US3891445A - Color photographic light-sensitive materials - Google Patents

Color photographic light-sensitive materials Download PDF

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US3891445A
US3891445A US480456A US48045674A US3891445A US 3891445 A US3891445 A US 3891445A US 480456 A US480456 A US 480456A US 48045674 A US48045674 A US 48045674A US 3891445 A US3891445 A US 3891445A
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coupler
group
couplers
photographic light
sensitive material
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Atsuaki Arai
Yasushi Oishi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • 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
    • G03C7/32—Colour coupling substances
    • G03C7/3212—Couplers characterised by a group not in coupling site, e.g. ballast group, as far as the coupling rest is not specific

Definitions

  • ABSTRACT A color photographic light-sensitive material which June 24, 1975 comprises a support having thereon at least one silver halide emulsion layer containing a coupler repre sented by the following general formula (l) 3 (R Q NHCOC o (1) wherein 0 represents a coupler residue which can form a dye on reaction with an oxidation product of an aromatic primary amino developing agent; R, represents an alkyl group, an aralkyl group, an alkoxy group, an alkoxyalkyl group, an acylamido group or an alkoxycarbonyl group, each having from 4 to 20 carbon atoms; R represents a hydrogen atom
  • the present invention relates to a color photographic light-sensitive material. More particularly, it relates to a color photographic light-sensitive material which contains a novel coupler having an aryloxyisobutyramido group, as an oleophilic group.
  • couplers having an oleophilic diffusionresistant group suitable for use in the production of color photographic light-sensitive materials having good photographic characteristics need to fulfill the following properties.
  • Both the coupler and the dye formed therefrom by color development should have a good solubility in a high boiling organic solvent (for example tricresyl phosphate) which is employed to disperse the coupler.
  • a high boiling organic solvent for example tricresyl phosphate
  • the coupler should have good stability when incorporated into a silver halide photographic emulsion and provide a stable coating on a support without deposition of the coupler.
  • the coupler should have good diffusion-resistance and should not diffuse into other layers.
  • the coupler should have a high coupling reactivity and should produce a dye image having good spectral absorption characteristics as well as good stability to heat, humidity and light.
  • the coupler should be capable of being produced in high purity from low cost raw materials in a simple manner with good reproducibility.
  • a substituted or unsubstituted aliphatic acyl group for example, l an n-tridecanoyl group as described in the specification of Japanese patent Application No. 21,454/73 and (2) a B-(N-n-pentadecyl-n-butyramido)propionyl group as described in the specification of Japanese Patent Publication No. 2837/64, is known.
  • a diffusion-resistant group containing an aromatic ring for example, (3) a 2,4-di-tert.-amylphenoxyacetyl group as described in the specification of U.S. Pat. Nos.
  • a coupler containing diffusion-resistant group l due to its high aliphatic character, has insufficient solubility in a high boiling organic solvent which is used as a solvent for dispersing an oil-soluble cou pler.
  • a benzoylacetoanilide type yellow coupler and a phenol type cyan couper containing such a group has poor coupler dispersion stability and often the deposition of coupler results.
  • a coupler containing diffusion resistant group (2 the purification and crystallization of the coupler during preparation of the coupler are generally difficult. Many procedures are needed to obtain a coupler of high purity, and hence, this is not advantageous from the standpoint of cost.
  • a coupler which contains as the diffusion-resistant group such a long alkyl group generally has a low melting point and is quite soluble in organic solvents at relatively high temperatures, but has the disadvantages that the solubility depends greatly on the temperature and coupler is difiicult to dissolve in organic solvents.
  • a coupler having an aryloxyalkylacylamido group is advantageous in that the solubility of such a coupler in organic solvents tends to be less temperature dependent.
  • an emulsion layer containing such a coupler has a high film strength and there is less movement of the coupler in an emulsion layer.
  • Diffusion-resistant groups (3), (4), (7) and (8) exhibit substantially similar properties, and particularly cyan, magenta and yellow couplers containing diffusion-resistant group (3) are described in many references as typical oil-soluble incorporated type couplers. For example. in the specification of US. Pat. No. 2,618,64l the following coupler examples (A, B and C) are described.
  • CouplerA (cyan) Cl I ⁇ HCOCH O-. )-C H (t) Coupler B (magenta) (t)H C -QOCH CO H- c a (t) colts-i3 N :8
  • CouplerC (yellow)
  • couplers have high melting points, a tendency toward crystallization and insufticicient solubility in conventional high boiling coupler solvents.
  • coupler deposition due to coupler deposition, a stable dispersion of the coupler in high concentration is difficult to obtain.
  • Couplers having diffusion-resistant group (4) generally have low melting points. This is because the raw material. 2,4-di-sec.-amylphenol, includes isomers which are introduced into the coupler, and consequently isolation and purification of the coupler in high purity are difficult, resulting in decreasing the yield of the coupler.
  • couplers having an oleophilic group in which an alkyl substituent is introduced into the (Jr-position of the alkylacyl group such as the diffusion-resistant groups (5) and (6) (in each of (5) and (6) an ethyl group is introduced) solubility in organic solvents is greatly improved, however,
  • the reaction between the a-halobutyric acid and phenol used in preparing the coupler is not very sufficient in view of the yield obtained and thus this is not advantageous from an economical standpoint. 5 Further. the most disadvantageous characteristic which couplers containing diffusion resistant groups (3) to (8) have is the dye images formed from these couplers by color development in multilayer color light-sensitive materials in which these couplers are incorporated tend to have reduced heat stability. This is particularly marked in indophenol type dye images prepared from cyan couplers.
