US3676137A - Color photographic light-sensitive element containing magenta coupler and alkyl phosphate solvent - Google Patents

Color photographic light-sensitive element containing magenta coupler and alkyl phosphate solvent Download PDF

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US3676137A
US3676137A US67330A US3676137DA US3676137A US 3676137 A US3676137 A US 3676137A US 67330 A US67330 A US 67330A US 3676137D A US3676137D A US 3676137DA US 3676137 A US3676137 A US 3676137A
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coupler
solvent
group
pyrazolone
phosphate
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Eiichi Mizuki
Yasushi Oishi
Masao Sawahara
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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
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • 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
    • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
    • G03C7/3005—Combinations of couplers and photographic additives
    • G03C7/3008—Combinations of couplers having the coupling site in rings of cyclic compounds and photographic additives
    • G03C7/3012—Combinations of couplers having the coupling site in pyrazolone rings and photographic additives
    • 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
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • G03C7/3885—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific solvent

Definitions

  • a light-sensitive material comprising at least a layer of a silver halide emulsion containing (1) a non-diffusing S-pyrazolone coupler having at least a hydrophobic ballasting group containing from 9 to 30 carbon atoms and (2) a coupler solvent having the formula wherein R and R each is an alkyl group and wherein R represents a member selected from a group consisting of an alkyl group and an aryl group, and wherein the total number of the carbon atoms in R R and R ranges from 14 to 40 carbon atoms, is disclosed.
  • the present invention relates to a color photographic light-sensitive element containing couplers. More particularly, the present invention relates to a color photographic light-sensitive element containing a S-pyrazolonetype magenta forming coupler and an alkyl phosphate for dissolving the cpupler. l
  • a magenta color image In color photography by the subtractive color process a magenta color image has light absorption mainly in the wave length region of from about 4 80 to about 600 mp. and the spectral absorption characteristics required for the magenta coupler in the wave length region depend upon the purposes of the color photograph. Particularly, for direct observations of the colors by the naked eye, it is necessary to keep low the absorption of the magenta color image in the red region at the longer wave length side.
  • each of the couplers is preliminarily incorporated in each of the silver halide emulsions having a ditferent spectral sensitivity during the course of producing color photographic light-sensitive elements
  • the couplers be provided with a diffusion resisting property in order to prevent the couplers from migrating into the other emulsions and from deteriorating the quality of the color reproduction by mixing with each other.
  • a hydrophobic radical having more than 8 carbon atoms is introduced to the coupler molecule.
  • aqueous solution system the coupler has a water-solubilizing radical and is added to a photographic emulsion mainly as an alkaline aqueous solution.
  • oil solution system the coupler is dissolved in an organic solvent, the solution thus obtained is dispersed by emulsification in an aqueous medium as fine colloidal particles, and then the dispersion is added to a photographic emulsion as described in the specification of, for example, US. Pat. No. 2,322,027.
  • a magenta-forming coupler incorporated in a photographic emulsion layer by the oil solution system or a system similar to the oil solution system generally provides a color image having excellent spectral absorption characteristics and high humidity resistance in comparison with a magenta-forming coupler incorporated by the aqueous solution system.
  • the coupler used in the oil solution system and the dye formed from the coupler be highly soluble in an organic solvent for dispersing the coupler and be less crystallizable.
  • a high boiling organic solvent is used for dispersing the coupler using the oil solution system.
  • the solvent contributes to the prevention of crystallization of the couplers, with crystallization causing a loss of the coupling reactivity of the coupler.
  • the solvents dissolve the dye formed by the coupling of the coupler at development, whereby deterioration of the spectral absorption characteristics by the excessive crystallization of the dye is prevented.
  • magenta-forming couplers 5-pyrazolone derivatives in general are widely used.
  • S-pyrazolone derivatives are generally weakly soluble in many high boiling organic solvents conventionally used for dis persing couplers, such as the fatty acid esters, the aromatic carboxylic acid esters, the phosphoric acid aryl esters, and the phenol ethers
