US3556799A - Light-sensitive silver halide color photographic material containing a mono-pyrazolone coupler and a bis-pyrazolone compound - Google Patents
Light-sensitive silver halide color photographic material containing a mono-pyrazolone coupler and a bis-pyrazolone compound Download PDFInfo
- Publication number
- US3556799A US3556799A US666936A US3556799DA US3556799A US 3556799 A US3556799 A US 3556799A US 666936 A US666936 A US 666936A US 3556799D A US3556799D A US 3556799DA US 3556799 A US3556799 A US 3556799A
- Authority
- US
- United States
- Prior art keywords
- pyrazolone
- bis
- mono
- light
- photographic material
- 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
Links
Classifications
-
- 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
- R is alkyl, aryl or substituted aryl and R is hydrogen, alkyl, aryl, substituted aryl or a heterocyclic radi cal with the proviso that at least one of R and R contains an aliphatic hydrocarbon radical of 12-20 carbon atoms.
- the invention is concerned with a light-sensitive, color photographic material to yield a magenta color image, which comprises a magenta coupler of the mono-pyrazolone 3,556,799 Patented Jan. 19, 1971 "ice type, wherein a bis-pyrazolone compound of the general formula wherein R is alkyl, non-substituted or substituted aryl, R
- This invention relates to a light-sensitive photographic is hydrogen, alkyl, non-substituted or substituted aryl, or a heterocyclic radical with the proviso that a least one of R and R should contain an aliphatic hydrocarbon radical having 12 to 20 carbon atoms is incorporated in the photographic material. It is a principal object of the present invention to provide a light-sensitive color photographic material which is free from color staining (magenta fog) during and color development.
- magenta couplers which are capable of forming of magenta color image in a light-sensitive, color photographic material.
- a magenta coupler of the mono-pyrazolone type can give a stable color image with good tone quality at high speed.
- a photographic material in which the magenta coupler alone is incorporated is disadvantageous because it suffers from color staining during storage or development.
- a magenta coupler of the mono-pyrazolone type, the pyrazolone ring of which is substituted at the 3-position with a long chain alkyl group is very likely to cause color staining.
- magenta coupler of the monopyrazolone type in combination with an antifoggant (stabilizer) such as 2,4-di-tert. butyl hydroquinone, etc.
- an antifoggant such as 2,4-di-tert. butyl hydroquinone, etc.
- the use of such a stabilizer invariably causes a serious decrease in the sensitivity of high speed photographic emulsion.
- a light-sensitive, color photographic material which contains a magenta coupler of the mono-pyrazolone type which is completely prevented from color staining while retaining all the advantages inherent in said magenta coupler.
- magenta coupler of the present invention Any compound of the pyrazolone type which is heretofore known may be used as the magenta coupler of the present invention.
- useful compounds are the following:
- the required amount of the bis-pyrazolone compound to be added may vary depending on the type of magenta coupler of the mono-pyrazolone type and further on the type of bis-pyrazolone compound used but it usually will be within the range of 150% by weight based on the weight of the magenta coupler.
- Incorporation of the specific compound of the bis-pyrazolone type into a photographic material of the present invention can be made in the manner heretofore known per se in the art. For example, it is possible to add the compound to a light-sensitive, color photographic emulsion containing a magenta coupler of the mono-pyrazolone type at any time just before, during or after the second ripening of the said emulsion.
- the bis-pyrazolone compound as a stabilizer for the magenta coupler is most preferably made at the stage after the second ripening.
- the bis-pyrazolone compound may be added to a starting material for the preparation of the emulsion, for example gelatine. It is desirable to add the bispyrazolone compound in solution dissolved in a suitable solvent, e.g. water, dilute alkali, methanol, ethanol, etc., if the addition is made to an emulsion.
- a suitable solvent e.g. water, dilute alkali, methanol, ethanol, etc.
- the photographic emulsion containing the said bis-pyrazolone compound can be sensitized with a gold, sulfur or other chemical or optical sensitizer.
- a light-sensitive, color photographic emulsion or the like expression used herein is to be understood to mean any conventionally known light-sensitive, color photographic emulsion which contains a magenta coupler of the mono-pyrazolone type.
- a suitable color photographic emulsion will be available with reference to Kagaku- Shashin-Binran (Manual of Photographic Science), vol. I, pp. 455-460 (Maruzen Co., Tokyo, Japan).
- emulsion to which the bis-pyrazolone compound has been added can be applied to a suitable support in the manner heretofore known per se in the art, e.g. coating or pouring.
- suitable supports include films, papers and glass plates.