  • An object of the present invention is to produce color light-sensitive materials which have excellent photographic properties and color image stability using couplers which have sufficient diffusion-resistance and high solubility in high boiling organic solvents and for which a stable dispersion can be obtained and the thickness of layers can be decreased due to use ofa decreased amount of solvent, and which can be easily prepared using readily available raw materials.
  • this invention provides a color photographic light-sensitive material which comprises a support having thereon at least one silver halide emulsion layer containing a coupler represented by the general formula (I) Cll wherein 0 represents a coupler residue forming a dye on reaction with the oxidation product of an aromatic primary amino developing agent; R, represents an alkyl group, an aralkyl group, an alkoxy group, an alkoxyalkyl group, an acylamino group or an alkoxy carbonyl group, each having from 4 to 20 carbon atoms; R; represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkyl group having l to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms; m is an integer of l to 4; n is an integer of 1 to 4; and the sum of m n is 2 to 5; and R and R may combine together to form a five-membered or a six membered nonmetallic atom containing
  • Q in the general formula (I) can be a phenol or a naphthol coupler residue containing a phenolic hydroxy group, a pyrazolone, a cyanoacetophenone or an acylacetonilide coupler residue containing an active methylene group, or a derivative thereof in which the active position is substituted (the so called twoequivalent type coupler).
  • the coupler When Q is a phenol or naphthol compound, the coupler is a cyan dye forming cou- A pler; when Q is a pyrazolone or a cyanoacetophenone compound, the coupler is a magenta dye forming coupler, and when Q is an acylacetoanilide compound the coupler is a yellow dye forming coupler.
  • m i ty are as follows:
  • coupler residues are residues of the couplers disclosed in the following U.S. Patents.
  • R, and R be positioned at the 3- and 5-positions on the phenoxy ring.
  • R, and R are connected together to form a ring, they are preferrably positioned at the 3- and 4-positions of the phenoxy ring as shown in the following formula:
  • A i.e., the combinations of R, and R represents a divalent group necessary to form a S-membered or 6-membered ring, and which can contain one or more oxygen atoms together with carbon atoms.
  • a divalent group having from 2 to about 35 carbon atoms for example, those represented by the following formula are preferred:
  • B represents CH- or O;
  • R R,, R and R. each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and p represents 0 or 1.
  • the total number of carbon atoms contained in the moiety 9 5 (R macoo 0 CH5 2 m is suitably from about 14 to 42, and preferably from 18 to 32.
  • R represents a mono-valent atom or group, such as a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, an acylamino group; R.
  • R represents an aryl group, particularly a phenyl group substituted with a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, an acylamino group, etc.;
  • R represents one or more mono-valent atoms or groups, such as a hydrogen atom, a halogen atom, an alkyl group.
  • R represents a mono-valent group, such as an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, an acylamino group, an ureido group, an anilino group, or an alicyclicamino group, etc.;
  • R represents one or more mono-valent atoms or groups, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or an acylamino group, etc.;
  • R represents a mono-valent atom or group, such as a hydrogen atom, an alkyl group, an aryl group, etc.;
  • R represents a di-valent group, such as an alkylene group.
  • X represents a hydrogen atom or a coupling-off group which splits off on coupling with the oxidation products of an aromatic primary amino developing agent, for example. such as a halogen atom, an alkoxy group. an aryloxy group, an acyloxy group, a sulfonyl group, an arylthio group, a heterocyclicthio group, a cyclic imido group, an arylazo group. a cyclic sulfonylacylamino group. etc.; Y represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a N,N-dialkylamino group, etc.
  • the couplers represented by the general formula (I), which can be used in the present invention can be prepared easily and in high yield by the reaction of an amino compound represented by the general formula (III):
  • yellow two-equivalent couplers and the magenta two-equivalent couplers illustrated as examples can be prepared from the coresponding fundamental couplers according to the methods such as those described in the specifications of US. Pat. Nos 3,447,928; 3,408,l94; and 3,265,506, German Offen- Iegungsshrift Nos. 2,213,461; and 2,263,875.
  • couplers which can be used in the present invention are illustrated below, but these are only examples of couplers represented by the general formula (I) described above and are not to be considered as limiting the invention.
  • Coupler I a-( 4-Methoxybenzoyl)-2-chloro-5- ⁇ a-( 4-tert.-amylphenoxy)-isobutyramidol acetanilide Coupler II a-Benzoyl-2-methoxy-5- ⁇ a-( 4-nonylphenoxy )isobutyramido ⁇ -acetanilide Coupler III a-( 4-Methoxybenzoyl )-2-chloro-5- ⁇ rx-( 3 -n-pentadecylphenoxy)isobutyramido ⁇ acetanilide Coupler IV a-( Z-Methoxybenzoyl )-a-acetoxy-2-chloro-5- a-( 3- n-pentadecylphenoxy )isobutyramido ⁇ acetanilide Coupler V a-( 4-Methoxybenzoyl )-a-(4-carboxyphenoxy )
  • Coupler Ill as colorless crystals with a melting point of 92C.
  • the reaction mixture was washed twice with 30 ml of cold water, and then to the reaction mixture were added 6.0 g of N-phenethylhydantoin and 3.2 g of triethylamine and the reaction mixture was refluxed on a water bath for 6 hours.
  • the reaction mixture was washed with water and concentrated under reduced pressure. The residue was recrystallized from a solvent mixture of petroleum ether and acetonitrile to give 5.7 g of Coupler XIV as white crystals with a melting point of 8285C.
  • Coupler XXXIX was obtained by removing some solid material by filtration, the filtrate was concentrated to half volume and crystals were collected. The crude crystals were recrystallized from acetonitrile to give 37.0 g of Coupler XXXIX as colorless crystals with a melting point of l53l 64C.
