US3490911A - Hardeners for photographic gelatin - Google Patents

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US3490911A
US3490911A US3490911DA US3490911A US 3490911 A US3490911 A US 3490911A US 3490911D A US3490911D A US 3490911DA US 3490911 A US3490911 A US 3490911A
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gelatin
bis
hardeners
photographic
parts
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Donald M Burness
Stanley W Cowan
Charles J Wright
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Eastman Kodak Co
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Eastman Kodak Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30Hardeners
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00Sulfones; Sulfoxides
    • C07C317/16Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/18Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/12Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds

Description

United States Patent US. Cl. 96-411 17 Claims ABSTRACT OF THE DISCLOSURE Certain compounds containing two or more vinylsulfonylalkyl groups attached to a plurality of tertiary or quaternary nitrogen atoms and/ or to a plurality of ether oxygen atoms are effective gelatin hardeners.

This application is a continuation-in-part of our copending application Ser. No. 488,797 filed Sept. 20, 1965 now abandoned.

This invention relatesto gelatin compositions in which a hardener has been incorporated, which hardener contains two or more vinylsulfonylalkyl groups. These groups can be attached to a plurality of tertiary or quaternary nitrogen atoms or to a plurality of ether oxygen atoms or a combination thereof.

Compounds having olefinic linkages have previously been referred to as useful for gelatin hardeners but nowhere in the prior art is there any indication that vinylsulfonylalkyl compounds are useful for this purpose.

One object of our invention is to provide effective hardeners for photographic gelatin and for gelatin-containing photographic emulsions. Another object of our invention is to provide gelatin hardeners which are free from undesirable photographic properties and have good water solubility, low volatility and low physiological activity. Other objects of our invention will appear herein.

We have found that compounds containing two or more vinylsulfonylalkyl groups (that is lower alkyl from 1 to 4 carbon atoms) attached to a plurality of tertiary or quaternary nitrogen atoms and/or a plurality of ether oxygen atoms are effective hardeners for gelatin and more particularly for photographic gelatin. The term photographic gelatin is interpreted as including gelatin derivatives and physical mixtures of gelatin and other colloids, such as mixtures of gelatin with compatible synthetic polymers exemplified by copolymers of methyl acrylate and acrylic acid or butyl acrylate and acrylic acid and the like. These compounds are effective not only in compositions in which gelatin is the sole vehicle but also where the vehicle is composed of a carboxylated polymer such as ethyl acrylate-acrylic acid copolymer and butyl acrylate-acrylic acid copolymer, for example, or a mixture thereof with gelatin. Some compounds which are useful as hardeners in accordance with this invention are as follows where V is used to represent CHFCHSO (CH where m is l or 2. These compounds are exemplified in the following:

voom-Q-cmov (VOC'H CCH (VOCH C HO VOCHz I OHzOV CHzOV VOCH2 and CH3 CH3 1 y fg-om-Qomlgivax- In the above R and R are alkyl of 1-4 carbons and X is an anion such as C H SO (310 CH OSO A structural formula representing compounds useful as hardeners in accordance with our invention is as follows:

in which n is an integer from 2 to 6; A is each R is an alkyl group of 1 to 4 carbon atoms, X is an anion, such as for example C l-I SO ClO CH OSO and the like; m is 1 or 2; Z is a polyvalent radical of n valences such as for example alkylene radicals of from 1 to 10 carbon atoms which can contain unsaturation or which can be interrupted by an arylene in which R and R are lower alkyl groups of 1-4 carbon atoms, each m is 1 or 2 and R represents an alkylene chain of from 1-10 carbon atoms which can contain unsaturation or which can be interrupted by an arylene radical, a cycloalkylene radical or by simple functional groups such as ether, sulfur or amide linkages. In addition, R and both R s together with the two nitrogen atoms can constitute a heterccyclic ring such as piperazine, alkyl substituted piperazines and the like, and X is any suitable anion, such as C l-I SO ClO CH OSO and the like.

The hardeners in accordance with our invention, when present in the gelatin composition, exert hardening action, however, for practical purposes ordinarily the amount of hardener used would be in the range of 05-15%, based on the weight of the gelatin in the compositions.

The compounds described in this application can be used effectively in combination with hardenable materials in general but they are most advantageously used with natural or synthetic polymers used as vehicles or binders in preparing photographic elements. Specific materials which can be hardened according to the practice of this invention include hardenable materials such as polymers, for example, gelatin, colloidal albumin, acid or watersoluble vinyl polymers, cellulose derivatives, proteins, various polyacrylamides, dispersed polymerized vinyl compounds, particularly those which increase the dimensional stability of photographic materials as exemplified by amine-containing polymers of alkyl acrylates, methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, maleic acid, and the like.

