; N-[3-(dodecyloxy)propyl]sulfamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]sulfamoyl, N-methyl-N-tetradecylsulfamoyl, and N-dodecylsulfamoyl; carbamoyl, such as N-methylcarbamoyl, N,N-dibutylcarbamoyl, N-octadecylcarbamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl, N-methyl-N-tetradecylcarbamoyl, and N,N-dioctylcarbamoyl; carbonyl, such as acetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl, p-dodecyloxyphenoxycarbonyl methoxycarbonyl, butoxycarbonyl, tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 3-pentadecyloxycarbonyl, and dodecyloxycarbonyl; sulfonyl, such as methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, 2-ethylhexyloxysulfonyl, phenoxysulfonyl, 2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl, phenylsulfonyl, 4-nonylphenylsulfonyl, and p-toluylsulfonyl; sulfonyloxy, such as dodecylsulfonyloxy, and hexadecylsulfonyloxy; sulfinyl, such as methylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl, 4-nonylphenylsulfinyl, and p-toluylsulfinyl; thio, such as ethylthio, octylthio, benzylthio, tetradecylthio, 2-(2,4-di-t-pentylphenoxy)ethylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, and p-tolylthio; acyloxy, such as acetyloxy, benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy, N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, and cyclohexylcarbonyloxy; amine, such as phenylanilino, 2-chloroanilino, diethylamine, dodecylamine; imino, such as 1 (N-phenylimido)ethyl, N-or 3-benzylhydantoinyl; phosphate, such as dimethylphosphate and ethylbutylphosphate; phosphite, such as diethyl and dihexylphosphite; a heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group, each of which may be substituted and which contain a 3 to 7 membered heterocyclic ring composed of carbon atoms and at least one hetero atom selected from the group consisting of oxygen, nitrogen and sulfur, such as 2-furyl, 2-thienyl, 2-benzimidazolyloxy or 2-benzothiazolyl; quaternary ammonium, such as triethylammonium; and silyloxy, such as trimethylsilyloxy.
- If desired, the substituents may themselves be further substituted one or more times with the described substituent groups. The particular substituents used may be selected by those skilled in the art to attain the desired photographic properties for a specific application and can include, for example, hydrophobic groups, solubilizing groups, blocking groups, releasing or releasable groups, etc. Generally, the above groups and substituents thereof may include those having up to 48 carbon atoms, typically 1 to 36 carbon atoms and usually less than 24 carbon atoms, but greater numbers are possible depending on the particular substituents selected.
- If desired, the photographic element can be used in conjunction with an applied magnetic layer as described in Research Disclosure, November 1992, Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 12a North Street, Emsworth, Hampshire P010 7DQ, ENGLAND, and as described in Hatsumi Kyoukai Koukai Gihou No. 94-6023, published March 15, 1994, avaliable from the Japanese Patent Office, the contents of which are incorporated herein by reference. When it is desired to employ the inventive materials in a small format film, Research Disclosure, June 1994, Item 36230, provides suitable embodiments.
- In the following discussion of suitable materials for use in the emulsions and elements of this invention, reference will be made to Research Disclosure, September 1994, Item 36544, available as described above, which will be identified hereafter by the term "Research Disclosure". The contents of the Research Disclosure, including the patents and publications referenced therein, are incorporated herein by reference, and the Sections hereafter referred to are Sections of the Research Disclosure.
- Except as provided, the silver halide emulsion containing elements employed in this invention can be either negative-working or positive-working as indicated by the type of processing instructions (i.e. color negative, reversal, or direct positive processing) provided with the element. Suitable emulsions and their preparation as well as methods of chemical and spectral sensitization are described in Sections I through V. Various additives such as UV dyes, brighteners, antifoggants, stabilizers, light absorbing and scattering materials, and physical property modifying addenda such as hardeners, coating aids, plasticizers, lubricants and matting agents are described, for example, in Sections II and VI through VIII. Color materials are described in Sections X through XIII. Scan facilitating is described in Section XIV. Supports, exposure, development systems, and processing methods and agents are described in Sections XV to XX. Desirable photographic elements and processing steps including other components suitable for use in photographic elements of the invention are also described in Research Disclosure, Item 37038, February 1995.
