EP0176656B1 - Fotographisches Trägermaterial für Schwarz/Weiss- und Farbfotografie - Google Patents

Fotographisches Trägermaterial für Schwarz/Weiss- und Farbfotografie Download PDF

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Publication number
EP0176656B1
EP0176656B1 EP85103457A EP85103457A EP0176656B1 EP 0176656 B1 EP0176656 B1 EP 0176656B1 EP 85103457 A EP85103457 A EP 85103457A EP 85103457 A EP85103457 A EP 85103457A EP 0176656 B1 EP0176656 B1 EP 0176656B1
Authority
EP
European Patent Office
Prior art keywords
oxide
carrier material
pigment
material according
white
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
EP85103457A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0176656A2 (de
EP0176656A3 (en
Inventor
Wieland Dr. Dipl.-Phys. Sack
Reiner Anthonsen
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.)
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Felex Schoeller Jr and GmbH and Co KG
Original Assignee
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Felex Schoeller Jr and GmbH and Co KG
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
Application filed by Felix Schoeller Jr Foto und Spezialpapiere GmbH, Felex Schoeller Jr and GmbH and Co KG filed Critical Felix Schoeller Jr Foto und Spezialpapiere GmbH
Priority to AT85103457T priority Critical patent/ATE57773T1/de
Publication of EP0176656A2 publication Critical patent/EP0176656A2/de
Publication of EP0176656A3 publication Critical patent/EP0176656A3/de
Application granted granted Critical
Publication of EP0176656B1 publication Critical patent/EP0176656B1/de
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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
    • 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
    • Y10S430/136—Coating process making radiation sensitive element
    • 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
    • Y10S430/143—Electron beam
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/3179—Next to cellulosic

