US3558319A - Color photographic silver halide emulsion containing magenta couplers - Google Patents

Color photographic silver halide emulsion containing magenta couplers Download PDF

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US3558319A
US3558319A US652891A US3558319DA US3558319A US 3558319 A US3558319 A US 3558319A US 652891 A US652891 A US 652891A US 3558319D A US3558319D A US 3558319DA US 3558319 A US3558319 A US 3558319A
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compound
coupler
mixture
silver halide
color
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Tsutomu Hamaoka
Kazuya Sano
Makoto Yoshida
Yasushi Oishi
Takeshi Hirose
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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
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/48—Two nitrogen atoms
    • C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

  • the present invention relates to color photography, and particularly to color photographic materials containing -pyrazolone couplers that carry ortho-substituted phenyl groups at position 1 and m-acylaminophenyl-ureido groups at position 3 of the pyraziolone nuclei.
  • magenta-colored image is produced by the oxidative coupling of a 5-pyrazolone and a p-phenylenediamine, in particular an N,Ndalkylp-phenylene (ortolylene-l-diamine.
  • the magneta image contributes greenlight absorption on the spectral region of 500 to 600 mp.. It is desired thatthe extinction be large in this region and small outside of this region, that is, in the blue and red regions.
  • the azomethine dye derived from a pyrazolone coupler has a second A.absorption maximum around 440 ma, together with the main absorption maximum near 550
  • the former is a serious obstruction to desirable color production of the blue color. This has led to many attempts to sol-ve the problem, and U.S. Pat. No. 2,369,489, which relates to ya 3-acylamino-5-pyrazolone, has brought about a considerable but by uo means quite satisfactory improvement.
  • the coupler must have a sufficient coupling activity toward p-phenylenediamine developers in order that the exposed photographic emulsion show high sensitively and high gradation and rapid development. It has hitherto been known that 1-aryl-3-acylamino-S-pyrazolone couplers provide fairly good absorption characteristics, while their coupling activities are usually low and hardly yield enough color density. On the contrary, the use of a coupler with excessively high coupling activity leads to color images of poor quality and increased fog. Thus, it is another object of this invention to provide color couplers that have enough, but not excessive, coupling activity.
  • a third requirement of the couplers relates to the fastness of the dye derived therefrom.
  • the magenta color image produced through conventional color development has a tendency to fade or discolor when exposed to light, heat or humidity.
  • the coupler that has survived the development process is apt to form yellow stains during storage.
  • a coupler is dissolved in an organic solvent and the solution is dispersed in an aqueous medium to form ne colloidal particles, before being added into the photographic emulsion, and
  • a coupler melt is directly dispersed into a photographic emulsion or is dispersed in an aqueous medium before being added to the emulsion.
  • the second process has been known to give better absorption characteristics and faster image dyes.
  • the coupler is dissolved in the smallest possible amount of solvent to secure a high level of photographic properties in the emulsion, high quality of the dye image, and good mechanical properties of the emulsion layers. This necessarily requires a high solubility of the coupler in the solvent in question.
  • 1aryl3arylureido S-pyrazolone is not very easily soluble in such non-polar solvents as are conventionally used, lalthough it has excellent absorption characteristics. Therefore, it is a fourth object of this invention to provide easily soluble l-phenyl- 3-aryl-ureido-S-pyrazolones.
  • RCO represents an acyl group having 18 to 25 carbon atoms and Ar represents a phenyl group having at least one substituent lat the ortho position, the suhstituent being chosen from the class consisting of halogens, lower alkyl groups and lower alkoxy groups.
  • the RCO group contributes the solubility of the coupler as well as its resistance to ditusion. If the RCO group carries less than 18 carbon atoms, the coupler wanders out of the layer because of the low solubility in the organic solvent and low diffusion-resistance, resulting in a worsened color reproduction. On the other hand, an excessively large RCO group, having more than 25 carbon atoms, brings about an excessively large molecular weight and thus too small an extinction per volume. Moreover the dispersion force due to this part of the molecule reduces the solubility of the coupler.
  • the RCO group is most suitably located meta to the ureido group since the compound of this location provides a higher solubility than its isomers. For example, the para isomer gives the dye of the absorption characteristics as excellent as the meta isomer but cannot be employed owing to its low solubility. This feature is well illustrated in Table 1.
  • the RCO group is preferably a substituted or an unsubstituted aliphatic acyl group or one of the following:
  • R1 represents a hydrogen atom or an alkyl group having not more than 3 carbon atoms
  • R2 represents an alkyl group having not more than carbon atoms
  • R3 represents an alkyl group having from 5 to 16 carbon atoms
  • n is an integer from 1 to 5.
  • the ortho substituent of the Ar group is quite important because the lack of the substituent gives rise to too low a solubility, and an excessive coupling activity, which leads to fogging, and thus, to worsening of the image quality.
  • the elfect of the ortho substituent is believed to be due to loss of the co-planarity of the pyrazolone and the aryl nuclei, which are affected by many kinds of substituents, such as halogens, alkyl groups and alkoxyl groups. These substituents are also effective in preventing the yellowing of the couplers by light. In particular, those that carry two substituents at the ortho positions are remarkably resistant to the action of light.
  • FIGS. 1, 2 and 3 show the spectral absorption curves of dye images obtained by processing couplers I, IV and 1X with 2-amino-5-diethylaminotoluene compared with those from the corresponding reference couplers.
  • Curves a and b of FIG. 1, c and d of FIG. 2 and e and f of FIG. 3 correspond to couplers I, A, 1V, B, IX and H, respectively.
  • magenta color image obtained from the color photographic material containing the coupler of this invention fades only reluctantly by the action of light, heat and environmental humidity, as is shown in Example 4, and the remaining coupler scarcely yellows when exposed to strong radiation. This makes this invention especially valuable from the viewpoint of image preservation.
  • the coupler of this invention gives high sensitivity and desirable gradation to the photographic emulsion, while giving rise to little fogging owing to its moderate couplng activity.
  • the present coupler shows a high rate of conversion to azomethine dyes and thus increases the sensitivity even more. This results in a smaller amount of coupler needed, and thus, in a thinner emulsion layer, which improves the image quality and the rate of development.
