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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins

Definitions

• gelatin as will be readily understood to those skilled in the art, defines a manufactured product from collagen, which is a naturally occurring fibrous protein and a major protein component of skin, bone and certain other animal tissue. It has long been known that, depending upon its source, gelatin possesses both various desirable and undesirable physical and chemical characteristics when used in photographic elements and, more particularly, in light-sensitive emulsions.
• gelatin derived from cattle and most desirably from cattle bone and hides, is most useful for photographic purposes because bindeds comprising said cattle-derived gelatin are relatively permeable to developing solutions, have good physical characteristics, permit reasonably short processing times, and form silver halide emulsions which exhibit higher speed and higher contrast in comparison to gelatin derived from other sources.
• This invention relates to new gelatin compounds having sulfoalkyl groups attached to the gelatin molecule.
• Said compounds can be derived from pig and more particularly pigskin and are characterized by specific physical and chemical properties which distinguish them from all other pigskin gelatins.
• These new gelatin compounds are particularly useful in photographic elements and as binders in light-sensitive photographic emulsions.
• a significant feature of this invention is that our new sulfoalkyl gelatins possess photographic, sensitometric and physical properties heretofore thought available only through use of cattle-derived gelatin.
• our invention comprises providing a chemically modified pig and pigskin gelatin whose inherent detrimental characteristics, for example, its development restraint, have been removed while its other desirable physical characteristics have been retained within desirable and reproducible limits, as illustrated in Charts I and II hereafter.
• restraint to physical development we mean an inhibition by an exposed photographic emulsion to respond to development within the time desirably required to produce a visible image with corresponding good sensitometric effects.
• Said gelatin is characterized, in part, by being chemically com- 3 bined with a plurality of sulfoalkyl units, that is, alkyls of 3 to 4 carbon atoms. Said sulfoalkyl units are chemically united in recurring numbers on the gelatin macromolecule by reacting upon gelatin in alkaline solution with an alkyl sultone.
• repeating sulfoalkyl units impart generally decreased development restraining properties to light-sensitive emulsions such as pig gelatin emulsions containing said units and corresponding decreased desensitizing effects in concentrations of greater than about 3 by weight of gelatin. In concentrations of about 4 to about 6% by weight, the resistance to development restraint is completely overcome, i.e., the gelatin is substantially photographically inert to physical development restraint.
• gelatin is a naturally occurring protein composed of known alpha-amino acids, the composite structural arrangement and position of said acids in the gelatin molecule is largely unknown and at best speculative.
• Lysine is known to have a reactive omega-amino functional group substituted thereon.
• the highly complex gelatin molecule contains a multiplicity of reactive sites, some of which are known and identifiable, others are unknown and to date are unidentifiable since factors which contribute to the ultimate reactivity of a gelatin molecule-contained alphaamino acid, are contingent upon said acids unknown structural relationship to other alpha-amino acids present in the gelatin molecule.
• Example 3 which follows, describes the characteristics of the chromatograms of the modified and unmodified gelatin.
• the comparative data of these examples show with certainty that the poly sulfoalkylation of gelatin occurs substantially on those two recurring alpha-amino acid sites. Further, said poly sulfoalkylation appears to occur on the epsilon-amino group of each of said amino acid sites.