  • use of the pyrazolone derivatives results in difiiculties in that a large amount of solvent is required for emulsifying dispersion.
  • the couplers tend to cause excessive crystallization during or after the production of the light-sensitive elements.
  • the spectral absorption characteristics of the dye image formed have the disadvantages in that the whole absorption band of the dye image shifts to extremely longer wave lengths in comparison with that of the solution in said solvent and also the width of absorption region band increases giving rise to an adverse influence on the color reproduction of the color photograph.
  • a magenta coupler cannot show sufiiciently high coupling reaction on development. This is believed to be caused by the organic solvent hindering the reaction of the magenta coupler with the oxidation product of a color developing agent.
  • the inventors have discovered that a series of compounds show excellent dissolving power for the S-pyrazolone derivatives and the azomethine dyes formed therefrom, giving spectral absorption characteristics preferable for color reproduction in the magenta color image.
  • One object of this invention is to provide a solvent having a high dissolving power for s-pyrazolone derivatives and the azomethine dyes derived therefrom.
  • Another object of this invention is to provide a color photographic light-sensitive element forming a magenta color image having less absorption for red light on color development.
  • Another object of this invention is to provide a color photographic light-sensitive element which can be produced without causing excessive crystallization of the coupler during production and which can be stably stored after production.
  • FIG. 1 is a graphical representation showing the spectral absorption curve obtained with one embodiment of this invention (Curve 1) in comparison with the use of conventional coupler solvents (Curves l1 and III).
  • FIG. 2 is a graphical representation showing the spectral absorption curve obtained with a second embodiment of this invention (Curve IV) in comparison with the use of conventional coupler solvents (Curve V).
  • FIG. 3 is a graphical representation of another embodiment of this invention (Curve VI) in comparison with the use of no coupler solvent (Curve VII).
  • the phosphoric acid ester shown by the general Formula I may cause dilficulties in that the ester difiuses into other emulsion layers and finally reaches the plastic support softening excessively the plastic support. Additionally, if a paper support is employed the reflection power of the paper support is reduced. On the other hand, if the total number of carbon atoms is greater than 40, the action of the phosphoric acid ester as a solvent for the coupler and the dye formed from the coupler is reduced, whereby the advantages of this invention cannot be obtained.
  • magenta couplers used in this invention can be selected from a wide range of magenta couplers.
  • S-pyrazolone compounds that find particularly excellent results when used together with the phosphoric acid esters having the above-described structural Formula I belong to the groups of the' compounds represented by the following general Formulae H and III:
  • R represents an aryl group or a substituted aryl group in which the preferred substituents for the aryl group are an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, a halogen atom, a trifluoromethyl group, a cyano group, an acyl group, a sulfonyl group, an acylamino group, a sulfonamino group, a ureido group, an amino group, a carboxyl group, an alkoxycarbonyl group, and a carbamyl group and in particular phenyl groups substituted by these substituents are preferred as the R group; wherein R represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, an amino group, a substituted amino group
  • the affinity between individual coupler molecules and between the coupler molecules and the solvent molecules is increased, whereby the coupler remains in or near fine particles of the solvent and then the coupler can be intimately contacted with the solvent.
  • the dye derived from such a coupler has an afiinity to the solvent.
  • the hydrophobic residual group is included in the R or the R group and is bonded to the coupler residual group directly or through a divalent organic residual group having an amide-bond, an ether bond, an ester bond, a urea bond, or a sulfonamido bond.
  • the hydrophobic residual group advantageous to the present invention is selected from a straight chain or branched alkyl group, an alkenyl group, an alkoxyalkyl group, an alkoxyaryl group, an aryl group, an allyloxyalkyl group, aryloxyaryl group, and acylaminoalkyl group. Specific examples of them are shown below:
  • opium ONH(3-CH- N ⁇ ': o
  • the S-pyrazolone coupler described above is dispersed in a photographic emulsion by an oil solution system. That is to say, the 5-pyrazolone compound is dissolved in the phosphoric acid ester and then the resulting solution is dispersed in a photographic aqueous medium. In this case, it is profitable to use a surface active agent described in the specification of Japanese Pat. No. 428,191 and Japanese patent application No. 60,130/ 68.