The hardening agents described herein can be used in various kinds of photographic emulsions. In addition to being useful in orthochromatic, panchromatic, and infrared emulsions, they are also useful in X-ray and other nonoptically sensitized emulsions. They can be added to the emulsions before or after the addition of any optically sensitizing dyes which may be used. They are effective in sulfur and gold sensitized silver halide emulsions.

The materials hardened in the practice of this inven tion can be coated on a wide variety of supports. Typical supports include those generally employed for photographic elements as exemplified by cellulose nitrate film, cellulose acetate film, polystyrene film, polyethylene terephthalate film, and related films or resinous materials as well as glass, paper, metal, wood, and the like. Supports such as paper that are coated with u-olefin polymers, particularly polymers of wolefins containing 2-10 carbon atoms, as for example, polyethylene, polypropylene, ethylene butene copolymers, and the like, can also be employed.

In addition to the hardening agents disclosed herein, photographic emulsions and elements can also contain additional additives, particularly those known to be beneficial in photographic emulsions, as exemplified by optical sensitizers, speed increasing materials, other hardeners, plasticizers, and the like, such as those described in Henn and Goife US. Patent 3,128,180 issued Apr. 7, 1964.

The emulsions hardened by new compounds can be used in photographic elements intended for color photography and thus may contain color-forming couplers or used as emulsions to be developed by solutions containing couplers or other color-generating materials or emulsions of the mixed-packet type.

The silver halides employed in the photographic emulsions include any of the photographic silver halides as exemplified by silver bromide, silver iodide, silver chloride, silver chlorobromide, silver chloroiodide, and the like. The silver halides used can be those which form latent images predominantly on the surface of the silver to limit the scope of the invention unless otherwise spev cifically indicated.

The following Examples 1-10 illustrate methods of preparing these hardening compounds and the tables following Examples 5 and 12 supply data indicating desirable photographic effects unexpectedly obtained using the various hardeners described herein.

EXAMPLE 1 N,N'-bis 2-vinylsulfonylethyl piperazine) A solution of 52 parts of divinyl sulfone in parts of dry chloroform is cooled to 10 C. and added dropwise thereto-with stirring at 10-15 C. is a solution of 17.2 parts of anhydrous piperazine in 100 parts of chloroform. A cloudy solution forms which is stirred for 7 hours and then left overnight. The mass is then treated with charcoal and the filtrate obtained is evaporated at reduced pressure on a water bath. The crude product is recrystallized first from ethyl acetate and then three times from acetone giving a colorless product having a melting point of -126 C.

EXAMPLE 2 N,N-bis 2-vinylsulfonylethyl) piperazine-bis- (methoperchlorate) A solution of 9.7 parts of N,N'-bis(2-vinylsulfonylethyl)piperazine and 16.7 parts of methyl p-toluenesulfonate in 50 parts of acetonitrile is stirred at room temperature for two hours and then refluxed overnight. The solution is treated with charcoal and the filtrate is evaporated at reduced pressure on a water bath to /2 volume and poured into ether. An oily precipitate is obtained. This precipitate is washed with ether, dissolved in a minimum amount of water and then treated with a concentrated solution of about 20 parts of sodium perchlorate in 10 parts of water. The product is induced to crystallize, is filtered, and then recrystallized from a minimum amount of water. The colorless product obtained melts at 191-192 C.

EXAMPLE 3 N,N' bis(2 vinylsulfonylethyl) N,N dimethyl 2 butene 1,4 diamine bis(metho p toluenesulfonate) (A) and the corresponding bis(methofluoborate) (B) The metho-toluene sulfonate is prepared in essentially the same manner as in the preceding example but using instead of N,N' bis(2 vinylsulfonylethyl) piperazine, N,N bis(2 vinylsulfonylethyl) N,N dimethyl 2 butene 1,4 diamine. The colorless product designated (A) melts at 235-236 C. Some of the product is converted to the fiuoborate by using aqueous fiuoboric acid producing a colorless product designated (B) having a melting point of approximately 288 C. at which temperature decomposition occurs.