  • the couplers which can be used in the present invention are especially advantageous from an economical standpoint in that they can be prepared in a simple manner and a good reproducibility by reacting a novel a-(subl0 stituted)isobutyric acid hydrochloride. which can be prepared in highly purity and high yield by reacting an easily available substituted phenol with acetone and chloroform in the presence of an alkali metal hydroxide. with a yellow. magenta or cyan color coupler residue containing an amino group.
  • the couplers which can be used in the present invention are a novel class ofcompounds. and in comparison with a similar series of couplers having diffusion resistant groups l to (8) including the known acylamide 0 group described hereinbefore. they have a low melting point and excellent solubility in a high boiling (e.g.. above l75C) organic solvent and thus stable emulsion layer can be obtained without the deposition of coupler crystals in the emulsion layer when they are dispersed 5 in a silver halide photographic emulsion and coated on a support and dried. Due to such characteristics, it is possible to greatly reduce an amount of the high boiling solvent needed for dispersion, which is extremely advantageous for improving the image sharpness of images. Further.
  • Coupler J for example Comparative Coupler J described hereinafter
  • Comparative Coupler J has a very low melting point but shows a low solubility at low temperature due to the high temperature dependency of the solubility and hence tends to be deposited at low temperature
  • the couplers according to the present invention do not have such disadvantages and furthermore they are characterized by less temperature dependence of solubility as compared with a similar series of couplers.
  • Coupler XL was recrystallized from acetonitrile to give 41.0 g of C1 Coupler XL as colorless crystals with a melting point of Coupler Diffusion Resistant Melting Solubility in Group W Point Ethyl Acetate at 20C (Cl (WW/F) A CH -O C -.H,,(t) 15s 1.3
  • the couplers of the present invention have in common lower melting points as compared with the comparison couplers 0f the homologous series, and stable and very fine dispersions can be obtained even when the dispersion is prepared under the conditions of a reduced amount of the high boiling organic solvent.
  • the coatings prepared under such conditions can also provide dye images of transparency and clear color hue by color development as will be seen in the Examples set out below.
  • the couplers of the present invention can be incorporated into a hydrophilic colloid of photographic materials using any known technique.
  • the coupler can be dissolved in a high boiling (e.g., above 175C) solvent such as dibutyl phthalate, tricresyl phosphate or trihexylphosphate as described in, e.g., U.S. Pat. No.
  • 2,322,027 together with, ifdesired, a subsidiary solvent such as ethyl acetate, tetrahydrofuran acetophenone, isopropyl acetate, ethyl propionate, B-ethoxyethyl acetate, n-butyl carbitol acetate, etc., and then the solution is dispersed in a hydrophilic colloid binder.
  • a subsidiary solvent such as ethyl acetate, tetrahydrofuran acetophenone, isopropyl acetate, ethyl propionate, B-ethoxyethyl acetate, n-butyl carbitol acetate, etc.
  • a coupler solution can be prepared using only the subsidiary solvent without using the high boiling solvent and the solution can be dispersed in a hydrophilic colloid binder.
  • the coupler dispersion prepared in the manner illustrated above is mixed with a silver halide emulsion such as a silver bromide, silver iodobromide, silver chloroiodobromide, silver chloride, silver chlorobromide or silver iodide emulsion or a so-called conversion halide type silver halide emulsion as described in British Pat. No. 635,841 and U.S. Pat. Nos. 2,592,250 and 3,622,3 l8, and together with, if desired, an additional hydrophilic colloid binder and then the mixture is applied to a support.
  • a silver halide emulsion such as a silver bromide, silver iodobromide, silver chloroiodobromide, silver chloride, silver chlorobromide or silver iodide emulsion or a so-called conversion halide type silver halide emulsion as described in British Pat. No. 635,841 and
  • the dispersion of at least one coupler of the present invention and, if desired. in combination with at least one known coupler which is not within the scope of the couplers of the present invention, in a hydrophilic colloid binder which is prepared by the above described method can be used as a component of at least one emulsion layer of a multi-layer silver halide photographic material which is based on the three color subtractive system and which has at least one bluesensitive silver halide emulsion layer containing a yellow dye forming coupler, at least one green-sensitive silver halide emulsion layer containing a magenta dye forming coupler and at least one red-sensitive silver halide emulsion layer containing a cyan dye forming coupler.
  • any known silver halide emulsion can be advantageously used, for example, such as those disclosed in U.S. Pat. Nos. 3,582,322; 3,622,3 l 8; 3,547,640; 3,672,898; 3,516,83l; 3,7l5,208; 3,737,3 l2, 3,705,803; 3,705,799; 3,703,375; 3,379,529; 3,402,046; 3,620,747; 3,450,536; 3,726,681; U.S. patent applications Ser. No. 206,060, filed Dec. 8, I97]; and Ser. No. 259,l09, filed June 2, 1972.
  • any known support which can be used for conventional photographic materials can be appropriately used. These include a cellulose ester film such as cellulose nitrate, cellulsoe acetate, etc., a polyester film such as polyethylene terephthalate, etc., a polyvinyl chloride film, a polystyrene film, a polycarbonate film, a paper, a so-called baryta coated paper which is prepared by coating a barium sulfate layer on a paper support, a film which is prepared by laminating a cellulose ester, polyester, polyvinyl chloride, polystyrene or polycarbonate on a paper or a baryta coated paper, a synthetic paper, etc.
  • a suitable coating amount of the coupler is about X to about l X 10 mol/m", preferably 2 X 10 to 3 X 10 mol/m and for the silver halide a suitable coating amount ranges from about 5 X 10 to about 1 X 10 mol/m preferably 2 X 10 to 3 X 10 mol/m'-.
  • hydrophilic colloid which can be used in the coupler dispersion of the present invention and the above described emulsion layer of photographic materials, for example, gelatin. a gelatin derivative (acylated gelatin. graft gelatin, etc.). albumin, gum arabic, agar agar, cellulose derivative (acetyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose. etc.), a synthetic resin (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamido, etc.), and any other known hydrophilic colloid can be employed.
