US3711286A - Light-sensitive silver halide color photographic emulsion - Google Patents

Light-sensitive silver halide color photographic emulsion Download PDF

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US3711286A
US3711286A US00157609A US3711286DA US3711286A US 3711286 A US3711286 A US 3711286A US 00157609 A US00157609 A US 00157609A US 3711286D A US3711286D A US 3711286DA US 3711286 A US3711286 A US 3711286A
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light
silver halide
compound
photographic emulsion
halide color
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K Sakamoto
T Endo
M Iwama
I Inoue
Y Takei
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Konica Minolta Inc
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Konica Minolta Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • C07D207/408—Radicals containing only hydrogen and carbon atoms attached to ring carbon atoms
    • C07D207/412—Acyclic radicals containing more than six carbon atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30523—Phenols or naphtols couplers
    • 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
    • G03C7/34—Couplers containing phenols
    • G03C7/344—Naphtholic couplers

Definitions

  • This invention relates to a light-sensitive gelatinosilver halide color photographic emulsion containing a new cyan coupler compound of the general formula wherein R is hydrogen atom or methyl group; R is an aliphatic hydrocarbon radical of eight to carbon atoms; n is an integer of l to 4; m is an integer of l or 2; A is a divalent group OH I E H c OHNCHgCHzNHC o onto-Gt 05H
  • This compound has good solubility in high boiling solvents, but it should be synthesized by using, as a starting material, di tert.amyl-phenoxyacetic acid which is very expensive.
  • Another example is a coupler of the formula CO(CHz)g-CH which is disclosed in Japanese Patent Publication No. 2837/1964. This compound exhibits improved solvent solubility but it should be synthesized through several complicated steps.
  • an alkali-soluble coupler having ing group i.e., an alkali-soluble coupler having ing group.
  • the coupler compounds of the present invention are readily soluble in high boiling solvents such as tricresyl phosphate, dibutyl phthalate, etc. and they are not liable to be separated from coatings after drying.
  • Developed color images obtained with the coupler compounds of the invention have good spectral absorption characteristics and are stable against light, heat and humidity. Remarkable improvements attained by this invention can be considered due to the existence of a long chain alkyl succinimide group in the molecular structure of new coupler compounds.
  • the coupler compound of the above-indicated general formula can be synthesized by condensing lhydroxy-2-naphthoic amide derivative having a primary amino group with a long chain alkyl succinic anhydride in hot'acetic acid.
  • the coupler is dissolved in pyridine and then brought into coupling reaction with a diazonium compound, thereby to obtain 4-arylazo derivative of high purity.
  • the long chain alkyl succinic anhydride which is the main starting material is prepared in commercial scale by using malonic ester and long chain alkyl halide.
  • the resulting mixture is emulsified by way of a high speed rotary mixer or a colloid mill.
  • the resulting emulsion is then directly added to a silver halide photographic emulsion which in turn is coated on a film base or baryta paper and dried to remove almost all part of the low boiling solvent.
  • the above coupler emulsion is once cooled, set, finely cut and washed with water to remove the low boiling solvent, and thereafter is added to a silver halide photographic emulsion which is coated on a photographic support and dried.
  • the amount of a coupler to be added to a photographic emulsion may vary within the preferred range of 10 to 100 g.
  • silver halide photographic emulsions can be used, which include silver chloride, silver iodide, or silver chlorobromide emulsion.
  • Such emulsions may contain sulfur sensitizer, reducing sensitizer, noble metal sensitizer, etc. They can further contain any photographic additives conventionally known, e.g., antifoggant, stabilizer, stain inhibitor, coating aid, etc.
  • Optical sensitizers for photographic emulsions e.g., carbocyanine dyes, merocyanine dyes, etc., also can be used.
  • a coupler useful in this invention may be incorporated in one or both of the two emulsion layers which are coated in superposed relationship and which have color sensitivity over the same spectral region. Further, the coupler can be used in combination with any conventionally known coupler.
  • a light-sensitive photographic material obtained by using a light-sensitive color-photographic emulsion of the invention is treated, after imagewise exposure, with a p-phenylenediamine type developer solution and then subjected to bleaching and fixing thereby to give a cyan color image having good spectral absorption characteristics with absorption maximum at 680-690 g.) and good transparency.