EXAMPLE 4 N,N-bis 2-vinylsulfonylethyl) -N,N'-dimethyl-ethylenediamine bis (metho-p-toluenesulfonate) This compound having a melting point of approximately 197 C. is prepared in the same manner as in the preceding examples but using N,N-dimethylethylenedi amine as the starting material,

EXAMPLE 5 1,2-bis (vinylsulfonylmethoxy) ethane 5,8-dioxa-3,10-dithiadodecane-1,12-diol is prepared by 6 EXAMPLE 8 Bis [2-(2-vinylsulfonylethoxy)ethyl]sulfone The procedure described is repeated using 25 parts of divinyl sulfone and 15.4 parts of bis(2-hydroxyethyl) sulthe reaction of two molar proportions of sodium 2-hy- 5 droxyethylmercaptide with l,2-bis(.chloromethoxy)ethane fone i 20 parts of q .hmethyl slllfoxlde. usmg SPdmm in methanol, followed by evaporation of the solvent ethoxide catalyst. A liquid product 1s obta1ned havmg an The bis-sulfide is oxidized to the disulfone in hydrogen average molecular Welght of approxlmately peroxide according to the method of H. S. Schultz et al., EXAMPLE 9 J. Org. Chem., 28, 1140 (1963). 10

1,2 bis(2 chloroethylsulfonylmethoxy)ethane is preblsm (zvmylsulfonylethoxy)ethyl] urea pared by adding the disulfone diol to a large excess of 25 parts of divinyl sulfone and 14.8 parts of N,N- thionyl chloride containing a catalytic amount of N,N- b1s(2-hydroxyethyl)urea are reacted in 25 Parts Of y dimethylformamide, at room temperature. Evaporation acetonitrile and parts of dimethyl sulfoxide using of the excess thionyl chloride furnishes the crude chloride 15 sodium ethoxide catalyst. A product is obtained having which is dissolved in tetrahydrofuran and treated with an ge lar Weight of approximately 384. two molar proportions of triethylamine at 0 to 5 C.

After 24 hours, the triethylamine hydrochloride and sol- EXAMPLE 10 vent are removed to give an oily product of 11 1.4975.

The identity of this product is confirmed by NMR Spec 1,14-b1s(vmylsulfonyl)-3,6,9,12-tetraoxatetetradecane troscopy and elemental analysis. parts of divinyl sulfone and 15 parts of triethylene Samples of the compounds prepared in the preceding glycol are reacted to glve the product designated hereexamples are added to separate portions of a high-speed The product Obtained has an average molecular sil-ver bromoiodide emulsion which is panchromatically welght of sensitized with 1211 1cyanine dye.fi1Each emulsion sample is 0 EXAM 11 coa e on a ce u ose acetate In support at a coverage of 459 mg. of silver and 1040 milligrams of gelatin per NN'bls[ZTQ'VmYISUIiODYMhOXY)ethyl]dlmethyl' square foot. A sample of each film coating is exposed on ammomum p'tosylate an Eastman 1B sensitometer, processed for five minutes The reaction of 23.8 grams of N-methyldiethanolamine in Kodak DK- developer, fixed, washed, and dried with and 47.3 grams of divinylsulfone in 300 milliliters of the following results. acetonitrile containing sodium methoxide as catalyst and Hagdener Fresh Tests Percent Swell one., Example g./n1ole Ag Rel. Speed Gamma Fog Developer Fix Wash 2.4 110 1.22 780 7.2 132 1.12 630 14.4 120 .98 330 100 1.20 940 2.4 120 1. 22 700 7.2 115 1.28 510 14.4 107 1.27 0 Control 100 1- 2 810 4.8 123 1.28 660 14.4 112 1. 23 510 4.8 123 1.30 720 14.4 120 1. 30 750 4.8 102 1.30 520 14.4 76 .93 360 Control 100 3 800 5 2.4 49 1. 30 400 Control 100 1. 800

EXAMPLE 6 0.1 gram of hydroquinone yields an amine adduct which 1,2-bis (2-vinylsulfonylethoxy)ethane A few drops of a solution made by reacting sodium with excess ethylene glycol are added to a stirred solution of 6.2 parts of ethylene glycol in 23.6 parts of freshly distilled divinyl sulfone stabilized with less than 0.1% of hydroquinone. A rapid temperature rise indicates reaction is occurring. The reaction temperature is kept below 35 C. and a few crystals of hydroquinone are added. After 48 hours, the reaction mixture is neutralized with glacial acetic acid and any volatile compounds are removed under vacuum (0.5 mm, 30 C., five hours) and the mass is filtered. A product is obtained having an average molecular weight of approximately 293.

