US3615502A - Color photographic development utilizing pyrazolone couplers - Google Patents

Color photographic development utilizing pyrazolone couplers Download PDF

Info

Publication number
US3615502A
US3615502A US24250A US3615502DA US3615502A US 3615502 A US3615502 A US 3615502A US 24250 A US24250 A US 24250A US 3615502D A US3615502D A US 3615502DA US 3615502 A US3615502 A US 3615502A
Authority
US
United States
Prior art keywords
color
pyrazolone
coupler
couplers
color photographic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US24250A
Other languages
English (en)
Inventor
Makoto Yoshida
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Application granted granted Critical
Publication of US3615502A publication Critical patent/US3615502A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/32—Colour coupling substances
    • G03C7/36—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

  • OPTiCAL DENSITY 400 500 660 700 WAVE LENGTH (nm) WAVE LENGTH (nm) INVENTOR MAKOTO YOSHIDA BY 7411 444 ATTORNEYS COLOR PHOTOGRAPHIC DEVELOPMENT UTILIZING PYRAZOLONE COUPLERS BACKGROUND OF THE INVENTION 1.
  • the present invention relates generally to color photography and more particularly to a color developer containing an improved coupler.
  • couplers There are two types of such couplers. The first is a coupler which is incorporated into a developer. The second is a coupler which is incorporated into a photographic emulsion layer prior to the exposure of the layer.
  • Such color development is generally performed by a subtractive color process, and couplers that fonn cyan, magenta, and yellow dyes are employed in the color development. Further it is necessary in color development processes, to employ couplers which form'dyes having desirable hues and transparencies.
  • the magenta-forming coupler is ideally required to form a dye having such a color hue that it completely absorbs green light but is completely transparent to both blue and red light.
  • the granularity of the dye particles formed be fine and the granularity contrast be low. This is particularly important in order to improve the sharpness of the image. It is further necessary that the dye formed be stable to heat, moisture, etc., and, in particular, it is most important that the dye possess excellent stability in the presence of light.
  • British Patent No. 886,723 specifically discloses the use of l-(2,4,6-trichlorophenyl)-3-(4-nitroanilino)- 5-pyrazolone.
  • US Pat. No. 3,152,896 relates to the use of l- (2,6-dichIoro-4-negative group-substituted phenyl)-3-anilino- S-pyrazolone.
  • British Patent No. 956,261 relates to the use of l-aryl-3(2-substituted anilino)-5-pyrazolone.
  • Belgian Patent No. 682,384 is concerned with the use of l- (2,5-dichlorophenyl)-3-(4-nitroanilino)-5-pyrazolone.
  • an object of the present invention is to provide a color developer containing a magenta coupler which produces a dye having excellent light fastness and excellent granularity.
  • Another object of the present invention is to provide'a color developer containing an improved coupler capable of forming a magenta dye having excellent color hue and a' magenta image sufiiciently satisfying the aforesaid requirements.
  • a further object of the present invention is to provide an improved magenta coupler to be used in a color developer for providing a magenta image sufficiently satisfying the aforesaid requirements.
  • magenta coupler a l-(2,6-dichloro-4-positive group-substituted phenyl)-3-(4-nitroanilino)-5-pyrazolone, which compounds are characterized by possessing a positive methyl or methoxy group in the 4-position of the l-phenyl nucleus and also possessing chlorine atoms in the 2- and 6- positions thereof.
  • magenta coupler of the instant invention is represented by the following general formula:
  • R represents a member selected from the group consisting of a methyl group and a methoxy group.
  • FIGS. 1 and 2 of the accompanying drawings are shown the comparison between the spectral absorption curves E and F of color images formed by the coupling reaction of couplers A and B of the present invention and the oxidation product of a color developing agent, 2-methyl-4-N-ethyl-N-methanesulfoamino ethylamino aniline, according to the process shown in example 1 and the spectral absorption curves G and H of the color images obtained by that of the control couplers C and D and the oxidation product of the same color developing agent as above.
  • the structural formulas of Couplers A and B of the present invention, as well as control Couplers C and D, are set forth below.