  • the dispersion containing the coupler of the present invention in the above described hydrophilic colloid or a mixture of the dispersion and a silver halide emulsion can be subjected to treatment under reduced pressure or washed with water as described in U.S. Pat. Nos. 2,949,360 and 3,396,027 prior to coating of the emulsion layer of the above described photographic material for removing the subsidiary solvent.
  • the dissolution of the coupler can be facilitated, if desired, using heat or ultrasonic waves as is known in the art.
  • the above described multi-layer photographic material which includes the couplers of the present inven tion can have, in addition to the above described silver halide emulsion layers, other layers conventionally employed in light-sensitive materials, for example, a protective layer, a filter layer, an intermediate layer, an anti-halation layer, a subbing layer, a backing layer, a layer containing an ultraviolet absorber, etc. Also, as the binders for these layers, the hydrophilic colloid used for the above described emulsion layers can be used as the binders for these layers.
  • Each layer of the above described material containing the coupler of the present invention can further contain a known compound as a hardening agent for the hydrophilic colloid, for example, as described in C. E. K. Mees & T. H. James, The Theory oft/1e P11010- grap/zic Process, 3rd Ed., pp. 5560, Macmillan, New York (1966), US. Pat. Nos. 3,316,095; 3,232,764;
  • aldehyde type compounds such as formaldehyde, glyoxal, succinaldehyde, glutaraldehyde, 2,3-dihydroxy-l,4-dioxane, mucochloric acid, dimethylolurea, etcs, active vinyl type compound such as divinyLsulfone, methylene bismaleimide, 5-acetyl- 1,3-diacryloyl- 1 ,3,5-hexahydrotriazine, N,N,N triacryloyl-l,3,5-hexahydrotriazine, etc.; active halogen type compounds such as 2,4-dichloro--oxytriazine sodium salt, 2,4-dichloro-6-methoxytriazine, sebacic acid bischloromethyl
  • the emulsion which can be used in the light-sensitive material containing the coupler of the present invention can be chemically sensitized using the natural sensitizers in gelatin or using a sulfur compound as described in U.S. Pat. Nos. 1,574,944; 1,623,499 and 2,410,689, Also, the emulsion can be sensitized with a salt of a noble metal such as palladium, gold, ruthenium, rhodium, platinum, etc., as described in US. Pat. Nos. 2,448,060; 2,399,083 and 2,642,361. Further the emulsion can be sensitized with a reducing agent such as a stannous salt as described in U.S. Pat. No.
  • the emulsion can also be sensitized with a polyalkylene oxide derivative as described in U.S. Pat. Nos. 2,886,437; 3,046,134; 2,944,900 and 3,294,540.
  • the emulsion can be spectrally sensitized with a sensitizing dye, such as a cyanine dye or a merocyanine dye, as disclosed in U.S. Pat. Nos. 2,526,632; 2,503,776; 2,493,748; 3,384,486; 2,933,390; and 2,937,089.
  • the emulsion can contain a stabilizer such as a mercury compound, an azaindene, etc., as described in U.S. Pat. Nos. 2,131,038; 2,694,716; 2,886,437; 2,444,605; 2,728,663; 3,287,135; 3,236,652; 2,403,927; 3,266,897; 3,397,987; 2,839,405;
  • a stabilizer such as a mercury compound, an azaindene, etc.
  • the emulsion can contain an antistatic agent as described in U.S. Pat. Nos. 2,861,056; 3,206,312; and 3,428,451, an ultraviolet absorber as described in U.S. Pat. Nos.
  • any known couplers in addition to the couplers of the present invention can also be used.
  • a yellow dye forming coupler there are the open chained ketomethylene type couplers and typical examples of such couplers are acylacetamide type couplers such as the benzoylacetanilides and the pivaloylacetanilides, etc., as desclosed in U.S. Pat. Nos. 3,277,155; 3,415,652; 3,447,928; 3,408,194; 2,875,057; 3,265,506; 3,409,439; 3,551,155; 3,551,156; 3,582,322, etc.
  • magenta dye forming coupler there are pyrazolone type couplers, indazolone type couplers, pyrazolobenzimidazole type couplers, cyanoacetyl type couplers, etc., as disclosed in U.S. Pat. Nos. 2,600,788; 2,983,608; 3,006,759; 3,062,653; 3,214,437; 3,253,924; 3,311,476; 3,419,391; 3,419,808; 3,476,560; 3,582,322, etc. Also as a cyan dye forming coupler there are phenol type couplers, naphthol type couplers, etc., as disclosed in U.S. Pat. Nos. 2,474,293; 2,698,794; 3,034,892;
  • Each of these couplers can have at the active carbon atom of the coupling position. replacing hydrogen atoms of the active carbon atom, an atom or group capable of being split off on oxidative coupling with an aromatic primary amine developing agent such as a halogen atom or an ether, a thioether, an acyloxy. a phthalimido, a hydantoinyl, a thiocyano, a sulfo, a sulfino, a saccharinyl, a benzotriazolyl, etc., group.
  • the coupler can be a so-called colored coupler having a chromophore such as a diazo group, a styryl group, etc., as a splitting-off group.
  • the coupler can have a so-called diffusion resistant group so as to prevent diffusion of the coupler in the emulsion layers.
  • the coupler can have a group such as a sulfo group, a carboxy group, etc., for dispersing the coupler in a micellar state as an alkali metal salt or an alkaline earth metal salt thereof.
  • any known surface active agent can be advantageously uses.
  • the light-sensitive material of the present invention can be treated. after exposure, using known processing methods.
  • the material can be treated using the following main steps:
  • step 2 can be omitted.