  • Suitable developers useful for the invention typically include the sulfates, sulfites and hydrochlorides of the following:
  • N-(2-n-octylsuccinimidoethyl)-1- hydroxy-Z-naphthoamide the compound (1 230 g. of N-(2-aminoethyl)-1-hydroxy-2-naphthoamide and 212 g. of n-octylsuccinic anhydride are dissolved in 2 l. of acetic acid. The resulting solution is boiled at reflux for 7 hours and then added with 2 l. of methanol. The reaction mixture is allowed to stand at room temperature and the seperated crystalline mass is collected by suction filtration, washed with methanol, and dried. Recrystallization from acetonitrile gives 160 g. of white crystalline powder (the compound 1) The compounds (2) to (8) can be synthesized in the same manner as of the compound (1).
  • the benzene layer is dehydrated and distilled to remove benzene.
  • the residue is added with n-hexane and the mixture is allowed to remain.
  • the separated mass is collected by filtration, washed with n-hexane and dried. 200 g. of pale brown crystalline powder is obtained.
  • EXAMPLE 1 20 g. of the coupler compound (2) is dissolved at 80C in a mixture of 20 ml. of dibutyl phthalate and 60 ml. of butyl acetate. The resulting solution is mixed with 10 ml. of an aqueous solution of 10 percent Alkanol B (alkyl naphthalene sulfonate produced by Du Pont, U.S.A.) and 200 ml. of an aqueous 5 percent gelatine solution. The resulting mixture is treated in a colloid mill. The thus obtained coupler dispersion is added to 1 kg. of a high speed gelatino-silver iodobromide photographic emulsion, which is then coated on a film base and dried.
  • Alkanol B alkyl naphthalene sulfonate produced by Du Pont, U.S.A.
  • the light-sensitive photographic film obtained is exposed to light and then treated at 20C for 10 minutes with a developing solution of the following formulation:
  • N,N-diethyl-p-phenylenediamine 2.5 g. hydrochloride Anhydrous sodium sulfite 2.0 g. Sodium carbonate monohydrate 82.0 g. Potassium bromide 2.0 g.
  • the developed film is treated in the ordinary manner by stopping and fixing and then, after washing with water for 10-15 minutes, treated for 5 minutes with a bleaching bath of the following formulation:
  • the film is washed with water for 5 minutes and further treated for 5 minutes in a fixing bath of the following formulation:
  • the film is washed with water for 20-25 minutes and dried. Clear cyan color image having absorption maximum at 690 p. is obtained.
  • the photographic film thus obtained is exposed to light and treated at 20C for 10 minutes with a developing solution of the formulation:
  • the film is subjected to secondary exposure using white light and then treated at 20C for 12 minutes with a developing solution of the formulation:
  • N,N-diethyl-p-phenylenediamine 5.0 g. hydrochloride Anhydrous sodium sulfite 2.0 g. Sodium carbonate (monohydi'ate) 82.0 g. Potzmsium bromide 1.0 g.
  • the film is followed by ordinary stopping, fixing, water' washing and bleaching steps. After washing for 20 minutes with running water and drying, clear cyan color positive image having absorption maximum at 685 p. is obtained.
  • EXAMPLE 3 10.0 g. of the coupler compound (6) is dissolved at 50C in 20 ml of dibutyl phthalate. The resulting solution is mixed with ml of an aqueous solution of 10 percent Alkanol B and 200 ml of an aqueous 5 percent 'gelatine solution. The resulting mixture is passed through a colloid mill several times to form a dispersion. The resulting dispersion is added to 500 g of a gelatino-silver chlorobromide emulsion, which is then coated on a baryta paper and dried.
  • the light-sensitive photographic material thus formed is exposed to light and then treated at C for 10 minutes with a developing solution of the following formulation:
  • Ethylenediaminetetraacetic acid 40.0 g. disodium salt
  • Ferric chloride 30.0 g. Sodium carbonate (monohydrat'e) 20.0 g.
  • Potassium bromide 30.0 g.
  • the coupler dispersion thus obtained is added to g of a high speed gelatino-silver bromoiodide emulsion, which is then coated on a film base and dried.
  • the light-sensitive photographic material thus obtained is then exposed to light and treated with the developing solution as usedin the Example 1.
  • a red positive image having absorption maximum of 500 p. and a cyan color image having absorption maximum at 690 p. are obtained.
  • the coupler dispersion thus obtained is added to 100 g of a red sensitive high speed gelatino-silver iodobromide emulsion, which is then coated on a film base and dried.
  • a light-sensitive silver halide color photographic emulsion having dispersed therein a solution of a cyan coupler in a high boiling solvent, said cyan coupler having the general formula wherein R is hydrogen or a methyl group, R is an aliphatic hydrocarbon radical of eight to 20 carbon atoms, n is an integer of l 4, m is l or 2, A is a divalent group of 2 or -0- E); and
  • x is hydrogen, a halogen, anaryl azo group or an aryl azo group substituted by a lower alkoxycarbonyl, lower acyl, lower alkyl or lower alkoxygroup.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

