US3782955A - Photographic material - Google Patents

Photographic material Download PDF

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Publication number
US3782955A
US3782955A US00127363A US3782955DA US3782955A US 3782955 A US3782955 A US 3782955A US 00127363 A US00127363 A US 00127363A US 3782955D A US3782955D A US 3782955DA US 3782955 A US3782955 A US 3782955A
Authority
US
United States
Prior art keywords
gelatin
drying
layer
emulsion
matt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00127363A
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English (en)
Inventor
W Himmelmann
B Mucke
K Lohmer
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.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE19702018552 external-priority patent/DE2018552A1/de
Priority claimed from DE19702033264 external-priority patent/DE2033264A1/de
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Application granted granted Critical
Publication of US3782955A publication Critical patent/US3782955A/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/151—Matting or other surface reflectivity altering material

Definitions

  • gelatine silver halide emulsion in which 20 to 90% by weight of the gelatin consists 'of gelatin derivatives which cannot be hardened with organic hardeners.
  • Such silver halide-gelatin layers can be covered by an outermost protective layer, the binding agent of which consists of hardened gelatin or of the gelatin derivative which cannot be hardened with organic hardeners or of mixtures thereof.
  • the binding agent of which consists of hardened gelatin or of the gelatin derivative which cannot be hardened with organic hardeners or of mixtures thereof Under gelatin derivatives which cannot be hardened with organic hardeners are reaction products of gelatin in which a high proportion of the hydroxyl and amino groups are blocked by acylation or in which the amino groups have been removed, e.g.
  • thedegree of gelatin conversion can be varied within wide limits by adding different quantities of acylating agents such as acid chlorides, acid anhydrides, sulfochlorides and isocyanates.
  • a protective layer is arranged on top of the silver halide gelatin emulsion layer as mentioned above, and the protective layer contains gelatin as binding agent, that gelatin is hardened with an excess of organic hardener.
  • Suitable .for use as hardeners are any known organic hardeners (aldehydes, acid halides, epoxides, ketenes). Alkoxy dichlorotriazines, formalin and the like are particularly suitable.
  • the photographic material of the present invention is suitable for high gloss drying as well as matt drying. Thus the contradictory requirements of both types of drying can be met with one and the same photographic material.
  • Non-hardenable gelatin modifications can be made by acylating gelatin with acid chlorides, acid anhydrides or sulfochlorides, or by reacting the gelatin with isocyanates, or by diazotization to convert its basis amino groups to hydroxyls.
  • the production of some non-hardenable gelatin derivatives which are suitable for the present purpose has been described in US. Pats. Nos. 2,614,928 and 2,768,079.
  • the acylation of some gelatin derivatives which may be used according to the invention is described in detail below.
  • COMPOUND II ACETYL GELATIN 12.5 g. of acetic anhydride are added instead of 7.5 g. The method is otherwise the same as described under I. Nitrogen value according to Van Slyke: 0.06%.
  • the meltingpoint of the layer is 31? C. after 24 hours storage of the layers at room temperature.
  • COMPOUND III PHTHALOYL GELATIN 60 g. of gelatin are dissolved in 1000 cc. of water, and 6 g. of phthalic acid anhydride dissolved in cc. of anhydrous acetone are added dropwise in the course of 15 minutes at 40. C. to .45? ,C. with stirring tion mixture is stirred for a further minutes and is then solidified and washed in water for 3 hours.
  • the Van Slyke nitrogen value is 0.11%.
  • the melting point of the layers after 24 hours storage of the layers at 22C. is found to be C.
  • COMPOUND IV METHYL UREA GELATIN COMPOUND v; METHYL UREA GELATIENQ
  • the procedure is the same as described for Compound IV except that 60 g. of methyl isocyanate are used. Van Slyke nitrogen value: 0.11%.
  • the melting point of the layers formed from the treated gelatin after the storage described above is 36 C.
  • COMPOUND VI MALEINOYL GELATIN 200 g. of gelatin are dissolved in 1400 cc. of Water, and 30 g. of maleic acid anhydride dissolved in 120 cc. of acetone are added dropwise at C. to C. The pH is kept at 8 by the addition of sodium hydroxidesolution. The reaction mixture is then stirred for 15 minutes at C., the pH is then adjusted to 7 and the mixture is solidified and rinsed with water. Van Slyke nitrogen value: 0.15%.
  • COMPOUND VII BENZOYL GELATIN 700 g. of gelatin are dissolved in 6300 cc. of Water, and a solution of 140 g. of benzoyl chloride in 250 cc. of acetone is slowly added dropwise at 40 C. At the same time the pH is kept at 9 to 10.with sodium hydroxide solution. The reaction mixture is stirred for 2 hours atpH 9 and 40 C., the pH is then adjusted to 7 and the mixture is filtered, solidified and rinsed with water for 4 hours. Van Slyke nitrogen value: 0.2%;
  • COMPOUND VIII SUCCINOYL GELATIN 100 g. of gelatin are reacted with 15 g. of succinic acid anhydride dissolved in acetone and worked up in the same way as described in VII. A derivative which has a Van Slyke nitrogen value of 0.25% is obtained. The derivative cannot be hardened with organic hardeners,. or is only slightly hardened.
  • the silver halide of the emulsions of the present invention consist substantially of silver chloride or silver bromide with a silver iodide content of up to 4%.,by weight.
  • Example 1 A silver bromide gelatin emulsion is prepared in'accordance with Fiat Final Report No. 354-360, page 28. This emulsion serves as comparison sample.
  • A11 emulsion according to the present invention isprepared by basically the same method except that 85 by weight of the gelatin is replaced by Compound VIII.
  • the two emulsions were separately applied onto barytacoated paper support, the amount of silver applied being 1.5 g. of Ag/m. the form of silver halide;
  • a protective layer of ordinary untreated gelatin is then applied to the two emulsions from'a 2% gelatin solution.
  • Thethickness of the protective layer is 3 microns.
  • the layers were hardened With formaldehyde, the amount added to the silver halide emulsion being 1.5 ml. of a 30% formaldehyde solution per kg., and the amount added to the 2% protective-layer forming solution being 10. m1. of said formaldehyde solution per kg.
  • some samples of'the separately applied layers were stored for 48 hours in a heating cupboardat C. and 40% relative humidity.
  • The'development time is 90 seconds, the development temperatu're20 C.
  • the material is then fixed and Washed in-the usualmanner.