EXAMPLE 7 1,4-bis(2-vinylsulfonylethoxy)butane A procedure is effected in the same .manner as the preceding example but using 24 parts of divinyl sulfone and 9 parts 1,4-butanediol in 20 parts of dry dichloromethane as the reaction medium. A liquid product is obtained having an average molecular weight of approximately 227.

is quaternized in solution with 37.2 grams of methyl p-tosylate. Isolation by precipitating into ether produces a light-colored oil of 11 1.5310.

EXAMPLE 12 N,N-bis [2- (2-vinylsulfonylethoxy) ethyl] dimethylammonium perchlorate -By treating 21.7 grams of the tosylate of the preceding example with 6 grams of sodium perchlorate in acetonitrile produces, after filtering and removing of the solvent, a viscous oil of n;,;, 1.4983.

Samples of the compounds prepared in Examples 6-12 are added to separate portions of a high-speed silver bromoiodide emulsion which are panchromatically sensitized with a cyanine dye. Each emulsion sample is coated on a cellulose acetate film support at a coverage of 459 mg. of silver and 1040 mg. of gelatin per square foot. Samples of the various films are exposed on an Eastman 1B sensitometer, processed for five minutes in Kodak Developer DK-50, fixed, washed, and dried. The proportions of hardener used, the example from which the hardener was derived, the photographic tests on the fresh Fresh Tests Example Hardener Cone. Rel. Percent No. (g./mle Ag) Speed Gamma Fog Swell 100 1. 23 13 750 95 1. 18 12 420 89 1. 13 12 270 85 1. 12 220 100 1. 32 750 87 1. 20 14 300 100 1. 34 21 750 S0 1. l3 16 200 82 1. 18 16 230 100 1. 19 760 105 1. 20 16 340 100 1. 34 28 620 170 1. 17 35 430 219 1. 00 37 320 204 O. 97 35 230 178 1. 05 39 410 155 0. 87 43 280 191 0. 93 46 260 The hardeners in accordance with our invention have shown themselves to be useful in color photography such as in photographic emulsions in which color couplers have been incorporated. The use of these hardeners results in reduced stain with no adverse sensitometric effects when used in levels producing satisfactory hardness in contrast with some of the aldehyde types of gelatin hardeners. No adverse effect upon dye hue or stability of the emulsion has been observed. For instance, in a photographic product in which coatings of the following structure were applied to a support these hardeners have been used with good effect:

Layer 6Gelatin layer.

Layer 5-Red-sensitive silver chlorobromide gelatin consisting of 90 mole percent bromide and a phenolic cyan coupler of the type described in U.S. Patent 2,423,730.

Layer 4Gelatin layer and an ultraviolet absorber.

Layer 3Gr een-sensitive silver chlorobromide gelatin emulsion consisting of 80 mole percent chloride and a pyrazolone magenta coupler of the types described in U.S. Patent 2,600,788.

Layer 2Gelatin layer.

Layer 1-Blue-sensitive silver chlorobromide gelatin emulsion consisting of 98 mole percent bromide and an acyl acetanilide yellow coupler of the type described in U.S. Patent 2,875,057.

The hardeners in accordance with our invention can be used in all six of the layers of the product or they can be used in the emulsion compositions with other hardeners being used in the gelatin layers if desired. In such use improvement in stain is obtained as compared with the use of a hardener such as formaldehyde or mucochloric acid.

Silver halide emulsions containing the hardeners of the invention can be used in diffusion transfer processes which utilize the undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer. Such processes are described in U.S. Patents 2,352,014 of Rott issued June 20, 1944; 2,543,181 of Land issued Feb. 27, 1951; and 3,020,155 of Yackel, Yutzy, Foster and Rasch issued Feb. 6, 1962. The emulsions can also be used in diffusion transfer color processes which utilize a diffusion transfer of an imagewise distribution of developer, coupler or dye, from a lightsensitive layer to a second layer, while the two layers are in close proximity to one another. Such processes are described in Rogers U.S. Patent 2,983,606 issued May 9, 1961; Weyerts et al. U.S. Patent 3,253,915 issued May 31, 1966; and Whitmore U.S. Patent 3,227,552 issued Jan. 4, 1966. Silver halide emulsions containing the hardeners of the invention can be processed in stabilization processes such as the ones described in U.S. Patent 2,614,927 of Broughton and Woodward issued Oct. 21,

8 1952, and as described in the article Stabilization Processing of Films and Papers by H. D. Russell, E. C. Yackel and J. S. Bruce in P. S. A. Journal, Photographic Science and Technique, vol. 16B, October 1950.