- films of the types such as cellulose esters, e.g. cellulose triacetate; polyesters obtained by the polycondensation of phthalic, isophthalic or terephthalic acid with a dihydric alcohol, e.g. polyethylene terephthalate, poly[cyc1ohexane-1,4-dimethylol]terephthalate, etc.', and polycarbonates including those obtained by the polycondensation of bisphenyl A with carbonic acid.
- cellulose esters e.g. cellulose triacetate
- polyesters obtained by the polycondensation of phthalic, isophthalic or terephthalic acid with a dihydric alcohol e.g. polyethylene terephthalate, poly[c
- EXAMPLE 1 8 g. of the magenta coupler of the above-indicated Formula 1 and 2 g. of the bis-pyrazolone compound of the above-indicated Formula IX are dissolved in 35 ml. of l N sodium hydroxide. The resulting solution is diluted with 400 ml. of water and then added to 1 kg. of a green light-sensitive, high speed photographic gelatino-silver iodobromide emulsion. Then, the emulsion is adjusted to pH 7.0 and coated on a cellulose acetate film support and dried. The thus obtained film is exposed to green light and treated at 20 C. for 10 minutes with a color developer having the following formulation:
- Example 1 These control samples also are subjected to sensitometric tests.
- photographic speed values are expressed as relative values based on the speed of the control sample (1) which is rated as 100.
- Condition A --For seven days at a temperature of 50 C. under a relative humidity of 20%.
- Condition B For five days at a temperature of 55 C. under a relative humidity of 80%.
- each set of the films are treated by color development in the same manner as before and then tested by sensitometry. The results are set forth in Table 2.
- Color images obtained by using the samples of Example 1 are excellent in tone quality and stability.
- EXAMPLE 2 7 g. of the magenta coupler of the above-indicated Formula 7 and 3 g. of the bis-pyrazolone compound of the above-indicated Formula IV are dissolved in 30 ml. of 1 N sodium hydroxide. The resulting solution is diluted with 500 ml. of water and added to 1 kg. of a green lightsensitive gelatino-silver chlorobromide emulsion, which is then adjusted to pH 6.9 with citric acid and coated on a. cellulose acetate film support. The resulting film is treated in the same manner as in Example 1 to obtain the results given in Table 3.
- control samples are prepared 10 by using in the control sample 3 10 g. of the magenta coupler of the Formula 7 alone and in the contral sample 4 10 g. of the same magneta coupler and 500 mg. of 2,4-di-tert. butyl hydroquinone. These control samples also are tested by sensitometry.
- a light-sensitive, color photographic material which comprises on a support a light-sensitive gelatino-silver halide emulsion layer containing a magenta coupler of the mono-pyrazolone type and a bis-pyrazolone compound of the formula wherein R is alkyl, aryl or carboxyl, sulfo or amido substituted aryl radical and R is hydrogen, alkyl, aryl, carboxyl, sulfo or amido substituted aryl or heterocyclic radical, with the proviso that at least one of said R and R contains an aliphatic hydrocarbon radical having 1220 carbon atoms in an amount sui'ficient to prevent color staining with said magenta coupler.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
COLOR STAINING OF CONVENTIONAL MONO-PYRAZOLONE MAGENTA COUPLERS IN PHOTOGRAPHIC MATERIALS IS PREVENTED BY USING, TOGETHER WITH THE MONO-PYRAZOLENE, A BIS-PYRAZOLONE IN AN AMOUNT OF 1-50% BY WEIGHT BASED ON THE MONO-PYRAZOLNE. THE BIS-PYRAZOLONE HAS THE FORMULA: F WHEREIN R IS ALKYL, ARYL OR SUBSTITUTED ARYL AND R'' IS HYDROGEN, ALKYL, ARYL, SUBSTITUTED ARYL OR A HETEROCYCLIC RADICAL WITH THE PROVISO THAT AT LEAST ONE OF R AND R'' CONTAINS AN ALIPHATIC HYDROCARBON RADICAL OF 12-20 CARBON ATOMS.