  • the coupler of this invention has a high solubility in such organic solvents as di-n-butyl phthalate and ethyl acetate. In other words, only a small amount of solvent is needed to disperse this kind of coupler. This necessarily simplifies the production of the photographic material. ⁇ It also excludes the need for a thick layer, guaranteeing higher quality of the image, a higher development' rate, and better mechanical properties of the emulsion layer.
  • Table 1 shows the solubilities and melting points of couplers I, V, IX and X, together with those of reference couplers C.1D.F. and B, which have structures similar to couplers I, V, IX and X, respectively.
  • the solubility has been designated as the amount of ethyl acetate needed to dissolve 1 part of the coupler at 60 C. It should be noted that a smaller value corresponds to a higher solubility.
  • dyes from the couplers of this invention give absorption characteristics suited for the subtractive color process.
  • Table 2 illustrates the absorption characteristics of ethyl acetate of dyes obtained by the oxidative coupling of the couplers of this invention with 2amino5-N,Ndi ethylaminotoluene along with those from the corresponding reference couplers.
  • Couplers of the invention Reference couplers I V A B E G J K Primary absorption max. wave length (mit) 534 541 525 535 537 519 541 539 Secondary absorption max. wave length (mp 433 431 441 438 435 445 431 438 B-value 0. 14 0. 13 0. 21 0. 17 0. l6 0. 46 0. 17 0. 17 W-value (mit) 74 76 79 78 75 78 79 80 S-value 0. 2l 0. 19 0. 26 0. 22 0 29 0. 35 0. 24 0. 24
  • couplers of the present invention are especially suited for color photography because of unusually small B- (second absorption) and S-(red absorption) values while maintaining moderate W-values.
  • step (d) 'Synthesis of Compound I.-A mixture of 15 g. of the amine obtained in step (c), 4.5 g. of sodium acetate and 2160 ml. of glacial acetic acid was warmed to 50-60 C., while stirring and into the solution was gradually added a solution of 14.5 g. of 2,4-di-t-amylphenoxyacetyl chloride in 75 ml. of glacial acetic acid. The mixture'was allowed to react for 2 hours at this temperature.
  • a sodium methylate solution prepared from 42 g. of sodium metal and 600 m1. of methanol maintained at 10 C. -Was added to the system. The solution was stirred for 90 more minutes at room temperature. Then, the reaction mixture was poured into 3 liters of cold Water. After neutralization with acetic acid, the product was extracted with ethyl acetate and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the remaining syrup was washed with hexane and digested with ether until it crystallized. It was recrystallized from ethyl acetate to give 64 g. of the pyrazolone melting at 166 C.
  • step (c) Reduction of the nitro group-The whole amount of the nitro compound prepared by step (b) was re- 1 1 Jerusalem as in step (c) of the preparation of Compound I.
  • the product thus obtained was recrystallized from a solvent mixture of acetonitrile and ethanol (1:1) containing a small amount of methyl Cellosolve to give 7.2 g. of the amine melting at 190 C.
  • the aminopyrazolone used here had been prepared by the reaction of 2,6-dichloro-4-methylphenylhydrazine with ethyl -amino--ethoxy-propionate in a similar way as step (a) of the preparation of Compound VI followed by recrystallization of the product from acetonitrile.
  • step (b) Reduction of the nitro compound-In the mixture of 500 ml. of methanol, 500 ml. of glacial acetic acid and 50 ml. of water were suspended 50 g. of the nitro compound obtained in step (a) and reduced with iron powder according to step (c) of the preparation of Compound I.
  • the product was recrystallized from the mixture of 2 parts of lmethanol and 1 part of acetonitrile to give 23 g. of the amino compound melting at 225 C.
  • This invention can be satisfactorily applied to many types of light-sensitive materials, for example, color-printing papers, positive color films, negative color films,
  • this invention is expected to be applicable not only to so-called multilayer color photographic materials, but also to so-called mixed grain type ones.
  • the invention will further be explained by the following examples.
  • EXAMPLE 1 A solution prepared by warming to 70 C. a mixture of l5 g. of Compound I, 30 g. of di-n-butyl phthalate and 20 ml. of butyl acetate was added to 300 ml. of an aqueous solution of 1.0 g. of sodium dodecylbenzenesulfonate and 25 g. of gelatin. The mixture was stirred for 30 minutes in a homogenizer, and the whole amount of the mixture was mixed with 500 g. of a green-sensitive photographic emulsion.
  • the coating contained 5.8% X 10-3 mole of silver iodobromide and 7.2)(10-4 mole of the coupler per square meter.
  • the lm was exposed and subjected to the following processing steps to yield a clear magenta image with an absorption maximum at 551 mit.
  • the spectral absorption curve has been shown in FIG. 1 by curve a.
  • EXAMPLE 2 A solution prepared by warming to 70 C. a mixture of l g. of Compound X, 30 g. of tricresyl phosphate, and 10 ml. of ethyl acetate was added to 100 ml. of an aqueous Solution containing 0.5 g. of sodium dodecyl sulfate and 7 g. of gelatin at 60 C., and the resulting mixture was stirred vigorously by means of an homogenizer to disperse the coupler nely together with the solvent.
  • the Whole amount of the emulsion thus obtained was added to 540 g. of a green-sensitive photographic emulsion. After addition of 30 ml. of 3% acetone solution of triethylenephosphoramide as a hardening agent and 7 g. of polyvinyl pyrrolidone, the resulting composition was applied to baryta paper as the middle layer to a dry-thickness of 4 104 cm. Its bottom layer was a ⁇ blue-sensitive photographic emulsion layer containing an emulsifed dispersion of coupler (L) having the following structure. On the middle layer thus formed was coated as the top layer a red-sensitive emulsion containing an emulsied dispersion of coupler (M) shown below.
  • the whole amount of the coupler-containing emulsied dispersion was mixed with 200 g. of a photographic emulsion. After addition of ml. of a 3% acetone solution of triethylene phosphoramide as a hardening agent, the mixture was applied to a cellulose triacetate film to a dry-thickness of 6 10f4 cm. and dried. In this case, the coating contained 7.2X104 mol coupler and 5.8X10f3 mol silver iodobromide per square meter. The film was exposed to graduated intensities of light with aid of a sensitometer and developed for 6 minutes at 24 C. in a developer of the following composition and then washed with water for l5 minutes at the same temperature; then it was exposed uniformly to white light and colordeveloped as described in Example 1.
