US3409439A - Color photographic materials - Google Patents

Color photographic materials Download PDF

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Publication number
US3409439A
US3409439A US427417A US42741765A US3409439A US 3409439 A US3409439 A US 3409439A US 427417 A US427417 A US 427417A US 42741765 A US42741765 A US 42741765A US 3409439 A US3409439 A US 3409439A
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Prior art keywords
coupler
yellow
color photographic
color
photographic material
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US427417A
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English (en)
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Yoshida Makoto
Tsuda Momotoshi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • 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
    • G03C7/362—Benzoyl-acetanilide couplers

Definitions

  • R is a member selected from the class consisting of an alkyl group having at least 8 carbon atoms and an aliphatic residual group having at least 8 carbon atoms and having at least one ether bond
  • X is a member selected from the class consisting of a hydrogen atom and a halogen atom
  • Y is a member selected from the class consisting of a hydrogen atom, a loweralkoxy group and a halogen atom.
  • the protective coupler in order to be used in the color photographic material, must fully suffice the photographic properties, such as, coupling efficiency of coupler, coupling rate, fogging, color tone of formed colored image, and the like as well as must have a sufiicient solubility in 3,409,439 Patented Nov. 5, 1968 a coupler solvent and a good dispersibi-lity in the emulsion.
  • various compounds have been synthesized and patented, but they have no sufiicient solubility in coupler solvents or insufficient dispersibility in emulsions, or they are very expensive from a view point of synthesis and raw materials.
  • dialkylphenoxy group e.g., United States Patent 2,875,05
  • dialkylcyclohexyloxy group e.g., United States Patent 2,920,- 961
  • an object of this invention is to provide a color photographic material containing a novel yellow coupler which can be easily synthesized at an extremely low cost.
  • a further object of this invention is to provide a color photographic material containing a novel yellow coupler having improved photographic properties.
  • the inventors have found improved yellow couplers that will be shown below, said couplers being produced by a simple synthetic process using easily available inexpensive raw materials.
  • the yellow couplers in this invention are, as will be explained later in detail, novel compounds of an extremely low cost from the view point of raw materials and synthesis as well as having a sufficient solubility in coupler solvents and a good dispersibility in the emulsions.
  • the couplers in this invention have excellent photographic properties, such as, coupling etficiency of coupler, coupling rate, fogging, color tone of obtained colored image and the like, and also the stability to light, heat and moisture of the formed colored image by using such a coupler is excellent.
  • the invention relates to a color photographic material containing the yellow coupler having the following general formula:
  • R is a member selected from the class consisting of an alkyl group (including the alkyl group having at least a side chain) having above 8 carbon atoms and an aliphatic residual group having above 8 carbon atoms and having one or more ether bonds
  • X is a member selected from the class consisting of a hydrogen atom and a halogen atom
  • Y is a member selected from the class consisting of a hydrogen atom, a lower alkoxy group and a halogen atom.
  • the coupler of this invention has been substituted with carboxyl acid ester group having an alkyl group or more than 8 carbon atoms at the meta-position of the anilide nucleus. Therefore, the coupler can be prevented from being come out of the added emulsion layer by diffusion as well as the solubility of the coupler in coupler solvents and the dispersibility in the emulsion are excellent. That is, the coupler of this invention is provided with sufiicient conditions necessary for a color photographic coupler even though it is substituted with such a simple substituent.
  • the coupler of this invention has a lower alkoxy group or a halogen atom at the ortho-position of the anilide nucleus, and this gives remarkable effects for improving the photographic properties, such as, coupling efliciency of coupler, coupling rate, color tone of the formed colored image, etc., and show extremely desirable yellow.
  • the raw materials, necessary for the syntheisis of the couplers such as, benzoyl acetate, 3-amin o- 4-methoxy benzoic acid, 3-amino-4-chlorobenzoic acid, the esters thereof, and lauryl alcohol are generally manufactured in a large scale as the raw materials for general organic compounds and hence easily available at a low cost. Also, it is easily understood that the cost of couplers TABLE 1 C 0 OR 6-0 0 CHQCONH Solubility, g./l00 g. solvent 0:) Structural Y R formula weight Dibutyl Tributyl Ethyl phthalate phosphate acetate C3H17 425 88 28.
  • the molecular weight of the coupler in this invention is, if, in the above-mentioned general formula, X is a hydrogen atom, R is a dodecyl group showing surficient diffusion resistance, and Y is a methoxy group (Structural Formula V) or a chlorine atom (Structural Formula XIII), 481 or 485.5 respectively, and is about 13% lower than that of a yellow coupler having dialkylphenoxy group, e.g., the coupler shown by the following structural formula:
  • the inventors have found, as the results of investigations for reducing the molecular weight of the couplers of this invention and increasing the coupling efiiciency, that when an octyl group having 8 carbon atoms used as R, the coupler shows a suflicient diffusion resistance and can be used practically without being accompanied with any troubles as well as the coupler has also an excellent solubility in coupler solvents and dispersibility in the emulsions.