  • Thecomparison material also showed improved high gloss after it had been stored under natural conditionsfoi years,-,butthe number of surface faults in this material increased with age. After one year, the comparison material had. become unusable owing to the-excessively largenumber of surface faults, whereas the material according to the invention had an excellent high gloss after it had been completely hardened, and this gloss did not change with storage.
  • the comparison sample shows a satisfactory high gloss in the fresh state after it has been processed but it is not suitable for matt drying because residues of fibres stick to the surface of the layer.
  • the capacity for matt drying improved in the course of storagevbu't the high gloss properties deteriorated to the same extent.
  • the material according to the invention remained unchanged in its good high gloss and matt drying properties even after prolonged storage.
  • Sensitometer strips of the material according to the invention showed a slightly warmer brownish image tone than the comparison sample even in the fresh state immediately after casting and drying of the emulsion layers. After storage in the heating cupboard and after storage under natural conditions over a period of one year, the comparison sample showed an undesirable shift in the image tone towards bluish black, whereas the material according to the invention retained its warm brown image tone.
  • Example 3 The procedure was the same as in the previous Example FIG. 1.
  • the comparison emulsion was prepared according to Fiat Final Report No. 354-360, page 18.
  • the emulsion prepared was a silver chloride gelatin emulsion.
  • 30% of the gelatin in this recipe was replaced by Compound II.
  • the emulsion according to the present invention has excellent high gloss and matt drying properties, whereas the comparison emulsion is not satisfactory in this respect.
  • EXAMPLE 4 A silver chloride/bromide gelatin emulsion with a Warm brownish image tone is prepared in accordance with Fiat Final Report No. 354-360, page 33. This emulsion is used as control sample.
  • the emulsion according to the invention is based on the same recipe, except that 80% by weight of the gelatin is replaced by an equivalent quantity of Compound III.
  • Both emulsions are separately cast onto a baryta paper layer support.
  • a 1.5 micron thick protective layer of Compound II is then applied to the emulsion layer containing modified gelatin.
  • the samples are hardened with formaldehyde, 1.5 ml. of a 30% by weight formaldehyde solution per kg. being added to the silver halide emulsions, and ml. of a 30% by weight formaldehyde solution per kg. to the protective layers.
  • formaldehyde 1.5 ml. of a 30% by weight formaldehyde solution per kg. being added to the silver halide emulsions, and ml. of a 30% by weight formaldehyde solution per kg.
  • the two samples are processed in the same way. First of all they are exposed behind a grey step wedge in a conventional sensitometer. The exposed material is developed in a developer of the following composition:
  • the developing time is seconds and the developing temperature 20 C.
  • the samples are then fixed in the usual way and rinsed with water. 1
  • the comparison material After natural storage for 3 months, the comparison material also showed improved high gloss. The number of surface faults in this material, however, increased with its age. After one year, the comparison material was unusable due to the excessive number of surface defects, whilst the material according to the invention showed outstanding high gloss which did not change with storage.
  • the material according to the invention is further distinguished by the outstanding stability of the warm brown image tone both during matt drying and also during high gloss drying.
  • the image tone is displaced to blueblack.
  • Example 5 The same emulsion samples as in Example 4 were prepared. A protective layer of Compound VII is applied in a thickness of 1.5 microns to the silver halide emulsion layer modified with the gelatin derivative. The conventional comparison emulsion receives a protective layer of pure gelatin.
  • the material according to the invention can be subjected to machine matt-drying and high-gloss-drying.
  • the comparison material is unsuitable for matt drying even after this brief period of storage, because numerous fibres from the cloth remain adhering to the layer.
  • Example 6 The same emulsion samples as in Example 4 were prepared. A 1.5 micron-thick protective layer of 50% by weight of Compound III and 50% by weight of untreated gelatin, is applied to the silver halide emulsion layer with the modified gelatin. The conventional com parison emulsion receives an equally thick protective layer of pure gelatin. Processing is carried out as in Example 1. After 3 months, 6 months and 1 year, the material was tested for machine high gloss and matt drying and for image-tone stability.
  • a light-sensitive photographic material of improved drying properties comprising a support and at least two layers forming a light-sensitive material supported on the support, and in superimposed, contacting relationship, said light-sensitive material consisting of an outer layer of gelatin hardenable by formaldehyde treatment, said hardening results from reaction of the gelatin with the formaldehyde and beneath said outer layer a light-sensitive photographic silver halide gelatin emulsion in which 20-90% of the total gelatin has been modified to have a Van Slyke nitrogen content less than 0.3% adjacent to the support so that the layer closer to the support is not hardenable by formaldehyde and is a support for the outer hardened layer.
  • the light-sensitive photographic material of claim 1 wherein the modified gelatin is gelatin that has been acylated or reacted with an isocyanate or in which its basic amino groups have been converted to hydroxyls.
  • the light-sensitive photographic material of claim 1 wherein the emulsion is a silver chlorine-silver bromine emulsion which produces upon photographic processing a warm brown image thereon.
  • a method of producing a photographic image in a photographic material which comprises incorporating in a. silver halide emulsion from 2090% of gelatin modified to have a Van Slyke nitrogen content less than 0.3% so as not to be hardenable by formaldehyde, casting the silver halide emulsion into a supported layer, covering said supported silver halide emulsion layer with a layer of gelatin, hardening the covering layer of gelatin With formaldehyde and supporting the hardened gelatin layer on the emulsion layer, exposing the supported layers to an original to be reproduced, developing the image in the supported silver halide emulsion layer andrapidlydrying the developed photograph on a heat drum dryer.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
US00127363A 1970-04-17 1971-03-23 Photographic material Expired - Lifetime US3782955A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19702018552 DE2018552A1 (en) 1970-04-17 1970-04-17 Photographic material with quick dryinggelatine emulsion
DE19702033264 DE2033264A1 (en) 1970-07-04 1970-07-04 Protective photographic layer - contng gelatine derivs not hardenable by organic hardeners