  • the reversal magenta color image thus obtained had an absorption maximum at 554 mp..
  • the spectral absorption curve has been shown in FIG. 3 of the attached drawing as curve e.
  • the coating contained 7.2 10*4 mol coupler and 5.8)(10-3 mol silver iodobromide per square meter.
  • the films were exposed to graduated intensities of light by means of a sensitometer and processed in the same manner as Example 1. Their photographic properties are as follows:
  • Film (P), (Coupler IV) according to the present invention gives a high sensitivity, a high gamma and a high maximum density compared with those of Film Q containing the conventional coupler (B), and that the color image 0btained is markedly fast to light, heat and humidity. Moreover, even intense radiation did not cause yellowing due to the remaining coupler.
  • a color photographic silver halide emulsion as 13 A color photographic silver halide emulsion as defined in claim 1 where the compound is: defined in claim 1 where the compound is:
  • JH2 defined in claim 1 where the compound is: N /C 0 nernoHuQ-oomooNH-Q C1 terLCsHu llIHooNH-C--CH C
  • 0 30 ⁇ N/ References Cited l UNITED STATES PATENTS C1' CH 3,393,071 7/1968 Monbaliu et a1. 96-100 3,462,270 8/1969 Eynde et al 96-100 H J. TRAVIS BROWN, Primary Examiner U.S. Cl. X.R. 96-74; 260-310

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Abstract

A COLOR PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING 1-ARYL-5-(M-ACYLAMINOPHENYLUREIDO)-5-PYRAZOLONE AS A MAGENTA COUPLER WHEREIN THE ACYL GROUP HAS 18 TO 25 CARBON ATOMS AND THE ARYL GROUP HAS AT LEAST ONE SUBSTITUENT AT THE ORTHO POSITION, THE SUBSTITUENT BEING CHOSEN FROM THE CLASS CONSISTING OF HALOGENS, ALKYL GROUPS AND ALKOXYL GROUPS.

Description

United States Patent O 3,558,319 COLOR PHOTOGRAPHIC SILVER HALIDE EMUL- SION CONTAINING MAGENTA COUPLERS Tsutomu Hamaoka, Kazuya Sano, Makoto Yoshida, Yasushi Oishi, and Takeshi Hrose, Kanagawa, Japan, assignors to Fuji Shashin Film Kabushiki Kasha, Kanagawa, Japan Filed July 12, 1967, Ser. No. 652,891 Claims priority, application Japan, July 13, 1966, 41/ 45,814 Int. Cl. G03c 1/40 U.S. Cl. 96--100 14 Claims ABSTRACT F THE DISCLOSURE A color photographic silver halide emulsion containing l aryl-3-(m-acylaminophenylureido)-S-pyrazolone as a magenta coupler wherein the acyl group has 18 to 25 carbon atoms and the aryl group has at least one substituent at the ortho position, the substituent being chosen from the class consisting of halogens, alkyl groups and alkoxyl groups.
BACKGROUND OF THE INVENTION l) Field of the invention The present invention relates to color photography, and particularly to color photographic materials containing -pyrazolone couplers that carry ortho-substituted phenyl groups at position 1 and m-acylaminophenyl-ureido groups at position 3 of the pyraziolone nuclei.
(2) yDescription of the prior art In the conventional substractive color photographic process, the magenta-colored image is produced by the oxidative coupling of a 5-pyrazolone and a p-phenylenediamine, in particular an N,Ndalkylp-phenylene (ortolylene-l-diamine. The magneta image contributes greenlight absorption on the spectral region of 500 to 600 mp.. It is desired thatthe extinction be large in this region and small outside of this region, that is, in the blue and red regions. The azomethine dye derived from a pyrazolone coupler, however, has a second A.absorption maximum around 440 ma, together with the main absorption maximum near 550 The former is a serious obstruction to desirable color production of the blue color. This has led to many attempts to sol-ve the problem, and U.S. Pat. No. 2,369,489, which relates to ya 3-acylamino-5-pyrazolone, has brought about a considerable but by uo means quite satisfactory improvement.
Another requirement for desirable color reproduction is that the extinction rapidly drops toward the longer wave lengths. As a matter of fact, the extinction of the pyrazolone azomethine dyes extends over 600 ma, resulting in an undesirable red light absorption. On the other hand, a simple trial of narrowing the absorption range will be accompanied by the reduction of the whole green absorption. In order to express the absorption characteristics as have been mentioned, the following formulas are often used:
Wvalue=Halfvalue width=distance between k max and the wave-length where the extinction is half as great as that at main absorption maximum S-value Thus, it is an object of this invention to provide couplers that yield dyes with small B- and S-Values and with a not too small W-value.
In addition, the coupler must have a sufficient coupling activity toward p-phenylenediamine developers in order that the exposed photographic emulsion show high sensitively and high gradation and rapid development. It has hitherto been known that 1-aryl-3-acylamino-S-pyrazolone couplers provide fairly good absorption characteristics, while their coupling activities are usually low and hardly yield enough color density. On the contrary, the use of a coupler with excessively high coupling activity leads to color images of poor quality and increased fog. Thus, it is another object of this invention to provide color couplers that have enough, but not excessive, coupling activity.
A third requirement of the couplers relates to the fastness of the dye derived therefrom. The magenta color image produced through conventional color development has a tendency to fade or discolor when exposed to light, heat or humidity. In addition, the coupler that has survived the development process is apt to form yellow stains during storage. Thus, it is a third object of this i11- vention to provide color couplers that are themselves resistant to light and which also form dyes Iwhich are resistant to light.
The following three methods have been employed t0 incorporate diffusion-resistant couplers into the emulsion layers of multi-layer materials.
(l) Into an emulsion is added a coupler which has been dissolved in an aqueous alkali with the aid of a carboxylic or a sulfonic acid group which the coupler carries. The emulsion can be neutralized, if necessary.