Description
United States Patent 0,
3,556,799 LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL CONTAINING A MONO-PYRAZOLONE COUPLER AND A BIS-PYRAZOLONE COMPOUND Toshihiko Yamamoto, Mitsuto Fujiwara, Tamotsu Kojima, and Kenro Sakamoto, Tokyo, Japan, assignors to Konishiroku Photo Industry Co., Ltd., Tokyo, Japan No Drawing. Filed Sept. 11, 1967, Ser. No. 666,936 Claims priority, application Japan, Sept. 19, 1966, 41/ 61,483 Int. Cl. G03c 1/40 US. Cl. 96-100 3 Claims ABSTRACT OF THE DISCLOSURE Color staining of conventional mono-pyrazolone magenta couplers in photographic materials is prevented by using, together with the mono-pyrazolone, a bis-pyrazolone in an amount of 1-50% by weight based on the mono-pyrazolne. The bis-pyrazolone has the formula:
wherein R is alkyl, aryl or substituted aryl and R is hydrogen, alkyl, aryl, substituted aryl or a heterocyclic radi cal with the proviso that at least one of R and R contains an aliphatic hydrocarbon radical of 12-20 carbon atoms.
material useful in color photography. Particularly, the invention is concerned with a light-sensitive, color photographic material to yield a magenta color image, which comprises a magenta coupler of the mono-pyrazolone 3,556,799 Patented Jan. 19, 1971 "ice type, wherein a bis-pyrazolone compound of the general formula wherein R is alkyl, non-substituted or substituted aryl, R
This invention relates to a light-sensitive photographic is hydrogen, alkyl, non-substituted or substituted aryl, or a heterocyclic radical with the proviso that a least one of R and R should contain an aliphatic hydrocarbon radical having 12 to 20 carbon atoms is incorporated in the photographic material. It is a principal object of the present invention to provide a light-sensitive color photographic material which is free from color staining (magenta fog) during and color development.
As is well known, there are many magenta couplers which are capable of forming of magenta color image in a light-sensitive, color photographic material. Among these, a magenta coupler of the mono-pyrazolone type can give a stable color image with good tone quality at high speed. However, a photographic material in which the magenta coupler alone is incorporated is disadvantageous because it suffers from color staining during storage or development. Particularly, a magenta coupler of the mono-pyrazolone type, the pyrazolone ring of which is substituted at the 3-position with a long chain alkyl group, is very likely to cause color staining. Heretofore it was therefore necessary to use a magenta coupler of the monopyrazolone type in combination with an antifoggant (stabilizer) such as 2,4-di-tert. butyl hydroquinone, etc. However, the use of such a stabilizer invariably causes a serious decrease in the sensitivity of high speed photographic emulsion.
In accordance with the present invention there is provided a light-sensitive, color photographic material which contains a magenta coupler of the mono-pyrazolone type which is completely prevented from color staining while retaining all the advantages inherent in said magenta coupler.
Any compound of the pyrazolone type which is heretofore known may be used as the magenta coupler of the present invention. Typically useful compounds are the following:
(1) HzC C-Cuflas aw-Q 1-(3-a-su1iostearoylamldophenyl)3-phenyl-5- pyrazolone. N
-NHCO 0110 m,
5 coupler of the pyrazolone type as referred to above is used together with a bis-pyrazolone compound of the above-indicated formula which typically may be the fol lowing:
4-bis-[l-phenyl-3-heptadecyl-5- pyrazolone].
4-bis-[1-(B-carboxylphenyD-B- heptadecyl-5-pyrazolone].
4-bis-[1-(4-su1io-pheny1)-3-heptadecy1-5- pyrazolone].
4-bis-[3-(4-wsulfopalmitoylamidophenyD-5-pyrazo1one].
C 0 O H y illolone] 4-bis-{l-pentadecyl-3-(4-carboxy- I phenyD-5-pyrazoloue].
4-bis-[l-(4-phenoxy-3-sulio-pl1enyl)-3- heptadecyl-S-pyrazolone].
These bis-pyrazolone compounds when used above (i.e. without addition of a magenta coupler of the monopyrazolone type) will give a clear stable color image which may be increased in maximum color density because of their bimolecular coupling reaction. However, when they are used in a high speed, color photographic emulsion, they are inferior in coupling activity and occasionally fail to give the desired photographic speed.
Such drawback of the bis-pyrazolone compounds as mentioned above can be avoided by jointly using the known mono-pyrazolone type magenta coupler in a lightsensitive, color photographic material. In accordance with the invention there is thus provided a light-sensitive, color photographic material which can give a stable color image with good tone quality at desired high speed.
The required amount of the bis-pyrazolone compound to be added may vary depending on the type of magenta coupler of the mono-pyrazolone type and further on the type of bis-pyrazolone compound used but it usually will be within the range of 150% by weight based on the weight of the magenta coupler. Incorporation of the specific compound of the bis-pyrazolone type into a photographic material of the present invention can be made in the manner heretofore known per se in the art. For example, it is possible to add the compound to a light-sensitive, color photographic emulsion containing a magenta coupler of the mono-pyrazolone type at any time just before, during or after the second ripening of the said emulsion. Addition of the bis-pyrazolone compound as a stabilizer for the magenta coupler is most preferably made at the stage after the second ripening. Alternatively, the bis-pyrazolone compound may be added to a starting material for the preparation of the emulsion, for example gelatine. It is desirable to add the bispyrazolone compound in solution dissolved in a suitable solvent, e.g. water, dilute alkali, methanol, ethanol, etc., if the addition is made to an emulsion.
