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US3325287A - Photographic gelatin hardening composition - Google Patents

Photographic gelatin hardening composition Download PDF

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Publication number
US3325287A
US3325287A US326219A US32621963A US3325287A US 3325287 A US3325287 A US 3325287A US 326219 A US326219 A US 326219A US 32621963 A US32621963 A US 32621963A US 3325287 A US3325287 A US 3325287A
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Prior art keywords
gelatin
photographic
solution
hardeners
water
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Expired - Lifetime
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US326219A
Inventor
Yamamoto Nobuo
Oishi Yasushi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Priority to US326219A priority Critical patent/US3325287A/en
Priority to GB47135/63A priority patent/GB1022656A/en
Priority to FR958288A priority patent/FR1379255A/en
Priority to DEF41858A priority patent/DE1284290B/en
Application granted granted Critical
Publication of US3325287A publication Critical patent/US3325287A/en
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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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30—Hardeners
    • G03C1/305—Hardeners containing a diazine or triazine ring

Definitions

  • gelatin In most photographic materials, gelatin is used as their constituting elements, in silver halide emulsion layers, protective coatings, substratum layers to film base, antihalation layers, backing layers and so on. In photographic uses, such a gelatin layer is often treated with a succession of aqueous solutions which may vary in pH and in. temperature. The layers composed of untreated gelatin have poor resistance to water; in water the gelatin layers swell excessively and are scratched easily. Especially at high temperature, the gelatin layers dissolve in aqueous solutions.
  • a number of classes of compounds have been found useful for treating gelatin to improve the resistance to water. These compounds are called hardeners in photographic arts. These include, for example, inorganic compounds such as chromium potassium sulfate and organic compounds such as aldehyde, polyfunctional expoxide,
  • hardeners of the classes known heretofore have exhibited unwanted effects when used in photographic products.
  • One serious drawback concerns the unwanted effects on photographic properties; for example, an increase in fog of the emulsion and a loss of photographic sensitivity.
  • Other difficulties frequently encountered with such hardeners are insufficient watersolubility causing nonuniformity of the gelatin layer, chemical instability of hardeners in solid or solution state, or toxicity in handling.
  • Some hardeners lose their hardening effect when used in the presence of other kinds of photographic additives suchas stabilizers and colorforming couplers.
  • One object of our invention is to provide hardeners for gelatin which exhibit no detrimental photographic efffects. Another object of our invention is to provide substances which when mixed make the geltain insoluble in aqueous solutions of varying pH or temperature. A further object of our invention is to provide for hardening of gelatin by the use of water-soluble dichlorotriazine compounds. Other objects of our invention will appear herein.
  • gelatin is made resistant to water even at elevated temperature by incorporating therein water-soluble salts of 2,4-dichloro-fi-hydroxy-s-triazine, characterized by the general formula:
  • M represents an alkalior alkaline-earth metal, e.g. a sodium, potassium, lithium, calcium, barium, or strontium atom, or a quaternary ammonium group, e.g. an ammonium tetramethylammonium, tetraethylammonium, tetrapropylammonium, or tetra'butylammonium group.
  • alkalior alkaline-earth metal e.g. a sodium, potassium, lithium, calcium, barium, or strontium atom
  • a quaternary ammonium group e.g. an ammonium tetramethylammonium, tetraethylammonium, tetrapropylammonium, or tetra'butylammonium group.
  • the cationic group represented by M in the foregoing formula can be selected from a wide range of cationic groups, because it plays a role only as a counter ion to a 2,4-dichloro-6-oxy-s-triazine anion which takes a part in crosslinking gelatin molecules.
  • a water-soluble salt of 2,4-dichloro-6-hydr0xy-s-triazine may be added to a gelatin composition directly in the form of a partial-hydrolysis liquid product without separating a solid salt, as illustrated in the examples.