  • a hardening step for hardening the photographic layer or a pretreatment step in an alkaline bath for removing a resin backing layer can be used prior to step 1.
  • a hardening step can be employed between step 1 and step 2 or step 2 and step 3, or after step 3.
  • a stabilizing step for improving the stability of the images can be used.
  • washing steps can be used between each of the steps or after the last step. After all of the processing steps are finished, the photographic material is dried. Suitable drying methods which can be used are natural dyring by allowing the material to stand in the air, heat drying, hot-air drying, drying with an infrared radiation, a drying with an electron beam, or any other known methods.
  • the material can be treated using the following main steps:
  • step 2 can be omitted when the color developer solution for step 3 contains a fogging agent.
  • a hardening step, an alkaline pre-bath step, a stabilizing step, a washing step can be, if desired, employed before or after each step described above, as in the above described nega-posi type processing step. Also after finishing all of the processing steps, the photographic material is dried in the same manner as described in the nega-posi type processing step.
  • processing baths of known compositions can be used.
  • a suitable color developer solution is an alkaline solution containing a color developing agent.
  • a color developing agent any known aromatic primary amino developing agent can be used, for example, phenylene diamines such as N,N-diethyl-paraphenylene diamine, N-ethyl-N-hydroxyethyl-para-phenylene diamine, N- ethyl-N-hydroxyethyl-2-methyl-para-phenylene diamine, N-ethyl-N-B-methanesulfonamidoethyl3-methyl-4-aminoaniline, N,N-diethyl-2-methyl-paraphenylene diamine, N-ethyl-N-ethoxyethyI-Z-methylpara-phenylene diamine, and the sulfates, hydrochlorides, sulfites, oxalates, etc.
  • the color developer solution can further contain conventional additives such as a sulfate, a carbonate, a bisulfite, a bromide or an iodide of an alkali metal, benzyl alcohol, a water softener (such as sodium hexametaphosphate, an alkali metal hydroxide, hydroxylamine, a sulfate or a hydrochloride of hydroxylamine, etc.), a competing coupler (such as mono sodium l-amino-S- naphthol-3.6-disulfonate, citrazinic acid, etc.), if desired.
  • the color developer solution can contain a fogging agent (such as N-butylamine, an alkali metal salt of borohydride, ethylene-diamine, etc.), when it is used as color developer for reversal type processing.
  • a solution containing any known pH-reducing agent such as acetic acid, phthalic acid, etc. can be used.
  • a solution containing any known fixing agent such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, etc. can be used.
  • a solution containing any known belaching agent such as a ferricyanide, a bichromate, a ferric salt of ethylene-diamine tetraacetic acid, etc.
  • belaching agent such as a ferricyanide, a bichromate, a ferric salt of ethylene-diamine tetraacetic acid, etc.
  • a solution containing any known silver halide solvent and any known silver oxidizing agent can be used.
  • silver halide solvents are a thiosulfate, a thiocyanate, an organic diol containing an oxygen atom or a sulfur atom (such as 3-thiol ,5-pentanediol, 3,6-dithial ,8-octanediol, 9- oxa-3,6, l 2, l S-tetrathia-l ,l7-heptadecanediol, etc.
  • a sulfur-containing organic dibasic acid or a salt thereof such as ethylenebisthioglycolic acid, a sodium salt thereof, etc.
  • imidazolidinethione and the like.
  • silver oxidizing agents are a ferricyanide, a quinone, a ferric salt. a cupric salt, a cobaltic salt, a complex salt of an ammonium ion or an alkali metal ion, and a ferric ion, a cupric ion or a cobalt ion, and an organic acid (examples of the organic acids are malonic acid, tartaric acid, ethylmalonic acid.
  • malic acid fumaric acid, diglycolic acid, dithioglycolic acid, ethyliminopropionic acid, nitrilotriacetic acid, ethyl- 25 enediamine tetraacetic acid, aminotriacetic acid, ethylenedithioglycolic acid. dithioglycolic acid. etc. or a chelate compound of ferric ion. cupric ion or a cobalt ion (examples of ligands of the chelate compounds are ethylenediamine, diethylenetriamine. triethylenetetraamine, diaminopropane, diaminocyclohexane. polyethyleneimine, acetylacetone, diethyldithiocarbamate, oxyquinoline, dithiozone. dipyridyl, phenanthrenine, etc.), and the like.
  • the couplers of the present invention can be used, in addition to the above described multi-layer photographic materials based on substractive three color system, in any silver halide light-sensitive materials which can form dye images by color development using an aromatic primary amino developing agent, such as color radiographic photographic materials, infrared-sensitive photographic materials, photographic materials for recording radar images, color micro-photographic materials, and the like.
  • EXAMPLE 1 A mixture of 3.0 g or Coupler lX (a yellow color forming coupler), 1.5 ml of di-n-butyl phthalate, 2.0 ml of ethyl acetate and 0.15 g of sodium di(2-ethylhexyl)- B-sulfosuccinate was dissolved by heating to 60C and mixed with 25 ml of an aqueous solution at 40C containing 2.0 g of gelatin, and the mixture was stirred using a high speed mixer at 50C for 10 minutes to prepare a fine dispersion of the coupler.
  • Coupler lX a yellow color forming coupler
  • the coupler dispersion was mixed with l50 g of a photographic emulsion containing 47 millimoles of silver iodobromide and 10 g of gelatin, and then 2 ml of a 1 percent aqueous solution of 4-hydroxy-6-methyll.3,3a.7-tetraazaindene, 5 ml of a 2 percent aqueous solution of the sodium salt of Z-hydroxy-4,6-dichloro-striazine and 2 ml of a 5 percent aqueous solution of saponin were added in order.