(2) A coupler is dissolved in an organic solvent and the solution is dispersed in an aqueous medium to form ne colloidal particles, before being added into the photographic emulsion, and
(3) A coupler melt is directly dispersed into a photographic emulsion or is dispersed in an aqueous medium before being added to the emulsion. Of the foregoing processes, the second process has been known to give better absorption characteristics and faster image dyes. In this case the coupler is dissolved in the smallest possible amount of solvent to secure a high level of photographic properties in the emulsion, high quality of the dye image, and good mechanical properties of the emulsion layers. This necessarily requires a high solubility of the coupler in the solvent in question. As a whole, 1aryl3arylureido S-pyrazolone is not very easily soluble in such non-polar solvents as are conventionally used, lalthough it has excellent absorption characteristics. Therefore, it is a fourth object of this invention to provide easily soluble l-phenyl- 3-aryl-ureido-S-pyrazolones.
SUMMARY OF TH-E INVENTION The inventors have found that the compound of the following general formula satisfies -all the requirements mentioned above:
I Ar
wherein RCO represents an acyl group having 18 to 25 carbon atoms and Ar represents a phenyl group having at least one substituent lat the ortho position, the suhstituent being chosen from the class consisting of halogens, lower alkyl groups and lower alkoxy groups.
The RCO group contributes the solubility of the coupler as well as its resistance to ditusion. If the RCO group carries less than 18 carbon atoms, the coupler wanders out of the layer because of the low solubility in the organic solvent and low diffusion-resistance, resulting in a worsened color reproduction. On the other hand, an excessively large RCO group, having more than 25 carbon atoms, brings about an excessively large molecular weight and thus too small an extinction per volume. Moreover the dispersion force due to this part of the molecule reduces the solubility of the coupler. The RCO group is most suitably located meta to the ureido group since the compound of this location provides a higher solubility than its isomers. For example, the para isomer gives the dye of the absorption characteristics as excellent as the meta isomer but cannot be employed owing to its low solubility. This feature is well illustrated in Table 1.
The RCO group is preferably a substituted or an unsubstituted aliphatic acyl group or one of the following:
(a) -o o cHoQ-R, (b) o o ono@ wherein R1 represents a hydrogen atom or an alkyl group having not more than 3 carbon atoms, R2 represents an alkyl group having not more than carbon atoms, R3 represents an alkyl group having from 5 to 16 carbon atoms, and n is an integer from 1 to 5.
The ortho substituent of the Ar group is quite important because the lack of the substituent gives rise to too low a solubility, and an excessive coupling activity, which leads to fogging, and thus, to worsening of the image quality.
The elfect of the ortho substituent is believed to be due to loss of the co-planarity of the pyrazolone and the aryl nuclei, which are affected by many kinds of substituents, such as halogens, alkyl groups and alkoxyl groups. These substituents are also effective in preventing the yellowing of the couplers by light. In particular, those that carry two substituents at the ortho positions are remarkably resistant to the action of light.
BRIEF DESCRIPTION OF THE DRAWING FIGS. 1, 2 and 3 show the spectral absorption curves of dye images obtained by processing couplers I, IV and 1X with 2-amino-5-diethylaminotoluene compared with those from the corresponding reference couplers. Curves a and b of FIG. 1, c and d of FIG. 2 and e and f of FIG. 3 correspond to couplers I, A, 1V, B, IX and H, respectively.
DETAILED DESCRIPTION OF THE INVENTION The couplers suitably used in the present invention are exemplified by the following:
(II) sec. cmu-@ocmooNH-Q 5 slee. 05H11 NHcoNH-(I-Iom N\ c=o ClsHaiCO NoHzcHzcoNH- 04H9 NHooNH-ccnl N\ c=o N t I (1V) terecnu -OCHQCONEQ termali NHcoNH-c--C'm N c=o cic1 sec. 05H
tert. 05H11 NHCONH-l-ICHz (VII) OHzCHaCONH- (VIII) (IJzHs tel'iLCsHu *O CHCONH- I tert. 05H11 l NEC ONH-C- CHz l tert. 05H11 l tert. 05H11 (XII) 30 Each of the following compounds has Someting in common with couplers I-XIII. Comparison of the two groups will serve to illustrate the merits of the couplers of the present invention.
sec.CiHu
tert. H11
teraom- -ooHcroNH tert. 05H11 (n @-s olNH-Il-cm, No N\ /c=o The magenta color image obtained from the color photographic material containing the coupler of this invention fades only reluctantly by the action of light, heat and environmental humidity, as is shown in Example 4, and the remaining coupler scarcely yellows when exposed to strong radiation. This makes this invention especially valuable from the viewpoint of image preservation.
In the second place, the coupler of this invention gives high sensitivity and desirable gradation to the photographic emulsion, while giving rise to little fogging owing to its moderate couplng activity. In addtion, the present coupler shows a high rate of conversion to azomethine dyes and thus increases the sensitivity even more. This results in a smaller amount of coupler needed, and thus, in a thinner emulsion layer, which improves the image quality and the rate of development.
Thirdly, the coupler of this invention has a high solubility in such organic solvents as di-n-butyl phthalate and ethyl acetate. In other words, only a small amount of solvent is needed to disperse this kind of coupler. This necessarily simplifies the production of the photographic material. `It also excludes the need for a thick layer, guaranteeing higher quality of the image, a higher development' rate, and better mechanical properties of the emulsion layer. Table 1 shows the solubilities and melting points of couplers I, V, IX and X, together with those of reference couplers C.1D.F. and B, which have structures similar to couplers I, V, IX and X, respectively. The solubility has been designated as the amount of ethyl acetate needed to dissolve 1 part of the coupler at 60 C. It should be noted that a smaller value corresponds to a higher solubility.
TABLE I.-MELTING POINTS AND SOLUBILITIES OF THE COUPLE RS OF THIS INVENTION COMPARED WITH THE REFERENCE COUPLERS t Solubility (defined above) 2.5 2.0 1.5 1.0 7.5 7.5 7.5 2.0
In the fourth place, dyes from the couplers of this invention give absorption characteristics suited for the subtractive color process.
Referring to the drawing, all the figures indicate that the couplers of the present invention, which carry 3-(macylaminophenyl-ureido) substitutents are superior to the reference couplers of known types, which carry 3-acylamino substituents, especially with regard to the absorption in the shorter waive-length region.