The hardeners of this invention can be used to harden silver halide emulsion and other photographic layers containing silver halide developing agents such as polyhydroxy benzene, amino phenol and 3-pyrazolidone developing agents.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be efiected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. A composition of matter comprising a hydrophilic colloid and a hardener of the formula:

[CH =CHSO (CH A] Z where each A is R being an alkyl group of 1 to 4 carbon atoms, X is an acid anion, Z is a polyvalent radical of n valences, n is an integer within the range of from 2 to 6 and m is 1 or 2.

2. A composition of matter comprising a hydrophilic colloid and a hardener of the following formula:

wherein each R is a lower alkyl group, R represents an alkylene chain which can contain unsaturation or which can be interrupted by an arylene or cycloalkylene radical or by simple functional groups, or R and both Rfs together with the two nitrogen atoms constitute a heterocyclic ring and m is 1 or 2.

3. A composition comprising a hydrophilic colloid and a hardener having the following formula:

in which each R and R are lower alkyl groups, in is 1 or 2, X is an acid anion, R represents an alkylene chain which can contain unsaturation or can be interrupted by an arylene radical, a cycloalkylene radical or simple functional groups, or R and both R s together with the two nitrogen atoms constitute a heterocyclic ring.

4. A composition of matter comprising gelatin and N,N'-bis(2Pvinylsulfonylethyl)piperazine.

5. A composition of matter comprising gelatin and N,N-bis(2 vinylsulfonylethyl)piperazine bis (methoperchlorate).

6. A composition of matter comprising gelatin and N,N'-bis(2 vinylsulfonylethyl)-N,N-dimethyl-2-butene- 1,4-diamine bis (metho-p-toluenesulfonate 7. A composition of matter comprising gelatin and N,N'-bis(2 vinylsulfonylethyl)-N,N'-dimethylethylene dia-mine bis (metho-p-toluenesulfonate 8. A composition of matter comprising gelatin and N,N'-bis[2 (-2 vinylsulfonylethoxy)ethyl]dimethylammonium p-tosylate.

9. A composition of matter comprising gelatin and N,N-bis[2 (2 vinylsulfonylethoxy)ethylJdimethylammonium perchlorate.

10. A gelatin-silver halide photographic emulsion containing as a hardener therein a compound having the structural formula:

[CH =CHSO (CH A Z where A is wherein R is an alkyl group of 1-4 carbon atoms, X is an acid anion, Z is a polyvalent radical of n valences and n is an integer from 2 to 6, and m is 2.

11. A gelatin-silver halide photographic emulsion containing therein as a hardener N,N'-bis(2-vinylsulfonylethyl) piperazine bis (methoperchlorate 12. A gelatin-silver halide photographic emulsion containing therein as a hardener N,N'-'bis(2-vinylsu1fonylethyl -N,N'-dimethyl-2-butene-1,4-diamine bis (metho-ptoluenesulfonate) 13. A gelatin-silver halide photographic emulsion for use in color photography containing a coupler and as a hardener therein a compound having the following structural formula:

[CH =CHSO (CH A] Z where A is wherein R is an alkyl group of 1 to 4 carbon atoms, X is an acid anion, Z is a polyvalent radical of n valences, n is an integer from 2 to 6, and m is 1 or 2.

14. A gelatin-silver halide photographic emulsion for use in color photography containing a coupler and, as a hardener therein, a compound having the following structural formula:

in which m is 1 or 2, each R is a lower alkyl group of 1 to 4 carbon atoms, R represents an alkylene chain of from 1 to 10 carbon atoms which can contain unsaturation or is interrupted by an arylene or cycloalkylene radical or by simple functional groups and R and both Rfs together with the two nitrogen atoms constitute a heterocyclic ring.

15. A composition of matter comprising a hydrophilic colloid and a hardener of the following formula:

in which each R and R are lower alkyl groups, m is 1 or 2, X is an acid anion, and R represents an alkylene chain.

17. A gelatin-silver halide photographic emulsion for use in color photography containing a coupler and as a hardener therein a compound having the following structural formula:

in which m is 1 or 2, each R is a lower alkyl group of 1-4 carbon atoms and R represents an alkylene chain.