• viscosity can be determined by the rolling ball test, which test employs a viscosimeter to determine the length of time in seconds required by a metal ball to fall through a given distance of a solution of gelatin. This can also be measured equally Well in terms of inherent viscosity in water at a concentration of 0.25 gram per 100 milliliters of solution at 25 C. Isoelectric point can be determined conveniently employing mixed resins according to the procedure of Janus, Kenchington and Ward described in Research, volume 4, page 247 (1951). Color clarity is the measured amount of light transmitted through various solutions and rated on a photometer, for example, a lumitron. A test for determining jelly strength is described hereafter.
• a preferred embodiment of our invention comprises poly(sulfoalkyl) gelatin being characterized by having the following properties:
• novel sulfoalkylated polymers of our invention can be derived by reacting gelatin, such as pig and preferably pigskin and pig bone gelatin, With a suitable sulfoalkylating compound.
• gelatin such as pig and preferably pigskin and pig bone gelatin
• a suitable sulfoalkylating compound such as sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium sulfoalkylating compound, sodium sultone, sodium sultone, sodium sultone, sodium sultone, sodium sultone, sodium sultone, sodium sultone, sodium sultone, sodium sultone, sodium sultone, sodium sultone, sodium sultone, sodium sultone, sodium sultone, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bicarbonate, sodium bi
• the modified gelatin of our invention is pre pared by first plumping gelatin into cold water (that is, having a temperature of less than about 15 C.), raising the temperature to about 50 C. thereby melting the gelatin.
• the pH is then adjusted in the resulting solution or suspension to about 10.5 with an alkaline substance, such as sodium hydroxide, potassium bydroxide and the like.
• Alkyl sultone previously dissolved in a suitable solvent such as acetone, alcohol, benzene and the like, is added preferably with agitation and the pH is maintained at greater than about 7 and preferably at about 9.5 to about 10.5.
• the chemically modified gelatin is conveniently recovered by acidifying the solution to a pH of less than about 6, for example, by the addition of dilute sulfuric acid, dilute hydrochloric acid and the like.
• the poly(sulfoalkyl) gelatin is then chilled, noodled and Washed with cold water as is well known to those skilled in the gelatin art.
• Another preferred embodiment of our invention comprises sulfoalkylating gelatin under cold conditions and is effected by plumping flakes of gelatin, that is, pig gelatin, for example, into cold water (for example, distilled water) having a temperature of less than about 15 C.
• the pH is adjusted to about 9.5 to about 10 such as by the addition of magnesium oxide, for example, and the alkyl sultone, in water, is added to the plumped gelatin flakes.
• the temperature is depressed, for example, to about 7 C. for about four days.
• the poly(sulfoalkyl) gelatin thus prepared is washed to remove the alkaline substance, for example, magnesium oxide, and after leaching with dilute acetic acid, for example, is melted, filtered, chilled and dried.
• jelly strength is meant the firmness of resistance to deformation of a gel prepared under standard conditions. This is determined by use of a Bloom Gelometer and the values are customarily referred to as Bloom jelly strengths. By definition, this is the weight in grams required to produce by means of a plunger 12.7 mm. in diameter a depression of 4 mm. in the surface of a gel of a concentration of 6%% by weight, measured at 10 C.i0.1 C.
• Shoom jelly strength is a modification of the above valuation in that the concentration of the gelatin is more dilute, that is, reduced to about 6.1% by weight. In all other respects, these jelly strength tests are the same.
• a high jelly strength is desirable, that is, at least 150 and preferably between 200 and 295.
• Unmodified pigskin gelatin has a Shoom jelly strength of about 280 to about 260 but is possessed of heretofore unalterable and undesirable development restraint, and therefore is generally unsuitable in photographic applications.
• our poly(sulfoalkyl) gelatins can contain photographic addenda such as gelatin plasticizers, coating aids, and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bisulfite), maleic dialdehyde, azirdines, dioxane derivatives, oxypolysaccharides, vinylsulfonyl ethers and the like.
• photographic addenda such as gelatin plasticizers, coating aids, and hardeners such as aldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehyde bis(sodium bisulfite), maleic dialdehyde, azirdines, dioxane derivatives, oxypolysaccharides, vinylsulfonyl ethers and the like.