Such excellent absorption characteristics are believed to be due not only to the high solubility of the dyes in the co-existing solvent, but also to their own nature.
Table 2 illustrates the absorption characteristics of ethyl acetate of dyes obtained by the oxidative coupling of the couplers of this invention with 2amino5-N,Ndi ethylaminotoluene along with those from the corresponding reference couplers.
Couplers of the invention Reference couplers I V A B E G J K Primary absorption max. wave length (mit) 534 541 525 535 537 519 541 539 Secondary absorption max. wave length (mp 433 431 441 438 435 445 431 438 B-value 0. 14 0. 13 0. 21 0. 17 0. l6 0. 46 0. 17 0. 17 W-value (mit) 74 76 79 78 75 78 79 80 S-value 0. 2l 0. 19 0. 26 0. 22 0 29 0. 35 0. 24 0. 24
It will be clearly seen that the couplers of the present invention are especially suited for color photography because of unusually small B- (second absorption) and S-(red absorption) values while maintaining moderate W-values.
The following exemplify the preparation of these compounds:
Preparation of Compound I (a) Preparation of m-nitrophenyl isocyanate-In a 5- liter three-necked flask were placed 500 m1. of ethyl acetate, saturated with phosgene at room temperature. While refluxing and passing phosgene, 150 g. of m-nitroaniline, dissolved in 1.5 liters of dry ethyl acetate were gradually added. After addition of m-nitroaniline over 4 hours at such a rate as to avoid accumulation of nitronaniline hydrochloride, phosgene was passed in for 5 minutes more, ethyl acetate Was distilled out, and the viscous residue was distilled under reduced pressure by means of an aspirator. AOne hundred and thirty grams of m-nitrophenyl isocyanate boiling at 161 C./ 25 mm. Hg was obtained.
(b) Synthesis of l-(2-chlorophenyl)-3-(3-nitrophenylureido) 5pyrazolone.-In a 1 liter three-necked flask were placed 76 g. of 1-(2-chlorophenyl)3 amino-S-pyrazolone (I. Am. Chem. Soc., 66 18612 (1944)) and 600 m1. of acetonitrile. While stirring under reux, a solution consisting of 200 ml. of acetonitrile and 60 g. of m-nitrophenyl isocyanate was added dropwise into the system. During the addition, the pyrazolone Went into solution then the solution rapidly began to separate crystals. After stirring for 2 hours under reflux, the product was collected by filtration and was recrystallized from a mixture of one part of dimethylformamide and two parts of ethanol to give 50 g. of the compound melting at 254 C.
(c) Reduction of the nitro group-While stirring under reflux the whole amount of the nitro compound obtained above in 500 ml. of methanol, 500 ml. of glacial acetic acid and 50 ml. of water, '50 g. of reduced iron powder were added gradually. After 2 hours, the reaction mixture was poured into 5 liters of hot water and was allowed to stand overnight. The product was collected by filtration and recrystallized from a solvent mixture of ethanol and acetonitrile (1:1) to give 30 g. of the amine melting at 207 C.
(d) 'Synthesis of Compound I.-A mixture of 15 g. of the amine obtained in step (c), 4.5 g. of sodium acetate and 2160 ml. of glacial acetic acid was warmed to 50-60 C., while stirring and into the solution was gradually added a solution of 14.5 g. of 2,4-di-t-amylphenoxyacetyl chloride in 75 ml. of glacial acetic acid. The mixture'was allowed to react for 2 hours at this temperature.
The reaction mixture was poured into 1.5 liters of cold water and the product was collected by iltration, dried and recrystallized from a mixture of methanol and acetonitrile (1:1) to give 8 g. of Compound I melting at 182 C.
Preparation of Compound II A mixture of g. of the amine obtained in step (c) in the preparation of Compound I, 4.5 of sodium acetate and 260 ml. of glacial acetic acid was warmed to 50-60 C. While stirring, a solution of 14.5 g. of 2,4-di-sec-amylphenoxyacetyl chloride in 75 ml. of glacial acetic acid was added dropwise. The mixture was allowed to react for 2 more hours at this temperature.
The reaction mixture was poured into 1.5 liters of cold Water and the product was collected by filtration, dried and recrystallized from a mixture of acetone and methanol (1:1) to give 6 g. of Compound 1I melting at 174 C.
Preparation of Compound IV (a) Synthesis of 1-(2,4,6-trichlorophenyl)-3-(3-nitrophenylureido)-5pyrazolone.-In a l-liter three-necked flask were placed 84 g. of 1-(2,4,6-trichlorophenyl)-3- amino-S-pyrazolone (see U.S. Pat. 2,600,788) and 600 ml. of anhydrous acetonitrile. While stirring under reflux, a solution consisting of 200 ml. of anhydrous acetonitrile and 49 g. of m-nitrophenyl isocyanate was added gradually. After the addition, the mixture became clear and after about 30 minutes began to separate a large amount of crystals which were collected lby ltration and washed with hot acetonitrile to give 40 g. of the nitro compound melting at 232 C.
(b) Reduction of the nitro compound.- The reduction of the nitro compound was conducted in the same way as the preparation of Compound I. Thus, by reduction of 40 g. of the nitro compound obtained above, l5 g. of the amine melting at 224 C. was obtained.
(c) Synthesis of Compound IV.-In 240 ml. of glacial acetic acid were suspended 15 g. of the amine obtained above, and 4.5 g. of sodium acetate, and, while stirring at 50-50" C., a solution of 13 g. of 2,4-di-t-amylphenoxyacetyl chloride and ml. of glacial acetic acid were gradually added dropwise into the suspension. After the addition, the mixture was allowed to react for 2 more hours. The reaction mixture Was poured into 1.5 liters of cold water. The product was collected and was recrystallized, after drying, from a solvent mixture of acetonitrile and methanol (1:1) to give 9 g. of Compound IV melting at 198 C.
Preparation of Compound VI (a) Preparation of 1-(2-ethoxyphenyl) 3 s amino-5- pyrazoline.-A mixture of 64 g. of o-ethoxyphenylhydrazine, 360 ml. of methanol and 70 g. of anhydrous sodium acetate was cooled below 10 C., and 90 g. of ethyl ethoxy--iminopropionate hydrochloride were gradually added. The resulting solution was stirred for minutes at room temperature.
