EP0027533B1 - Photographische Materialien, Verfahren zu ihrer Herstellung, ihre Verwendung und die Verwendung von Gelatinen - Google Patents

Photographische Materialien, Verfahren zu ihrer Herstellung, ihre Verwendung und die Verwendung von Gelatinen Download PDF

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Publication number
EP0027533B1
EP0027533B1 EP80105372A EP80105372A EP0027533B1 EP 0027533 B1 EP0027533 B1 EP 0027533B1 EP 80105372 A EP80105372 A EP 80105372A EP 80105372 A EP80105372 A EP 80105372A EP 0027533 B1 EP0027533 B1 EP 0027533B1
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EP
European Patent Office
Prior art keywords
gelatin
photographic
weight
photographic material
production
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP80105372A
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German (de)
English (en)
French (fr)
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EP0027533A1 (de
Inventor
Ivan Dr. Tomka
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cessione ilford AG
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Ciba Geigy AG
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Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0027533A1 publication Critical patent/EP0027533A1/de
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Publication of EP0027533B1 publication Critical patent/EP0027533B1/de
Expired legal-status Critical Current

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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

  • the present invention relates to a photographic material which contains in at least one layer as a binder a gelatin containing microgel, oligomers of a-gelatin, a-gelatin and fragments of a-gelatin (peptides).
  • gelatin is a purified protein which is obtained from the scleroprotein (scaffold protein) collagen by partial hydrolysis. Due to the diversity of the raw materials used in gelatin production, namely the skin material of cattle and calves, pork rind and ossein (demineralized, mostly shredded bones), as well as the technologically very different manufacturing processes, the gelatin obtained varies considerably in its chemical and physical properties.
  • the raw material is usually subjected to an alkaline digestion, for example by means of lime milk or sodium hydroxide solution (so-called “ashing") and then melted out in an essentially neutral solution.
  • an alkaline digestion for example by means of lime milk or sodium hydroxide solution (so-called “ashing") and then melted out in an essentially neutral solution.
  • the so-called “acid digestion process” is known, in which the alkaline pretreatment is omitted and is melted out in an acid medium.
  • the gelatin solutions obtained in each case are filtered, concentrated and dried. Details of the gelatin production process are known eg from G. Reich, "collagen", 1966, p 242 ff, Verlag Theodor Steinkopff, Dresden and AG Ward and A. Courts, "S c i ence and Technology of Gelatin", 1977, Academic Press, known.
  • the properties of the gelatin obtained in this way depend to a large extent on the raw material used, on the selected pulping process and particularly strongly on the reaction conditions during the pulping, extraction and drying.
  • the methods of gelatin production and the achievement of certain desired properties are largely based on empirical experience. A considerable degree of reproducibility is thus achieved.
  • gelatins which are used for the production of photographic products must always be tested in a practical test. Otherwise it would not be possible to produce photographic materials with the required uniformity.
  • the main component of the raw materials is the so-called tropocollagen, a well-defined protein molecule, which consists of two identical ⁇ 1 chains and a slightly different ⁇ 2 chain, which are linked together near their N-terminal amino acid.
  • the amino acid sequence of the a 1 chain is precisely known in the case of calf skin collagen; the polypeptide consists of a linear chain of 1,052 amino acids. See PI Rose & S. Gross “Photographic Gelatine", (Ed. RJ Cox), p. 89, Academic Press 1976.
  • microgel the fraction with the highest molecular weight, called “microgel,” does not contribute much to the network structure of the gelatinized gelatin because of its already small proportion and, in particular, is unable to significantly influence the rate of solidification. Because of its sometimes extremely high molecular weight, this fraction is, to a large extent, decisive for the viscosity of the aqueous gelatin solutions.
  • a high proportion of microgel is therefore desirable in cases where a high viscosity is preferred for casting reasons; In these cases, viscosity-increasing additives can be dispensed with; if low viscosity is desired in other cases, gelatin with a low microgel content will be preferred.
  • the fraction of the peptides i.e. the split pieces of a-gelatin is - in terms of physical properties - the least valuable component of gelatin. It has been shown that the peptides do not participate in the construction of the network, but remain largely in sol form. This weakens the network structure and delays gel formation. Slowly solidifying gelatins always contain a large amount of peptides.