Light-sensitive gelatino-silver halide color photographic emulsions containing a new cyan coupler compound of the formula


X is hydrogen, halogen or an arylazo group.
D R A W I N G

Description

United States Patent 1 Sakamoto et al.
[54] LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC EMULSION [75] Inventors: Kenro Sakamoto, Tokyo; Takaya Endo, Hino-shi, Tokyo; Masakuni Iwama, Yamato-cho, Tokyo; Isaburo Inoue; Yutaka Takei, both of Hino-shi, Tokyo, all of Japan [73] Assignee: Konishiroku Photo Industry Co., Ltd., Tokyo, Japan [22] Filed: June 28, 1971 [21] Appl. No; 157,609
Related US. Application Data [63] Continuation of Ser. No 796,927, March 5, 1969,
abandoned [52] US. Cl. ..96/100, 96/562, 96/9 [51] Int. Cl. ..G03c 1/40 [58] Field of Search ..96/100 [56] References Cited UNITED STATES PATENTS Anderson ..96/ l 00 Anderson ..96/1OO 1 1 Jan. 16, 1973 graphic cmulsions containing a new cyan coupler compound of the formula wherein R is hydrogen or methyl; R is an aliphatic hydrocarbon radical of eight to 20 carbon atoms; n is 1 to 4; m is l or 2; A is a divalent group X is hydrogen, halogen or an arylazo group.
9 Claims, No Drawings LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC EMULSION This Application isa continuation of our earlier application Ser. No. 796,927, filed Feb. 5, 1969 and now abandoned.
This invention relates to a light-sensitive gelatinosilver halide color photographic emulsion containing a new cyan coupler compound of the general formula wherein R is hydrogen atom or methyl group; R is an aliphatic hydrocarbon radical of eight to carbon atoms; n is an integer of l to 4; m is an integer of l or 2; A is a divalent group OH I E H c OHNCHgCHzNHC o onto-Gt 05H This compound has good solubility in high boiling solvents, but it should be synthesized by using, as a starting material, di tert.amyl-phenoxyacetic acid which is very expensive. Another exampleis a coupler of the formula CO(CHz)g-CH which is disclosed in Japanese Patent Publication No. 2837/1964. This compound exhibits improved solvent solubility but it should be synthesized through several complicated steps.
We have now found that a compound of the aboveindicated formula is quite useful as a protected coupler. This compound can be synthesized by simple cyclization, with splitting off of water, of a long chain alkyl succin-monoamide type coupler compound which is conventionally known as so-called Agfa-type coupler,
i.e., an alkali-soluble coupler having ing group.
The coupler compounds of the present invention are readily soluble in high boiling solvents such as tricresyl phosphate, dibutyl phthalate, etc. and they are not liable to be separated from coatings after drying. Developed color images obtained with the coupler compounds of the invention have good spectral absorption characteristics and are stable against light, heat and humidity. Remarkable improvements attained by this invention can be considered due to the existence of a long chain alkyl succinimide group in the molecular structure of new coupler compounds.
The coupler compound of the above-indicated general formula can be synthesized by condensing lhydroxy-2-naphthoic amide derivative having a primary amino group with a long chain alkyl succinic anhydride in hot'acetic acid. The coupler is dissolved in pyridine and then brought into coupling reaction with a diazonium compound, thereby to obtain 4-arylazo derivative of high purity. The long chain alkyl succinic anhydride which is the main starting material is prepared in commercial scale by using malonic ester and long chain alkyl halide.
The following are typical couplers useful in this invention. However, it should be understood that they are not construed as limiting the scope of the invention.
a diffusion-inhibit- C O-CH2 I c o-cu-omHawtn) 60 OCH;
in the actual use of cyan coupler of this invention, it
CO-CH? propionate, etc. The mixture of the high boiling solvent and low boiling one also may be used. The resulting solution is mixed with an aqueous gelatine solution,