  • the couplers of this invention show excellent solubilities, as shown in the above table, in coupler solvents, in particular, in esteric organic solvents, such as phthalic acid esters, phosphoric acid esters, and acetic acid esters, and then the deposition of the coupler crystals when the solution of the coupler is in a super cooled state, is extremely small or slow, the use of such couplers is very profitable.
  • coupler solvents in particular, in esteric organic solvents, such as phthalic acid esters, phosphoric acid esters, and acetic acid esters
  • the deposition of the coupler crystals when the solution of the coupler is in a super cooled state is extremely small or slow, the use of such couplers is very profitable.
  • X is a hydrogen atom
  • Y is a chlorine atom
  • the inventors have found also, as the results of the investigations about the improvement of the solubility in coupler solvents of the coupler in which Y is a chlorine atom, that by using an alkyl group having side chains as R instead of using a straight-chain alkyl group, the melting point of such a coupler can be reduced and the solubility in coupler solvents can be remarkably improved. That is, by using an aliphatic alcohol having side chains, such as, commercially available 2-ethylhexanol, isodecyl alcohol or triisodecyl alcohol instead of using a straight chain aliphatic alcohol, the coupler suitable for the purposes can be easily synthesized and the solubility of the coupler in coupler solvents can be extremely increased as shown in Table 1.
  • the carbon number of R in the abovementioned general formula may be an odd number but on considering the availability, purity, and cost of them, it is naturally more profitable that the carbon number of R be an even number.
  • the coupler of this invention has the feature that one active methylene hydrogen atom in the molecule can be easily replaced with a halogen atom. Since the halogen atom-substituted coupler of this invention forms a dye by 2 equivalents of silver ions at coupling, the coupler has an advantage that the dye can be formed with a half of silver ions as compared with the coupler. wherein the active methylene hydrogen atom is not replaced with a halogen atom.
  • the numerical values for the solubility shown in Table 1 are ones obtained at room temperature, but the solubility increases rapidly as the temperature increases and a large amount of the coupler can be dissolved in a small proportion of the coupler solvent at a raised temperature.
  • the fact that the solubility of a coupler in a coupler solvent is high is an important property for a processwherein the coupler is dissolved in the coupler solvent, the solution is then dispersed in gelatin, and the dispersion is added in a photographic emulsion.
  • the above-mentioned addition process is the case where the coupler of this invention is dissolved in a coupler solvent, the solution is dispersed in gelatin and the dispersion is added in a photographic emulsion, but the addition of the coupler of this invention is not limited to the above case but the coupler may be added to other process.
  • the coupler having a low melting point may be fused into a liquid by heating and then dispersed in gelatin.
  • the present addition process will be explained practically in Example 6.
  • the coupler may be added in a photographic emulsion as an alkaline aqueous solution of it. This process will be explained practically in Example 4.
  • the couplers of this invention incorporated in silver halide photographic emulsions by the various processes as described above show very excellent coupling by a color developer mainly consisting of N,N-disubstituted paraphenylenediaminic developer and provide color photographic materials having excellent photographic properties.
  • the yellow image formed by the couplerof this invention has a good transparency and color reproducing property, and shows a strong absorption spectrum to a blue light of 400-480 millimicronsbut shows no harmful absorption spectrum to a green light of 500-600 millimicrons which is a cause for giving reddish tonein the yellow tone of the image, these properties of which are extremely preferable light absorption characteristics for color photography.
  • the light absorption curve will be shown in Examples 1, 2, 3 and 5.
  • Yellow colored images obtained from yellow couplers that have been usually used in conventional color photography are easily influenced and faded by the external conditions such as light, heat and moisture, and colorphotographs obtained by using such a conventional coupler are frequently discolored during storage.
  • the yellow colored image obtained by using the yellow coupler of this invention is extremely fast and stable and scarcely faded and discolored by the influences of light, heat, moisture, and chemicals.
  • a coupler having a chlorine atom at the ortho-position of the anilide nucleus isparticularly fast and stable to light.
  • the couplers of this invention are not limited to the use for color photography but can be used for obtaining 2-col0r images or mono-color images as well as for print- L As the yellow couplers of this invention, the following examples are illustrated.
  • a four-necked flask of 1 liter was equipped with an agitator, a thermometer, an inlet pipe for nitrogen gas, and a distilling pipe for distilling lay-produced methanol and in the flask was charged 181 g. (1 mole) of methyl- 3-amino-4-methoxy benzoate and 279 g. (1.5 moles) of n-dodecyl alcohol.
  • the charged materials were fused by heating 80 C.'in the inside temperature, added with 2.5 ml. of titanium butoxide, and by-produced methanol was distilled off by introducing a nitrogen gas.