  • the 5-pyrazolone coupler can be incorporated in a photographic emulsion using a method in which the coupler is dissolved in an alkaline aqueous solution, the solution thus obtained is added to a photographic emulsion in the presence of a dispersion of the phosphoric acid ester, and then the emulsion is neutralized.
  • an organic solvent miscible with water such as methanol, ethanol, dioxane, dimethyl formamide, and dimethyl sulfoxide.
  • a S-pyrazolone coupler having one carboxyl group is particularly useful.
  • the carboxyl group is present mainly in the form of the free acid and shows a good affinity to the solvent except when the coupler is added to the emul- 11 sion as an alkaline aqueous solution.
  • this kind of coupler and the dye derived therefrom shows afiinity for the coupler solvent represented by the general Formula I, and hence by the combination of the coupler and the coupler solvent, the above-described advantages of this invention, such as the good spectral absorption character- 12 and 12 of this invention and the numerical values in the examples.
  • the S-pyrazolone-type coupler added to a photographic emulsion as an emulsified dispersion thereof together with the coupler solvent represented by the general Formula I on color development gives a magenta dye image having less absorption of red light having a wave length longer than 600 millimicrons. Consequently, the color photographic light-sensitive element of this invention can reproduce a clear red color. This is illustrated by the spectral absorption curves obtained in Examples 1, 2,
  • the comparatively low viscosity of the solvent facilitates dispersion of the coupler in an aqueous medium.
  • the solvent for the coupler represented by the general Formula I has a refractive index of about 1.44 and when the 5-pyrazolone compound is dissolved in the solvent, the refractive index of the solution reaches about 1.54 which is the refractive index of air-dried gelatin. Therefore, the gelatin layer containing the solvent and the 5- pyrazolone compound or the azomethine dye therefrom is less turbid and is clear.
  • triaryl phosphate-type coupler solvent known hitherto for example, a tri-o-cresyl phosphate
  • the coupler solvent represented by the general Formula I is less hydrolizable, whereas a conventionally known triaryl phosphate coupler solvent is readily hydrolyzed, this being one of the causes reducing the fastness of the color image formed.
  • solvents (c) and (f) of this invention have higher solvent action to the 5- pyrazolone coupler and to the dye derived therefrom than conventional coupler solvents, tri-o-cresyl phosphate (TCP) and di-n-butyl phosphate (DB-P).
  • N,N-di-substituted-o-phenylene diamine derivatives used for developing the color photographic light-sensitive element of this invention are as follows: N,N-dimethyl-p-phenylenediamine, N,N-di- TABLE 1 [Properties of aliphatic phosphorate-type solvent for coupler] No.
  • the S-pyrazolone coupler shown above by the structural formula K was dissolved in 4 types of coupler solvents at 25 C. to saturation. For this purpose, an excess amount of the coupler was added thereto and with frequent stirring, the mixture was allowed to stand for about 1 month. Then, the content of the coupler in the saturated solution was measured, the results are shown in Table 2.
  • the azomethine dye having the following structure derived from the '5-pyrazolone coupler K was also dissolved in the 4-types of the solvent for coupler to saturation and the content of the dye in the saturated solution was measured, the results are also shown in Table 2.
  • ortho-substituted developing agents have a high dyeforming faculty as well as excellent advantages of giving a fast color image to light, heat, and humidity, they are still deficient at the point of bright red reproduction since the absorption of the color image obtained is at the longer wave length side.
  • the use of the solvent for the coupler represented by the general Formula I compensates for the shift of the absorption of the color image to longer wave lengths and facilitates the use of ortho-substituted developing agents. That is to say, by the combination of both components, a color image having a clear red reproduction, a high color density, and a high fastness can be obtained. This is one of the advantages obtained by this invention.
  • the invention can be applied to various types of color photographic light-sensitive elements and can give color images having good properties.
  • Examples are color printing papers, color photographic positive films, color photographic negative films, and color photographic reversal films.
  • the invention can be applied to the so-called multilayer type color photographic light-sensitive element in which multiple emulsion layers, each containing a silver halide emulsion with a different spectral sensitivity and a corresponding diffusion-resisting coupler, are applied to a support and also to a mixed grain-type color photographic light-sensitive element as well as other types of light-sensitive elements.