Definitions

  • the invention relates to a carrier material for black / white and color photographic layers which contains at least one coating hardened by means of electron beams.
  • a variety of substrates for photographic layers are known.
  • the most common media include film materials and papers. Papers are usually additionally coated. Waterproof papers coated in particular with synthetic resin layers have found wide use as supports for photographic layers. Resin films and laminates coated with special layers are also known. Papers coated on both sides with polyolefin resin and film materials coated with pigmented layers (DAS 14 47 815, US 38 33 380, US 36 30 742, US 39 28 037) were most widespread. However, such coatings only have a limited pigment absorption, are not scratch-resistant and are unsuitable for thermal image development.
  • Resin coatings are not only resistant to water, but also to acidic and alkaline photographic process solutions and thus prevent these solutions from penetrating into any underlying paper. As a result, the time-consuming washing process for paper or nonwoven base is significantly shortened.
  • All resin coatings can contain pigments, dyes, optical brighteners, image stabilizers, antioxidants or other additives, insofar as this is desirable or necessary in view of the desired properties of an overlay photographic image.
  • pigments and dyes are of the greatest importance for the visual impression of a photographic image on the coating. They determine the color character of color images and are decisive for the sharpness of the photographic images.
  • the photographic layers are applied to the surface of the resin layer either directly or after previously applying an adhesion-promoting intermediate layer.
  • These photographic layers are preferably layers which are known under the term silver salt photography and which are used either to produce black / white or color images.
  • Resin coatings hardened with electron beams in accordance with DOS 30 22 451 or DOS 30 22 709 are produced by applying a flowable mixture to the surface of a paper or other base support, distributing it uniformly there and then solidifying it with high-energy electron beams under a protective gas or other covering.
  • the mixtures contain as a crucial component at least one substance with ethylenically unsaturated double bonds, which have the ability to polymerize with one another when this is initiated by radiation.
  • the layers hardened with electron beams now have many advantages compared to polyolefin layers, but so far they have also had disadvantages.
  • Despite the wide range of variations in the composition of radiation-hardened layers it was not possible to create a layer that showed equally good behavior in all photographic process solutions. Rather, it was found that the layers hardened with electron beams behave differently towards different process solutions.
  • There are commercially available color developer preparations which, in combination with subsequent exposure to oxygen, lead to a yellowish discoloration of the surface of the radiation-hardened layer. This discoloration is slight, but clearly visible and can neither be prevented by the stop bath, nor by thorough washing. It occurs especially when using photographic developer solutions containing an aromatic amine derivative (e.g. derivatives of phenylenediamine, toluidine, etc.).
  • an aromatic amine derivative e.g. derivatives of phenylenediamine, toluidine, etc.
  • the discoloration of radiation-hardened coatings with color developer is evident both with pigment-free coatings and with coatings that contain white pigment. As a rule, the discoloration is even stronger with pigment-containing coatings than with pigment-free coatings, as shown in Table 1 below.
  • the binder used here consisted of 62% by weight of polyester tetraacrylate, 22.5% by weight of glycerol propoxitriacrylate and 15.5% by weight of hexanediol diacrylate).
  • This object is achieved in that a titanium dioxide is used as the white pigment which bears an inorganic surface coating which makes up at least 2% by weight of the total pigment.
  • Titanium dioxide pigments used in coating layers can be untreated like the Ti0 2 (rutile 2) contained in Table 1. In many cases, however, they are surface-treated to improve dispersibility with inorganic oxides (Al 2 O 3 , AIO (OH), SiO 2 , ZnO, etc.), ie coated. Oxides in the broader sense are also understood to mean oxide hydrates. Such surface-coated types are, for example, the Ti0 2 (anatase) and Ti0 2 (rutile 1) contained in Table 1, which are coated with 0.6 and 1.0% by weight Al oxide, and like the other white pigments in Table 1 lead to increased discoloration with color developers.
  • inorganic oxides Al 2 O 3 , AIO (OH), SiO 2 , ZnO, etc.
  • Oxides in the broader sense are also understood to mean oxide hydrates.
  • Such surface-coated types are, for example, the Ti0 2 (anatase) and Ti0 2 (rutile 1) contained in Table 1, which are coated with 0.6 and
  • the discoloration with color developer is significantly less if a titanium dioxide is used which is surface-coated with 2% by weight or more than 2% by weight of an inorganic oxide or hydrated oxide.
  • the inorganic oxide or hydrated oxide can be an aluminum oxide or silica or zinc oxide or magnesium oxide or tin oxide or zirconium oxide or antimony oxide or one of the alkaline earth metal oxides or mixtures of such compounds. Due to the surface coverage, the titanium dioxide particles are provided with a more or less closed coating of foreign oxide or oxide hydrate.
  • the coating can consist of one or more layers and contain other oxides in addition to those mentioned, provided that these are not coloring.
  • Titanium dioxide pigments coated in this way can be produced by any process. They can also exist as mixed oxides with another white oxide under the surface coverage, and they can additionally be treated in any way with organic compounds. It is crucial that the pigment particles contain a sufficiently strong coating of an inorganic oxide or hydrated oxide other than Ti0 2 .