  • the system was further heated to maintain the inside temperature at 170-180" C., whereby the ester exchange reaction proceeded slowly and methanol began to distill off, and after 4 hours about of the theoretical amount of methanol was distilled off. Then, the system was cooled slowly and when the inside temperature reached 4050 C., the product was withdrawn from the flask and added into '1 liter of methanol. By standing alone the solution for one night, brown crystals were deposited, which were filtered by suction, washed with 500 rnl. of methanol and dried to give dodecyl-3-amino-4-methoxy benzoate. The yield was 271 g. (81%) and melting point of the product was 47- 48 C.
  • a three-necked flask was equipped with an agitator, a thermometer, and a pipe for distilling by-produced ethanol, and in the flask was placed 192 g. (1 mole) of ethylbenzoyl acetate and 335 g. (1 mole) of dodecyl-3-amino- 4 methoxy benzoate obtained in Synthesis 1.
  • methanol began to distill off and about 60% of the theoretical amount of ethanol was distilled oif over about 6 hours.
  • the agitator was removed and ethanol was further distilled off for another 30 minutes under a reduced pressure.
  • chloroform was distilled off under low temperature and low pressure.
  • 400 ml. of acetonitrile was added and the system was allowed to cool in a cold place, white crystals were deposited.
  • the crystals were recovered by filtration and subjected to a recrystallization by using 300 ml. of petroleum ether to give benzoylchloroaceto-Z- methoxy-S-dodecyloxycarbonyl anilide.
  • the yield was 37 g. (72%) and the melting point of the product was 74-75 C.
  • the following table shows the melting points and the results of nitrogen analysis of the typical examples of the yellow couplers of the present invention.
  • Example 1 Into a mixture of 1.2 ml. of dibutyl phthalate, 3.0 ml. of ethyl acetate, and 0.8 m1. of isopropanol were dissolved by heating 4.0 g. of the coupler shown by the above-mentioned structural Formula V and 0.8 g. of a copolymer of vinylpyrolidon and vinyl acetate (mole ratio 7:3), and the solution was added in ml. of a 10% gelatin aqueous solution containing 2.0 ml. of a 10% aqueous solution of sodium alkylbenzene sulfonate. The system was subjected to a high speed agitation of 3 minutes at 40-50 C.
  • the total amount of the emulsified dispersion was mixed with a gelatin silver halide emulsion containing 4.5 g. of silver bromide and 7.5 g. of gelatin, and the mixture was applied on a film base of cellulose acetate followed by drying to give a color photographic material.
  • the color photographic material was exposed and subjected to a color development with a developer having the following composition:
  • Bleaching solution G. Potassium ferricyanide 100 Boric acid 7.5 Potassium alum Water to make 1 liter.
  • Example 2 In this example, the coupler shown by the above-mentioned Structural Formula XIII was used instead of the coupler shown by the Formula V in Example 1, and the color photographic material in this case was also treated as in Example 1.
  • Example 4 A mixture of 2 g. of the coupler shown by the abovementioned Stnuctural Formula V, 6 ml. of l N. sodium hydroxide aqueous solution, and 16 ml. of methanol was heated to form a solution and the solution was added with water to make 40 ml. of the whole solution, a 5% coupler solution. The whole of the above-mentioned coupler solution was added into 100 g. of a photographic emulsion containing 5 g. of silver bromide and 6 g. of gelatin and then the solution was neutralized with the addition of 1 ml. of a 2% citric acid. Thus prepared emulsion was applied on a film base, dried and treated as in Example 3.
  • Example 5 Instead of the coupler having the Structural Formula V used in Example 3, a coupler having the Structural Fonmula XIII was used. Two grams of the coupler was dissolved into 6 g. of dibutyl phthalate by heating and then by emulsifying and coating as in Example 3, a color photographic material was obtained. The photographic material was exposed, and developed as in Example 3.
  • yellow-colored film had the absorption spectnum as shown in FIG. 4, that is, showed a visually desirable clear yellow tone having little reddish tone.
  • yellow-colored image was stable to light, heat and moisture and could be preserved for a long time.
  • the mixture was subjected to a high-speed agitation at C. for 10 minutes in a homo-blender to form an emulsified dispersion.
  • Example 7 Two grams of the coupler having the above-mentioned Structural Formula XIV was dissolved into 4 ml. of ethyl acetate by heating, the solution wasadded in 30 ml. of a 7% gelatin solution containing 0.1 g. of sodium dodecylbenzene sulfonate, and the mixture was agitated with a high speed at 50 C. for 10 minutes to give an emulsified dispersion. From thus prepared emulsion, a color photographic material was obtained as in Example 6. The photographic material was exposed and developed as in Example 3.
  • Example 8 instead of the coupler having the Structural Formula XIV used in Example 7, a coupler having the Structural Formula XX was used. By emulsifying and coating the coupler as in Example 7, a color photographic material was obtained, which was exposed and developed as in Example 3.
  • Example 9 instead of the coupler having the Structural Formula V used in Example 3, a coupler having the Structural Formula XX was used. Two grams of the coupler was dissolved in 6 g. of dibutyl phthalate by heating and the solution was emulsified and coated on a film base as in Example 3 to give a color photographic material.
  • a color photographic material comprising a support and at least one silver halide photographic emulsion layer containing a coupler having the following general formula COOR Q- w -Q wherein R is a member selected from the class consisting of an alkyl group having at least 8 carbon atoms and an aliphatic residual group having at least 8 carbon atoms and having at least one ether bond; X is a member selected from the class consisting of a hydrogen atom and a halogen atom; and Y is a member selected from the class consisting of a hydrogen atom, a lower alkoxy group and a halogen atom.