  • the phosphate represented by the general Formula I to be used in this invention can be prepared by the reaction of phosphoryl tri-chloride and an alcohol or a phenol. Also, by utilizing the difference in the step-wise reactivity of the chlorine atoms of sulphoryl trichloride, a mixed ester can be produced easily.
  • the alkyl group rep resented by R R and R of the general Formula I is preferably a primary alkyl group from a standpoint of the yield in producing the ester. Examples of producing the esters are illustrated by the following:
  • reaction mixture was maintained at the same temperature for 1 hour and at room temperature for 2 hours, and then refluxed for 2 hours. After reducing the temperature of the reaction mixture to room temperature, 400 m1. of water was added to dissolve the pyridine hydrochloride. The benzene layer was separated, washed with water, 'washed then with a 5% aqueous sodium bicarbonate solution, washed further with water twice, and dried by sodium sulfate. By distilling away the benzene under reduced pressure and then distilling the residue immediately, the fractions having boiling points of -205 C./1.5 mm. Hg were collected and distilled again to give 414 g. of the above-mentioned product having a boiling point of 178-182 C./mm. Hg.
  • the S-pyrazolone couplers shown by the general Formula II to be used in this invention can be produced by well known methods.
  • a 3-alkyl-5-pyrazolone or a 3-aryl-5-pyrazolone can be produced by condensing an aryl hydrazine and a corresponding ethyl acyl acetoacetate.
  • 3-amino-5-pyrazolone can be produced by the condensation of an aryl hydrazine and ethyl fi-ethoxyfl-iminopropionate acid.
  • 3-amino-5-pyrazolone By reacting the 3-amino-5-pyrazolone thus obtained with a carboxylic acid chloride, an isocyanate compound or an arylsulfonyl chloride, 3-acylamino-S-pyrazolone, 3-ureido-5-pyrazolone, or 3-sulfonamido-S-pyrazolone can be obtained respectively. Furthermore, by heating the 3-amino-5-pyrazolone and an aniline to cause a diamination reaction, 3-anilino-5-pyrazolone can be obtained.
  • a bis-S-pyrazolone represented by the general Formula III can be obtained by condensing 2 mols of the 5-pyrazolone obtained above and one mole of an aldehyde.
  • Examples of the production of the 5-pyrazolones used in this invention are described in the specifications of British Pat. Nos. 547,064; 680,488; 843,497; 904,852; 953,454; 953,455; 977,554; 1,018,810; 1,044,778; 1,057,436; 1,066,- 334; 1,069,534; 1,076,544; 1,077,873; 1,077,875; 1,078,- 164; 1,118,745; and 1,142,553; US. Pat. No. 2,618,641; and Belgian Pat. Nos. 679,766 and 697,112.
  • EXAMPLE 1 A solution obtained by heating 17 g. of the 5-pyrazolone-type coupler L shown by the above structural formula, 15 ml. of the coupler solvent and 15 ml. of butyl acetate at 70 C., was added to 300 ml. of an aqueous solution containing 25 g. of gelatin and 1.0 g. of sodium dodecylbenzene sulfonate and after stirring the mixture for 30 minutes using a homogenizer, the entire amount of the dispersion obtained was added to 500 g. of a photographic emulsion containing 36.7 g. of silver iodobromide and 45 g. of gelatin. After adding 15 m1.
  • the photographic emulsion was applied to a triacetyl cellulose film to a dry thickness of 4.0 10'- cm.
  • the coating density was 1.11 10 mol/m. with respect to the coupler and 9.00 10- mol/m. with respect to the silver iodobromide.
  • the light-sensitive film was exposed and processed as follows, whereby a magenta image was obtained.
  • compositions of the processing solutions used above were as follows:
  • FIG. 1 The spectral absorption curves of the magenta images obtained are shown in FIG. 1 of the accompanying drawings and the values of the characteristics thereof are shown in Table 3.
  • Curve I represents the spectral absorption curve when coupler solvent (j) was used
  • Curve II represents the spectral absorption curve when DBP was used
  • Curve III represents the spectral absorption curve when T CP was used.
  • the entire amount of the emulsified dispersion was added to 1 kg. of a green-sensitive photographic emulsion containing 2.69 l0- mol of silver iodobromide and 70 g. of gelatin, and after adding additionally 50 ml. of a 3% acetone solution of triethylene phosphamide as a hardening agent, the resulting emulsion was applied to a polyethylene terephthalate film at a dry thickness of 5.5
  • the light-sensitive film contained the coupler in an area density of l.27 10- mol/m
  • the light-sensitive film was subjected to sensitometric exposures and then processed as in Example 1 except that the color developer had the following composition:
  • the spectral absorption curve of the magenta image thus obtained is shown in FIG. 2 of the accompanying drawings and the values of the characteristics thereof are shown in Table 4.
  • Curve IV represents the spectral absorption curve where coupler solvent (f) (trin-hexyl-phosphate) was used and Curve V represents the spectral absorption curve where tri-o-cresyl phosphate was used as the coupler solvent.