  • the mixture was coated on a cellulose acetate film base in a dry thickness of 5 microns.
  • a gelatin layer of a dry thickness of 1 micron was coated as a protective layer.
  • the film was subjected to stepwise exposure for sensitometry and processed in the following steps.
  • EXAMPLE 2 A solution prepared by heating to 80C a mixture of 7 g of Coupler ill (a yellow color forming coupler), 3.5 ml of di-n-butyl phthalate. 7 ml of n-butyl acetate and 0.1 g of sorbitan monolaurate was added I20 g of an aqueous solution at 50C containing 10 g of gelatin and 0.5 g of sodium triisopropylnaphthalene sulfonate (Alkanol B made by E. l. du Pont de Nemous, U.S.A.) and the mixture was passed 5 times through a pre-heated colloid mill to prepare a fine dispersion of the coupler.
  • Coupler ill a yellow color forming coupler
  • a film was prepared by earring out the same procedures as described above except that 7 g of a coupler having the following structure was used.
  • Comparison Coupler (a) Melting Point 955C Comparison Coupler (a) had the same structure as that of Coupler Ill except for the oil-soluble diffusion resistant group, and was prepared according to the method described in US. Pat. No. 2,908,573.
  • the color paper containing Coupler 111 and the sample containing Comparison Coupler (21) provided yellow dye images having an absorption maximum at 449 and 451 microns, respectively.
  • EXAMPLE 3 A solution prepared by heating to 65C a mixture of 10 g of Coupler XXV (a magenta color forming coupler), 5 g of tricresyl phosphate, 0.6 g of di-(Z- ethylhexyl)-B-sulfosuccinate and 5 ml of ethyl acetate was mixed with g of a 7 percent gelatin solution. and the mixture was stirred vigrorously using a high speed mixer for 10 min. to prepare a fine dispersion of the coupler.
  • Coupler XXV a magenta color forming coupler
  • the coupler dispersion 50 g was mixed with 170 g of a photographic emulsion containing 60 millimoles of silver iodobromide and 12 g of gelatin, and 5 ml of a 3 percent methanol solution of triethylene phosphamide was added.
  • the mixture was coated on a cellulose acetate film base in a dry thickness of 5 microns and on the emulsion layer a gelatin layer having a dry thickness of 1 micron was coated as a protective layer and dried.
  • a film was prepared by carrying out the same procedures as described above except that 8.7 g of a coupler having the following structure was used.
  • Comparison Coupler (B) Melting Point l77-l 78C Comparison Coupler (B) has the same structure as that of Coupler XXV except for the oil-soluble diffusion resistant group.
  • Color Developer Solution lll pH Water 1000 ml Benzyl Alcohol 3.8 ml Sodium Sulfite (anhydrous) 2.0 g Sodium Hydroxide 1N solution) 14 ml 4 Amino-3methyl-N-ethyl-N-B- 5.0 g metha nesulfonamidoethyl )aniline Sesquisulfate Monohydrate Potassium Bromide 1.0 g Sodium Carbonate (monohydrate) 50.0 g
  • both films After processing and drying, both films provided magenta dye images having the spectral absorption characteristics shown in the following table.
  • the color lightsensitive material according to the present invention containing Coupler XXV can provide a spectral absorption curve of a sharply cut form in comparison with the light-sensitive material containing known Comparison Coupler (B).
  • the magenta dye image having such spectral absorption characteristics provides colors of high purity. especially a red color. in color reproduction based on the subtractive photographic system.
  • the cyan dye images formed according to the present invention are more stable to fading due to heat and humidity. particularly to heat fading under dry conditions. than the cyan dye images formed from known couplers having similar structures. This fact illustrates that the color photographic images formed from the lightsensitive material of the present invention are more stable than those formed from conventionally known couplers, and can be stored for a long period of time.
  • a color printing paper was prepared according to the following procedures. Coating Solution 1 and Coating Solution 2 were simultaneously coated on a surface of a paper laminated on both sides with polyethylene using a slit hopper as described in U.S. Pat. No. 2,761,419. Coating Solution 1 and Coating Solution 2 were coated in order on the support and the dry thickness of each layer was 2.5 and 1.0 micron, respectively. Then Coating Solutions 3,4,5 and 6 were coated, in order, on the coating described above using the same slit hopper. The dry thickness of each layer was 3.0, 2.0, 2.0 and 1.0 micron, respectively.
  • Coupler XIII a yellow color forming coupler
  • di-n-butyl phthalate 18 g
  • di-n-butyl phthalate 18 g
  • ethyl acetate ml
  • ethyl acetate aqueous solution containing 40 g of gelatin and 1.5 g of sodium dodecylbenzene sulfonate
  • the mixture was passed 3 times through a homogenizer to prepare a coupler dispersion.
  • Coupler dispersion was added to 500 g of a photographic emulsion containing 0.] mole of silver chlorobromide (bromide content: mole percent, average grain size: 0.8 p.) and 40 g of gelatin, and then 60 mg of 5-methyl-6-hydroxyl .3,4-triazaindene and 20 ml of a 3 percent methanol solution of triethylene phosphamide was added.
  • Coating Solution 2 A mixture of 5 g of n-pentadecylhydroquinone. l5 g of di-n-butylphthalate and I ml of ethyl acetate was dissolved by heating to 50C. the solution thus obtained was added to l.000 ml of an aqueous solution containing 70 g of gelatin. 0.8 g of sodium dodecylbenzene sulfonate and 0.l g of sodium bisulfite. and then the mixture was passed 3 times through a homogenizer to prepare a dispersion.