  • gelatin In numerous applications of gelatin in the food, pharmaceutical and photographic fields, it is highly desirable to have gelatin which solidifies quickly, for example because it is technologically particularly easy to handle and results in reproducible products of constant quality.
  • the setting times of known gelatins (measured at 16 ° C and with 2.5 g gelatin in 1 dl water) are well above one minute, which leads to considerable difficulties in many applications.
  • the object is achieved according to the invention in that the gelatin content of fragments of the a-gelatin (peptides) is less than 25% by weight.
  • the present invention therefore relates to a photographic material which contains gelatin on a support in at least one layer as binder, containing microgel, oligomers of a-gelatin, a-gelatin and fragments of a-gelatin (peptides), characterized in that that the content of fragments of a-gelatin (peptides) with a molecular weight of at most g. 104 is less than 25 percent by weight.
  • the present invention further relates to a process for the preparation of the photographic materials according to the invention, the use of the new gelatins as binders in photographic layers (materials) and the use of the photographic layers (materials) for the production of photographic images.
  • the peptide content is in particular below 20 percent by weight and preferably also below 10 percent by weight.
  • the content of amino acid residues with D configuration in the gel-forming fractions is at most 5 percent by weight.
  • the molecular weight of the constituents of the microgel is approximately between 10 7 and 10 8 , the oligomers of the a-gelatin have molecular weights in the range of approximately 10 5 to 10 6 , while the molecular weight of the a-gelatin is approximately 9.5.10 4 and the fragments the a-gelatin (peptides) have such a value of about 10 4 to 9,104.
  • a gelatin used according to the invention is also characterized in that it has a high viscosity.
  • the preferred viscosity range is between 2.5 and 12.5 mPa.s, preferably between 4.5 and 10.5 mPa.s.
  • the viscosity values given relate to a 6.67% gelatin solution (6.67 g gelatin in 100 ml water) at 60 ° C. For 6.67% solutions of gelatin and at 40 ° C the viscosity is about 8 to 20 mPa.s.
  • a preferred method for producing a gelatin used according to the invention is characterized in that the gelatin is made from raw material which has been pretreated in an alkaline manner in a conventional manner in a temperature range (brewing temperature) between 70 and 100 ° C. for a period (brewing time) of 5 to 120 minutes at a pH of Value (brew pH) between 5.5 and 7.0 is melted out (extracted).
  • the pH is between about 5.5 and 7.0, preferably between 6.5 and 7.0.
  • a weakly alkaline brew pH up to about 8.5 can also be suitable.
  • a particularly advantageous range for the brewing temperature is between about 70 and 82 ° C, a particularly preferred brewing time is between about 20 and 40 minutes.
  • the aqueous gelatin solutions obtained in this way are cooled within 1 to 60 minutes, preferably within 1 to 5 minutes, to temperatures below 55 ° C., preferably below 45 ° C. It is also important to transfer to the gel phase at short notice. In the production processes according to the invention, this transfer takes place within 5 to 45 minutes, preferably within 5 to 15 minutes.
  • the known methods extract for more than 2 hours and at relatively low temperatures below 70 ° C, it is necessary for the gelatin used according to the invention to extract for a very short time while ensuring good heat transfer conditions at higher temperatures.
  • the method according to the invention can be carried out in such a way that gelatins with high viscosities and low peptides are obtained at certain times in certain withdrawal sequences.
  • Another method for producing the gelatins used according to the invention is the fractionation of commercially available gelatins, the composition being checked with the aid of gel chromatography.
  • the gelatins used in accordance with the invention not only have a particularly favorable setting time, but are at the same time, due to their high viscosity, suitable for use in certain modern casting techniques, e.g. Curtain casting, particularly suitable because it does not contain any substances that increase viscosity, e.g. for the production of photographic layers, for example sodium cellulose sulfate, need to be added. In some applications, these additives adversely affect the other properties of the gelatin product (discoloration).
  • gelatin drying process can be shortened in industrial processes. While maintaining a customary drying section, the temperatures of the drying air can be increased, for example, since the melting point of the gelatin used according to the invention is 1 to 3 ° C higher than conventional types of gelatin. In other industrial processes, blowing with cooling air can be omitted or reduced.