- It is also contemplated that the concepts of the present invention may be employed to obtain reflection color prints as described in Research Disclosure, November 1979, Item 18716, available from Kenneth Mason Publications, Ltd, Dudley Annex, 12a North Street, Emsworth, Hampshire P0101 7DQ, England, incorporated herein by reference.
- With negative-working silver halide, the processing step described above provides a negative image. The described elements can be processed in the known Kodak C-41 color process as described in The British Journal of Photography Annual of 1988, pages 191-198. Where applicable, the element may be processed in accordance with color print processes such as the RA-4 process of Eastman Kodak Company as described in the British Journal of Photography Annual of 1988, Pp 198-199. Such negative working emulsions are typically sold with instructions to process using a color negative method such as the mentioned C-41 or RA-4 process. To provide a positive (or reversal) image, the color development step can be preceded by development with a non-chromogenic developing agent to develop exposed silver halide, but not form dye, and followed by uniformly fogging the element to render unexposed silver halide developable. Such reversal emulsions are typically sold with instructions to process using a color reversal process such as E-6. Alternatively, a direct positive emulsion can be employed to obtain a positive image.
- Preferred color developing agents are p-phenylenediamines such as:
- 4-amino-N,N-diethylaniline hydrochloride,
- 4-amino-3-methyl-N,N-diethylaniline hydrochloride,
- 4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl)aniline sesquisulfate hydrate,
- 4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline sulfate,
- 4-amino-3-(2-methanesulfonamido-ethyl)-N,N-diethylaniline hydrochloride and
- 4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonic acid.
-
- Development is usually followed by the conventional steps of bleaching, fixing, or bleach-fixing, to remove silver or silver halide, washing, and drying.
- The entire contents of the various patent applications, patents and other publications referred to in this specification are incorporated herein by reference.
-
- Methyl-4,4-dimethyl-3-oxovalerate (15.8 g, 0.1 mol) and 2-methoxy-5-nitroaniline (16.8 g, 0.01 mol) were taken up in toluene (150 mL) in a round bottomed flask fitted with a Dean-Stark trap. The mixture was heated to a vigorous reflux while the MeOH side-product was distilled off and removed. After 4 hours, the mixture was cooled and the toluene removed in vacuo. The residue was recrystallized from acetonitrile to yield 27 g of the desired condensation product.
- A solution of 2-(4,4-dimethyl-3-oxo-valeramido)-4-nitroanisole (20 g) in EtOH (100 mL) with 1 g Pd/C was catalytically reduced under hydrogen to give the corresponding amine in quantitative yield. After filtering the mixture, HCl gas was bubbled through the solution. Upon cooling, white crystals of 2-(4,4-dimethyl-3-oxo-valeramido)-4-aminoanisole hydrochloride formed. The crystals were collected and dried in vacuo to yield 17 g of product.
- A solution of 2-dodecyl-2-(4-aceto-3-tert-butylaryloxy)-acetylchloride (19.4 g, 0.043 mol) in acetonitrile (100 mL) was added to a solution of 2-(4,4-dimethyl-3-oxovaleramido)-4-aminoanisole hydrochloride (13.1 g, 0 043 mol) in acetonitrile (50 mL). Diisopropylethylamine (11.2 g, 0.086 mol) was added dropwise. After 1 hour, EtOAc (100 mL) was added. The mixture was submitted to an aqueous, acidic workup. The organics were dried over MgSO4, filtered and the solvents removed in vacuo. The isolated product (27 g) was suitably pure for use in the next step.
- To a solution of 2-(4,4-dimethyl-3-oxovaleramido)-4-[2-dodecyl-2-(4-aceto-3-tert-butylaryloxy)acetamido]anisole (25.0 g, 0.0367 mol) in dichloromethane (150 mL) was added sulfuryl chloride (2.9 mL, 0.0367 mol). The mixture was stirred for 30 minutes at room temperature. The solvent was removed in vacuo. The product was formed quantitatively and was suitably pure for use in the next reaction.