  • the light-sensitive films prepared above showed good coupling on color development. Also, in the light-sensitive films of this invention, the turbidity by the coupler dispersed in the unexposed area thereof was particularly low and the unexposed portions were transparent. Furthermore, the magenta images obtained by the coupling of the coupler demonstrated high resistance to light, heat and humidity in the light-sensitive films of this invention.
  • EXAMPLE 3 A solution prepared by heating a mixture of 7.3 g. of the S-pyrazolone-type coupler T shown by the above-described general formula, 10 ml. of the coupler solvent, 1 g. of sodium di-isooctyl sulfosuccinate, and 20 ml. of ethyl acetate was added to m1. of an aqueous solution containing 10 g. of gelatin, and the mixture was mechanically stirred for 15 minutes vigorously using a homogenizer, thereby the coupler and the solvent were finely dispersed. The dispersion was stored for 30 days at 5 C.
  • the entire amount of the dispersion was heated to 50 C. and mixed with 500 g. of a photographic emulsion containing 1.03 x mol of silver chlorobromide and 35 g. of gelatin. After adding additionally 20 ml. of a 3% acetone solution of triethylene phosphamide as a hardening agent, the resultant emulsion was filtered using a glass filter and applied to a triacetyl cellulose film at a dry thickness of 5.5 microns.
  • EXAMPLE 5 A color photographic printing paper was prepared in the following manner.
  • TBP tri-n-butyl phosphate
  • diethyl-decyl phosphate diethyl-decyl phosphate
  • tri-n-amyl phosphate were used respectively.
  • a solution produced by heating 16 g. of the 5-pyrazolone-type magenta-forming coupler N shown in the above-described structural formula, 30 ml. of the coupler solvent (f), and 25 ml. of ethyl acetate was added to 300 ml. of an aqueous solution containing 25 g. of gelatin and 1.0 g. of sodium dodecylbenzene sulfonate, and the mixture was stirred for 30 minutes using a homogenizer to give a dispersion. The entire amount of the emulsified dispersion was added to 500 g. of a green-sensitive photographic emulsion containing 36.7 g. of silver bromide and 45 g.
  • the color photographic positive film thus produced was exposed through a color negative and developed as in Example 1 to obtain a color slide for projection having clear colors. When the color slide was projected, it was confirmed that the reddish color was especially clear.
  • EXAMPLE 7 A color negative film was prepared in the following manner.
  • the entire amount of the dispersion thus prepared was added to 1.6 kg. of a green-sensitive photographic emulsion containing 2.8 10-' mol of silver iodobromide and 97 g. of gelatin. After adding thereto 30 ml. of a 3% acetone solution of triethylene phosphamide as a hardening agent, the resultant emulsion was applied as the third layer to the above-formed layer at a dry thickness of 4 microns.
  • a gelatin solution containing a yellow silver colloid as the fourth layer, a blue-sensitive photographic emulsion containing the yellow-forming coupler (vi) shown above t me OoHO-Q-Qmim @mrooomo oNH--o CH; $51111)
  • a gelatin layer of 1 micron To the blue-sensitive layer was applied a gelatin layer of 1 micron.
  • the entire amount of the emulsified dispersion thus produced was added to 1 kg. of a green-sensitive photographic emulsion containing 2.8 10" mol of silver chlol0 g. of each of the various magenta couplers shown by the above described structures was dissolved by heating in a mixture of 25 ml. of ethyl acetate and 18 ml. of eachof the various coupler solvents shown by the abovedescribed structures.
  • Each of the coupler solutions prepared above was mixed with 200 ml. of an aqueous solution containing 15 g. of gelatin and 1.0 g. of sodium dodecylbenzene sulfonate and the mixture was mechanically stirred vigorously for 30 minutes using a high speed rotary mixer to disperse finely the coupler and the solvent.
  • each coupler dispersion was added to 300 g. of a silver halide photographic emulsion and after adding thereto 10 ml. of a 3% acetone solution of triethylenephosphamide as a hardening agent, the resultant emulsion was applied to a triacetyl cellulose film at a dry thickness of microns.
  • the light-sensitive film thus obtained was developed in the same manner as in Example 2 and the spectral absorption of the magenta image obtained was measured, the results of which are shown in Table 8.
  • the aboveprepared coupler solution was added to the photographic emulsion obtained above with stirring and then the pH was adjusted to 6.0 with a 6% acetic acid solution. Then, after adding 3 ml. of a 3% acetone solution a triethylene phosphamide thereto as a hardening agent, the resultant emulsion was applied to a triacetyl cellulose film at a dry thickness of 5 microns.
  • a light-sensitive film was prepared in the same manner as above except that tri-namyl phosphate and sodium dodecylbenzene sulfonate were not used.
  • the emulsion was heated to 40 C. and mixed with the hot solution of the coupler M prepared as above followed by stirring. Then, the mixture was passed five times through an emulsifier having Pohlman Whistle, whereby the coupler was dispersed finely.
  • the photographic emulsion was applied to a triacetyl cellulose film at a dry thickness of 5 microns.