Use of the bis-pyrazolone compound as a stabilizer does not adversely influence the sensitivity of the color photographic emulsion concerned. The photographic emulsion containing the said bis-pyrazolone compound can be sensitized with a gold, sulfur or other chemical or optical sensitizer.
As is well known to those skilled in the art, the term, a light-sensitive, color photographic emulsion or the like expression used herein is to be understood to mean any conventionally known light-sensitive, color photographic emulsion which contains a magenta coupler of the mono-pyrazolone type. A suitable color photographic emulsion will be available with reference to Kagaku- Shashin-Binran (Manual of Photographic Science), vol. I, pp. 455-460 (Maruzen Co., Tokyo, Japan).
The emulsion to which the bis-pyrazolone compound has been added can be applied to a suitable support in the manner heretofore known per se in the art, e.g. coating or pouring. Suitable supports include films, papers and glass plates. Particularly suitable are films of the types, such as cellulose esters, e.g. cellulose triacetate; polyesters obtained by the polycondensation of phthalic, isophthalic or terephthalic acid with a dihydric alcohol, e.g. polyethylene terephthalate, poly[cyc1ohexane-1,4-dimethylol]terephthalate, etc.', and polycarbonates including those obtained by the polycondensation of bisphenyl A with carbonic acid.
The present invention will now be explained in detail in conjunction with the following examples.
EXAMPLE 1 8 g. of the magenta coupler of the above-indicated Formula 1 and 2 g. of the bis-pyrazolone compound of the above-indicated Formula IX are dissolved in 35 ml. of l N sodium hydroxide. The resulting solution is diluted with 400 ml. of water and then added to 1 kg. of a green light-sensitive, high speed photographic gelatino-silver iodobromide emulsion. Then, the emulsion is adjusted to pH 7.0 and coated on a cellulose acetate film support and dried. The thus obtained film is exposed to green light and treated at 20 C. for 10 minutes with a color developer having the following formulation:
G. N,N-diethy1p-phenylenediamine sulfate 2.0 Sodium sulfite (anhydrous) 2.0 Sodium carbonate monohydrate 82.0 Potassium bromide 2.0
Water to make up 1000 ml.
The treated film is then treated by stopping and fixing in the usual manner. After rinsing for 10-20 minutes, this film was treated for 5 minutes with a bleaching solution of the following formulation:
G. Potassium ferricyanide Potassium bromide 50 Water to make up 1000 ml.
Example 1. These control samples also are subjected to sensitometric tests.
The test results are set forth in Table 1.
In the above and also in Tables 2 and 3 which appear later, photographic speed values are expressed as relative values based on the speed of the control sample (1) which is rated as 100.
Separately, two sets of the above three film samples are stored under the following condition:
Condition A.--For seven days at a temperature of 50 C. under a relative humidity of 20%.
Condition B.For five days at a temperature of 55 C. under a relative humidity of 80%.
After the specified storage, each set of the films are treated by color development in the same manner as before and then tested by sensitometry. The results are set forth in Table 2.
Color images obtained by using the samples of Example 1 are excellent in tone quality and stability.
EXAMPLE 2 7 g. of the magenta coupler of the above-indicated Formula 7 and 3 g. of the bis-pyrazolone compound of the above-indicated Formula IV are dissolved in 30 ml. of 1 N sodium hydroxide. The resulting solution is diluted with 500 ml. of water and added to 1 kg. of a green lightsensitive gelatino-silver chlorobromide emulsion, which is then adjusted to pH 6.9 with citric acid and coated on a. cellulose acetate film support. The resulting film is treated in the same manner as in Example 1 to obtain the results given in Table 3.
On the other hand, two control samples are prepared 10 by using in the control sample 3 10 g. of the magenta coupler of the Formula 7 alone and in the contral sample 4 10 g. of the same magneta coupler and 500 mg. of 2,4-di-tert. butyl hydroquinone. These control samples also are tested by sensitometry.