  • Photographic materials generally consist of a flat base on which at least one, but usually several, thin layers are applied. At least one of these layers is light sensitive and, in the case of conventional photographic material, consists of a fine dispersion of silver halide in a hydrophilic colloidal binder.
  • the light-sensitive and optionally further, non-light-sensitive layers can also contain a number of other substances, such as e.g. Dyes, color couplers, sensitizers, stabilizers, solvents, wetting agents or curing agents, and also contain additional, non-hydrophilic binders in dispersed form.
  • gelatins with very different properties have to be available. This applies above all to their chemical properties, on which the sensitometry of the light-sensitive layers depends to a large extent.
  • gelatin industry has succeeded in meeting the changing requirements of photographic technology to an ever greater extent, and in particular also the demands placed on the reproducibility of the material; to satisfy.
  • the physical properties of the gelatin used play a crucial role in addition to the chemical ones. Two properties are particularly important: the viscosity of the aqueous solutions and their rate of solidification.
  • Aqueous gelatin solutions are known to be liquid only at higher temperatures. Below about 30 ° C they solidify into an elastic gel within a shorter or longer time. An exception to this are only very dilute solutions with a concentration of less than about 1%, which remain liquid at all temperatures. The ability to solidify into a non-flowing gel is an important feature that greatly facilitates, if not enables, the production and drying of precise thin layers.
  • the photographic layers are always applied to the base in a liquid state, often even several liquid layers being applied at the same time.
  • the layers must then be dried. The quickest and most convenient way of doing this is by inflating warm air. Since it is not possible to roll up a material with undried layers, layer application and drying must always be carried out continuously in one pass. During the drying process, it is essential that the layers poured on with high precision are not deformed either by gravity or by the moving warm air. With gelatin-containing layers, this requirement can be met in a particularly simple manner by allowing the layers to solidify to a gel as quickly as possible before the drying process begins, by passing the coated carrier through a cooling section. The faster the layer solidifies, the lower the technical effort for the cooling section and the higher the throughput speed can be selected.
  • a general description of the coating and drying technology of photographic materials can be found e.g. in B.M. Deryagin et al. "Film Coating Theory •, Focal Press 1964.
  • the rate of solidification of gelatin solutions is generally dependent on concentration and temperature. It can be improved by increasing the gelatin concentration in the coating solution.
  • coating technology places certain limits on such a method of operation that cannot be exceeded. Casting solutions that are too concentrated are often also unstable chemically and can e.g. tend to separate or flocculate individual components.
  • the present invention therefore also relates to the use of these gelatins as binders for the production of photographic layers (materials) or to a process for the production of photographic materials consisting of a support and at least one photographic layer, characterized in that the binders used for at least one layer uses one of these gelatins.
  • Another object of the invention are the photographic materials thus obtained. You or the layers of the material are characterized by good mechanical properties.
  • the good compatibility of the gelatin used according to the invention with photographic additives (e.g. dyes or color couplers) and the optimal behavior in photographic processing (after exposure of the photographic material) have an extremely advantageous effect on the image reproduction.
  • the gelatins used according to the invention are of particular advantage in the pharmaceutical and food industries.
  • medical preparations are often packaged in hard gelatin capsules.
  • These hard capsules are produced in a dipping process, in which particularly uniform capsules are obtained in a reproducible manner if the setting time of the gelatin used is very short.
  • This hard capsule production in the immersion process is another important area of application for the rapidly solidifying gelatin used according to the invention, and because of the high viscosity of this gelatin, the flow properties can also be advantageously used.
  • a gelatin with a short solidification time is also advantageous in the household, since it is no longer necessary, for example, to make "jellies” or “jellied meat” to put the containers filled with gelatin solution in the refrigerator for several hours.
  • the too slow solidification of commercially available gelatins has so far been an insurmountable obstacle to the use of gelatin in the production of cake icing. Due to the too slow solidification, the still liquid gelatin solution penetrates into the cake base and softens it. For this reason, only quick-setting gelling agents such as pectin, agar-agar, carragheene and alginates are used for cake icing.
  • Shortening the setting time also opens up this area of application for gelatin, the replacement of the aforementioned gelling agents with gelatin being particularly advantageous because those gelling agents which are frequently used not only in the confectionery industry but also in other branches of the food industry because of their short setting time are associated with taste and texture disadvantages.
  • Bone meal from freshly slaughtered raw bones is gently degreased by water degreasing and macerated in a conventional manner under mild conditions. It is then alkaline ashed and neutralized in the usual way.
  • a first draw is extracted at a brew pH of 6.5 and a temperature of 72 ° C for 35 minutes and a second draw at the same pH at 78 ° C for a further 20 minutes.
  • the third draw-off corresponding to 50 to 65% of the total yield, is then extracted in a conventional stirred kettle for 25 minutes at a brew pH of 6.5 and at 80 ° C.
  • a semi-continuous extraction process leads to the same results.
  • the gelatin solution obtained is cooled down to 50 ° C. in the course of 3 to 5 minutes and converted into the gel phase in the course of about 10 minutes.
  • the gelatin obtained in the third print has the characteristic data given in Table 2 under sample number 4.
  • the second (table 2, sample number 3) and fourth (table 2, sample number 1) deduction (brew pH 6.7, at 84 ° C and 20 minutes), generally the middle deductions corresponding to about 45 to 75 % of the total yield can still give usable, highly viscous gelatins with kidney peptide content in the sense of the invention.
  • Example 1 Vigorous beef slit is cut as usual, washed and washed with aqueous calcium hydroxide or sodium hydroxide solution under the usual conditions. This is followed as in Example 1. Highly viscous, low-peptide gelatins are obtained, and in the first few deductions corresponding to 0 to 20% of the total yield.
  • the values for brew pH, brewing temperature and brewing time are: 7.0, 90 ° C and 15 minutes.
  • the gelatin solutions obtained are cooled to 50 ° C. in the course of 3 to 5 minutes and converted into the gel phase in the course of about 10 minutes.
  • the data of a gelatin obtained in this way are given in the table under sample number 2.
  • Table 3 illustrates the importance of the gelatin composition of the gelatins used according to the invention and their content in the various fractions, in particular in peptide split pieces and in microgel.
  • the gelatin samples designated with the numbers 6 to 10 are produced by fractionating commercially available gelatins.
  • the composition of the fractions is determined by preparative gel chromatography.
  • Table 3 shows a direct relationship between the setting time and the gelatin content of peptides.
  • the gel strength and the viscosity of the gelatin solutions are largely independent of the peptide content within the range shown in Table 3.
  • Table 4 shows the corresponding values of five different commercial gelatins.
  • the ready-to-pour solution is applied to a glass support with a layer thickness corresponding to a basis weight of 20 g per m 2 , solidified by brief cooling and finally dried by blowing warm air.
  • a light-sensitive layer is obtained which, after exposure under a transparent template and after the usual processing by color development, silver bleaching and fixing, gives a negative cyan image of the template.
  • a casting solution is made from 5.2 g of gelatin according to the invention of sample number 16 (cf. Table 5), 1.5 g of magenta dye of the formula and 93.3 g of water. (Casting solution No. 1).
  • the cooling time is the time within which the setting temperature at which the setting time of the gelatins is determined and is set in the measuring apparatus.
  • the measured solidification time is in all cases a function of the solidification temperature and the longer the higher the selected solidification temperature, the longer.
  • the gelatin 16 behaves in any case more favorably than the comparison gelatins 17 and 18; however, the effect is more pronounced at a higher solidification temperature.
  • gelatins used according to the invention behave in sensitometric terms the same as commercially available comparison gelatins.
  • a silver halide emulsion suitable for graphic materials is produced by once the silver halide in a solution of gelatin no. 16, and for comparison in a solution of the commercially available gelatin no. 18 precipitated and then further processed by physical and chemical ripening in the usual way to form a ready-to-use emulsion.
  • the table shows that with gelatin no. 16 in this case, too, photographic emulsions can be produced under identical production conditions, the sensitometric properties (sensitivity and ratio of maximum blackening and fog) are very similar to those which are produced from a commercially available gelatin.
  • gelatin no. 16 emulsion produced because of its shorter solidification time of higher use value for the production of photographic materials.

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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)
  • Jellies, Jams, And Syrups (AREA)
  • Medicinal Preparation (AREA)
  • Peptides Or Proteins (AREA)
EP80105372A 1979-09-12 1980-09-08 Photographische Materialien, Verfahren zu ihrer Herstellung, ihre Verwendung und die Verwendung von Gelatinen Expired EP0027533B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH825379 1979-09-12
CH8253/79 1979-09-12

Publications (2)

Publication Number Publication Date
EP0027533A1 EP0027533A1 (de) 1981-04-29
EP0027533B1 true EP0027533B1 (de) 1982-09-22

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EP80105372A Expired EP0027533B1 (de) 1979-09-12 1980-09-08 Photographische Materialien, Verfahren zu ihrer Herstellung, ihre Verwendung und die Verwendung von Gelatinen

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Country Link
US (1) US4360590A (show.php)
EP (1) EP0027533B1 (show.php)
JP (1) JPS5685744A (show.php)
AR (1) AR225461A1 (show.php)
DE (1) DE3060878D1 (show.php)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5785051A (en) * 1980-11-18 1982-05-27 Toppan Printing Co Ltd Water-soluble photosensitive material
US4707433A (en) * 1981-05-18 1987-11-17 Matsushita Electric Industrial Co., Ltd. Water-soluble photosensitive material with dichromate and low molecular weight gelatin
JPS5839495A (ja) * 1981-09-02 1983-03-08 Mitsubishi Paper Mills Ltd 平版印刷板
US4510228A (en) * 1982-04-22 1985-04-09 Mitsubishi Paper Mills, Ltd. Lithographic printing plate with gelatin layers having pH values below isoelectric point
HU192642B (en) * 1984-12-19 1987-06-29 Forte Fotokemiai Ipar Process for the extraction of nucleinic acids and purine bases from gelatine
JPS61148443A (ja) * 1984-12-24 1986-07-07 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPH06130532A (ja) * 1992-10-14 1994-05-13 Konica Corp ハロゲン化銀写真感光材料
DE69400690T2 (de) * 1993-08-05 1997-05-15 Agfa Gevaert Nv Bildelement und Verfahren zur Herstellung lithographischer Druckplatten nach dem Silbersalz-Diffusionübertragungsverfahren
US6120971A (en) * 1997-07-31 2000-09-19 Mitsubishi Paper Mills Limited Lithographic printing plate material
US5908921A (en) * 1998-11-03 1999-06-01 Eastman Kodak Company Method of manufacturing gelatin
US5919906A (en) * 1998-11-05 1999-07-06 Eastman Kodak Company Protease produced gelatin
US6573037B1 (en) * 2002-05-30 2003-06-03 Eastman Kodak Company Imaging element comprising solubilized collagen gelatin and hardener
US6706467B2 (en) * 2002-05-30 2004-03-16 Eastman Kodak Company Coating fluid for imaging element comprising solubilized collagen gelatin colloidal dispersion

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2868661A (en) * 1954-08-04 1959-01-13 Wilson & Co Inc Sensitizing photographic gelatin

Also Published As

Publication number Publication date
EP0027533A1 (de) 1981-04-29
US4360590A (en) 1982-11-23
JPS5685744A (en) 1981-07-13
DE3060878D1 (en) 1982-11-04
JPH0239779B2 (show.php) 1990-09-07
AR225461A1 (es) 1982-03-31

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