- A solution of 2-(2-chloro-4,4-dimethyl-3-oxovaleramido)-4-[2-dodecyl-2-(4-aceto-3-tert-butylaryloxy)-acetamido]anisole (15.0 g, 0.021 mol), 4,4-dimethyloxazolidinedione (3.4 g, 0.026 mol) and triethylamine (2.2g, 0.023 mol) in acetonitrile (200 mL) was stirred and heated to reflux. After 4 hours, the mixture was cooled to room temperature and submitted to aqueous, acidic workup. The organics were extracted into EtOAc, dried over MgSO4, filtered and the solvent stripped in vacuo. The residue was recrystallized from isopropyl ether to yield 15.2 g (90%) of the desired yellow coupler. The results of NMR analysis were consistent with the compound Y-2. 1H NMR (CDCl3/TMS): d = 0.9 (t, 3 H), 1.4 (m, 46 H), 2.3 (s, 3H), 3.9 (s, 3 H), 4.6 (t, 1 H), 5.6 (s, 1 H), 6.9 (m, 4H), 7.8 (d, 1 H), 8.1 (m,br, 2 H), 9.0 (s, 1H).
MS (FDMS) m/e = 807C45 H65 N3 O10 calc 66.89 H 8.11 N 5.2 found 66.85 H 8.01 N 5.0 - Dispersions of the couplers were prepared in the following manner, exemplified with representative coupler Y2. In one vessel, 1.55 g of the coupler, Y2, 0.72g of dibutyl phthalate, 0.6g of 2-(2-butoxyethoxy)ethyl acetate and 4.6g of ethylacetate were combined and warmed to 60°C to dissolve. In a second vessel, 21.2g of 11.55% gelatin, 2.44g of Alkanol XC™ (surfactant and trademark of E. I. Dupont Co., USA) and 9.62g of water were combined and warmed to 40°C. The two mixtures were combined and passed three times through a Gaulin colloid mill.
- The photographic elements were prepared by coating the following layers in the order listed on a resin-coated paper support:
1st layer Gelatin 3.23 g/m2 2nd layer Coupler dispersion 8.8 x 10-4 mole coupling moieties/m2 AgCl emulsion 0.28g Ag/m2 and blue-sensitized 3rd layer Gelatin 1.4 g/m2 Bis (vinylsulfonylmethyl)ether 0.14 g/m2 - The photographic elements were subjected to stepwise exposure to blue light and processed as follows at 35° C:
Color Developer 45 seconds Bleach-Fix 45 seconds Wash (running water) 90 seconds - The developer and bleach-fix were of the following compositions:
Developer Water 700 mL Triethanolamine 12.41 g Blankophor REU TM (Mobay Corp) 2.3 g Lithium polystyrene sulfonate (30%) 0.3 g N,N-diethylhydroxylamine (85%) 5.4 g Lithium sulfate 2.7 g N-{2-[(4-amino-3-methylphenyl)ethylamino]-ethyl}-methanesulfonamide, sesquisulfate 5.0 g 1-hydroxyethyl-1,1-diphosphonic acid (60%) 0.81 g Potassium carbonate, anhydrous 21.16 g Potassium chloride 1.6 g Potassium bromide 7.0 g Water to make 1.0 L pH at 26.7°C adjusted to 10.2 Bleach-Fix Water 700 mL Solution of Ammonium thiosulfate(56.4% plus Ammonium sulfite (4%) 127.4 g Sodium metabisulfite 10.0 g Acetic Acid (glacial) 10.2 g Solution of Ammonium ferric ethylenediaminetetraacetate (44%) + ethylenediaminetetraacetic acid (3.5%) 110.4 g Water to make 1.0 L pH at 26.7° C adjusted to 6.7 - Yellow dyes were formed upon processing of the photographic elements. The coatings were assessed sensitometrically for the following characteristics:
- D-max (the maximum density to blue light),
- Dmin (the minimum density to blue light),
-
- Contrast (the ratio of (S-T)/0.6 where S is the density at a log exposure 0.3 units greater than the Speed value, and T is the density at a log exposure 0.3 units less than the Speed value),
- Speed (the relative reciprocal of exposure required to yield a density to blue light of 1.0), and Lambda-max (the wavelength of peak absorption at a density of 1.0).
- The data is reported in Table I. The data shows that the couplers of the invention are comparable or superior in sensitometry to the comparison couplers.
Sensitometric Data Coupler Type Dmax Dmin Contrast Speed λmax Y-1 Inv 2.75 0.06 2.65 182.4 439 Y-2 Inv 2.75 0.09 2.65 188.4 439 Y-3 Inv 2.74 0.08 2.64 198.1 438 Y-4 Inv 2.76 0.09 2.80 199.5 437 Y-5 Inv 2.83 0.05 2.84 186.9 436 Y-6 Inv 2.81 0.08 2.59 197.0 440 C-1 Comp 2.70 0.05 2.55 191.7 446 C-2 Comp 2.62 0.05 2.60 188.2 438 C-3 Comp 2.42 0.06 2.40 177.6 441 C-4 Comp 2.71 0.04 2.51 178.4 442 -
- Couplers C-1 and C-2 represent couplers actually in use in commercial photographic film. Couplers C-3 and C-4 are provides as additional comparisons.