• Spectral sensitizers which can be used are the cyanines, merocyanines, complex (trinuclear) cyanines, complex (trinuclear) merocyanines, styryls, and hemicyanines.
• Sensitizing dyes useful in sensitizing such emulsions are described, for example, in 11.5. Pats. 2,526,632 of Brooker et al. issued Oct. 24, 1950, and 2,503,776 of Sprague issued Apr. 11, 1950.
• Developing agents can also be incorporated into the silver halide emulsion if desired or can be contained in a contiguous layer.
• silver salts can be used as the sensitive salt such as silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide or silver bromoiodide.
• the silver halides used can be those which form latent images predominantly on the surface of the silver halide grains or those which form latent images predominantly on the surface of the silver halide grains or those which form latent images inside the silver halide crystals such as described in US. Pat. 2,592,250 of Davey ct al. issued Apr. 8, 1952.
• the silver halide emulsion layer of a photographic element containing the poly(sulfoalkyl) gelatins of our invention can contain combined with, and in addition to, our gelatins any of the hydrophilic, water-permeable binding materials suitable for this purpose.
• concentration of our poly(sulfoalkyl) gelatins can vary from more than about to about 90%, by weight, of binding agent, e.g., gelatin used, and preferably is present in a concentration range of about 40 to about 75% by weight of total binder.
• Suitable materials include other gelatin, modified or unmodified, colloidal albumin, polyvinyl compounds, cellulose derivatives, acrylamide polymers, etc. Mixtures of these latter binding agents can also be used in combination with our sulfoalkyl gelatins.
• the binding agents for the emulsion layer of the photographic element can also contain dispersed polymerized vinyl compounds.
• dispersed polymerized vinyl compounds are disclosed, for example, in U.S. Pats. 3,142,568 of Nottorf issued July 28, 1964; 3,193,386 of White issued July 6, 1965; 3,062,674 of Houck et al. issued Nov. 6, 1962; and 3,220,844 of Houck et al., issued Nov. 30, 1965; and include the water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.
• novel poly(sulfoalkyl) gelatins of our invention are particularly useful in photographic elements and layers, for example, in various layers or protective coatings, and layers such as overcoats, antihalation layers, interlayers, and the like and in emulsion layers comprising light-sensitive materials as set forth herein.
• the silver halide emulsion of a photographic element containing the chemically modified gelatins of our invention can be coated on a wide variety of supports.
• Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, poly(ethylene terephthalate) film and related films or resinous materials as well as glass, paper, metal and the like.
• Supports such as paper which are coated with alpha-olefins polymers, particularly polymers of alpha-olefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethylene-butene copolymers and the like can also be employed.
• the speed of the photographic emulsions containing the new gelatins of our invention can be further enhanced by including in the emulsions a variety of hydrophilic colloids such as carboxymethyl protein of the type described in US. Pat. 3,011,890 of Gates et al. issued Dec. 5, 1961, and polysaccharides of the type described in Canadian Pat. 635,206 of Koller et al. issued Jan. 23, 1962.
• hydrophilic colloids such as carboxymethyl protein of the type described in US. Pat. 3,011,890 of Gates et al. issued Dec. 5, 1961, and polysaccharides of the type described in Canadian Pat. 635,206 of Koller et al. issued Jan. 23, 1962.
• Photographic elements and emulsions containing the gelatins of the invention herein can also contain speedincreasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers. Frequently, useful effects can be obtained by adding the aforementioned speed increasing compounds to the photographic developer solutions instead of, or in addition to, the photographic emulsions.
• speedincreasing compounds such as quaternary ammonium compounds, polyethylene glycols or thioethers.
• Photographic elements containing our new gelatins can be used in various kinds of photographic systems. In addition to being useful in X-ray and other non-optically sensitized systems, they can also be used in orthochromatic, panchromatic and infrared sensitive systems.