References Cited UNITED STATES PATENTS 2,994,611 8/1961 Heyna et a1. 96111 3,061,436 10/ 1962 Hemmelmonn 961 11 X 3,132,945 5/1964 Ryan 96-111 X NORMAN G. TORCHIN, Primary Examiner R. E. FICHTER, Assistant Examiner US. Cl. X.R. 106l25; 260117

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Cited By (45)

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US3642486A (en) * 1970-03-19 1972-02-15 Eastman Kodak Co Vinylsulfonyl-containing compounds as hardening agents
US3868257A (en) * 1971-12-30 1975-02-25 Mitsubishi Paper Mills Ltd Hardeners for photographic gelatin
US3977881A (en) * 1974-01-31 1976-08-31 Ciba-Geigy Ag Acylurea compounds
DE2635518A1 (en) * 1975-08-09 1977-03-10 Konishiroku Photo Ind A method for hardening photographic gelatin and its use for producing a silver halide photographic material
US4028320A (en) * 1975-04-25 1977-06-07 Fujii Photo Film Co., Ltd. Method of hardening gelatin using sulfonyl compounds
US4088495A (en) * 1974-10-14 1978-05-09 Konishiroku Photo Industry Co., Ltd. Silver halide photographic element containing a gelatinous layer hardened with an aliphatic hydrocarbon having at least three vinylsulfonyl groups
JPS5376025A (en) * 1976-12-17 1978-07-06 Fuji Photo Film Co Ltd Prevention method for uneven transfer of color diffusion transfer image
US4108848A (en) * 1973-10-08 1978-08-22 Konishiroku Photo Industry Co., Ltd. Method for hardening gelatin
US4120898A (en) * 1976-02-04 1978-10-17 Ciba-Geigy Ag Sulfur containing vinyl amide cross-linking agents
US4134765A (en) * 1975-10-31 1979-01-16 Ciba-Geigy Ag Vinylsulphone hardener
US4134770A (en) * 1976-09-22 1979-01-16 Mitsubishi Paper Mills, Ltd. Gelatin-containing photographic layer incorporated with hardener
US4161407A (en) * 1977-10-06 1979-07-17 Eastman Kodak Company Crosslinkable polymers having vinylsulfonyl groups or styrylsulfonyl groups and their use as hardeners for gelatin
US4190447A (en) * 1978-01-09 1980-02-26 Eastman Kodak Company Cover sheets for integral imaging receiver elements
EP0115351A2 (en) 1983-01-28 1984-08-08 Fuji Photo Film Co., Ltd. Silver halide light-sensitive material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
US4840890A (en) * 1985-06-29 1989-06-20 Agfa-Gevaert Aktiengesellschaft Hardened proteinic binder layer
US4874687A (en) * 1986-11-18 1989-10-17 Fuji Photo Film Co., Ltd. Method for forming an image
US5187259A (en) * 1990-11-14 1993-02-16 Eastman Kodak Company Chain extended gelatin
US5219992A (en) * 1990-06-18 1993-06-15 Eastman Kodak Company Modification of gelatin
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
US5286450A (en) * 1992-06-01 1994-02-15 Eastman Kodak Company Bilirubin assay using crosslinkable polymers
US5302506A (en) * 1991-06-26 1994-04-12 Konica Corporation Silver halide photographic materials
US5318889A (en) * 1992-12-21 1994-06-07 Eastman Kodak Company Use of chain-extended acid processed ossein gelatin in the preparation of photographic elements
US5378598A (en) * 1992-12-21 1995-01-03 Eastman Kodak Company Use of acid processed ossein gelatin and chain-extened acid processed ossein gelatin as peptizers in the preparation of photographic emulsions
US5405741A (en) * 1992-06-01 1995-04-11 Eastman Kodak Company Fast-acting viscosity enhancers for gelatin solutions
US5441852A (en) * 1991-12-27 1995-08-15 Konica Corporation Method of stabilizing a color silver halide image
US5514535A (en) * 1995-05-10 1996-05-07 Eastman Kodak Company Stabilized vinyl sulfone hardening compositions useful in photographic manufacturing
US5580705A (en) * 1991-12-27 1996-12-03 Konica Corporation Method of bleaching silver halide color photographic light-sensitive materials using particular ferric chelates
US5658721A (en) * 1995-12-21 1997-08-19 Eastman Kodak Company Stabilized vinyl sulfone hardening compositions useful in photographic manufacturing
US5800977A (en) * 1996-07-24 1998-09-01 Eastman Kodak Company Hardening a hydrophilic colloid composition
US6020398A (en) * 1998-05-22 2000-02-01 Eastman Kodak Company Pigmented ink jet inks for poly (vinylalcohol) receivers
US6045219A (en) * 1998-05-22 2000-04-04 Eastman Kodak Company Pigmented ink jet prints on gelatin overcoated with hardeners
US6074057A (en) * 1998-05-22 2000-06-13 Eastman Kodak Company Pigmented ink jet inks and recording elements containing hardening agents
US6082853A (en) * 1998-05-22 2000-07-04 Eastman Kodak Company Printing apparatus with processing tank
US6161929A (en) * 1998-05-22 2000-12-19 Eastman Kodak Company Inkjet images on PVA overcoated with hardener solution
US6176574B1 (en) 1998-05-22 2001-01-23 Eastman Kodak Company Printing apparatus with spray bar for improved durability
US6254230B1 (en) 1998-05-22 2001-07-03 Eastman Kodak Company Ink jet printing apparatus with print head for improved image durability
US6435678B1 (en) 1998-05-22 2002-08-20 Eastman Kodak Company Waterfast ink jet images treated with hardeners
US20060062898A1 (en) * 2004-09-17 2006-03-23 Eastman Kodak Company Method of making a display sheet comprising discontinuous stripe coating
US20060181658A1 (en) * 2005-02-16 2006-08-17 Eastman Kodak Company Conductive absorption layer for flexible displays
US20060215077A1 (en) * 2005-03-22 2006-09-28 Eastman Kodak Company High performance flexible display with improved mechanical properties
US7507449B2 (en) 2006-05-30 2009-03-24 Industrial Technology Research Institute Displays with low driving voltage and anisotropic particles
DE112007001129T5 (en) 2006-06-29 2009-07-09 Industrial Technology Research Institute Guest-host polymer dispersed liquid crystal display on a single substrate
EP2385425A1 (en) 2010-05-07 2011-11-09 Fujifilm Corporation Silver halide photographic light-sensitive material for movie