Publications (1)

Publication Number Publication Date
US3782955A true US3782955A (en) 1974-01-01

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US00127363A Expired - Lifetime US3782955A (en) 1970-04-17 1971-03-23 Photographic material

Country Status (5)

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US (1) US3782955A (enrdf_load_stackoverflow)
BE (1) BE765750A (enrdf_load_stackoverflow)
CH (1) CH570634A5 (enrdf_load_stackoverflow)
FR (1) FR2089807A5 (enrdf_load_stackoverflow)
GB (1) GB1339077A (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2919054A1 (de) * 1978-05-10 1979-11-22 Minnesota Mining & Mfg Schichtmaterial und verfahren zur bildung von kolloidreliefbildern
US4476218A (en) * 1981-06-16 1984-10-09 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US5422235A (en) * 1991-12-19 1995-06-06 Eastman Kodak Company Process for manufacturing photographic paper

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3730319C2 (de) * 1987-09-10 1996-05-09 Agfa Gevaert Ag Fotografisches Aufzeichnungsmaterial
CN103319729B (zh) * 2013-06-04 2015-10-28 武汉工程大学 一种功能明胶改性的方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2919054A1 (de) * 1978-05-10 1979-11-22 Minnesota Mining & Mfg Schichtmaterial und verfahren zur bildung von kolloidreliefbildern
FR2425658A1 (fr) * 1978-05-10 1979-12-07 Minnesota Mining & Mfg Preparation d'images en relief
US4363864A (en) * 1978-05-10 1982-12-14 Minnesota Mining And Manufacturing Company Colloid relief images by oxidized developer transfer
US4476218A (en) * 1981-06-16 1984-10-09 Fuji Photo Film Co., Ltd. Silver halide photographic light-sensitive materials
US5422235A (en) * 1991-12-19 1995-06-06 Eastman Kodak Company Process for manufacturing photographic paper

Also Published As

Publication number Publication date
CH570634A5 (enrdf_load_stackoverflow) 1975-12-15
FR2089807A5 (enrdf_load_stackoverflow) 1972-01-07
GB1339077A (en) 1973-11-28
BE765750A (nl) 1971-10-15

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