  • the light-sensitive film thus obtained was exposed and developed as in Example 2, whereby a clear magenta image having an absorption maximum at 538 millimicrons was obtained.
  • EXAMPLE l1 5 ml. of tri-(Z-ethylhexyl) phosphate [coupler solvent (m)] was added to 70 ml. of an aqueous solution containing 5 g. of gelatin and 0.3 g. of sodium cetylsulfate and the mixture was stirred vigorously in a small emulsifying blender to disperse the solvent finely.
  • the entire amount of the dispersion was added together with 50 ml. of warm water to g. of a photographic emulsion containing 0.27 mol of silver iodobromide and 7 g. of gelatin, and the mixture was mixed with 18 ml. of a 6% acetic acid solution.
  • the same c'oupler was added to the photographic emulsion using an aqueous solution system without using the coupler solvent and sodium cetylsulfate to prepare a control film sample.
  • EXAMPLE 112 1 6 g. of the S-pyrazolone coupler M shown by the aforesaid structural formula was dissolved in 40 ml. of butyl acetate by heating. The solution was added to an aqueous solution containing 11 g. of gelatin and 1 g. of sodium di-isooctylsulfosuccinate at 50 C. and stirred for 15 minutes in a homogenizer to disperse the coupler finely.
  • Coupler solvent (h) 24 ml. of di-n-hexyl-phenyl phosphate [coupler solvent (h)] was added at 50 C. to an aqueous solution containing 6 g. of gelatin and 0.6 g. of sodium di-isooctylsulfosuccinate and the mixture was stirred for 15 minutes in a homogenizer to disperse [finely the solvent for the coupler.
  • the coupler dispersion and the coupler solvent dispersion prepared above were added to 1 kg. of a greensensitive photographic emulsion containing 0.21 mol of silver chlorobromide and 70 g. of gelatin and after adding thereto 30 ml. of a 3% acetone solution of triethylene phosphamide as a hardening agent, the emulsion was applied ot a polyethylene terephthalate film at a dry thickness of 5 microns.
  • a control sample was prepared by adding only the coupler dispersion to the photographic emulsion without adding the coupler solvent dispersion.
  • the coupler solvent contributed to the shift in the absorption to shorter wave lengths side and to the reduction in the absorption in the red region.
  • a light-sensitive material comprising at least a layer of a silver halide emulsion containing (1) a non-diffusing S-pyrazolone coupler having at least a hydrophobic ballasting group containing from -9 to 30 carbon atoms and (2) a coupler solvent having the formula wherein R and R each is an alkyl group and wherein R represents a member selected from a group consisting of an alkyl group and an aryl group, and wherein the total number of the carbon atoms in R R and R ranges from :14 to 40 carbon atoms.
  • S-pyrazolone coupler is a member selected from the group consisting of compounds having the following formulae:
  • R is a member selected from a group consisting of aryl and substituted aryl, said substituted aryl having a group member selected from the group consisting of aryl, alkoxyl, aryloxy, alkylthio, arylthio, halogen, tritluoromethyl, cyano, acyl, sulfonyl, acylamino, sulfonamino, ureido, amino, carboxyl, al koxycarbonyl, and carbamyl, wherein R is a member selected from a group consisting of alkyl, alkenyl, aryl, amino, acylamino, ureido, alkoxyl and sulfonamino, wherein R is a member selected from a group consisting of a lower alkyl and a lower aryl group, wherein X represents a substituent displaceable on the reaction with the oxidation product of a primary aromatic amino developing agent and is
  • R R and R each is a primary alkyl group.
  • a process for producing a colored image by reacting a non-diffusing S-pyrazolone coupler with the oxidation product of a primary aromatic amino developing agent oxidized by exposed silver halide, in the presence of a coupler solvent having the formula I Ra wherein R and R each is an alkyl group and wherein R represents a member selected from the group consisting of an alkyl and an aryl group, and wherein the total number of carbon atoms in R R and R ranges from 14 to 40 carbon atoms.
  • said S-pyrazolone coupler is a member selected from the group consisting of compounds having the following formulae wherein R is a member selected from a group consisting of aryl and substituted aryl, said substituted aryl having a group member selected from the group consisting of aryl, alko/xyl, aryloxy, alkylthio, arylthio, halogen, trifluoromethyl, cyano, acyl, sulfonyl, acylamino, sulfonamino, ureido, amino, carboxyl, al'koxycarbonyl, and carbamyl, wherein R is a member selected from the group consisting of alkyl, alkenyl, aryl, amino, acylamino, ureido, alkoxyl and sulfonamino, wherein R is a member selected from a group consisting of a lower alkyl and a lower
  • said coupler solvent is a member selected from the group consisting of diethyl decyl phosphate, tri-n-amyl phosphate, di-n-butyl 2-ethylhexyl phosphate, tri-n-hexyl phosphate, di-n-hexyl phenyl phosphate, tri-(Z-ethylhexyl) phosphate, di (2-ethylhexyl) n-butyl phosphate, and tri-n-heptyl phosphate.
  • R and R each is a primary alkyl group and wherein R is a mono-nuclear aryl group.