containing a surface active agent. The resulting mixture is emulsified by way of a high speed rotary mixer or a colloid mill. In one way, the resulting emulsion is then directly added to a silver halide photographic emulsion which in turn is coated on a film base or baryta paper and dried to remove almost all part of the low boiling solvent. in another way, the above coupler emulsion is once cooled, set, finely cut and washed with water to remove the low boiling solvent, and thereafter is added to a silver halide photographic emulsion which is coated on a photographic support and dried. The amount of a coupler to be added to a photographic emulsion may vary within the preferred range of 10 to 100 g. per mole of silver halide contained in the emulsion, but this range is not critical. Any types of silver halide photographic emulsions can be used, which include silver chloride, silver iodide, or silver chlorobromide emulsion. Such emulsions may contain sulfur sensitizer, reducing sensitizer, noble metal sensitizer, etc. They can further contain any photographic additives conventionally known, e.g., antifoggant, stabilizer, stain inhibitor, coating aid, etc. Optical sensitizers for photographic emulsions, e.g., carbocyanine dyes, merocyanine dyes, etc., also can be used. A coupler useful in this invention may be incorporated in one or both of the two emulsion layers which are coated in superposed relationship and which have color sensitivity over the same spectral region. Further, the coupler can be used in combination with any conventionally known coupler.
A light-sensitive photographic material obtained by using a light-sensitive color-photographic emulsion of the invention is treated, after imagewise exposure, with a p-phenylenediamine type developer solution and then subjected to bleaching and fixing thereby to give a cyan color image having good spectral absorption characteristics with absorption maximum at 680-690 g.) and good transparency.
The above explanation is given in connection with use of colorless-coupler compounds. lf certain arylazo compounds (for example, the compounds (lO)-(l2)) which are orange red or red color are used, the photographic material containing these when subjected to imagewise exposure and color development will give a cyan color negative image and an orange-red or red color positive image simultaneously. The positive color image serves as a masking image to compensate undesired absorptions at the blue and green regions due to the cyan color negative image when this cyan color image is to be printed on a positive material.
Suitable developers useful for the invention typically include the sulfates, sulfites and hydrochlorides of the following:
N,N-diethyl-p-phenylene diamine,
N-ethyl-N-B-methanesulfonamidoethyl-3-methyl-4- aminoaniline,
N-ethyl-N-hydroxyethyl-p-phenylene diamine,
N-ethyl-N-hydroxyethyl-Z-methyl-p-phenylene diamine, and
N,N-diethyl-Z-methyl-p-phenylene diamine.
Typical synthetic procedures for the couplers will be mentioned below.
Synthesis 1. N-(2-n-octylsuccinimidoethyl)-1- hydroxy-Z-naphthoamide (the compound (1 230 g. of N-(2-aminoethyl)-1-hydroxy-2-naphthoamide and 212 g. of n-octylsuccinic anhydride are dissolved in 2 l. of acetic acid. The resulting solution is boiled at reflux for 7 hours and then added with 2 l. of methanol. The reaction mixture is allowed to stand at room temperature and the seperated crystalline mass is collected by suction filtration, washed with methanol, and dried. Recrystallization from acetonitrile gives 160 g. of white crystalline powder (the compound 1) The compounds (2) to (8) can be synthesized in the same manner as of the compound (1).
Synthesis 2. N-[4-(2-n-dodecylsuccinimido-phenoxy)-butyl]-l-hydroxy-Z-naphthoamide (the compound (9) 350 g. of N-[4-(2-aminophenoxy)-butyl]-1-hydroxynaphthoamide and 268 g. of n-dodecylsuccinic anhydride are dissolved in 1.5 l. of acetic acid. The resulting solution is boiled at reflux for 7 hours. The reaction mixture is poured into 20 l. of water. The separated oily mass is extracted with benzene and washed with 5 percent aqueous sodium carbonate solution. The benzene layer is dehydrated and distilled to remove benzene. The residue is added with n-hexane and the mixture is allowed to remain. The separated mass is collected by filtration, washed with n-hexane and dried. 200 g. of pale brown crystalline powder is obtained.
