US3623877A - Silver halide color photographic materials containing alkaline earth metal salts of color couplers - Google Patents
Silver halide color photographic materials containing alkaline earth metal salts of color couplers Download PDFInfo
- Publication number
- US3623877A US3623877A US843175A US3623877DA US3623877A US 3623877 A US3623877 A US 3623877A US 843175 A US843175 A US 843175A US 3623877D A US3623877D A US 3623877DA US 3623877 A US3623877 A US 3623877A
- Authority
- US
- United States
- Prior art keywords
- color
- silver halide
- color coupler
- alkaline earth
- gelatin
- 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
- -1 Silver halide Chemical class 0.000 title abstract description 36
- 229910052709 silver Inorganic materials 0.000 title abstract description 18
- 239000004332 silver Substances 0.000 title abstract description 18
- 229910052784 alkaline earth metal Inorganic materials 0.000 title abstract description 8
- 239000000463 material Substances 0.000 title description 5
- 108010010803 Gelatin Proteins 0.000 abstract description 20
- 229920000159 gelatin Polymers 0.000 abstract description 20
- 239000008273 gelatin Substances 0.000 abstract description 20
- 235000019322 gelatine Nutrition 0.000 abstract description 20
- 235000011852 gelatine desserts Nutrition 0.000 abstract description 20
- 239000000839 emulsion Substances 0.000 abstract description 17
- 239000006185 dispersion Substances 0.000 abstract description 14
- 239000000084 colloidal system Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 10
- 159000000003 magnesium salts Chemical class 0.000 abstract description 6
- 238000010348 incorporation Methods 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 15
- 239000002609 medium Substances 0.000 description 9
- 125000002843 carboxylic acid group Chemical group 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 4
- 159000000008 strontium salts Chemical class 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 150000003949 imides Chemical group 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- RCIJACVHOIKRAP-UHFFFAOYSA-N sodium;1,4-dioctoxy-1,4-dioxobutane-2-sulfonic acid Chemical compound [Na+].CCCCCCCCOC(=O)CC(S(O)(=O)=O)C(=O)OCCCCCCCC RCIJACVHOIKRAP-UHFFFAOYSA-N 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical group O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- LCIHLIWEHOKVCG-UHFFFAOYSA-N 3-(4-methoxyphenyl)-3-oxo-n-phenylpropanamide Chemical compound C1=CC(OC)=CC=C1C(=O)CC(=O)NC1=CC=CC=C1 LCIHLIWEHOKVCG-UHFFFAOYSA-N 0.000 description 1
- CFKMVGJGLGKFKI-UHFFFAOYSA-N 4-chloro-m-cresol Chemical compound CC1=CC(O)=CC=C1Cl CFKMVGJGLGKFKI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011928 denatured alcohol Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- RSAZYXZUJROYKR-UHFFFAOYSA-N indophenol Chemical compound C1=CC(O)=CC=C1N=C1C=CC(=O)C=C1 RSAZYXZUJROYKR-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000005543 phthalimide group Chemical group 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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
- G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
Definitions
- This application describes a process for the incorporation into a gelatino silver halideemulsion of a color coupler containing a carboxylic acid group which is characterised in that it comprises reacting an alkali metal salt of the color coupler with a water-soluble alkaline earth metal salt or magnesium salt in the presence of gelatin or a colloid medium compatible with gelatin to form a dispersion of the color coupler in the colloid medium and incorporating the said dispersion in the gelatino silver halide emulsion.
- This invention relates to color photographic materials and their production.
- color photographic materials which comprise photographic silver halide emulsions containing color couplers.
- These color couplers are destined to react with the oxidation products of aromatic amino color developing agents, such as N,N-dialkyl paraphenylenediamines and like compounds, formed during developing of the silver image, to form a colored dye image, usually an image in an indophenol or azornethine dye.
- color coupler to the silver halide emulsion layer, the colloid medium of which is usually gelatin.
- One Well known method is to employ a color coupler which has an acidic solubilising group and to dissolve the said color coupler in a solution of alkali metal hydroxide and add the resulting solution of the emulsion.