  • Patent Abstracts of Japan, Vol. 1, No. 103, p. 3238 E77 describes recording materials which contain titanium dioxide pigment in non-hardening binders, which surface covers with 0.5-5% by weight aluminum and / or silicon oxide is. This surface coating serves both to improve the adhesion on the base paper and to improve the adhesion of emulsion layers applied later.
  • titanium dioxide pigments which are coated with 2 or more% by weight of any white oxides or hydrated oxides, have a particularly advantageous effect in the radiation-hardened coating mixtures on the coloring of the hardened coating layer with photographic color developer. This is all the more surprising since the corresponding oxides and hydrated oxides lead to increased discoloration even when used alone in radiation-hardened layers (see Table 1).
  • titanium dioxide pigments with 2 or more% by weight of other oxide or oxide hydrate coatings in radiation-hardened layers according to the invention can be seen both in layers which are hardened by means of electron beams and in layers of unsaturated starting component hardened in another way.
  • the coating layers can be on paper, film, metal foil, paper laminate or any other support and contain known other additives.
  • titanium dioxide pigment is used, the surface covering of which consists largely or even predominantly of silica.
  • a small proportion of an aluminum oxide and / or zinc oxide and / or antimony oxide and / or zirconium oxide and / or alkaline earth metal oxide can be present. It is of minor importance whether the coating of the Ti0 2 is more or less closed. The degree of occupancy is obviously decisive.
  • An additional organic surface covering e.g. with polyhydric alcohol, (poly) siloxane, organic titanates, organophosphates, lactone, amino compounds etc.
  • Substances which generally serve to improve the dispersibility are possible and also have their known advantages in the case of the titanium dioxide pigments coated with inorganic oxides.
  • Titanium dioxide pigment in the sense of the invention is not only to be understood to mean the known Ti0 2 modifications rutile and anatase, but also other pure or mixed titanium oxides and white pigment-like titanates.
  • titanium dioxide surface-coated with at least 2% by weight of foreign oxide is used in a hardenable mixture which contains hydroxyl-functional unsaturated substances.
  • the particular advantage of this combination lies in the fact that the molar concentration of the OH groups in the mixture can be less than 2 and still layers are obtained which show no visible coloring with color developer.
  • the invention has a particularly advantageous effect if the substances curable by electron beams are mixtures which contain at least one substance which contains two or more double bonds.
  • non-reactive substances without double bonds can also be contained in a mixture to a limited extent.
  • Substances containing acrylate or methacrylate groups are primarily used as reactive components. However, esters of maleic acid, fumaric acid, mesaconic acid, citraconic acid or itaconic acid, other derivatives of these acids, allyl compounds and linear and cyclic dienes or trienes are also suitable as reactive mixture components. Those esters of the acids mentioned which are derived from polyhydric alcohols are preferred. Examples are hexanediol diacrylate, trimethylolpropane triacrylate, polyester acrylates, polyurethane acrylates, polyether acrylates, polyepoxy diacrylates, alkyd resin acrylates or the methacrylates corresponding to the acrylates mentioned.
  • the flow properties of such curable mixtures are adjusted according to the invention by mixing constituents of higher molecular weight with low molecular weight substances.
  • the hardness and flexibility of the hardened layers is determined by the ratio of double bonds to the molecular size in the starting material and can be varied widely by mixing different substances.
  • a mixture of 62 wt .-% polyester tetraacrylate (average molecular weight c a. 1000), 22.5 wt% and 15.5 wt .-% Glycerinpropoxitriacrylat hexanediol diacrylate was added to a hand without added pigment and secondly with the addition of 20 wt .-% Titanium dioxide pigment with 2 or more wt .-% inorganic surface coating evenly brought onto a polyethylene / paper laminate and by means of Hardened electron beams. The hardened coating had a thickness of approximately 20 pm.
  • the layer coatings were then treated with commercially available photographic developer for color paper, washed and the samples were stored for four days at room temperature with access to air.
  • the discoloration of the layer surface that occurred during storage was determined according to DIN 4512 as a change in the optical density compared to the initial value and is listed in Table 2.
  • a basic mixture of 50% by weight tripropylene glycol diacrylate, 45% by weight trimethylolpropane triacrylate and 5% by weight glycidil methacrylate was placed on a photographic base paper on the one hand without the addition of pigment (2a) and on the other hand with the addition of 30% by weight of titanium oxide pigment (2b), leveled to a thickness of approx. 35 pm with the aid of a doctor rod and hardened in a known manner by means of electron beams.
  • a basic mixture of 45% by weight of pentaerythritol triacrylate, 50% by weight of triethylene glycol diacrylate and 5% by weight of hydroxyethyl acrylate was uniformly applied to a polyethylene on the one hand without pigment addition and on the other hand with the addition of 40% by weight of different titanium oxide pigments / Paper laminate brought and cured by means of electron beams.
  • the hardened coating had a thickness of approx. 20 pm each.
  • the OH molality of the basic mixture is 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Dental Preparations (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
EP85103457A 1984-09-28 1985-03-23 Fotographisches Trägermaterial für Schwarz/Weiss- und Farbfotografie Expired - Lifetime EP0176656B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85103457T ATE57773T1 (de) 1984-09-28 1985-03-23 Fotographisches traegermaterial fuer schwarz/weiss- und farbfotografie.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19843435639 DE3435639A1 (de) 1984-09-28 1984-09-28 Fotografisches traegermaterial fuer schwarz/weiss- und farbfotografie
DE3435639 1984-09-28

Publications (3)

Publication Number Publication Date
EP0176656A2 EP0176656A2 (de) 1986-04-09
EP0176656A3 EP0176656A3 (en) 1988-09-21
EP0176656B1 true EP0176656B1 (de) 1990-10-24

Family

ID=6246603

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85103457A Expired - Lifetime EP0176656B1 (de) 1984-09-28 1985-03-23 Fotographisches Trägermaterial für Schwarz/Weiss- und Farbfotografie

Country Status (8)

Country Link
US (1) US4665013A (enrdf_load_stackoverflow)
EP (1) EP0176656B1 (enrdf_load_stackoverflow)
JP (1) JPH0619521B2 (enrdf_load_stackoverflow)
AT (1) ATE57773T1 (enrdf_load_stackoverflow)
DE (2) DE3435639A1 (enrdf_load_stackoverflow)
ES (1) ES8609749A1 (enrdf_load_stackoverflow)
GR (1) GR852331B (enrdf_load_stackoverflow)
PT (1) PT80747B (enrdf_load_stackoverflow)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3518113C2 (de) * 1985-05-21 1987-03-19 Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück Trägermaterial für thermisch entwickelbare fotografische Aufzeichnungsmaterialien
US4752559A (en) * 1987-03-24 1988-06-21 Helland Randall H Primer/antihalation coating for photothermographic constructions
JPH0654373B2 (ja) * 1988-04-07 1994-07-20 三菱製紙株式会社 写真用支持体
JP2726087B2 (ja) * 1988-12-23 1998-03-11 三菱製紙株式会社 写真用支持体の製法
JPH02235045A (ja) * 1989-03-08 1990-09-18 Konica Corp 写真用反射支持体
US5180658A (en) * 1989-03-16 1993-01-19 Konica Corporation White polyester composition and support for photography
US5173397A (en) * 1989-03-28 1992-12-22 Mitsubishi Paper Mills Limited Photographic support with titanium dioxide pigmented polyolefin layer
US5057405A (en) * 1989-04-04 1991-10-15 Fuji Photo Film Co., Ltd. Silver-halide color photographic light-sensitive material
JP2655198B2 (ja) * 1990-07-16 1997-09-17 富士写真フイルム株式会社 写真フイルム要素
JPH04320257A (ja) * 1991-04-19 1992-11-11 Oji Paper Co Ltd 写真印画紙用支持体
EP0492887B1 (en) * 1990-12-21 1997-08-27 Oji Paper Co., Ltd. Support sheet for photographic printing sheet
US5374508A (en) * 1990-12-21 1994-12-20 New Oji Paper Co., Ltd. Support sheet for photographic printing sheet
JP2871356B2 (ja) * 1992-06-25 1999-03-17 王子製紙株式会社 写真印画紙用支持体
US5252424A (en) * 1992-09-04 1993-10-12 Eastman Kodak Company Photographic paper
US5424129A (en) * 1992-11-16 1995-06-13 Xerox Corporation Composite metal oxide particle processes and toners thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5235625A (en) * 1975-09-13 1977-03-18 Oriental Shashin Kogyo Kk Photographic material
JPS5446035A (en) * 1977-09-19 1979-04-11 Mitsubishi Paper Mills Ltd Support for photosensitive printing paper
DE3022451A1 (de) * 1980-06-14 1982-01-07 Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück Wasserfestes fotografisches papier
DE3022709A1 (de) * 1980-06-18 1982-01-07 Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück Wasserfestes fotografisches papier und verfahren zu seiner herstellung
DE3043864A1 (de) * 1980-11-21 1982-07-08 Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück Weisser fotografischer papiertraeger und verfahren zu seiner herstellung
JPS57108849A (en) * 1980-12-25 1982-07-07 Mitsubishi Paper Mills Ltd Preparation of photographic base
JPS59164550A (ja) 1983-03-09 1984-09-17 Mitsubishi Paper Mills Ltd 写真用熱可塑性樹脂組成物の製法
JPS60126649A (ja) * 1983-12-14 1985-07-06 Fuji Photo Film Co Ltd 写真印画紙用支持体

Also Published As

Publication number Publication date
US4665013A (en) 1987-05-12
GR852331B (enrdf_load_stackoverflow) 1985-11-27
ES8609749A1 (es) 1986-07-16
DE3435639C2 (enrdf_load_stackoverflow) 1988-09-22
JPS6186747A (ja) 1986-05-02
DE3580232D1 (de) 1990-11-29
PT80747B (pt) 1987-09-30
ES545895A0 (es) 1986-07-16
EP0176656A2 (de) 1986-04-09
DE3435639A1 (de) 1986-04-10
PT80747A (de) 1985-08-01
ATE57773T1 (de) 1990-11-15
EP0176656A3 (en) 1988-09-21
JPH0619521B2 (ja) 1994-03-16

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