• the sensitizing addenda can be added to photographic systems before or after any sensitizing dyes which are used.
• Silver halide emulsions containing the sulfoalkyl gelatins of the invention can be used in color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other color-generating materials, emulsions of the mixed-packet type such as described in US. Pat. 2,698,- 794 of Godowsky issued 1 an. 4. 1955; in silver dye-bleach systems; and emulsions of the mixed-grain type such as described in US. Pat. 2,592,243 of Carroll et al. issued Apr. 8, 1952.
• Silver halide emulsions and elements containing the gelatins of the invention can be sensitized using any of the well-known techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur, selenium, tellurium compounds and/or gold compounds.
• the emulsions can also be sensitized with salts of noble metals of Group VIII of the Periodic Table which have an atomic weight greater than 100.
• Silver halide emulsions and elements containing the sulfoalkyl gelatins of our 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.
• 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 7 described in US. Pats. 2,352,014 of Rott issued June 20, 1944; 2,543,181 of Land issued Feb. 27, 1951; and 3,020,- 155 of Yackel et al. 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 light-sensitive layer to a second layer, while the two layers are in close proximity to one another.
• Silver halide emulsions and elements containing the gelatins of the invention can be processed in stabilization processes such as the ones described in US. Pat. 2,614,927 of Broughton et a1. issued Oct. 21, 1952, and as described in the article Stabilization Processing of Films and Papers by H. D. Russell et al. in P.S.A. Journal, Photographic Science and Technique, vol. 16B, October 1950.
• gelatins of this invention can be incorporated to advantage during manufacture in silver halide emulsions and elements representing the variations described.
• EXAMPLE 1 900 grams of pigskin gelatin are dissolved in 9 liters of distilled water at 50 C. Sodium hydroxide is added so as to adjust the pH of the solution to 10.5. Added with stirring are 27 grams (3% by weight of the pig gelatin) of 1,3-propanesultone in solution in 75 milliliters of acetone. Stirring is continued for 30 minutes with the pH of the solution being maintained at 10.0 by addition of sodium hydroxide as needed. Thereupon, the pH of the solution is lowered to 6.0 by adding dilute sulfuric acid. The resulting chemically modified gelatin solution is chilled, noodled, Washed and dried in customary fashion.
• Each sample is dried at 60 C. in vacuum for 16 hours.
• a sample of each of about 4 milligrams weight is weighed S exactly and is hydrolyzed in 5.5 N hydrochloric acid for 22 hours at 110 C. in a sealed system.
• Each is evaporated to dryness in a vacuum desiccator and is dissolved at pH 2.2 in a citrate buffer A (pH 2.2) and is diluted to 5 milliliters with citrate buffer A.
• One milliliter of the diluted solution is placed on a water jacketed ion exchange column containing sulfonated polystyrene resin (Beckman type B resin), said column being 50 centimeters long and 0.9 centimeter in diameter.
• the equipment used is a Beckman model 120 B amino acid analyzer.
• the column is eluted with citrate buffer B (pH of 3.28).
• the column temperature is in itially held at 30 C. changing to 50 C. after milliliters of eluent is passed through the column.
• Citrate buffer C pH 4.5
• the column eluent is automatically mixed with minhydrin reagent and the stream is put through a heated reaction coil at C. to develop characteristic blue colors for each amino acid.
• the colors formed are monitored in a Stream Colorimeter whose output is recorded on a strip chart recorder. This gives a separation of the acidic and neutral amino acids.
• Second 1 milliliter aliquot portions of each of the hydrolyzed samples in solution in citrate buffer A are taken and placed on a jacketed column of 0.6 centimeter diameter and 10 centimeters length which contain sulfonated polystyrene resin (Beckman type 15A).
• the sample is eluted with citrate buffer D (pH 5.28).
• citrate buffer D pH 5.28
• the column eluent is automatically mixed with ninhydrin reagent, the stream is put through a heated reaction coil at 100 C.
• the citrate buffers are principally composed of aqueous solutions of a mixture of sodium citrate and hydrochloric acid whose proportions are adjusted to supply the desired pH.