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US427417A 1964-02-01 1965-01-22 Color photographic materials Expired - Lifetime US3409439A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3779765A (en) * 1972-08-31 1973-12-18 Eastman Kodak Co Silver halide emulsions containing coupler solvents
US3849140A (en) * 1971-03-25 1974-11-19 Agfa Gevaert Ag Diffusion-resistant dispersible yellow couplers for the production of photographic color images
US3892576A (en) * 1970-02-24 1975-07-01 Agfa Gevaert Nv Photographic water-insoluble compounds having a hydrophobic diffusion-fast substituent

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5908955A (en) * 1997-01-14 1999-06-01 Sankio Chemical Co., Ltd. Process for producing alkyl 3-amino-4-substituted benzoates

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2418747A (en) * 1944-05-20 1947-04-08 Gen Aniline & Film Corp Nondiffusing phenolic color couplers
US2908573A (en) * 1956-07-25 1959-10-13 Eastman Kodak Co Photographic color couplers containing mono-n-alkyl groups

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE543742A (US20020125480A1-20020912-P00900.png) * 1954-12-20

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2418747A (en) * 1944-05-20 1947-04-08 Gen Aniline & Film Corp Nondiffusing phenolic color couplers
US2908573A (en) * 1956-07-25 1959-10-13 Eastman Kodak Co Photographic color couplers containing mono-n-alkyl groups

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892576A (en) * 1970-02-24 1975-07-01 Agfa Gevaert Nv Photographic water-insoluble compounds having a hydrophobic diffusion-fast substituent
US3849140A (en) * 1971-03-25 1974-11-19 Agfa Gevaert Ag Diffusion-resistant dispersible yellow couplers for the production of photographic color images
US3779765A (en) * 1972-08-31 1973-12-18 Eastman Kodak Co Silver halide emulsions containing coupler solvents

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DE1285885B (de) 1968-12-19
CH436984A (fr) 1967-05-31
GB1052488A (US20020125480A1-20020912-P00900.png)

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