Synthesis 3. N-[3-(n-dodecylsuccinimido)-propyl]- 1-hydroxy-4-(2-ethoxycarbonyl-phenylazo)-(the compound (10) 165.2 g. of ethyl anthranilate dissolved in dilute hydrochloric acid is added with an aqueous sodium nitrite solution. The diazotized solution is added at room temperature to 490 g. of N-[S-(n-dodecyl-succinimido )-propyl]- l -hydroxy-2-naphthoamide dissolved in 4 1. of pyridine, with stirring. Stirring is continued for 30 minutes at room temperature. To the mixture, 5 l. of acetonitrile is added. The separated crystalline mass is collected by filtration, washed with acetonitrile and dried. Recrystallization from n-hexane and ethyl acetate (1:1) gives 580 g. of red crystalline powder (the compound (10) The compounds (11) to (13) can be synthesized in the same manner as above.
The melting points and elementary analyses of the thus obtained couplers are listed in Table 1.
EXAMPLE 1 20 g. of the coupler compound (2) is dissolved at 80C in a mixture of 20 ml. of dibutyl phthalate and 60 ml. of butyl acetate. The resulting solution is mixed with 10 ml. of an aqueous solution of 10 percent Alkanol B (alkyl naphthalene sulfonate produced by Du Pont, U.S.A.) and 200 ml. of an aqueous 5 percent gelatine solution. The resulting mixture is treated in a colloid mill. The thus obtained coupler dispersion is added to 1 kg. of a high speed gelatino-silver iodobromide photographic emulsion, which is then coated on a film base and dried.
The light-sensitive photographic film obtained is exposed to light and then treated at 20C for 10 minutes with a developing solution of the following formulation:
N,N-diethyl-p-phenylenediamine 2.5 g. hydrochloride Anhydrous sodium sulfite 2.0 g. Sodium carbonate monohydrate 82.0 g. Potassium bromide 2.0 g.
Water to make up 1 l.
The developed film is treated in the ordinary manner by stopping and fixing and then, after washing with water for 10-15 minutes, treated for 5 minutes with a bleaching bath of the following formulation:
Potassium ferricyanide Potassium bromide Water to make up 1 l.
I00 g. g.
The film is washed with water for 5 minutes and further treated for 5 minutes in a fixing bath of the following formulation:
Sodium thiosulfate pentahydrate Water to make up 1000 ml.
The film is washed with water for 20-25 minutes and dried. Clear cyan color image having absorption maximum at 690 p. is obtained.
EXAMPLE 2 TABLE 1 Elementary analysis (percent) Calcd. Found Solvent for recrystallization C H N C H N Acetonitrlle 70. 72 7. 6. 60 70. 50 7. 42 6. 38 n-Hexane. 72.84 8. 56 5. 66 72.55 8.61 5. 71 0 68.67 8.00 5.30 67.79 7.98 5.48 Ethanol... 74. 9. 40 4.84 74. 81 9. 77 5. 11 .do 77.08 8.52 4.39 76.10 8.91 4. 40 Methanol plus acetic acid. 73.13 7.93 4. 16 72. 87 8.35 4.40 Ethyl acetal 76. 64 8. 68 4. 47 76. 36 8.92 4. 54 ....do 75.19 8.71 4.18 75.37 9.06 4.34 n-Hexane 73.97 8.05 4. 66 73.93 8. 50 4. 92 n-Hexane plus ethyl acetate..- 69. 82 7. 51 8. 35 70.12 7. 8. 52 Ethanol plus n-Hexane 71. 22 7. 55 8. 75 71.04 7. 71 8. 99 Methanol 74. 38 8.06 7. 23 74. 26 8. 31 7. 42 Ethyl acetate 73. 50 7. 6.86 73.21 8. 21 6. 75
The following examples will explain the invention in detail, without limiting its scope thereto.
film base and dried.
The photographic film thus obtained is exposed to light and treated at 20C for 10 minutes with a developing solution of the formulation:
Metol Anhydrous sodium sulfite 603) 8- Hydroquinone 6.0 g. Anhydrous sodium carbonate 8- Potassium bromide 2- Water to make up 1000 ml.
After following ordinary stopping, film hardening and water-washing steps, the film is subjected to secondary exposure using white light and then treated at 20C for 12 minutes with a developing solution of the formulation:
N,N-diethyl-p-phenylenediamine 5.0 g. hydrochloride Anhydrous sodium sulfite 2.0 g. Sodium carbonate (monohydi'ate) 82.0 g. Potzmsium bromide 1.0 g.
Water to make up 1000 ml.
The film is followed by ordinary stopping, fixing, water' washing and bleaching steps. After washing for 20 minutes with running water and drying, clear cyan color positive image having absorption maximum at 685 p. is obtained.
EXAMPLE 3 10.0 g. of the coupler compound (6) is dissolved at 50C in 20 ml of dibutyl phthalate. The resulting solution is mixed with ml of an aqueous solution of 10 percent Alkanol B and 200 ml of an aqueous 5 percent 'gelatine solution. The resulting mixture is passed through a colloid mill several times to form a dispersion. The resulting dispersion is added to 500 g of a gelatino-silver chlorobromide emulsion, which is then coated on a baryta paper and dried.
The light-sensitive photographic material thus formed is exposed to light and then treated at C for 10 minutes with a developing solution of the following formulation:
N ethyl-N-hydroxyethyl-p-phenylene- 2.5 g. diamine sulfate Anhydrous sodium sulfite 2.0 g. l-lydroxyamine hydrochloride 1.0 g. Sodium carbonate (monohydrate) 82.0 g. Potassium bromide 2.0 g.
Water to make up i000 ml.
Ethylenediaminetetraacetic acid 40.0 g. disodium salt Ferric chloride 30.0 g. Sodium carbonate (monohydrat'e) 20.0 g. Potassium bromide 30.0 g. Sodium thiosulfate (pentahydrate) 200.0 g.
Water to make up 1000 ml The material is washed with water for 20 minutes and then treated for 2 minutes in a stabilizing bath and dried. A cyan color image having absorption maximum at 695 p. and excellent in fastness to light and heat as well as in storability is obtained.
8 EXAMPLE 4 2.0 g. of the coupler compound (10) is dissolved in the mixture of 2 ml of dibutyl phthalate and 6 ml of butyl acetate at C. The resulting solution is mixed with 1 ml of an aqueous solution of 10 percent Alkanol B and 20 ml of an aqueous 5 percent gelatine solution to form a dispersion.
The coupler dispersion thus obtained is added to g of a high speed gelatino-silver bromoiodide emulsion, which is then coated on a film base and dried.
The light-sensitive photographic material thus obtained is then exposed to light and treated with the developing solution as usedin the Example 1. A red positive image having absorption maximum of 500 p. and a cyan color image having absorption maximum at 690 p. are obtained.
EXAMPLE 5 2.0 g of the coupler compound (2) is dissolved in 5 ml of butyl acetate and the resulting solution is mixed with 1.5 ml of an aqueous solution of 10 percent A1- kanol and 20 ml of an aqueous 5 percent gelatine solution to form a dispersion.
The coupler dispersion thus obtained is added to 100 g of a red sensitive high speed gelatino-silver iodobromide emulsion, which is then coated on a film base and dried.
After exposure to light in the ordinary manner, the film is treated with the developing solution as used in the Example IV A clear cyan color image having absorption maximum of 685 u is obtained.
We claim:
1. A light-sensitive silver halide color photographic emulsion having dispersed therein a solution of a cyan coupler in a high boiling solvent, said cyan coupler having the general formula wherein R is hydrogen or a methyl group, R is an aliphatic hydrocarbon radical of eight to 20 carbon atoms, n is an integer of l 4, m is l or 2, A is a divalent group of 2 or -0- E); and
x is hydrogen, a halogen, anaryl azo group or an aryl azo group substituted by a lower alkoxycarbonyl, lower acyl, lower alkyl or lower alkoxygroup.
2. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula 3. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula C O-GH:
4. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula 5. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula 6. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula C OHN-CHr-CHr-CHz-O CO-OHQ 7. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula (JO-CH2 I N=N (5O OC H l N=N O C Ha 9. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula OCHa