• Photocopies of the chromatograms of the samples of Example 2 and other examples which follow hereafter show the appearance of a new peak at each of the elution times of about 71 and 116 minutes.
• peaks When each of these peaks is compared to the percentage substitution, they indicate a linearity in the to about range and a leveling off in the 7% to about range.
• the lysine content decreases linearly up to about 7% or, to a value of .120 to .193 micromole per milligram.
• This new peak at each elution time appears to represent a primary sulfoalkylation of said reactive receiving sites.
• samples 25 and 7-11 are poly(sulfoalkylated) gelatins, the chemically modified reaction product between propanesulfone and pigskin gelatin.
• Example 1 is repeated but using 36 grams (4% by weight) of 1,3-propanesultone rather than the 27 grams.
• Example 1 is repeated but 54 grams (6% by weight) of 1,3-propanesultone are used.
• the gelatin is chilled, noodled, washed and dried in the usual manner.
• the chemically modified sulfoalkylated gelatins provide excellent sensitometric results and particularly good development restraint control within the time required for the various commercially available developers.
• our poly(sulfoalkyl) gelatin compares most favorably with cattle bone gelatin and in preferred ranges is inert to physical development restraint.
• EXAMPLE 6 200 grams of pigskin gelatin are plumped and melted in 2 /2 liters of distilled water at 50 C. Sodium hydroxide is added to adjust the pH to 10.5. 10 grams of 2,4-butanesultone in solution in acetone are stirred into the solution. The solution is held for minutes with occasional addition of NaOH to maintain the pH at 10.0. Thereupon the pH is lowered to 6.0 by adding dilute sulfuric acid.
• the gelatins obtained by the various examples are evaluated photographically by using the various modified and unmodified gelatins respectively as binders in a high speed silver bromoiodide (6 mole percent iodide) photographic emulsion.
• These various emulsions are coated on a cellulose acetate film base at a coverage of 540 milligrams of silver and 1225 milligrams of gelatin per square foot in which operation the coatings after application are chill set and dried.
• Each film strip is exposed on an Eastman Sensitometer Type IB and a continuous step wedge is used.
• the films are processed for the times specified in the following tables in Kodak Developer DK50 or in Developer D19 and are fixed for 5 minutes in Kodak Fixing Bath F5, washed and dried.
• the properties of these films when freshly processed and in some cases after a one-week incubation period holding at 50% relative humidity and 120 F. temperature are as follows:
• Poly(sulfoalkyl) gelatin containing recurring lysine sites of which about to about are sulfoalkylated and hydroxylysine sites of Which about 50 to about are sulfoalkylated, said gelatin being poly(sulfoall ;ylated) substantially on the epsilon amino groups of said lysine and hydroxylysine sites.
• Poly(sulfoalkyl) gelatin of claim 1 being characterized by having the following properties:
• Shoom jelly strength of about 150 to about 285; Color clarity of about to about Isoelectric point of about 4.3 to about 5.7; Viscosity of about 9.4 to about 12.7; Lysine micromoles per milligram of about 100 to about 200; and Hydroxylysine micromoles per milligram of about .015 to about .030. 3.
• a photographic element comprising a support and layer containing the poly(sulfoalkyl) gelatin of claim 1.
• a photographic gelatin silver halide emulsion comprising the poly(sulfoalkyl) gelatin of claim 1.
• the poly(sulfoalkyl) gelatin of claim 1 derived from pig collagen.
• a method of preparing a gelatin derivative which comprises reacting upon gelatin in alkaline solution with an alkyl sultone, the alkyl being of 3 to 4 carbon atoms.

Landscapes

• 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)
• Peptides Or Proteins (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=27002642

Family Applications (1)

Country Status (3)

Cited By (2)

Families Citing this family (7)

Citations (2)

• 1965
  • 1965-02-06 DE DEE28640A patent/DE1244573B/de active Pending
  • 1965-05-04 GB GB18736/65A patent/GB1033189A/en not_active Expired
• 1969
  • 1969-10-07 US US864556A patent/US3539353A/en not_active Expired - Lifetime

Patent Citations (2)

Also Published As

Similar Documents