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US3642486A (en) * 1970-03-19 1972-02-15 Eastman Kodak Co Vinylsulfonyl-containing compounds as hardening agents
US3868257A (en) * 1971-12-30 1975-02-25 Mitsubishi Paper Mills Ltd Hardeners for photographic gelatin
US4108848A (en) * 1973-10-08 1978-08-22 Konishiroku Photo Industry Co., Ltd. Method for hardening gelatin
US3977881A (en) * 1974-01-31 1976-08-31 Ciba-Geigy Ag Acylurea compounds
US4088495A (en) * 1974-10-14 1978-05-09 Konishiroku Photo Industry Co., Ltd. Silver halide photographic element containing a gelatinous layer hardened with an aliphatic hydrocarbon having at least three vinylsulfonyl groups
US4028320A (en) * 1975-04-25 1977-06-07 Fujii Photo Film Co., Ltd. Method of hardening gelatin using sulfonyl compounds
DE2635518A1 (en) * 1975-08-09 1977-03-10 Konishiroku Photo Ind A method for hardening photographic gelatin and its use for producing a silver halide photographic material
US4134765A (en) * 1975-10-31 1979-01-16 Ciba-Geigy Ag Vinylsulphone hardener
US4120898A (en) * 1976-02-04 1978-10-17 Ciba-Geigy Ag Sulfur containing vinyl amide cross-linking agents
US4134770A (en) * 1976-09-22 1979-01-16 Mitsubishi Paper Mills, Ltd. Gelatin-containing photographic layer incorporated with hardener
JPS5376025A (en) * 1976-12-17 1978-07-06 Fuji Photo Film Co Ltd Prevention method for uneven transfer of color diffusion transfer image
US4161407A (en) * 1977-10-06 1979-07-17 Eastman Kodak Company Crosslinkable polymers having vinylsulfonyl groups or styrylsulfonyl groups and their use as hardeners for gelatin
US4190447A (en) * 1978-01-09 1980-02-26 Eastman Kodak Company Cover sheets for integral imaging receiver elements
EP0115351A2 (en) 1983-01-28 1984-08-08 Fuji Photo Film Co., Ltd. Silver halide light-sensitive material
US4568635A (en) * 1983-01-28 1986-02-04 Fuji Photo Film Co., Ltd. Silver halide light-sensitive material
EP0204530A2 (en) 1985-05-31 1986-12-10 Konica Corporation Method for forming direct positive color image
US4840890A (en) * 1985-06-29 1989-06-20 Agfa-Gevaert Aktiengesellschaft Hardened proteinic binder layer
US4874687A (en) * 1986-11-18 1989-10-17 Fuji Photo Film Co., Ltd. Method for forming an image
US5219992A (en) * 1990-06-18 1993-06-15 Eastman Kodak Company Modification of gelatin
US5187259A (en) * 1990-11-14 1993-02-16 Eastman Kodak Company Chain extended gelatin
US5302506A (en) * 1991-06-26 1994-04-12 Konica Corporation Silver halide photographic materials
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
US5441852A (en) * 1991-12-27 1995-08-15 Konica Corporation Method of stabilizing a color silver halide image
US5580705A (en) * 1991-12-27 1996-12-03 Konica Corporation Method of bleaching silver halide color photographic light-sensitive materials using particular ferric chelates
US5405741A (en) * 1992-06-01 1995-04-11 Eastman Kodak Company Fast-acting viscosity enhancers for gelatin solutions
US5286450A (en) * 1992-06-01 1994-02-15 Eastman Kodak Company Bilirubin assay using crosslinkable polymers
US5378598A (en) * 1992-12-21 1995-01-03 Eastman Kodak Company Use of acid processed ossein gelatin and chain-extened acid processed ossein gelatin as peptizers in the preparation of photographic emulsions