  • One advantage of our novel hardeners is a fast rate of hardening of gelatin in photographic products.
  • the fast hardening is important in order to manufacture photographic products of constant quality without afterhardening.
  • Another advantage of our hardeners is that they have no influence on the photographic properties.
  • a further advantage of our novel hardeners is that hardening process is not affected adversely by the presence of other kinds of photographic additives. Consequently our novel hardeners are especially suited for hardening color photographic materials with color-forming couplers incorporated in gelatin layers.
  • a further advantage of our novel hardeners is the very low level of toxicity to human bodies.
  • Incorporating our novel hardeners in gelatin layers is performed in various ways, for example, by adding a hardener to a gelatin solution before coating or by dipping a dried gelatin layer into a hardener solution.
  • a pH of an aqueous gelatin composition is preferably kept within a range of 5 to 12. Beyond the range, a salt of 2,4-di chloro-6- hydroxy-s-triazine is hydrolyzed gradually to a dior tri-hydroxy derivative which gives a weaker'hardening effect than a monohydroxy derivative does.
  • our novel hardeners may be varied depending on the particular type of gelatin dispersion or emulsion employed, the amounts ranging 1.0 to 50 grams of hardeners per kilogram of dry gelatin are preferred in general, but when it is used in photographic materials l.0 to 30 grams are most suitable. In these amounts, eifective hardening is obtained to the extent that the treated gelatin layers are not damaged by the photographic process even at elevated temperature. In some cases, our novel hardeners can be used in combination withother classes of hardeners known heretofore, to give a better hardening effect.
  • EXAMPLE 1 66 grams of cyanuric chloride were added little by little to an alkaline solution of grams of sodium bicarbonate in 430 milliliters of water at 35 C. over one hour. The solution was kept at 35 C. for further one hour to produce a clear solution, and filtered. The filtrate was cooled overnight at about 5 C. to separate 50 grams of crude sodium salt of 2,4-dichloro-6-hydroxy-s-triazine as a precipitate. The pure hardener was obtained by recrystallizing the crude one from a slightly alkaline aqueous solution containing sodium bicarbonate.
  • the emulsion treated with the hardener showed the same photographic properties, color densities, speed, and fog, as those of the type not treated.
  • EXAMPLE 2 With vigorous stirring a hot solution of 660 grams of cyanuric chloride in 2.4 liters of acetone was added dropwise to a solution of 663 grams of sodium bicarbonate in 4 liters of water over one hour at 35 C. to obtain a clear solution of a pH of about 8.5. The solution was cooled to 20 C., filtered, and added with enough water to make 6.6 liter. Analysis indicated that the solution contained about 10 weight percent of sodium salt of 2,4- dichloro-6-hydroxy-s-triazine. The solution was mixed with l kilogram of iodobromide photographic emulsion containing 70 grams of gelatin. A cellulose triacetate film base was coated with the emulsion and dried at room temperature. The following results were obtained:
  • Photographic tests showed that the hardened film was free from fog and had not lost any speed or contrast when compared with the unhardened type.
  • the hardened material had excellent storage stability and did not suffer from any deterioration of photographic properties durmg storage.
  • EXAMPLE 3 to a pH of 7, cast over a cellulose triacetate film base, and dried at room temperature.
  • M is a member selected from the group consisting of alkali metals, alkaline earth metals, and NR radicals, and R is an alkyl radical containing 1 to 4 carbon atoms; casting said gelatin solution on said support'and drying.
  • M is a member selected from the group consisting of alkali metals, alkaline earth metals, and NR radicals, and R is an alkyl radical containing 1 to 4 carbon atoms; casting said emulsion on said support and drying.
  • M is a member selected from the group consisting of alkali metals, alkaline earth metals, and NR, radicals, and R is an alkyl radical containing 1 to 4 carbon atoms; and drying.
  • gelatin layer as claimed in claim 8, wherein said alkali metal is sodium.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