- The coating strips were exposed to a high intensity Xenon light source at a luminous flux level of 50 Klux with a WRATTEN 2C filter interposed between the light source and sample. After 2 weeks and 4 weeks, the strips were removed and the decrease in density from initial densities of 1.7, 1.0 and 0.5 were measured. The data is recorded in Table 2 as a measure of the per cent dye retained for each sample dye. These results compare the light fastness of dyes from couplers of the present invention with those of the comparisons.
Coupler Type Dye Retained from Initial Density 1.0 14-Day 28-Day Y-1 Inv 96% 85% Y-2 Inv 96% 86% Y-3 Inv 91% 79% Y-4 Inv 91% 82% Y-5 Inv 94% 79% Y-6 Inv 95% 85% C-1 Comp 51% 17% C-2 Comp 72% 40% C-3 Comp 78% 40% C-4 Comp 91% 77% - As can be seen from Table II, the couplers of the invention have superior light fastness as compared to couplers C-1 and C-2 typically used in the art and are advantageous over comparisons C-3 and C-4. The amount of dye remaining after exposure averages 82.6% for the inventive couplers compared to an average of 43.5% for the comparative couplers. At 14 days the corresponding values are 93.8 and 73.0, respectively. The inventive couplers are stable enough that they can be used without light stabilizing addenda when a neutral fade position with typical magenta and cyan dyes is desired.
- Neutral fade could also be achieved even if extremely stable magenta and cyan dyes were utilized by incorporating light stabilizing addenda along with the yellow couplers of this invention in an analogous photographic format to that described above with the following weight ratios: Yellow coupler : coupler solvent such as dibutylphthalate : auxiliary solvent such as 2-(2-butoxyethoxy)ethylacetate : stabilizer addenda 54:15:18:13. The stabilizer addenda typically used are those exemplified by compounds 1-3 but are not limited to these. Also suitable are polymeric stabilizing addenda. The polymers can be homopolymers or copolymers which are miscible with the coupler and coupler solvent which are present, for example, as a latex or as an organic solution. Especially useful are polymers containing monomers derived from styrene and/or acrylics such as acrylamide (particularly t-butyl acrylamide such as P1 below where x=99 and y=1), acrylates, methacrylamides, and methacrylates.
- Table III describes 2-week and 4-week light fade data for dyes formed from representative couplers using compound 1 as stabilizing addenda.
Coupler + Compound 1 Coupler Type Dye Retained from Initial Density 1.0 14 day 28 day Y-1 Inv 97% 90% Y-2 Inv 100% 93% Y-3 Inv 96% 86% Y-4 Inv 93% 84% Y-5 Inv 93% 90% Y-6 Inv 95% 85% C-1 Comp 88% 69% C-3 Comp 91% 71% - As shown in Table III, the couplers of this invention yield dyes which show highly superior resistance to light fade when coated with stabilizing addenda.
- This can be particularly useful if one desires to use certain emulsion additives to achieve unique photographic features, as is sometimes done in the art. Although the presence of these emulsion additives give desirable photographic features, they can sometimes be detrimental to dye stability. Coupler Y-2 was coated in a format similar to that described above with the weight ratio of coupler : dibutylphthalate : stabilizing addenda of 3:2:1. Emulsion addenda ADD-1 was present in the emulsion in the amount of 0.88 mg/ft2. The data in Table IV thus show that coupler Y-2 is still quite stable even without stabilizing addenda and can be made even more stable in the presence of stabilizing addenda.