  • the couplers A and B of the present invention have sharper absorption curves, less cyan and yellow components, and better absorption characteristics than the control coupler C or D. That is, as will be understood from table 1, the longer wave length side value AA L and the shorter wave length side value AA S are smaller in couplers A and B than in either of the control couplers C and D. Also, the values of D /DA and D IDA are much smaller in couplers A and B than in the control couplers C and D.
  • magenta is a color between cyan and yellow, it is required, from the view point of color reproduction for color photography, that the absorption curve thereof be sharp and to have as small as possible proportions of unnecessary cyan and yellow components
  • the magenta coupler of the present invention sufficiently fulfills these requirements and is therefore excellent in comparison with conventional couplers.
  • each sample having the color image corresponding to the spectral absorption curve shown in the accompanying drawing was exposed for 50 hours to a XF-2O type xenon lamp Fade Tester manufactured by K .K. Shimazu Seisakusho and the fading of the color image was then measured.
  • the results are shown in table 3, which shows that the color image obtained from the couplers of the present invention had better light fastness than those obtained from the control couplers.
  • control coupler D is similar to coupler B of this invention in that the l-phenyl nucleus has two chlorine atoms and one methyoxy group, and the molecular formula and the molecular weight of these two couplers are completely the same. The difference between them is only in the positions of the two chlorine atoms. Thus, the mere difference in the positions of chlorine atoms is seen to produce a decisive change in the photographic properties of the coupler.
  • the coupler of the present invention can be used not only for natural color photography but also for monochromatic or dichromatic photography.
  • the couplers of the present invention may generally be prepared according to the processes disclosed in British Patent No. 886,723 or Belgian Patent No. 682,384. Examples of preparing the couplers of this invention are shown below:
  • EXAMPLE 1 A photographic light-sensitive film prepared by applying an ordinary green-sensitive silver iodobromide emulsion to a film and drying was exposed to green light using a stage-type wedge. After developing the exposed film in a black and white developer for 3 minutes, the film was subjected to reversal exposure with green light, developed for 5 minutes in a magenta developer containing the Coupler A of the present invention, and washed with water.
  • the developed film was Subjected to silver bleaching by an ordinary process and fixed in a hypo-containingfixer, whereby a positive magenta image having excellent transparency was obtained.
  • the spectral absorption curve of the color image is shown as curve E. in the accompanying drawing.
  • compositions of the black and white developer and the magenta developer were as follows;
  • EXAMPLE 3 By followingthe same procedure as in example 1, but using a magenta developer having the following composition instead of the developer of example l, a positive magenta image having excellent transparency and A at 545 rn p. was obtained.
  • EXAMPLE 4 A multilayer reversal color photographic film of a type to be developed in color developers containing couplers was exposed, developed for 3 minutes in the black and white developer of examplewashed with water, subjected to reversal exposure with red light, and developed for 4 minutes in a cyan developer havingthe following composition.
  • diethylaminoaniline hydrochloride 1.5 g. MonobenzyLpaminophenol 0.4 g. Methanol 5 ml.
  • the developed film was washed with water, exposed to blue light, and then developed for 4 minutes in a yellow developer having the following composition;
  • magenta developer having the following composition
  • a silver halide color photographic developing process which comprises color developing an exposed silver halide image using a solution containing an aromatic primary amino developing agent and couple of the formula wherein R is a member selected from the group consisting of a methyl group and a methoxy group.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US24250A 1969-04-07 1970-03-31 Color photographic development utilizing pyrazolone couplers Expired - Lifetime US3615502A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP44026266A JPS4818858B1 (ja) 1969-04-07 1969-04-07

Publications (1)

Publication Number Publication Date
US3615502A true US3615502A (en) 1971-10-26

Family

ID=12188449

Family Applications (1)