TAB LE 3 Photographic speed E Sample of Example 9 126 0. 02 Control sample (3) 100 0. 07 Control sample (4) 85 0. 05
What we claim is:
1. A light-sensitive, color photographic material which comprises on a support a light-sensitive gelatino-silver halide emulsion layer containing a magenta coupler of the mono-pyrazolone type and a bis-pyrazolone compound of the formula wherein R is alkyl, aryl or carboxyl, sulfo or amido substituted aryl radical and R is hydrogen, alkyl, aryl, carboxyl, sulfo or amido substituted aryl or heterocyclic radical, with the proviso that at least one of said R and R contains an aliphatic hydrocarbon radical having 1220 carbon atoms in an amount sui'ficient to prevent color staining with said magenta coupler.
2. A light-sensitive, color photographic material as claimed in claim 1, wherein said photographic material is a tricolor photographic film.
3. A light-sensitive, color photographic material as claimed in claim 1, wherein said bis-pyrazolone compound is present in the amount of l% by weight based on the weight of said magenta coupler.
References Cited UNITED STATES PATENTS 12/1946 Bauley 96100 12/1955 Loria et a1. 9656
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6148366 | 1966-09-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3556799A true US3556799A (en) | 1971-01-19 |
Family
ID=13172352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US666936A Expired - Lifetime US3556799A (en) | 1966-09-19 | 1967-09-11 | Light-sensitive silver halide color photographic material containing a mono-pyrazolone coupler and a bis-pyrazolone compound |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US3556799A (en) |
| BE (1) | BE703983A (en) |
| DE (1) | DE1597622A1 (en) |
| GB (1) | GB1153029A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2229453A1 (en) * | 1971-06-16 | 1972-12-28 | Massachusetts Institute of Technolo gy, Cambridge, Mass (V St A) | Process for producing a metallic liquid solid mixture for casting processes |
-
1967
- 1967-09-11 US US666936A patent/US3556799A/en not_active Expired - Lifetime
- 1967-09-15 DE DE19671597622 patent/DE1597622A1/en active Pending
- 1967-09-18 BE BE703983D patent/BE703983A/xx unknown
- 1967-09-19 GB GB42718/67A patent/GB1153029A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2229453A1 (en) * | 1971-06-16 | 1972-12-28 | Massachusetts Institute of Technolo gy, Cambridge, Mass (V St A) | Process for producing a metallic liquid solid mixture for casting processes |
Also Published As
| Publication number | Publication date |
|---|---|
| BE703983A (en) | 1968-02-01 |
| GB1153029A (en) | 1969-05-21 |
| DE1597622A1 (en) | 1970-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4195999A (en) | Silver halide photographic material containing ultraviolet light absorbing agent | |
| US3923517A (en) | Method for rapidly forming photographic images | |
| JPS60250344A (en) | Color photographic sensitive material | |
| US3637393A (en) | Light-sensitive color photographic material with reduced fog and no decrease in speed during development | |
| US3769024A (en) | Light-sensitive silver halide photographic material with sensitizing dye combination | |
| US5279920A (en) | Silver halide photographic light sensitive material | |
| US3656950A (en) | Color photographic processes | |
| US3457079A (en) | Photographic silver halide emulsions stabilized with gallic acid or an alkyl ester thereof | |
| US4028115A (en) | Silver halide photographic emulsion sensitized to red with four carbocyanine dyes | |
| US3488193A (en) | Silver halide emulsions containing naphthol color couplers | |
| US4309500A (en) | Silver halide color photographic light-sensitive material | |
| US3554757A (en) | Stabilized photographic silver halide composition | |
| US3556799A (en) | Light-sensitive silver halide color photographic material containing a mono-pyrazolone coupler and a bis-pyrazolone compound | |
| US3580724A (en) | Light-sensitive supersensitized silver halide color photographic emulsions | |
| US3632349A (en) | Silver halide supersensitized photographic emulsion | |
| US3565631A (en) | 6 - amidinothio - 5,7 - dihydroxy - s - triazolo(2,3-a) pyrimidino compounds as stabilizers for silver halide emulsion | |
| US4734358A (en) | Silver halide photographic light-sensitive material | |
| JPS6346439A (en) | Silver halide photographic sensitive material | |
| US3625697A (en) | Sensitization of light-sensitive silver halide photographic emulsions | |
| US3764327A (en) | Color photographic light sensitive material | |
| US3663230A (en) | Light-sensitive silver halide photographic emulsions | |
| US3888680A (en) | Light-sensitive silver halide color photographic material containing bis-pyrazolone couplers | |
| US3790388A (en) | Direct positive color photographic materials | |
| US3881939A (en) | Photographic silver halide emulsions containing sydnones or sydnone imines as stabilizers | |
| JPS61282834A (en) | Silver halide photographic sensitive material |