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US67330A 1969-08-27 1970-08-27 Color photographic light-sensitive element containing magenta coupler and alkyl phosphate solvent Expired - Lifetime US3676137A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP44067797A JPS4832727B1 (ja) 1969-08-27 1969-08-27

Publications (1)

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US3676137A true US3676137A (en) 1972-07-11

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Family Applications (1)

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US67330A Expired - Lifetime US3676137A (en) 1969-08-27 1970-08-27 Color photographic light-sensitive element containing magenta coupler and alkyl phosphate solvent

Country Status (8)

Country Link
US (1) US3676137A (ja)
JP (1) JPS4832727B1 (ja)
BE (1) BE755248A (ja)
CA (1) CA962879A (ja)
DE (1) DE2042581C3 (ja)
FR (1) FR2058102A5 (ja)
GB (1) GB1311945A (ja)
NL (1) NL7012621A (ja)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2432041A1 (de) * 1973-07-03 1975-01-23 Fuji Photo Film Co Ltd Lichtempfindliches, photographisches halogensilberelement
US3897254A (en) * 1973-05-11 1975-07-29 Mitsubishi Paper Mills Ltd Silver halide containing pyrazolone magenta coupler
DE2909021A1 (de) * 1978-03-09 1979-09-20 Fuji Photo Film Co Ltd Lichtempfindliches farbphotographisches silberhalogenidmaterial
DE2932368A1 (de) * 1978-08-10 1980-02-21 Fuji Photo Film Co Ltd Fotografisches lichtempfindliches silberhalogenidmaterial und verfahren zur herstellung eines solchen
US4211836A (en) * 1978-01-23 1980-07-08 Fuji Photo Film Co., Ltd. Method for dispersing oil-soluble photographic additives
US4217410A (en) * 1978-03-10 1980-08-12 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive materials with phosphate solvent
US4326022A (en) * 1979-12-07 1982-04-20 Konishiroku Photo Industry Co., Ltd. Photographic material containing a high boiling solvent
US4353979A (en) * 1979-07-25 1982-10-12 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
EP0170164A2 (en) * 1984-07-19 1986-02-05 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US4808502A (en) * 1987-09-21 1989-02-28 Eastman Kodak Company Photographic recording material comprising a magenta dye image forming coupler compound
US4935321A (en) * 1987-09-21 1990-06-19 Eastman Kodak Company Photographic recording material comprising a dye image-forming compound
US4954432A (en) * 1988-01-07 1990-09-04 Konica Corporation Photographic material with solvent having dielectric constant of 6 or less and yellow coupler
US4973535A (en) * 1987-09-21 1990-11-27 Eastman Kodak Company Photographic recording material comprising a dye image-forming coupler compound
US5019493A (en) * 1986-10-13 1991-05-28 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material and method of forming a dye image thereon
US5426019A (en) * 1993-12-30 1995-06-20 Eastman Kodak Company Color photographic element
US5451497A (en) * 1993-12-30 1995-09-19 Eastman Kodak Company Photographic dispersion having improved stability
US5695921A (en) * 1995-03-31 1997-12-09 Eastman Kodak Company Photographic elements with magenta dye forming couplers and stabilizers
WO2012014954A1 (ja) 2010-07-30 2012-02-02 富士フイルム株式会社 新規なアゾ化合物、水溶液、インク組成物、インクジェット記録用インク、インクジェット記録方法、インクジェット記録用インクカートリッジ、及びインクジェット記録物
WO2012014955A1 (ja) 2010-07-30 2012-02-02 富士フイルム株式会社 新規なアゾ化合物、水溶液、インク組成物、インクジェット記録用インク、インクジェット記録方法、インクジェット記録用インクカートリッジ、及びインクジェット記録物
EP2455431A1 (en) 2003-10-23 2012-05-23 Fujifilm Corporation Ink and ink set for inkjet recording
EP2712894A1 (en) 2012-09-26 2014-04-02 Fujifilm Corporation Azo compound, aqueous solution, ink composition, ink for inkjet recording, inkjet recording method, ink cartridge for inkjet recording, and inkjet recorded material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0711804A3 (de) 1994-11-14 1999-09-22 Ciba SC Holding AG Kryptolichtschutzmittel