Then, a sodium methylate solution prepared from 42 g. of sodium metal and 600 m1. of methanol maintained at 10 C. -Was added to the system. The solution was stirred for 90 more minutes at room temperature. Then, the reaction mixture was poured into 3 liters of cold Water. After neutralization with acetic acid, the product was extracted with ethyl acetate and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure and the remaining syrup was washed with hexane and digested with ether until it crystallized. It was recrystallized from ethyl acetate to give 64 g. of the pyrazolone melting at 166 C.
(b)y Preparation of 1 (2 ethoxyphenyl)3-(3nitro phenylureido) -5-pyrazolone.-By the reaction of 44 g. of the pyrazolone prepared above with 33 g. of m-nitrophenyl isocyanate in the same procedure as step (b) of the preparation of Compound I, 30 g. of the above compound melting at 210 C. was obtained.
(c) Reduction of the nitro group-The whole amount of the nitro compound prepared by step (b) was re- 1 1 duced as in step (c) of the preparation of Compound I. The product thus obtained was recrystallized from a solvent mixture of acetonitrile and ethanol (1:1) containing a small amount of methyl Cellosolve to give 7.2 g. of the amine melting at 190 C.
(d) Synthesis of Compound VI.-7.2 g. of the amine prepared above and 2 g. of anhydrous sodium acetate were suspended in 100 ml. of glacial acetic acid and, while stirring, an acetic acid solution of 6.4 g. of 2,4-dit-amylphenoxyacetyl chloride was added dropwise into the suspension. After 2 hours, the reaction mixture was poured into cold water. The product was collected by filtration, washed well with water and dried to give 7 g. of Compound VI ymelting at 120 C.
Preparation of Compound IX (a) Preparation of 1-(2,6-dichloro-4-methylpheny1)-3- (3-nitropheny1ureido)-5-pyrazolone.-In 700 ml. of acetonitrile were dissolved 100 g. of 1-(2,6-dichloro-4-methylphenyl)3amino-5pyrazolone and while stirring under reflux, 64 g. of m-nitrophenyl isocyanate dissolved in 200 ml. of acetonitrile were added dropwise. After about 40 minutes a large quantity of product precipitated. After 1.5 hours, the precipitates were collected by filtration and washed with Ihot acetonitrile to give 110 g. of the nitro compound melting at 248 C.
The aminopyrazolone used here had been prepared by the reaction of 2,6-dichloro-4-methylphenylhydrazine with ethyl -amino--ethoxy-propionate in a similar way as step (a) of the preparation of Compound VI followed by recrystallization of the product from acetonitrile.
(b) Reduction of the nitro compound-In the mixture of 500 ml. of methanol, 500 ml. of glacial acetic acid and 50 ml. of water were suspended 50 g. of the nitro compound obtained in step (a) and reduced with iron powder according to step (c) of the preparation of Compound I. The product was recrystallized from the mixture of 2 parts of lmethanol and 1 part of acetonitrile to give 23 g. of the amino compound melting at 225 C.
(c) Synthesis of Compound yIX.-In 360 g. of glacial acetic acid were placed 23 g. of the amine thus prepared and 6 g. of anhydrous sodium acetate. A solution of 19.5 g. of 2,4-di-t-aminophenoxyacetyl chloride in 72 ml. of glacial acetic acid was added dropwise into the solution within 10 minutes. After 2 hours, the mixture was poured into cold water to precipitate the product, which was recrystallized from a mixture of 3 parts of methanol and 2 parts of acetonitrile to give 10 g. of Compound IX melting at 150 C.
Preparation of Compound X (a) Preparation of 1-(2,6-dichloro-4-methoxyphenyl) 3-(3-nitro-phenylureido)5-pyrazolone.-In 500 ml. of acetonitrile were treated 40 g. of m-nitrophenyl isocyanate with 67 g. of 1-(2,6-dichloro-4-methoxyphenyl)-3-amino- 5-pyrazolone, (see British Pat. 904,852) according to step (b) of the preparation of Compound 1I to give 67 g. of the nitro compound melting at 227 C.
(b) Reduction of the nitro group-In a mixture of 670 m1. of methanol, 670 ml. of glacial acetic acid and 67 rnl. of water were reduced 67 g. of the nitro compound obtained above by means of 67 g. of reduced iron powder, and the product thus prepared was recrystallized from a mixture of 3 parts of ethanol and 2 parts of dimethylformamide to provide 52 g. of the amine, melting at 200- 201 C.
(c) Synthesis of Compound X.-In 520 ml. of glacial acetic acid were suspended 52 g. of the amino compound prepared in step (b) and 12.5 g. of anhydrous sodium acetate, and while stirring, 40 g. of 2,4-di-t-amy1phenoxyacetyl chloride and 120 ml. of glacial acetic acid were added dropwise into the suspension at 50-60" C. After 1 hour, the mixture was poured into cold water to precipitate the product, which was collected by filtration, dried,
and recrystallized from methanol to give 69 g. of the crystal of Compound X melting at 139 C.
Preparation of Compound XIII-In 200 ml. of glacial acetic acid were suspended l g. of the amine prepared by step (c) of the preparation of Compound I and 2.5 g. of anhydrous sodium acetate and, while stirring at 50-60 C., a solution of 8 g. of palmitoyl chloride in 50 ml. of glacial acetic acid was added dropwise into the suspension within minutes. After 1 hour, the reaction mixture was poured into 1 liter of cold water. The product was collected by filtration, dried and recrystallized twice from a mixture of methanol and acetonitrile (1:1) and once from ethanol to give 4 g. of Compound XIII melting at 178 C. Couplers described in this application can be mixed with a small amount of cyanor yellow-forming coupler to improve the color reproduction according to Japanese patent publication No. 391/ 1965.
This invention can be satisfactorily applied to many types of light-sensitive materials, for example, color-printing papers, positive color films, negative color films,
reversal color films and so forth.
Also this invention is expected to be applicable not only to so-called multilayer color photographic materials, but also to so-called mixed grain type ones. The invention will further be explained by the following examples.