- a difiiculty which arises is that there is frequently a tendency for reaction to occur between the acid group of the color coupler and the gelatin of the emulsion, giving rise to an increase in viscosity, with attendant difficulties in coating the resulting emulsion.
- a process for the incorporation into a gelatino silver halide emulsion of a color coupler containing a carboxylic acid group which comprises reacting on alkali metal salt of the color coupler with a water-soluble alkaline earth metal salt or magnesium salt in the presence of gelatin or a colloid medium compatible with gelatin to form a dispersion of the color coupler in the colloid medium and incorporating the said dispersion in the gelatino silver halide emulsion.
- the calcium salt of the color coupler is obtained as a fine dispersion.
- This dispersion is of viscosity comparable with that of aqueous gelatin of the same concentration, i.e. is less than than the viscosity achieved 3,623,877 Patented Nov. 30, 1971 by the direct addition of the color coupler which comprises the free carboxylic acid or the alkali metal salt thereof to the gelatin.
- the method of the invention may be employed in association with any color coupler which has one or more free carboxylic acid groups or is capable of easily yielding a free carboxylic acid group and is thus able to form an alkali metal salt, it is of particular value in connection with color couplers which contain a phthalimide ring or a succinimide ring, and other analagous color couplers of which fission of the ring leads to compounds with free carboxylic acid groups, as described in British patent specification Nos. 944,838, 949,944, 1,004,075, 1,039,452 and 1,069,061.
- color couplers are 4-(4-dodecylphenylaminocarbonyl) N (l-phenyl-S-pyrazonyl-3-)phthalimide, 4 (4-dodecylphenylaminocarbonyl)-N-[4-(4 rnethoxybenzoyl acetamide)phenyl]phthalimide, 4-(n-octadecylaminocarbonyl)-N-[p-( l-hydroxy-Z- naphthamido) ethyl]phthalimide, l-phenyl 3[zx.-(N-I1- octadecylsuccinido) acetylamido] -5-pyrazolone.
- Examples of other color couplers of use in the process of the present invention are 1-phenyl-3-(fi-[N-(p-ndodecylphenyl)-acety1amino]-flcarboxyl n propionylamino)-5-pyrazolone, 2 (fi-[N-(-p-n-dodecylphenyl)isobutyrylamino]-,8-carboxy-n-propionylamino) 4-chloro-5- methylphenol, 4' methoxybenzoylacet-5-(B-n-hexadecylsulphonylamino-/3-carboxy-n-propionylamino -2-methoxyanilide, 1-phenyl-3-[a-[N-n-hexadecylacetylamino)-[3-carboxy-n-propionylamino]-5-pyrazolone.
- the color coupler is dissolved in an alkali metal hydroxide solution e.g. caustic soda solution.
- an alkali metal hydroxide solution e.g. caustic soda solution.
- color coupler (A) has the formula:
- the imide ring opens to yield the sodium salt of the color coupler.
- the imide ring may open in one of two senses thus:
- Solution II Dissolve 160 g. of color coupler A (see above) in 240 ml. of 2 N potassium hydroxide solution and dilute with distilled water to 1600 ml.
- EXAMPLE 2 Solution I Disperse 120 g. of gelatin in 1080 ml. of distilled water and add to this 300 ml. of 10% w./v. aqueous poly (vinyl alcohol) solution, 360 ml. of 4% w./v. aqueous 4 Manoxol O.T. solution (dispersing agent) and ml. of N acetic acid.
- the dispersions were added to gelatino silver halide photographic emulsions and coated as a green sensitive layer in the case of Example 1 and as blue sensitive layers in the cases of Examples 2 and 3 in standard reversal color material. No significant sensitometric differences were observed when compared with control coatings containing the same color couplers added by the conventional technique.
- a process for the production of a photographic gelatino silver halide emulsion comprising a color coupler, uniformly dispersed therein, which comprises incorporating into a gelatino silver halide emulsion a color coupler which contains a carboxylic acid group of which a calcium, barim or strontium salt is water-insoluble, by forming a dispersion of a said water-insoluble salt of the color coupler in an aqueous medium comprising gelatin or a colloid compatible with gelatin by reaction between an alkali metal salt of the color coupler and a water-soluble calcium, barium or strontium salt, in the presence of aqueous gelatin or an aqueous solution of a said compatible colloid, and incorporating said dispersion in the gelatino silver halide emulsion.