United States Patent 3,325,287 PHOTOGRAPHHC GELATIN HARDENING COMPOSITION Nobuo Yamamoto and Yasushi Oishi, Ashigarakami-gun, Kanagawa-ken, Japan, assignors to Fuji Shashin Film Kabushiki Kaisha, Ashigarakami-gun, Kanagawa-ken, Japan, a corporation of Japan No Drawing. Filed Nov. 26, 1963, Ser. No. 326,219 Claims. (Cl. 96111) This invention relates to an aqueous gelatin composition and hardening of gelatin with the Water-soluble dichlorotriazine compounds to impart enhanced resistance to water.
In most photographic materials, gelatin is used as their constituting elements, in silver halide emulsion layers, protective coatings, substratum layers to film base, antihalation layers, backing layers and so on. In photographic uses, such a gelatin layer is often treated with a succession of aqueous solutions which may vary in pH and in. temperature. The layers composed of untreated gelatin have poor resistance to water; in water the gelatin layers swell excessively and are scratched easily. Especially at high temperature, the gelatin layers dissolve in aqueous solutions.
A number of classes of compounds have been found useful for treating gelatin to improve the resistance to water. These compounds are called hardeners in photographic arts. These include, for example, inorganic compounds such as chromium potassium sulfate and organic compounds such as aldehyde, polyfunctional expoxide,
polyfunctional ethyleneimine, and polyfunctional acti- V vated vinyl compounds. The use of these hardeners in photographic products has been well known.
Almost all hardeners of the classes known heretofore, however, have exhibited unwanted effects when used in photographic products. One serious drawback concerns the unwanted effects on photographic properties; for example, an increase in fog of the emulsion and a loss of photographic sensitivity. Other difficulties frequently encountered with such hardeners are insufficient watersolubility causing nonuniformity of the gelatin layer, chemical instability of hardeners in solid or solution state, or toxicity in handling. Some hardeners lose their hardening effect when used in the presence of other kinds of photographic additives suchas stabilizers and colorforming couplers.
One object of our invention is to provide hardeners for gelatin which exhibit no detrimental photographic efffects. Another object of our invention is to provide substances which when mixed make the geltain insoluble in aqueous solutions of varying pH or temperature. A further object of our invention is to provide for hardening of gelatin by the use of water-soluble dichlorotriazine compounds. Other objects of our invention will appear herein.
We have found that gelatin is made resistant to water even at elevated temperature by incorporating therein water-soluble salts of 2,4-dichloro-fi-hydroxy-s-triazine, characterized by the general formula:
wherein M represents an alkalior alkaline-earth metal, e.g. a sodium, potassium, lithium, calcium, barium, or strontium atom, or a quaternary ammonium group, e.g. an ammonium tetramethylammonium, tetraethylammonium, tetrapropylammonium, or tetra'butylammonium group.
The cationic group represented by M in the foregoing formula can be selected from a wide range of cationic groups, because it plays a role only as a counter ion to a 2,4-dichloro-6-oxy-s-triazine anion which takes a part in crosslinking gelatin molecules.
The foregoing compounds are prepared by partial hydrolysis of cyanuric chloride in an alkaline aqueous solution under carefully controlled conditions, in a manner analogus to that described in the Journal of the Society of Organic Synthetic Chemistry, Japan, vol. 18, p. 175-183 (1960).
A water-soluble salt of 2,4-dichloro-6-hydr0xy-s-triazine may be added to a gelatin composition directly in the form of a partial-hydrolysis liquid product without separating a solid salt, as illustrated in the examples.
One advantage of our novel hardeners is a fast rate of hardening of gelatin in photographic products. The fast hardening is important in order to manufacture photographic products of constant quality without afterhardening. Another advantage of our hardeners is that they have no influence on the photographic properties. A further advantage of our novel hardeners is that hardening process is not affected adversely by the presence of other kinds of photographic additives. Consequently our novel hardeners are especially suited for hardening color photographic materials with color-forming couplers incorporated in gelatin layers. A further advantage of our novel hardeners is the very low level of toxicity to human bodies.
Incorporating our novel hardeners in gelatin layers is performed in various ways, for example, by adding a hardener to a gelatin solution before coating or by dipping a dried gelatin layer into a hardener solution.
'To obtain effective hardening a pH of an aqueous gelatin composition is preferably kept within a range of 5 to 12. Beyond the range, a salt of 2,4-di chloro-6- hydroxy-s-triazine is hydrolyzed gradually to a dior tri-hydroxy derivative which gives a weaker'hardening effect than a monohydroxy derivative does.
While the exact amount of our novel hardeners may be varied depending on the particular type of gelatin dispersion or emulsion employed, the amounts ranging 1.0 to 50 grams of hardeners per kilogram of dry gelatin are preferred in general, but when it is used in photographic materials l.0 to 30 grams are most suitable. In these amounts, eifective hardening is obtained to the extent that the treated gelatin layers are not damaged by the photographic process even at elevated temperature. In some cases, our novel hardeners can be used in combination withother classes of hardeners known heretofore, to give a better hardening effect.
While the following examples describe in detail the methods for accomplishing the objects stated above, it is to be understood that they are given merely for the purpose of illustration and are not to be construed as limiting the scope of our invention.