Dye Retained from Initial Density 1.0 Coupler + Addenda Emulsion with ADD-1 Coupler Type Addenda 21 days C-2 Comp None 53% Y-2 Inv None 77% C-2 Comp Cmpd. 1 75% Y-2 Inv Cmpd. 1 84% C-2 Comp Cmpd. 2 74% Y-2 Inv Cmpd. 2 87% C-2 Comp Cmpd. 3 74% Y-2 Inv Cmpd. 3 87% C-2 Comp P1 74% Y-2 Inv P1 80%
Claims (11)
- A photographic element comprising a light sensitive silver halide emulsion layer having associated therewith an open chain α-carbonyl acetanilide yellow dye-forming coupler having the formula: whereinR1 is selected from the group consisting of alkyl, aryl, heterocyclic, and amino groups, provided that R1 may form a ring bonded to another carbon atom which is a member of Ring "A";each R2 is independently selected from the group consisting of t ose substituents having a Hammett's sigma value of 0 or less, and m is from 0 to 4;each R3 and R4 for each of the n carbon atoms is independently selected from the group consisting of hydrogen, alkoxy, aryl, heterocyclic, aryloxy, amino and alkyl groups, and n is 0 to 16;each R5 is independently selected from the group consisting of halogen, amino, alkyl groups, and groups linked to the "B" ring by oxygen or sulfur, and p is 0 to 3, provided that two R5 groups may join to form a ring;each L is independently a divalent linking group and q is 0 to 3; andRing "A" is bonded indirectly to the 3-, 4-, or 5-position of Ring "B",R6 is selected from the group consisting of alkyl, aryl, and amino groups; and(1) when an R5 is halogen, Z is hydrogen or a coupling-off group selected from the group consisting of:(a) an aryloxy or arylthio group;(b) a heterocyclic group containing, in a five or six membered ring, one or two nitrogen atoms, wherein the group Z is bonded to the remainder of the coupler through a nitrogen atom in the ring; and(c) a benzotriazole group wherein the group Z is bonded to the remainder of the coupler through a nitrogen atom in the triazole group; and(2) when no R5 is halogen, Z is hydrogen, or a group capable of coupling-off when the coupler reacts with an oxidized color developing agent
provided that if L is other than wherein R is hydrogen or an alkyl group and R' is an alkylene group, then there is present at least one R2 substituent on ring "A" ortho to the acyloxy group to which R1 is attached. - The element of claim 1 wherein said coupling-off group is as defined in (1)(b) or (1)(c) of claim 1 when an R5 is halogen, or is a heterocyclic group containing, a nitrogen atom in a five or six membered ring, wherein the group Z is bonded to the remainder of the coupler through a nitrogen atom in the ring when no R5 is halogen.
- The element of claim 1 wherein said coupling-off group is a benzotriazole group wherein the group Z is bonded to the remainder of the coupler through a nitrogen atom in the triazole group.
- The element of claim 1 wherein said coupling-off group is an aryloxy or arylthio group.
- The element of claim 1 wherein m is at least 1.
- The element of claim 5 wherein there is at least one R2 substituent on ring "A" ortho to the acyloxy group to which R1 is attached.
- The element of claim 6 wherein said at least one R2 substituent on ring "A" ortho to the acyloxy group to which R1 is attached contains branching.
- The element of claim 7 wherein said at least one R2 substituent on ring "A" ortho to the acyloxy group to which R1 is attached is a branched alkyl group.
- The element of claim 8 wherein said at least one R2 substituent on ring "A" ortho to the acyloxy group to which R1 is attached is selected from the group consisting of i-propyl, t-butyl, t-amyl, and t-octyl groups.
- The element of claim 1 wherein R1 contains at least 4 carbon atoms.
- The element of claim 1 wherein at least one R5 is bonded at the 2-,4-, or 6-position of ring "B".