- the color coupler is of the type which comprises a phthalimide or succinimide ring before conversion to the alkali metal salt thereof.
- a gelatino silver halide emulsion which comprises a color coupler containing a carboxylic acid group of which a calcium, barim or strontium salt is water-insoluble, which has been incorporated therein by a process which comprises reacting an alkali metal salt of the color coupler with a water-soluble calcium, barium or strontium salt in the presence of aqueous gelatin or an aqueous colloid medium compatible with gelatin to form a dispersion of the color coupler in the colloid medium and incorporating the said dispersion in the gelatino silver halide emulsion.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB35339/68A GB1262653A (en) | 1968-07-24 | 1968-07-24 | Colour photographic materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3623877A true US3623877A (en) | 1971-11-30 |
Family
ID=10376624
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US843175A Expired - Lifetime US3623877A (en) | 1968-07-24 | 1969-07-18 | Silver halide color photographic materials containing alkaline earth metal salts of color couplers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3623877A (de) |
| BE (1) | BE736465A (de) |
| CH (1) | CH512089A (de) |
| DE (1) | DE1937485A1 (de) |
| GB (1) | GB1262653A (de) |
| NL (1) | NL140994B (de) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0915376A1 (de) * | 1997-11-06 | 1999-05-12 | Fuji Photo Film Co., Ltd. | Emulgierte Dispersion von einer photographischen, hydrophobischen Verbindung und ein photographisches, lichtempfindliches Silberhalogenidmaterial |
| US20040033449A1 (en) * | 2002-04-11 | 2004-02-19 | Rikio Inoue | Photothermographic material |
| US20040234910A1 (en) * | 2003-05-22 | 2004-11-25 | Hajime Nakagawa | Photothermographic material and image forming method |
-
1968
- 1968-07-24 GB GB35339/68A patent/GB1262653A/en not_active Expired
-
1969
- 1969-07-18 US US843175A patent/US3623877A/en not_active Expired - Lifetime
- 1969-07-23 BE BE736465D patent/BE736465A/xx unknown
- 1969-07-23 DE DE19691937485 patent/DE1937485A1/de active Pending
- 1969-07-24 CH CH1139669A patent/CH512089A/de not_active IP Right Cessation
- 1969-07-24 NL NL696911413A patent/NL140994B/xx unknown
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0915376A1 (de) * | 1997-11-06 | 1999-05-12 | Fuji Photo Film Co., Ltd. | Emulgierte Dispersion von einer photographischen, hydrophobischen Verbindung und ein photographisches, lichtempfindliches Silberhalogenidmaterial |
| US6309812B1 (en) | 1997-11-06 | 2001-10-30 | Fuji Photo Film Co., Ltd. | Emulsified dispersion of photographic hydrophobic compound and silver halide photographic light-sensitive material |
| US20040033449A1 (en) * | 2002-04-11 | 2004-02-19 | Rikio Inoue | Photothermographic material |
| US7138223B2 (en) * | 2002-04-11 | 2006-11-21 | Fuji Photo Film Co., Ltd. | Photothermographic material |
| US20070003887A1 (en) * | 2002-04-11 | 2007-01-04 | Rikio Inoue | Photothermographic material |
| US7439011B2 (en) | 2002-04-11 | 2008-10-21 | Fujifilm Corporation | Photothermographic material |
| US20040234910A1 (en) * | 2003-05-22 | 2004-11-25 | Hajime Nakagawa | Photothermographic material and image forming method |
| US7144688B2 (en) | 2003-05-22 | 2006-12-05 | Fuji Photo Film Co., Ltd. | Photothermographic material and image forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| BE736465A (de) | 1969-12-31 |
| NL140994B (nl) | 1974-01-15 |
| CH512089A (de) | 1971-08-31 |
| GB1262653A (en) | 1972-02-02 |
| DE1937485A1 (de) | 1970-01-29 |
| NL6911413A (de) | 1970-01-27 |
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