EXAMPLE 1 66 grams of cyanuric chloride were added little by little to an alkaline solution of grams of sodium bicarbonate in 430 milliliters of water at 35 C. over one hour. The solution Was kept at 35 C. for further one hour to produce a clear solution, and filtered. The filtrate was cooled overnight at about 5 C. to separate 50 grams of crude sodium salt of 2,4-dichloro-6-hydroxy-s-triazine as a precipitate. The pure hardener was obtained by recrystallizing the crude one from a slightly alkaline aqueous solution containing sodium bicarbonate.
Analysis.-Calculated for C Cl N ONa: C, 25.00%; N, 22.34%. Found: C, 24.83; N, 22.17%.
20 milliliters of a 2% aqueous solution of the hardener obtained were added to 1 kilogram of iodobromide photographic emulsion containing 80 grams of gelatin and 15 grams of a coupler formulated below. The emulsion was adjusted to a pH of 7, cast over a film base of polyethylene terephthalate, and dried.
comparison with an emulsion not treated with the hardener. The results are as follows:
Time elapsed after coating 2 days, 45 (3., 80% EH.
4 days 15 days 28 days Melting points in water, 0.
Not treated with hardener Treated with hardener-..
32 above 90 above 90 When developed in a color developer containing 4-amino-3-methyl-N,N-diethylaniline, the emulsion treated with the hardener showed the same photographic properties, color densities, speed, and fog, as those of the type not treated.
EXAMPLE 2 With vigorous stirring a hot solution of 660 grams of cyanuric chloride in 2.4 liters of acetone was added dropwise to a solution of 663 grams of sodium bicarbonate in 4 liters of water over one hour at 35 C. to obtain a clear solution of a pH of about 8.5. The solution was cooled to 20 C., filtered, and added with enough water to make 6.6 liter. Analysis indicated that the solution contained about 10 weight percent of sodium salt of 2,4- dichloro-6-hydroxy-s-triazine. The solution was mixed with l kilogram of iodobromide photographic emulsion containing 70 grams of gelatin. A cellulose triacetate film base was coated with the emulsion and dried at room temperature. The following results were obtained:
Time elapsed after coating Fresh 4 days 28 days Melting points in water, C.
Milliliters of the 10% hardener solutlon per 1 kg. of emulsion:
32 32 32 45 75 above 90 70 above 90 above 90 85 above 90 above 90 Photographic tests showed that the hardened film was free from fog and had not lost any speed or contrast when compared with the unhardened type. The hardened material had excellent storage stability and did not suffer from any deterioration of photographic properties durmg storage.
EXAMPLE 3 to a pH of 7, cast over a cellulose triacetate film base, and dried at room temperature.
SIO3H The following results were obtained:
Time elapsed after coating 4 days 15 days 28 days Melting points in water, C.
32 above 90 32 above 90 N 0t treated with hardener Treated with hardener EXAMPLE 4 A solution of 92 grams of cyanuric chloride in 300 milliliters of dioxane was poured into 700 milliliters of cold water of 0 to 5 C. with vigorous stirring to give a cyanuric chloride suspension. At the same temperature to this suspension 1,000 milliliters of 10% aqueous solution of tetramethyl ammonium hydroxide were added dropwise for one hour. The mixture was continued to be stirred for sufficient time to give a clear solution. The resulting solution was adjusted to a pH of about 8 and added with water to make 2.4 liters. Analysis of chlorine indicated that the solution contained 5 weight percent of tetramethyl ammonium salt of 2,4-dichloro-6-hydroxy s-triazine. 2O milliliters of the solution were added to 1 kilogram of 8% gelatin solution containing silver colloid. The dispersion was coated onto paper to produce a positive material for the diffusion transfer copying process. The hardened gelatin layer stored for 1 month at room temperature did not dissolve even in boiling water.
EXAMPLE 5 on 1the weight of gelatin of a compound having the formu a:
N C-Cl wherein M is a member selected from the group consisting of alkali metals, alkaline earth metals, and NR radicals, and R is an alkyl radical containing 1 to 4 carbon atoms; casting said gelatin solution on said support'and drying.
2. The gelatin layer as claimed in claim wherein said alkali metal is sodium.
3. The gelatin layer as claimed in claim 1 wherein said alkali metal is potassium.
4. A photographic silver halide-gelatin layer having a support therewith, the gelatin of which is hardened by incorporating in an aqueous emulsion of pH 5 to 12, 0.1 to 3 percent based on the weight of gelatin of a compound having the formula:
wherein M is a member selected from the group consisting of alkali metals, alkaline earth metals, and NR radicals, and R is an alkyl radical containing 1 to 4 carbon atoms; casting said emulsion on said support and drying.
5. The photographic emulsion layer as claimed in claim 4 wherein said alkali metal is sodium.
6. The photographic emulsion layer as claimed in claim 4 wherein said alkali metal is potassium.
7. The photographic emulsion layer as claimed in claim 4 wherein said aqueous emulsion contains a color-forming coupler.
8. A gelatin layer having a support therewith, the gelatin of which is hardened by incorporating by dipping said layer in an aqueous solution of pH 5 to 12 containing a hardening amount of compound having the formula:
wherein M is a member selected from the group consisting of alkali metals, alkaline earth metals, and NR, radicals, and R is an alkyl radical containing 1 to 4 carbon atoms; and drying.
9. The gelatin layer as claimed in claim 8, wherein said alkali metal is sodium.
10. The gelatin layer as claimed in claim 8, wherein said alkali metal is potassium.
References Cited UNITED STATES PATENTS OTHER REFERENCES Journal of the Society of Organic Synthetic Chemistry, Japan, Vol.18, pages to 183 (1960).
NORMAN G. TORCHIN, Primary Examiner. J. TRAVIS BROWN, Examiner.
J. RAUBITSCHEK, A. E. TANENll-IOLTZ,
Assistant Examiners.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,325,287 June 13, 1967 Nobuo Yamamoto et al.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 1, line 50, "efffect" read effect column 4,
lines 3 to 9, the formula should appear as shown below instead of as in the patent:
\ CONHCNHSS column 4, lines 60 to 65, the formula should appear as shown below instead of as in the patent:
column 4, line 72, for "claim" read claim 1 Signed and sealed this 6th day of August 1968.
ISEAL) Attest:
EDWARD M.FLETCHER,JR.
EDWARD J. BRENNER Attestlng Officer Commissioner of Patents