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US56551795A | 1995-11-30 | 1995-11-30 | |
US565517 | 1995-11-30 | ||
US68074396A | 1996-07-15 | 1996-07-15 | |
US08/680,191 US5677114A (en) | 1995-11-30 | 1996-07-15 | Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process |
US680743 | 1996-07-15 | ||
US680191 | 1996-07-15 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0777151A2 EP0777151A2 (en) | 1997-06-04 |
EP0777151A3 EP0777151A3 (en) | 1997-07-02 |
EP0777151B1 true EP0777151B1 (en) | 2000-05-31 |
Family
ID=27415967
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19960203192 Expired - Lifetime EP0777151B1 (en) | 1995-11-30 | 1996-11-15 | Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0777151B1 (en) |
JP (1) | JPH09179259A (en) |
DE (1) | DE69608648T2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9717166D0 (en) * | 1997-08-14 | 1997-10-22 | Eastman Kodak Co | Image dye-forming couplers and photographic elements containing them |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB536939A (en) | 1939-08-24 | 1941-06-03 | Eastman Kodak Co | Improvements in and relating to photographic colour development |
US2407210A (en) | 1944-04-14 | 1946-09-03 | Eastman Kodak Co | Color couplers |
BE543742A (en) | 1954-12-20 | |||
US3048194A (en) | 1958-11-26 | 1962-08-07 | Gen Fire Extinguisher Corp | Fire extinguisher head assembly |
US3265506A (en) | 1964-05-04 | 1966-08-09 | Eastman Kodak Co | Yellow forming couplers |
US3447928A (en) | 1965-07-26 | 1969-06-03 | Eastman Kodak Co | Silver halide emulsion containing twoequivalent yellow dye-forming coupler |
JPS51102636A (en) | 1974-04-03 | 1976-09-10 | Fuji Photo Film Co Ltd | Karaashashingazo no keiseihoho |
US4248962A (en) | 1977-12-23 | 1981-02-03 | Eastman Kodak Company | Photographic emulsions, elements and processes utilizing release compounds |
JPS5630126A (en) * | 1979-08-20 | 1981-03-26 | Konishiroku Photo Ind Co Ltd | Silver halide photographic material |
US4443536A (en) | 1981-08-25 | 1984-04-17 | Eastman Kodak Company | Nondiffusible photographic couplers and photographic elements and processes employing same |
-
1996
- 1996-11-15 DE DE1996608648 patent/DE69608648T2/en not_active Expired - Fee Related
- 1996-11-15 EP EP19960203192 patent/EP0777151B1/en not_active Expired - Lifetime
- 1996-12-02 JP JP32175296A patent/JPH09179259A/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
DE69608648T2 (en) | 2001-02-08 |
EP0777151A2 (en) | 1997-06-04 |
JPH09179259A (en) | 1997-07-11 |
DE69608648D1 (en) | 2000-07-06 |
EP0777151A3 (en) | 1997-07-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4556630A (en) | Color photographic light-sensitive material | |
JPH10207024A (en) | Photographic element | |
JP2001194761A (en) | Photographic element and image forming method | |
EP0777151B1 (en) | Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process | |
US6071683A (en) | Image dye-forming couplers and photographic elements containing them | |
US5677114A (en) | Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process | |
US5932407A (en) | Color photographic element containing oxidized developer-scavenging naphtholic coupler forming wash-out dye | |
US5834167A (en) | Photographic element containing yellow dye-forming coupler comprising a dye light stability enhancing ballast and process | |
EP0813112B1 (en) | Photographic elements containing new magenta dye-forming couplers | |
JPH0777785A (en) | Masking coupler and photographic element | |
US6190852B1 (en) | Photographic element containing nitrogen heterocycle substituted cyan coupler and process | |
JP2000194101A (en) | Photographic element | |
JPH08234386A (en) | Photographic element | |
US6077658A (en) | Silver halide elements containing yellow couplers with improved dye stability | |
US6221573B1 (en) | Yellow coupler, photographic element, and process | |
GB2304421A (en) | Photographic material containing acrylate or acrylamide yellow couplers | |
US5498515A (en) | Photographic element containing a certain sulfonated acylacetanilide coupler in combination with low- or non-chloride emulsions | |
US5919969A (en) | Synthesis of yellow couplers | |
US6348306B1 (en) | Photographic element containing improved stabilizer | |
US5976777A (en) | Photographic element containing magenta coupler with particular substituent | |
US6040126A (en) | Photographic yellow dye-forming couplers | |
JPH1152523A (en) | Photographic processing method | |
US6071685A (en) | Photographic element, pyrazole derived couplers and process | |
US5928851A (en) | Photographic couplers which release useful groups anchiomerically and their synthesis | |
EP0608958A1 (en) | Photographic material and process comprising a thiol bleach assist in the low sensitivity layer of a triple coat |
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 |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): DE FR GB |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): DE FR GB |
|
17P | Request for examination filed |
Effective date: 19971204 |
|
17Q | First examination report despatched |
Effective date: 19980212 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
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 |
|
REF | Corresponds to: |
Ref document number: 69608648 Country of ref document: DE Date of ref document: 20000706 |
|
ET | Fr: translation filed | ||
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 |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20031002 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20031105 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20031128 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20041115 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050601 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20041115 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050729 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |