EP0457087B1 - Matériau photographique avec couche NC - Google Patents

Matériau photographique avec couche NC Download PDF

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Publication number
EP0457087B1
EP0457087B1 EP91106889A EP91106889A EP0457087B1 EP 0457087 B1 EP0457087 B1 EP 0457087B1 EP 91106889 A EP91106889 A EP 91106889A EP 91106889 A EP91106889 A EP 91106889A EP 0457087 B1 EP0457087 B1 EP 0457087B1
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EP
European Patent Office
Prior art keywords
layer
acid
gelatine
gelatin
recording material
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
EP91106889A
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German (de)
English (en)
Other versions
EP0457087A1 (fr
Inventor
Werner Dr. Krafft
Günter Dr. Helling
Günter Matschke
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0457087A1 publication Critical patent/EP0457087A1/fr
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Anticipated expiration legal-status Critical
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
    • 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
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing
    • Y10S430/109—Polyester
    • 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
    • Y10S430/131—Anticurl layer
    • 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
    • Y10S430/162—Protective or antiabrasion layer

Definitions

  • the invention relates to a photographic material, in particular a photographic material with an NC layer, which is designed in such a way that damage to the material, in particular during drying, is avoided or at least reduced during the processing process.
  • Photographic recording materials e.g. 35mm or roll films consist of a transparent base, e.g. of cellulose triacetate and a plurality of layers applied on one side of the base, which consist essentially of gelatin, in which the photographically important components such as silver halide grains, color couplers and other substances are embedded.
  • these materials show a tendency to bulge in such a way that the emulsion side, that is to say the side of the base on which the photographically important layers of gelatin are applied, lies on the inside (E i state).
  • This tendency to bulge is intentional and is caused in the manufacture of the material by the tensile force that the gelatin exerts when it dries. So that this tendency to roll up does not become too strong, so-called NC layers ("non-curling" layers) are often applied to the back of the underlay, which counteract the curvature tendency and in the camera or in the printer (copier) for one Make sure that there is sufficient flatness so that blurring is avoided during exposure and copying.
  • NC layers non-curling layers
  • the compact laboratories are usually designed so that the beginning of a film to be processed is attached to a perforated drag belt and is transported with it through the device. The end of the film is free to move.
  • the film is usually dried with air at a temperature of about 50 ° C.
  • the object of the invention is to change the entry and strength of the E a curvature occurring during drying at least so that no more damage occurs to the emulsion layers.
  • Photographic recording materials with an NL layer consisting of gelatin and a (meth) acrylamide copolymer are known from DE-A-1904527.
  • Photographic recording materials with a hydrophilic polymer according to formula (I), which are used, for example, as oil formers, are known from EP-A-0358073. The use of the polymers leads to an improved maximum density.
  • the object can be achieved by adding a certain hydrophilic polymer to the NC layer and maintaining certain quantitative ratios with respect to the gelatin on the emulsion side to the gelatin in the NC layer to the polymer according to the invention.
  • the amounts of polymer and gelatin should preferably be matched to one another such that the ratio of the water absorption capacity of the layers on the emulsion side to the water absorption capacity of the NC layer ( ⁇ WAM) is 1 to 1.5.
  • the polymer of the formula I particularly preferably makes up at least 90% by weight of the amount of the hydrophilic polymer.
  • it can also be a black and white silver halide recording material in which the total gelatin application on the light-sensitive side of the support is 8 to 12 g / m2 and in the NC layer 3 to 6 g / m2.
  • the polymers of formula I have acid numbers of 30 to 340, preferably 50 to 200 mg KOH / g.
  • the compounds of the formula I are prepared by reacting polyester diols of the formula II with carboxylic anhydrides of the formula III or corresponding di- and tetracarboxylic acids at temperatures from 20 to 200 ° C. in a molar ratio of 1: 1 to 1: 2, if appropriate in inert solvents:
  • the condensation reaction is preferably carried out without solvent, in particular at temperatures from 50 to 150 ° C.
  • the alkyl groups have in particular one to four carbon atoms.
  • the polyester diols II are known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 19, p. 305 ff. They are produced by polycondensation of one or more diols with one or more dicarboxylic acids and / or one or more oxy acids. Diols and dicarboxylic acids are preferably used. The oxyacids can be used as lactones.
  • Ethylene glycol 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol are preferred.
  • Preferred dicarboxylic acids are succinic acid, adipic acid, phthalic acid, sebacic acid, dodecanedicarboxylic acid.
  • the lactone of an oxycarboxylic acid is e.g. Caprolactone into consideration.
  • the average molecular weight, determined from the OH number by the end group method, of the polyester diols of the formula (II) is about 500 to 20,000, preferably 800 to 5,000.
  • the molar ratio of polyhydric alcohol to polybasic carboxylic acid is greater than 1. Examples of polyester diols are listed in Table 1.
  • Carboxylic anhydrides of the formula (III) are, for example
  • hydrophilic polymers which can make up to 40% by weight, preferably up to 10% by weight, of the hydrophilic polymer according to the invention are both naturally occurring high-molecular compounds such as proteins, protein derivatives, cellulose derivatives, e.g. Cellulose esters, gelatin derivatives e.g. acetylated gelatin, phthaloyl gelatin, ureidogelatin, polysaccharides e.g. Dextran, gum arabic, casein, collagen derivatives, albumin as described in Research Disclosure December 1989 page 1003-1004.
  • proteins protein derivatives
  • cellulose derivatives e.g. Cellulose esters
  • gelatin derivatives e.g. acetylated gelatin, phthaloyl gelatin, ureidogelatin
  • polysaccharides e.g. Dextran, gum arabic, casein, collagen derivatives, albumin as described in Research Disclosure December 1989 page 1003-1004.
  • the NC layer may also contain plasticizer additives. Suitable plasticizers and monohydric and polyhydric alcohols, acid amides, esters, for example phosphate esters such as tricresyl phosphate, phthalate esters such as dibutyl phthalate, polyacrylic acid esters such as polybutyl acrylate, polyethyl acrylate, polyurethane latices with anionic, cationic or nonionic groups as listed in Research Disclosure 12/89 page 1006.
  • plasticizer additives Suitable plasticizers and monohydric and polyhydric alcohols, acid amides, esters, for example phosphate esters such as tricresyl phosphate, phthalate esters such as dibutyl phthalate, polyacrylic acid esters such as polybutyl acrylate, polyethyl acrylate, polyurethane latices with anionic, cationic or nonionic groups as listed in Research Disclosure 12/89 page 1006.
  • the NC layer can also contain aqueous microgels.
  • Aqueous microgels are water-swellable particles with an average particle diameter of less than 1 »m.
  • microgels are crosslinked polystyrene sulfonic acid salts, crosslinked poly (meth) acrylic acid salts, crosslinked poly (meth) acrylamides, crosslinked polymers with quaternary ammonium groups.
  • the NC layer according to the invention can be constructed in one or more layers, for example in two or three layers.
  • the "NC layer” always means the NC layer package.
  • a cellulose triacetate base of 95 »m thickness provided with an adhesive layer on both sides is coated on the front with a light-sensitive, 3-color structure, dry layer thickness 21.5» m; Gelatin application 16.9 g / m2.
  • the dry layer thickness of the NC layer is 5.4 »m.
  • the layer is applied in one pass using a triple cascade.
  • the drying properties of this roll film are shown in Table 2.
  • 35 mm wide film strips are cut from the coated material (60 cm wide). These are exposed, developed, bleached, fixed, washed and dried.
  • the film was suspended in a conventional drying cabinet with a hot air blower at 50 ° C.
  • the end of the film (total length 80 cm) is weighted with a clip of approx. 20 g weight.
  • the curvature of the film is measured at intervals of one minute in the beginning, every 20 seconds during the bulging phase, and then again every minute thereafter.
  • the values (curvature versus time) are plotted against each other and connected to form a curve. From the curve, the values A o , T o , E a K, D1, D4 and E15 defined in Fig. 1 are read.
  • Example 1 The values of Example 1 are shown in Table 2 below.
  • Example 1 On a 95 »m thick triacetate base provided on both sides with an adhesive layer, the same light-sensitive three-color structure of Example 1 is applied on the front side and different NC layers are applied to the rear side, in which 2 different polymers or mixtures of polymers are added to the gelatin in the partial layer .
  • Polymer 1 is a reaction product of a polyester diol from adipic acid and neopentyl glycol with benzene-1,2,4,5-tetracarboxylic acid, acid number 73.
  • Polymer 2 is a polymer of the formula:
  • Polymer 3 is a polyester urethane made from a polyester diol, hexamethylene diisocyanate and diaminocaproic acid, the polyester diol being produced from adipic acid and neipentyl glycol (MW: 80,000).
  • An additional advantage of the NC layer according to the invention is the reduction of the flatness amphitude, ie the curvature of the film which is dependent on moisture becomes smaller.
  • Table 4 shows, the flatness difference in the particularly practical humidity range of 50-20% for the starting film according to Example 1 is significantly larger than that of the comparison films with NC layers, which contain polymer 1 according to the invention alone or in admixture with an additional polymer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (3)

  1. Matériau d'enregistrement photographique ayant un support, au moins une couche d'émulsion d'halogénure d'argent sensible à la lumière contenant de la gélatine sur une face du support et une couche NC contenant de la gélatine sur l'autre face du support, caractérisé en ce que la couche NC contient au moins un polymère hydrophile qui correspond pour au moins 60 % en poids à la formule :
    Figure imgb0028
     dans laquelle
    R₁   représente un groupe alkylène, arylène, araikylène ou cycloalkylène,
    L   représente le reste d'un polyesterdiol d'un poids moléculaire moyen de 500 à 20 000
    m   est égal à 0 ou 1
    n   est un nombre de 0 à 30 et
    m+n≧1
    en quantité de 0,9 à 4g/m², le rapport pondéral de la gélatine sur la face d'émulsion à la gélatine dans la couche NC étant de 2 à 3 et le rapport pondéral de la gélatine dans la couche NC au polymère hydrophile étant de 2 à 5.
  2. Matériau d'enregistrement photographique selon la revendication 1, caractérisé en ce que le rapport de la capacité d'absorption de l'eau des couches sur la face d'émulsion à la capacité d'absorption de l'eau de la couche NC (ΔWAM) est de 1 à 1,5.
  3. Matériau d'enregistrement photographique selon la revendication 1, caractérisé en ce qu'il s'agit d'un matériau d'enregistrement photographique couleur à l'halogénure d'argent ayant au moins une couche sensible au rouge à laquelle est associé un coupleur pour cyan, au moins une couche sensible au vert à laquelle est associé un coupleur pour magenta et au moins une couche sensible au bleu à laquelle est associé un coupleur pour jaune, la quantité totale de gélatine étant de 12 à 18 g/m² sur la face du support sensible à la lumière et de 4 à 8 g/m² dans la couche NC.
EP91106889A 1990-05-11 1991-04-27 Matériau photographique avec couche NC Expired - Lifetime EP0457087B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4015161 1990-05-11
DE4015161A DE4015161A1 (de) 1990-05-11 1990-05-11 Fotografisches material mit nc-schicht

Publications (2)

Publication Number Publication Date
EP0457087A1 EP0457087A1 (fr) 1991-11-21
EP0457087B1 true EP0457087B1 (fr) 1995-03-29

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EP91106889A Expired - Lifetime EP0457087B1 (fr) 1990-05-11 1991-04-27 Matériau photographique avec couche NC

Country Status (4)

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US (1) US5070006A (fr)
EP (1) EP0457087B1 (fr)
JP (1) JP2872443B2 (fr)
DE (2) DE4015161A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05297514A (ja) * 1992-04-20 1993-11-12 Konica Corp ハロゲン化銀写真感光材料
JPH06123932A (ja) * 1992-10-13 1994-05-06 Konica Corp ハロゲン化銀写真感光材料
JPH0764239A (ja) * 1993-08-30 1995-03-10 Konica Corp ハロゲン化銀写真感光材料
US5753426A (en) * 1995-06-30 1998-05-19 Eastman Kodak Company Photographic elements containing a transparent magnetic recording layer
US5891612A (en) * 1997-08-28 1999-04-06 Eastman Kodak Company Photographic elements comprising highly loaded particulate material containing layer

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1533835A (fr) * 1966-08-12 1968-07-19 Eastman Kodak Co Produit photographique à révélateur incorporé comprenant une nouvelle sous-couche antigode
DE1904527A1 (de) * 1969-01-30 1970-08-27 Agfa Gevaert Ag Photographisches Material
JPS5737347A (en) * 1980-08-15 1982-03-01 Fuji Photo Film Co Ltd Photographic sensitive material
US4729945A (en) * 1983-08-12 1988-03-08 Felix Schoeller, Jr. Multilayer photographic support material
JP2540307B2 (ja) * 1986-07-18 1996-10-02 コニカ株式会社 巻ぐせカ−ルの改良されたハロゲン化銀写真印画紙
DE3830522A1 (de) * 1988-09-08 1990-03-15 Agfa Gevaert Ag Fotografisches aufzeichnungsmaterial
EP0360616B1 (fr) * 1988-09-22 1995-02-01 Konica Corporation Matériau photosensible à l'halogénure d'argent s'incurvant peu et adapté à un traitement rapide

Also Published As

Publication number Publication date
DE59105029D1 (de) 1995-05-04
JP2872443B2 (ja) 1999-03-17
DE4015161A1 (de) 1991-11-14
US5070006A (en) 1991-12-03
EP0457087A1 (fr) 1991-11-21
JPH04229855A (ja) 1992-08-19

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