Claims (1)

  1. 4. A PHOTOGRAPHIC SILVER HALIDE-GELATIN LAYER HAVING A SUPPORT THEREWITH, THE GELATIN OF WHICH IS HARDENED BY INCORPORATING IN AN AQUEOUS EMULSION OF PH 5 TO 12, 0.1 TO 3 PERCENT BASED ON THE WEIGHT OF GELATIN OF A COMPOUND HAVING THE FORMULA:
US326219A 1963-11-26 1963-11-26 Photographic gelatin hardening composition Expired - Lifetime US3325287A (en)

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Application Number Priority Date Filing Date Title
US326219A US3325287A (en) 1963-11-26 1963-11-26 Photographic gelatin hardening composition
GB47135/63A GB1022656A (en) 1963-11-26 1963-11-28 Improvements in or relating to gelatin compositions
FR958288A FR1379255A (en) 1963-11-26 1963-12-24 New hard gelatin compositions
DEF41858A DE1284290B (en) 1963-11-26 1964-01-29 Process for curing photographic gelatin layers

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US326219A US3325287A (en) 1963-11-26 1963-11-26 Photographic gelatin hardening composition
GB47135/63A GB1022656A (en) 1963-11-26 1963-11-28 Improvements in or relating to gelatin compositions
FR958288A FR1379255A (en) 1963-11-26 1963-12-24 New hard gelatin compositions

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Cited By (40)

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US3542549A (en) * 1967-02-16 1970-11-24 Gaf Corp 2,4,6-trichloropyrimidine hardening agents for gelatin
US3645743A (en) * 1968-08-27 1972-02-29 Agfa Gevaert Ag Process for hardening protein layers
JPS4843320A (en) * 1971-10-01 1973-06-22
FR2208134A1 (en) * 1972-11-28 1974-06-21 Fuji Photo Film Co Ltd
JPS519609B1 (en) * 1971-05-18 1976-03-29
FR2353877A1 (en) * 1977-05-10 1977-12-30 Agfa Gevaert HARDENING SOLUTIONS FOR PHOTOGRAPHIC ELEMENTS
US4076538A (en) * 1974-12-03 1978-02-28 Ciba-Geigy Ag Process for crosslinking hydrophilic colloids with triazine compounds
US4116700A (en) * 1976-04-14 1978-09-26 Agfa-Gevaert, A.G. Process for hardening photographic layers
DE2820108A1 (en) * 1977-05-10 1978-11-23 Agfa Gevaert Ag CURING PROTEIN CONTAINING MATERIAL
US4222777A (en) * 1975-02-28 1980-09-16 Fuji Photo Film Co., Ltd. Process for forming color images
US4429039A (en) 1975-03-31 1984-01-31 Fuji Photo Film Co., Ltd. Photographic element
US4618570A (en) * 1984-03-27 1986-10-21 Konishiroku Photo Industry Co., Ltd. Silver halide photographic materials
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
US4661441A (en) * 1984-04-20 1987-04-28 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material
EP0228084A2 (en) 1985-12-25 1987-07-08 Fuji Photo Film Co., Ltd. Image forming process
US5108884A (en) * 1990-03-30 1992-04-28 Mitsubishi Paper Mills Limited Antistatically finished silver halide photographic photosensitive material
EP0514675A1 (en) 1991-04-22 1992-11-25 Fuji Photo Film Co., Ltd. Silver halide photographic materials and method for processing the same
US5252446A (en) * 1991-09-25 1993-10-12 Konica Corporation Silver halide color photographic light-sensitive material comprising a 1-pentachlorinated phenyl-5-pyrazolone coupler and specific red sensitizing dyes
US5275926A (en) * 1991-09-25 1994-01-04 Konica Corporation Silver halide color photographic light-sensitive material
US5302506A (en) * 1991-06-26 1994-04-12 Konica Corporation Silver halide photographic materials
US5470986A (en) * 1994-06-27 1995-11-28 E. I. Du Pont De Nemours And Company Imidazolium hardeners for hydrophilic colloid
EP0671655A3 (en) * 1994-03-11 1996-02-28 Du Pont Improved hardening of hydrophylic colloids with imidazolium and triazine combinations.
EP0724194A1 (en) 1995-01-30 1996-07-31 Fuji Photo Film Co., Ltd. Silver halide color photographic material
US5601971A (en) * 1991-06-18 1997-02-11 Sterling Diagnsotic Imaging, Inc. Hardening of hydrophilic colloids with imidazolium and triazine combinations
EP0782045A1 (en) 1995-12-27 1997-07-02 Agfa-Gevaert N.V. Silver halide colour photographic film element having a thermoplastic support capable of being marked by means of a laser
US6071688A (en) * 1998-07-29 2000-06-06 Eastman Kodak Company Providing additives to a coating composition by vaporization
US6570011B1 (en) * 1998-09-10 2003-05-27 Degussa Ag Method for producing a stabilized aqueous alkali metal-2-hydroxy-4,6-dichloro-s-triazine solution and the use thereof
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same
EP1974941A1 (en) 2007-03-29 2008-10-01 FUJIFILM Corporation Image-forming method using heat-sensitive transfer system
EP1974947A1 (en) 2007-03-28 2008-10-01 FUJIFILM Corporation Heat-sensitive transfer recording material and method of producing the same
EP1974950A1 (en) 2007-03-30 2008-10-01 FUJIFILM Corporation Thermal transfer image-receiving sheet and method for producing it
EP1974949A1 (en) 2007-03-28 2008-10-01 FUJIFILM Corporation Heat-sensitive transfer image-receiving sheet and production method thereof
EP1980408A2 (en) 2007-03-29 2008-10-15 FUJIFILM Corporation Heat-sensitive transfer sheet and image-forming method
EP1982839A1 (en) 2007-03-27 2008-10-22 FUJIFILM Corporation Heat-sensitive transfer image-forming method
EP1982840A1 (en) 2007-03-27 2008-10-22 FUJIFILM Corporation Heat-sensitive transfer sheet and image-forming method
EP2030798A2 (en) 2007-08-29 2009-03-04 Fujifilm Corporation Heat-sensitive transfer sheet
EP2042333A2 (en) 2007-09-28 2009-04-01 Fujifilm Corporation Heat-sensitive transfer sheet
EP2085244A1 (en) 2008-01-30 2009-08-05 Fujifilm Corporation Heat-sensitive transfer imageforming method
EP2298569A1 (en) 2009-09-16 2011-03-23 Fujifilm Corporation Heat-sensitive transfer image-receiving sheet
EP2338690A1 (en) 2009-12-25 2011-06-29 Fujifilm Corporation Method for forming images using a thermal transfer image-receiving sheet having a lenticular lens

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US2476536A (en) * 1947-11-18 1949-07-19 Gen Aniline & Film Corp 1, 3, 5-triazines as stabilizing agents for silver-halide emulsions
US2487569A (en) * 1948-07-21 1949-11-08 Gen Aniline & Film Corp Antistain baths for color photographic materials
US2819965A (en) * 1956-02-23 1958-01-14 Eastman Kodak Co Carboxymethylmercapto compounds as stabilizers for photographic emulsions
US2936227A (en) * 1955-01-14 1960-05-10 Geigy Ag J R Method for inhibiting the growth of plants
DE1085663B (en) * 1958-11-06 1960-07-21 Wolfen Filmfab Veb Process for hardening, in particular photographic glue and gelatin layers
US2950196A (en) * 1955-10-12 1960-08-23 Eastman Kodak Co Supersensitization of photographic emulsions using triazines
DE1090427B (en) * 1958-02-18 1960-10-06 Wolfen Filmfab Veb Process for hardening gelatin and glue, in particular photographic glue and gelatin layers
US2976152A (en) * 1958-12-19 1961-03-21 Gen Aniline & Film Corp Photographic gelatin layers containing triazine hardeners
US2983611A (en) * 1957-09-16 1961-05-09 Eastman Kodak Co Gelatin compositions containing hardeners
FR1319540A (en) * 1961-04-07 1963-03-01 Ciba Geigy Gelatin hardening process
US3138461A (en) * 1960-06-10 1964-06-23 Polaroid Corp Process for preparing silver halide emulsions containing gelatin derivatives

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2476536A (en) * 1947-11-18 1949-07-19 Gen Aniline & Film Corp 1, 3, 5-triazines as stabilizing agents for silver-halide emulsions
US2487569A (en) * 1948-07-21 1949-11-08 Gen Aniline & Film Corp Antistain baths for color photographic materials
US2936227A (en) * 1955-01-14 1960-05-10 Geigy Ag J R Method for inhibiting the growth of plants
US2950196A (en) * 1955-10-12 1960-08-23 Eastman Kodak Co Supersensitization of photographic emulsions using triazines
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US3645743A (en) * 1968-08-27 1972-02-29 Agfa Gevaert Ag Process for hardening protein layers
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US3898089A (en) * 1972-11-28 1975-08-05 Fuji Photo Film Co Ltd Silver halide photographic material containing a polyhydric alcohol, a glyoxal and a triazine
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US4222777A (en) * 1975-02-28 1980-09-16 Fuji Photo Film Co., Ltd. Process for forming color images
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US4181529A (en) * 1977-05-10 1980-01-01 Agfa-Gevaert N.V. Hardening of proteinaceous materials
US4216108A (en) * 1977-05-10 1980-08-05 Agfa-Gevaert N.V. Hardening solution for proteinaceous materials
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US5302506A (en) * 1991-06-26 1994-04-12 Konica Corporation Silver halide photographic materials
US5275926A (en) * 1991-09-25 1994-01-04 Konica Corporation Silver halide color photographic light-sensitive material
US5252446A (en) * 1991-09-25 1993-10-12 Konica Corporation Silver halide color photographic light-sensitive material comprising a 1-pentachlorinated phenyl-5-pyrazolone coupler and specific red sensitizing dyes
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US5470986A (en) * 1994-06-27 1995-11-28 E. I. Du Pont De Nemours And Company Imidazolium hardeners for hydrophilic colloid
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US6071688A (en) * 1998-07-29 2000-06-06 Eastman Kodak Company Providing additives to a coating composition by vaporization
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FR1379255A (en) 1964-11-20
GB1022656A (en) 1966-03-16

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