Application Number Title Priority Date Filing Date
US24250A Expired - Lifetime US3615502A (en) 1969-04-07 1970-03-31 Color photographic development utilizing pyrazolone couplers

Country Status (7)

Country Link
US (1) US3615502A (ja)
JP (1) JPS4818858B1 (ja)
DE (1) DE2016587C3 (ja)
FR (1) FR2042962A5 (ja)
GB (1) GB1257286A (ja)
NL (1) NL7004787A (ja)
SE (1) SE350133B (ja)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3992404A (en) * 1973-04-17 1976-11-16 Bayer Aktiengesellschaft Pyrazol-5-ones
US4000294A (en) * 1973-04-17 1976-12-28 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
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
US4056533A (en) * 1973-04-17 1977-11-01 Bayer Aktiengesellschaft Pyrazol-5-ones
US4061653A (en) * 1972-06-23 1977-12-06 Bayer Aktiengesellschaft 1-Substituted-3-amino-pyrazol-5-ones
US4069334A (en) * 1973-12-20 1978-01-17 Bayer Aktiengesellschaft Pyrazole derivatives
US4081596A (en) * 1973-04-17 1978-03-28 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

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5383857U (ja) * 1976-12-14 1978-07-11

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061653A (en) * 1972-06-23 1977-12-06 Bayer Aktiengesellschaft 1-Substituted-3-amino-pyrazol-5-ones
US3992404A (en) * 1973-04-17 1976-11-16 Bayer Aktiengesellschaft Pyrazol-5-ones
US4000294A (en) * 1973-04-17 1976-12-28 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
US4081596A (en) * 1973-04-17 1978-03-28 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

Also Published As

Publication number Publication date
FR2042962A5 (ja) 1971-02-12
DE2016587C3 (de) 1975-11-13
DE2016587B2 (de) 1975-04-03
DE2016587A1 (de) 1970-10-29
NL7004787A (ja) 1970-10-09
JPS4818858B1 (ja) 1973-06-08
GB1257286A (ja) 1971-12-15
SE350133B (ja) 1972-10-16

Similar Documents

Publication Publication Date Title
US2600788A (en) Halogen-substituted pyrazolone couplers for color photography
US3061432A (en) Pyrazolino benzimidazole color coupler
US4004929A (en) Color corrected photographic elements
US3615502A (en) Color photographic development utilizing pyrazolone couplers
US3152896A (en) Magenta-forming couplers
US4009038A (en) Silver halide color photographic materials
US3811890A (en) Silver halide color photographic material
JPS6015058B2 (ja) 新規なるマゼンタ形成性カラ−カツプラ−ならびに写真におけるその利用
US3746539A (en) Color photographic light-sensitive materials for color prints showingexcellent color reproduction
US3725072A (en) Color photographic light-sensitive materials containing a novel yellow-forming coupler
US2976146A (en) Novel cyan-forming couplers
DE2626821A1 (de) Farbphotographisches aufzeichnungsmaterial
US3488193A (en) Silver halide emulsions containing naphthol color couplers
US3677764A (en) Silver halide emulsion containing purple coupler for color photography and process of making the same
US3926634A (en) Color silver halide photographic materials containing couplers having an oleophilic group
JPH0314168B2 (ja)
US3503741A (en) Silver-dye-bleach process utilizing formazan dyes
US3551156A (en) Light sensitive silver halide materials containing yellow-forming couplers
JPH01553A (ja) 新規なシアンカプラーを含有するハロゲン化銀カラー写真感光材料
JPS63153548A (ja) ハロゲン化銀カラ−写真感光材料
US3642485A (en) Color-photographic silver halide materials containing colored and uncolored couplers
US3576635A (en) Light-sensitive silver halide color-photographic material
US2411951A (en) 4,4'-bis (pyrazolone) couplers for color photography
US3598594A (en) Photographic material for the silver dye bleaching process
US2500487A (en) Yellow diffusion-fast color formers of the benzimidazole class