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897254A (en) * 1973-05-11 1975-07-29 Mitsubishi Paper Mills Ltd Silver halide containing pyrazolone magenta coupler
DE2432041A1 (de) * 1973-07-03 1975-01-23 Fuji Photo Film Co Ltd Lichtempfindliches, photographisches halogensilberelement
US3936303A (en) * 1973-07-03 1976-02-03 Fuji Photo Film Co., Ltd. Photographic photosensitive element and developing method thereof
US4211836A (en) * 1978-01-23 1980-07-08 Fuji Photo Film Co., Ltd. Method for dispersing oil-soluble photographic additives
DE2909021A1 (de) * 1978-03-09 1979-09-20 Fuji Photo Film Co Ltd Lichtempfindliches farbphotographisches silberhalogenidmaterial
US4220711A (en) * 1978-03-09 1980-09-02 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive element
US4217410A (en) * 1978-03-10 1980-08-12 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive materials with phosphate solvent
DE2932368A1 (de) * 1978-08-10 1980-02-21 Fuji Photo Film Co Ltd Fotografisches lichtempfindliches silberhalogenidmaterial und verfahren zur herstellung eines solchen
US4353979A (en) * 1979-07-25 1982-10-12 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
US4326022A (en) * 1979-12-07 1982-04-20 Konishiroku Photo Industry Co., Ltd. Photographic material containing a high boiling solvent
EP0170164B1 (en) * 1984-07-19 1988-10-05 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
USH122H (en) 1984-07-19 1986-09-02 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
EP0170164A2 (en) * 1984-07-19 1986-02-05 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US5019493A (en) * 1986-10-13 1991-05-28 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material and method of forming a dye image thereon
US4935321A (en) * 1987-09-21 1990-06-19 Eastman Kodak Company Photographic recording material comprising a dye image-forming compound
US4973535A (en) * 1987-09-21 1990-11-27 Eastman Kodak Company Photographic recording material comprising a dye image-forming coupler compound
US4808502A (en) * 1987-09-21 1989-02-28 Eastman Kodak Company Photographic recording material comprising a magenta dye image forming coupler compound
US4954432A (en) * 1988-01-07 1990-09-04 Konica Corporation Photographic material with solvent having dielectric constant of 6 or less and yellow coupler
US5426019A (en) * 1993-12-30 1995-06-20 Eastman Kodak Company Color photographic element
US5451497A (en) * 1993-12-30 1995-09-19 Eastman Kodak Company Photographic dispersion having improved stability
US5695921A (en) * 1995-03-31 1997-12-09 Eastman Kodak Company Photographic elements with magenta dye forming couplers and stabilizers
EP2455431A1 (en) 2003-10-23 2012-05-23 Fujifilm Corporation Ink and ink set for inkjet recording
WO2012014954A1 (ja) 2010-07-30 2012-02-02 富士フイルム株式会社 新規なアゾ化合物、水溶液、インク組成物、インクジェット記録用インク、インクジェット記録方法、インクジェット記録用インクカートリッジ、及びインクジェット記録物
WO2012014955A1 (ja) 2010-07-30 2012-02-02 富士フイルム株式会社 新規なアゾ化合物、水溶液、インク組成物、インクジェット記録用インク、インクジェット記録方法、インクジェット記録用インクカートリッジ、及びインクジェット記録物
EP2712894A1 (en) 2012-09-26 2014-04-02 Fujifilm Corporation Azo compound, aqueous solution, ink composition, ink for inkjet recording, inkjet recording method, ink cartridge for inkjet recording, and inkjet recorded material

Also Published As

Publication number Publication date
DE2042581C3 (de) 1979-07-05
DE2042581B2 (de) 1974-09-19
GB1311945A (en) 1973-03-28
DE2042581A1 (de) 1971-03-11
FR2058102A5 (ja) 1971-05-21
BE755248A (fr) 1971-02-01
NL7012621A (ja) 1971-03-02
CA962879A (en) 1975-02-18
JPS4832727B1 (ja) 1973-10-08

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