EXAMPLE 1 A solution prepared by warming to 70 C. a mixture of l5 g. of Compound I, 30 g. of di-n-butyl phthalate and 20 ml. of butyl acetate was added to 300 ml. of an aqueous solution of 1.0 g. of sodium dodecylbenzenesulfonate and 25 g. of gelatin. The mixture was stirred for 30 minutes in a homogenizer, and the whole amount of the mixture was mixed with 500 g. of a green-sensitive photographic emulsion.
After addition of 30 ml. of a 3% acetone solution of triethylene-phosphoramide and adjustment of the pH to 7.0, the resulting composition was applied to cellulose triacetate film to a dry-thickness of 5.0 104 cm.
The coating contained 5.8% X 10-3 mole of silver iodobromide and 7.2)(10-4 mole of the coupler per square meter. The lm was exposed and subjected to the following processing steps to yield a clear magenta image with an absorption maximum at 551 mit. The spectral absorption curve has been shown in FIG. 1 by curve a.
COLO R DEVELOPMENT PROCESSES Tempera- Period,
Step ture, C. minutes Color development 21 10 Rinsing 21 1 First fixing 21 4 Rinsing 21 3 Bleaching.. 21 3 Rinsing.. 21 2 Second fixing-. 21 3 5 5 Washing 18 20 The compositions used in the above processes are as follows Boric acid- 10 g. Borax--S g. Potassium ybromide---7 g.
EXAMPLE 2 A solution prepared by warming to 70 C. a mixture of l g. of Compound X, 30 g. of tricresyl phosphate, and 10 ml. of ethyl acetate was added to 100 ml. of an aqueous Solution containing 0.5 g. of sodium dodecyl sulfate and 7 g. of gelatin at 60 C., and the resulting mixture was stirred vigorously by means of an homogenizer to disperse the coupler nely together with the solvent.
The Whole amount of the emulsion thus obtained was added to 540 g. of a green-sensitive photographic emulsion. After addition of 30 ml. of 3% acetone solution of triethylenephosphoramide as a hardening agent and 7 g. of polyvinyl pyrrolidone, the resulting composition was applied to baryta paper as the middle layer to a dry-thickness of 4 104 cm. Its bottom layer was a` blue-sensitive photographic emulsion layer containing an emulsifed dispersion of coupler (L) having the following structure. On the middle layer thus formed was coated as the top layer a red-sensitive emulsion containing an emulsied dispersion of coupler (M) shown below.
(EO O 0121125 CH3 Cl l @commune EXAMPLE 3 A mixture of 6 g. of Compound IX and 18 g. of dibutyl phthalate was warmed to 80 C., and added to 50 ml. of an aqueous solution containing 5 g. of gelatin and 0.3 g. of sodium dodecylbenzenesulfonate, and the resulting mixture was stirred vigorously by means of an homogenizer to prepare an emulsied dispersion.
The whole amount of the coupler-containing emulsied dispersion was mixed with 200 g. of a photographic emulsion. After addition of ml. of a 3% acetone solution of triethylene phosphoramide as a hardening agent, the mixture was applied to a cellulose triacetate film to a dry-thickness of 6 10f4 cm. and dried. In this case, the coating contained 7.2X104 mol coupler and 5.8X10f3 mol silver iodobromide per square meter. The film was exposed to graduated intensities of light with aid of a sensitometer and developed for 6 minutes at 24 C. in a developer of the following composition and then washed with water for l5 minutes at the same temperature; then it was exposed uniformly to white light and colordeveloped as described in Example 1.
Black and white developer (pH 10.8):
Water-1,000 ml. Metol-3 g. Sodium sulite (anhydrous)-5O g. Sodium carbonate, monohydrate-lOO g. Potassium thiocyanate3.6 g. Potassium bromide-2 g.
The reversal magenta color image thus obtained had an absorption maximum at 554 mp.. The spectral absorption curve has been shown in FIG. 3 of the attached drawing as curve e.
EXAMPLE 4 Two films (P) and (Q) were prepared as follows:
Film (P).-A solution prepared by heating to 70 C. a mixture of 15 g. of Compound IV, 30 g. of tricresyl phosphate and 20 ml. of butyl acetate was mixed with 300 ml. of an aqueous solution containing 25 g. of gelatin and 1.0 g. of sodium dodecylbenzenesulfonate. The mixture Was stirred for 30 minutes by means of a homoblender to disperse the coupler. The whole amount of the dispersion was mixed with 500 g. of photographic emulsion. After addition of 30 m1. of 3% acetone solution of trethylenephosphoramide as a hardening agent, the mixture was neutralized to pH 7.0 and was applied to a cellulose triacetate film to a dry-thickness of 5.0X10-4 cm. The coating contained 7.2 10*4 mol coupler and 5.8)(10-3 mol silver iodobromide per square meter.
Film (Q).-A similar procedure to the preparation of Film (P) was repeated using Compound B (control) instead of Compound IV.
The films were exposed to graduated intensities of light by means of a sensitometer and processed in the same manner as Example 1. Their photographic properties are as follows:
Sensitivity Maximum Sample Coupler Fog (relative) Gamma density Film P IV 0.09 2.20 3.05 Film Q B 0. 08 100 1. 61 2. 16
The fastness of the color image was tested, and the results are shown in the following table:
(B), (A),initial increase (C),initial (D), initial NOTE: (A) Fading (percent) by light (after 40 hours, exposure in a xenon tester) (B) Coloring of uncoupled portion by light (after 40 hours, exposure in a xenon tester), (C) Fading (percent) at a high temperature and a high humidity (60 C. 75% RH for 20 days), and (D) Fading (percent) by heat (at 120 C., for 4 hours).
From the above results, it is clear that Film (P), (Coupler IV) according to the present invention, gives a high sensitivity, a high gamma and a high maximum density compared with those of Film Q containing the conventional coupler (B), and that the color image 0btained is markedly fast to light, heat and humidity. Moreover, even intense radiation did not cause yellowing due to the remaining coupler.
The spectral absorption curve of the color image formed by Compound IV has been shown in FIG. 2 of the attached drawing by curve c.
What is claimed is:
1. A color photographic silver halide emulsion containing at least one magenta coupler of the formula wherein RCO represents an acyl group having from 18 to 25 carbon atoms and Ar represents a phenyl group having at least one substituent at the ortho position, the substituent being one selected from the group consisting of halogens, alkyl groups and alkoxyl groups.