  • Coupler XXVlll a magenta color forming coupler
  • 2.5-di-tertoctylhydroquinone 1.5 g
  • 2.5-di-tertoctylhydroquinone 1.5 g
  • tri-o-cresyl phosphate and 50 ml of ethyl acetate
  • the solution thus obtained was added to 600 ml of an aqueous solution containing 40 g of gelatin and L5 g of sodium pdodecylbenzene sulfonate. and then the mixture was passed 3 times through a homogenizer to prepare a coupler dispersion.
  • Coupler dispersion was added to l .000 g of a green-sensitive photographic emulsion containing 0.2 moles of silver chlorobromide (bromide content: 40 mole percent, average grain size: 0.25 14) and 90 g of gelatin. and then 120 mg of 5methyl-6-hydroxy-l ,3.4- triazaindene and 40 ml of a 3 percent methanol solution of triethylene phosphamide was added.
  • Coating Solution 4 A mixture of 5 g of 2-benzotriazolyl-4-tertbutylphenol. g of 2-benzotriazolyl-4-tert-butyl-6- iso-butylphenol, 5 g of 2.5-di-tert-octylhydroquinone, 35 g of di-n-butyl phthalate and 50 ml of ethyl acetate was dissolved by heating to 50C and the solution thus obtained was added to 750 ml of an aqueous solution containing 50 g of gelatin, I.8 g of sodium pdodecylbenzene sulfonate and 0.1 g of sodium bisulfite. and then the mixture was passed 3 times through a homogenizer to prepare a dispersion.
  • All of the dispersion was mixed with 750 ml of an aqueous solution containing 50 g of gelatin and 30 ml of a 3 percent methanol solution of triethylene phosphamide.
  • Coupler XL a cyan color forming coupler
  • di-n-butyl phthalate g of di-n-butyl phthalate
  • 40 ml of ethyl acetate was dissolved by heating to 50C and the solution thus obtained was added to 600 ml of an aqueous solution containing 40 g of gelatin and L5 g of sodium p-dodecylbenzene sulfonate and then the mixture was passed 3 times through a homogenizer to prepare a coupler dispersion.
  • Coupler dispersion was added to 500 g of a red-sensitive photographic emulsion containing 0.1 mole of silver chlorobromide (bromide content: 40 mole percent, average grain size: 0.25 p) and 45 g of gelatin, and then 60 mg of 5-methyl-6-hydroxy-l .3,4- triazaindene and ml of a 3 percent methanol solution of triethylene phosphamide was added.
  • Coating Solution 6 To 1.000 ml of an aqueous solution containing 40 g of gelatin. there were added l50 ml of a 2 percent aqueous solution of the potassium salt of poly-psulfostyrene. 20 ml of a 2 percent aqueous solution of sodium p-dodecylbenzene sulfonate and 50 ml of a 3 percent methanol solution of triethylene phosphamide.
  • the color printing paper thus prepared was exposed through a color negative image and subjected to the color developing treatment as described in Example 2.
  • a clear color print comprising a yellow dye image hav' ing an absorption maximum at 442 mp. a magenta dye image having an absorption maximum at 540 mp. and a cyan dye image having an absorption maximum at 665 my. and having a maximum blue light density of 2.45. a maximum green light density of 2.55 and a maximum red light density of 2.40 was obtained.
  • EXAMPLE 6 A mixture of IO millimoles of a coupler of the present invention (as shown in the following table). 5.0 g of a high boiling coupler solvent and 10 ml of ethyl acetate was dissolved at refluxing and the solution was added to ml of an aqueous solution containing 0.5 g of pdodecylbenzene sulfonate and I0 g of gelatin and then the mixture was stirred vigorously using a homoblender to prepare a fine dispersion of the coupler.
  • All ofthe coupler dispersion was mixed with 400 g of a photographic emulsion containing 0.] mole of silver iodobromide (iodide content: 3 mole percent, average grain size: 0.4 microns) and 35 9 of gelatin and then 12.0 ml of a 3 percent methanol solution of triethylene phosphamide and 500 cc of water were added.
  • the mixture of each dispersion thus prepared was coated on a transparent cellulose acetate film base in a dry thickness of 6.0 microns to prepare films.
  • Coupler Ratio of Remaining Dye Control 94.6 Coupler A 49.9 Coupler D 84.2 Coupler G 52.0 Coupler H 83.7 Coupler XXXIX 93. l Coupler XL 92.8 Coupler XLI 91.7
  • a color photographic light-sensitive material which comprises a support having thereon at least one silver halide emulsion layer containing a coupler represented by the general formula CE I 3 (R Q NHCOC 0- wherein 0 represents a coupler residue forming a dye upon reaction with an oxidation product of an aromatic primary amino developing agent; R represents an alkyl group, an aralkyl group.
  • R represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkyl group having from I to 5 carbon atoms or an alkoxy group having from I to 5 carbon atoms;
  • In represents an integer of l to 4;
  • n represents an integer of l to 4; and the sum of m n is 2 to 5; and
  • R and R can form a non-metallic atom-containing five membered ring or a six membered ring.
  • R represents a hydrogen atom. a chlorine atom, a methyl group or a methoxy group.
  • R represents a hydrogen 35 36 atom. a chlorine atom. a methyl group or a methoxy group.
  • R is bonded to the 3-position, 4-position or 5-position of the anilide ring and represents a hydrogen atom or a monovalent group selected from the group consisting of a halogen atom. a cyano group. a carbamoyl group. an alkoxycarbony] group. a sulfamoyl group. an acylamino group, a nitro group. an alkyl group, an aryl group. an alkoxy group. an aryloxy group, an imido group.
  • R represents an aryl group selected from the group consisting ofa phenyl group substituted with a halogen atom. an alkyl group. an alkoxy group. an aryloxy group. a nitro group. a cyano group or an acylamino group; R, represents one or more monovalent atoms or groups selected from the group consisting of a hydrogen atom. a halogen atom, an alkyl group, an alkoxy group or an aryloxy group; Ru; represents a monovalent group selected from the group consisting of an alkyl group, an aryl group.