Claims (8)

  1. 2. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula
  2. 3. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula
  3. 4. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula
  4. 5. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula
  5. 6. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula
  6. 7. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula
  7. 8. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula
  8. 9. A light-sensitive silver halide color photographic emulsion as claimed in claim 1, wherein said cyan coupler is a compound of the following structural formula
US00157609A 1968-02-07 1971-06-28 Light-sensitive silver halide color photographic emulsion Expired - Lifetime US3711286A (en)

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US15760971A 1971-06-28 1971-06-28

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312715A (en) * 1963-06-17 1967-04-04 Ilford Ltd Colour couplers and their production and use in colour photography
US3328419A (en) * 1963-06-17 1967-06-27 Ilford Ltd Colour couplers and their production and use in colour photography
US3383214A (en) * 1964-02-20 1968-05-14 Ilford Ltd Color photography utilizing color couplers which yield quinone imine or azamethine dye images
US3615605A (en) * 1967-03-22 1971-10-26 Konishiroku Photo Ind Light-sensitive silver halide color-photographic material containing naphthal color couplers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312715A (en) * 1963-06-17 1967-04-04 Ilford Ltd Colour couplers and their production and use in colour photography
US3328419A (en) * 1963-06-17 1967-06-27 Ilford Ltd Colour couplers and their production and use in colour photography
US3383214A (en) * 1964-02-20 1968-05-14 Ilford Ltd Color photography utilizing color couplers which yield quinone imine or azamethine dye images
US3615605A (en) * 1967-03-22 1971-10-26 Konishiroku Photo Ind Light-sensitive silver halide color-photographic material containing naphthal color couplers

Also Published As

Publication number Publication date
GB1211651A (en) 1970-11-11
DE1905864C3 (en) 1974-11-21
DE1905864B2 (en) 1974-04-18
DE1905864A1 (en) 1969-08-28

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