2. A color photographic silver halide emulsion as delined in claim 1 where the compound is:
tert. cmu-@ oomooNH@ l tort. 05H11 NHCONH-C-OHg 3. A color photographic silver halide emulsion as dened in claim 1 where the compound is:
sec. @LIQ-H20 ONE@ NHG ONH-C--CHz 4. A color photographic silver halide emulsion as dened in claim 1 Where the compound is:
CusHsxC 0 )NoHzcHzooNH-Q 5. A color photographic silver halide emulsion as dened in claim 1 where the compound is:
tert. 05H11- -OCHaCONH tert. 05H11 NHG ONH-IC- CH2 Cl- -Cl 6. A color photographic silver halide emulsion as dened in claim 1 where the compound is:
@-00150 ONE@ SBC. 05H11- sec. 05H11 NHCONH-C--Clh N C=O Cl- -Cl 7. A a color photographic silver halide emulsion as defined in claim 1 where the compound is:
@-oouzoomr@ tert. 05H11 NHCONH-C-CHz N C=O 8. A color photographic silver halide emulsion as delined in claim 1 where the compound is:
9. A color photographic silver halide emulsion as defined in claim 1 where the compound is:
10. A color photographic silver halide emulsion as dened in claim 1 where the compound is:
17 18 11. A color photographic silver halide emulsion as 13. A color photographic silver halide emulsion as defined in claim 1 where the compound is: defined in claim 1 where the compound is:
l o oHCoNH-Q terr.. cmu-Q-oomoolm-Q l meenam NHooNn-c-om N :0
o=o N o1 o1- c1 on a" l 14. A color photographic silver halide emulsion as I O CHS defined in claim 1 where the compound is:
owHuooNH-Q l 12. A color photographic silver halide emulsion as NHCONH-|3-(|JH2 defined in claim 1 where the compound is: N /C=0 nernoHuQ-oomooNH-Q C1 terLCsHu llIHooNH-C--CH C|=0 30 \N/ References Cited l UNITED STATES PATENTS C1' CH 3,393,071 7/1968 Monbaliu et a1. 96-100 3,462,270 8/1969 Eynde et al 96-100 H J. TRAVIS BROWN, Primary Examiner U.S. Cl. X.R. 96-74; 260-310
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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
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Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3086855A (en) * 1958-11-05 1963-04-23 Geigy Ag J R Herbicidal compositions and method
CH448113A (en) * 1960-07-21 1967-12-15 Ciba Geigy Process for the production of new triazines
NL267406A (en) * 1960-08-10
NL277028A (en) * 1961-04-19
CH441351A (en) * 1964-06-02 1967-08-15 Geigy Ag J R Process for the preparation of N2-substituted 2,4,6-triamino-1,3,5-triazines

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US3861923A (en) * 1972-05-31 1975-01-21 Fuji Photo Film Co Ltd Silver halide color photographic materials containing a 3-ureido-5-pyrazolone coupler and an aldehyde compound
US4061653A (en) * 1972-06-23 1977-12-06 Bayer Aktiengesellschaft 1-Substituted-3-amino-pyrazol-5-ones
US3939176A (en) * 1972-07-03 1976-02-17 Minnesota Mining And Manufacturing Company Magenta couplers
US4081596A (en) * 1973-04-17 1978-03-28 Bayer Aktiengesellschaft Pyrazol-5-ones
US4005215A (en) * 1973-04-17 1977-01-25 Bayer Aktiengesellschaft Pyrazol-5-ones
US4032646A (en) * 1973-04-17 1977-06-28 Bayer Aktiengesellschaft Pyrazol-5-ones
US4045571A (en) * 1973-04-17 1977-08-30 Bayer Aktiengesellschaft Pyrazol-5-ones
US4056533A (en) * 1973-04-17 1977-11-01 Bayer Aktiengesellschaft Pyrazol-5-ones
US4000294A (en) * 1973-04-17 1976-12-28 Bayer Aktiengesellschaft Pyrazol-5-ones
US3992404A (en) * 1973-04-17 1976-11-16 Bayer Aktiengesellschaft Pyrazol-5-ones
USRE30420E (en) * 1973-04-17 1980-10-21 Bayer Aktiengesellschaft Pyrazol-5-ones
US4288446A (en) * 1973-04-17 1981-09-08 Bayer Aktiengesellschaft Pyrazol-5-ones
US4069334A (en) * 1973-12-20 1978-01-17 Bayer Aktiengesellschaft Pyrazole derivatives
US4053621A (en) * 1974-06-06 1977-10-11 Bayer Aktiengesellschaft 1-[2-(βNaphthyloxy)ethyl]-3-methylpyrazolone-(5) and antithrombotic and antithrombolytic compositions and methods utilizing them
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
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
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
US5252446A (en) * 1991-09-25 1993-10-12 Konica Corporation Silver halide color photographic light-sensitive material comprising a 1-pentachlorinated phenyl-5-pyrazolone coupler and specific red sensitizing dyes
US5275926A (en) * 1991-09-25 1994-01-04 Konica Corporation Silver halide color photographic light-sensitive material
EP0711804A2 (en) 1994-11-14 1996-05-15 Ciba-Geigy Ag Latent light stabilizers
EP0782044A1 (en) 1995-12-27 1997-07-02 Konica Corporation Silver halide light-sensitive color photographic material

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DE1597572C3 (en) 1975-09-18
AT286998B (en) 1971-01-11
FR7305M (en) 1969-09-29
SE361477B (en) 1973-11-05
GB1142546A (en) 1969-02-12
SE361478B (en) 1973-11-05
GB1142553A (en) 1969-02-12
AT288410B (en) 1971-03-10
CH508900A (en) 1971-06-15
NL6710011A (en) 1968-01-22
DE1670529C3 (en) 1974-01-10
BE701268A (en) 1967-12-18
DE1597572A1 (en) 1970-05-06
US3530121A (en) 1970-09-22
SE335859B (en) 1971-06-14
CH507263A (en) 1971-05-15
DE1670529B2 (en) 1973-06-07
IL28200A (en) 1972-02-29
DE1597572B2 (en) 1975-02-06
DE1670529A1 (en) 1972-03-02
BE701427A (en) 1967-12-18

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