US5536630A (en) * 1992-12-21 1996-07-16 Eastman Kodak Company Use of acid processed ossein gelatin and chain-extended acid processed ossein gelatin as peptizers in the preparation of photographic elements
US5318889A (en) * 1992-12-21 1994-06-07 Eastman Kodak Company Use of chain-extended acid processed ossein gelatin in the preparation of photographic elements
US5514535A (en) * 1995-05-10 1996-05-07 Eastman Kodak Company Stabilized vinyl sulfone hardening compositions useful in photographic manufacturing
US5658721A (en) * 1995-12-21 1997-08-19 Eastman Kodak Company Stabilized vinyl sulfone hardening compositions useful in photographic manufacturing
US5800977A (en) * 1996-07-24 1998-09-01 Eastman Kodak Company Hardening a hydrophilic colloid composition
US6435678B1 (en) 1998-05-22 2002-08-20 Eastman Kodak Company Waterfast ink jet images treated with hardeners
US6045219A (en) * 1998-05-22 2000-04-04 Eastman Kodak Company Pigmented ink jet prints on gelatin overcoated with hardeners
US6074057A (en) * 1998-05-22 2000-06-13 Eastman Kodak Company Pigmented ink jet inks and recording elements containing hardening agents
US6082853A (en) * 1998-05-22 2000-07-04 Eastman Kodak Company Printing apparatus with processing tank
US6020398A (en) * 1998-05-22 2000-02-01 Eastman Kodak Company Pigmented ink jet inks for poly (vinylalcohol) receivers
US6176574B1 (en) 1998-05-22 2001-01-23 Eastman Kodak Company Printing apparatus with spray bar for improved durability
US6254230B1 (en) 1998-05-22 2001-07-03 Eastman Kodak Company Ink jet printing apparatus with print head for improved image durability
US6161929A (en) * 1998-05-22 2000-12-19 Eastman Kodak Company Inkjet images on PVA overcoated with hardener solution
US20060062898A1 (en) * 2004-09-17 2006-03-23 Eastman Kodak Company Method of making a display sheet comprising discontinuous stripe coating
US20060181658A1 (en) * 2005-02-16 2006-08-17 Eastman Kodak Company Conductive absorption layer for flexible displays
US7630029B2 (en) 2005-02-16 2009-12-08 Industrial Technology Research Institute Conductive absorption layer for flexible displays
US20060215077A1 (en) * 2005-03-22 2006-09-28 Eastman Kodak Company High performance flexible display with improved mechanical properties
US7557875B2 (en) 2005-03-22 2009-07-07 Industrial Technology Research Institute High performance flexible display with improved mechanical properties having electrically modulated material mixed with binder material in a ratio between 6:1 and 0.5:1
US7507449B2 (en) 2006-05-30 2009-03-24 Industrial Technology Research Institute Displays with low driving voltage and anisotropic particles
DE112007001129T5 (en) 2006-06-29 2009-07-09 Industrial Technology Research Institute Guest-host polymer dispersed liquid crystal display on a single substrate
EP2385425A1 (en) 2010-05-07 2011-11-09 Fujifilm Corporation Silver halide photographic light-sensitive material for movie

Also Published As

Publication number Publication date Type
DE1808684A1 (en) 1969-07-24 application
BE686440A (en) 1967-02-15 grant
DE1547733B2 (en) 1973-01-25 application
GB1256709A (en) 1971-12-15 application
DE1547733A1 (en) 1970-01-02 application
BE723807A (en) 1969-04-16 grant
FR1591428A (en) 1970-04-27 grant
US3642908A (en) 1972-02-15 grant
GB1158263A (en) 1969-07-16 application

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