  • R represents one or more monovalent atoms or groups selected from the group consisting of a halogen atom, and alkyl group, an alkoxy group.
  • R represents a monovalent atom or group selected from the group consisting ofa hydrogen atom, an alkyl group or an aryl group
  • Rm represents a divalent group sea 38 lected from the group consisting of an alkylene group or an arylene group
  • X represents a hydrogen atom or a coupling-off group which is split off on coupling with the oxidation product of an aromatic primary amino developing agent and is selected from the group consisting of a halogen atom, an alkoxy group, an aryloxy group.
  • Y represents a hydrogen atom, a halogen atom. an alkyl group, an alkoxy group, an aryloxy group or a N.N-dialkylamino group.

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4073651A (en) * 1975-04-28 1978-02-14 Mitsubishi Paper Mills, Ltd. Image-forming layer containing silver halide emulsion and magenta coupler
US4217410A (en) * 1978-03-10 1980-08-12 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive materials with phosphate solvent
US4241172A (en) * 1978-06-01 1980-12-23 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic material
US4286053A (en) * 1978-11-24 1981-08-25 Konishiroku Photo Industry Co., Ltd. Process for forming dye images
US4295460A (en) * 1979-02-02 1981-10-20 Epoxon Products, Inc. Combination heat transfer panel and wall shield for use with stoves and other radiant heaters
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4524132A (en) * 1983-09-06 1985-06-18 Fuji Photo Film Co., Ltd. Color photographic silver halide light-sensitive material
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0202616A2 (en) 1985-05-16 1986-11-26 Konica Corporation Method for color-developing a silver halide photographic light-sensitive material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
US4758501A (en) * 1986-06-11 1988-07-19 Eastman Kodak Company Photographic acetanilide couplers and photographic elements containing them
US5354646A (en) * 1986-03-26 1994-10-11 Konishiroku Photo Industry Co., Ltd. Method capable of rapidly processing a silver halide color photographic light-sensitive material
EP0711804A2 (de) 1994-11-14 1996-05-15 Ciba-Geigy Ag Kryptolichtschutzmittel
EP0813112A1 (en) * 1996-06-16 1997-12-17 Eastman Kodak Company Photographic elements containing new magenta dye-forming couplers
US20100144772A1 (en) * 2007-02-28 2010-06-10 Advinus Therapeutics Private Limited 2,2,2-tri-substituted acetamide derivatives as glucokinase activators, their process and pharmaceutical application

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5382411A (en) * 1976-12-28 1978-07-20 Konishiroku Photo Ind Co Ltd Silver halide color photographic material
EP0568196A1 (en) * 1992-03-31 1993-11-03 Konica Corporation Light-sensitive silver halide color photographic material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3285747A (en) * 1964-08-26 1966-11-15 Gen Analine & Film Corp Color formers containing a m-alkyl-phenoxyacyl group
US3737318A (en) * 1970-05-14 1973-06-05 Konishiroku Photo Ind Light-sensitive color photographic material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3285747A (en) * 1964-08-26 1966-11-15 Gen Analine & Film Corp Color formers containing a m-alkyl-phenoxyacyl group
US3737318A (en) * 1970-05-14 1973-06-05 Konishiroku Photo Ind Light-sensitive color photographic material

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4073651A (en) * 1975-04-28 1978-02-14 Mitsubishi Paper Mills, Ltd. Image-forming layer containing silver halide emulsion and magenta coupler
US4217410A (en) * 1978-03-10 1980-08-12 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive materials with phosphate solvent
US4241172A (en) * 1978-06-01 1980-12-23 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide color photographic material
US4286053A (en) * 1978-11-24 1981-08-25 Konishiroku Photo Industry Co., Ltd. Process for forming dye images
US4295460A (en) * 1979-02-02 1981-10-20 Epoxon Products, Inc. Combination heat transfer panel and wall shield for use with stoves and other radiant heaters
EP0112162A2 (en) 1982-12-13 1984-06-27 Konica Corporation Light-sensitive silver halide photographic material
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4524132A (en) * 1983-09-06 1985-06-18 Fuji Photo Film Co., Ltd. Color photographic silver halide light-sensitive material
EP0147854A2 (en) 1983-12-29 1985-07-10 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
EP0202616A2 (en) 1985-05-16 1986-11-26 Konica Corporation Method for color-developing a silver halide photographic light-sensitive material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
EP0209118A2 (en) 1985-07-17 1987-01-21 Konica Corporation Silver halide photographic material
EP0228914A2 (en) 1985-12-28 1987-07-15 Konica Corporation Method of processing lightsensitive silver halide color photographic material
US5354646A (en) * 1986-03-26 1994-10-11 Konishiroku Photo Industry Co., Ltd. Method capable of rapidly processing a silver halide color photographic light-sensitive material
US4758501A (en) * 1986-06-11 1988-07-19 Eastman Kodak Company Photographic acetanilide couplers and photographic elements containing them
EP0711804A2 (de) 1994-11-14 1996-05-15 Ciba-Geigy Ag Kryptolichtschutzmittel
EP0813112A1 (en) * 1996-06-16 1997-12-17 Eastman Kodak Company Photographic elements containing new magenta dye-forming couplers
US20100144772A1 (en) * 2007-02-28 2010-06-10 Advinus Therapeutics Private Limited 2,2,2-tri-substituted acetamide derivatives as glucokinase activators, their process and pharmaceutical application
US8940900B2 (en) * 2007-02-28 2015-01-27 Advinus Therapeutics Private Limited 2,2,2-tri-substituted acetamide derivatives as glucokinase activators, their process and pharmaceutical application

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