EP0684145A1 - Heat mode recording element - Google Patents

Heat mode recording element Download PDF

Info

Publication number
EP0684145A1
EP0684145A1 EP95201166A EP95201166A EP0684145A1 EP 0684145 A1 EP0684145 A1 EP 0684145A1 EP 95201166 A EP95201166 A EP 95201166A EP 95201166 A EP95201166 A EP 95201166A EP 0684145 A1 EP0684145 A1 EP 0684145A1
Authority
EP
European Patent Office
Prior art keywords
layer
heat mode
recording element
mode recording
roughening agent
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.)
Granted
Application number
EP95201166A
Other languages
German (de)
French (fr)
Other versions
EP0684145B1 (en
Inventor
Dirk C/O Agfa-Gevaert N.V. D'hont
Luc C/O Agfa-Gevaert N.V. Voet
Luc C/O Agfa-Gevaert N.V. Leenders
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 NV
Original Assignee
Agfa Gevaert NV
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 Agfa Gevaert NV filed Critical Agfa Gevaert NV
Priority to EP19950201166 priority Critical patent/EP0684145B1/en
Publication of EP0684145A1 publication Critical patent/EP0684145A1/en
Application granted granted Critical
Publication of EP0684145B1 publication Critical patent/EP0684145B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/24Ablative recording, e.g. by burning marks; Spark recording
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42Intermediate, backcoat, or covering layers

Definitions

  • the present invention relates to an improved heat mode recording element containing a thin metal recording layer.
  • Recording materials have been disclosed on which records are made thermally by the use of intense radiation like laser beams having a high energy density.
  • information is recorded by creating differences in reflection and/or in transmission optical density on the recording layer.
  • the recording layer has high optical density and absorbs radiation beams which impinge thereon.
  • the conversion of radiation into heat brings about a local temperature rise, causing a thermal change such as evaporation or ablation to take place in the recording layer.
  • the irradiated parts of the recording layer are totally or partially removed, and a difference in optical density is formed between the irradiated parts and the unirradiated parts (cf. US Pat. Nos. 4,216,501, 4,233,626, 4,188,214 and 4,291,119 and British Pat. No. 2,026,346)
  • the recording layer of such heat mode recording materials is usually made of metals, dyes, or polymers. Recording materials like this are described in 'Electron, Ion and Laser Beam Technology", by M. L. Levene et al.; The Proceedings of the Eleventh Symposium (1969); “Electronics” (Mar. 18, 1968) , P. 50; “The Bell System Technical Journal”, by D. Maydan, Vol. 50 (1971), P. 1761; and “Science”, by C. O. Carlson, Vol. 154 (1966), P. 1550.
  • DRAW direct read after write
  • Human readable records are e.g. micro-images that can be read on enlargement and projection.
  • An example of a machine readable DRAW recording material is the optical disc.
  • tellurium and its alloys have been used most widely to form highly reflective thin metal films wherein heating with laser beam locally reduces reflectivity by pit formation (ref. e.g. the periodical 'Physik in phy Zeit', 15. Jahrg. 1984/Nr. 5, 129-130 the article "Optische aside” by Jochen Fricke).
  • Tellurium is toxic and has poor archival properties because of its sensitivity to oxygen and humidity.
  • Other metals suited for use in DRAW heat-mode recording are given in US-P-4499178 and US-P-4388400.
  • Other relatively low melting metals such as bismuth have been introduced in the production of a heat-mode recording layer.
  • Heat mode recording materials usually do not require development and fixing processes and do not require darkroom operations because of their insensitivity to room light. Therefore they constitute a valuable alternative to conventional photosensitive materials based on silver halide emulsions, e.g. for phototype-setting or image-setting applications.
  • silver halide materials have the advantage of high potential intrinsic sensitivity and excellent image quality.
  • they show the drawback of requiring several wet processing steps employing chemical ingredients which are suspect from an ecological point of view. For instance the commonly used developing agent hydroquinone is allergenic and the biodegradation of disposed phenidone is too slow. As a consequence it is undesirable that depleted solutions of this kind would be discharged into the public sewerage; they have to be collected and destroyed by combustion, a cumbersome and expensive process.
  • a heat mode recording element comprising, in order :
  • the metal layer is a vacuum-deposited thin bismuth layer having a thickness preferably comprised between 0.1 and 0.6 ⁇ m.
  • the average particle size of the roughening agent preferably ranges between 0.3 and 2.0 ⁇ m, most preferably around 1.0 ⁇ m.
  • a preferred roughening agent is composed of polymethylmethacrylate beads.
  • the layer containing the roughening agent can be the subbing layer of the support or can be an extra layer between the subbing layer and the metal layer.
  • the protective element preferably comprises a cover sheet and an adhesive layer.
  • the support of the heat mode element can in principle be an opaque paper base preference is given to a transparent organic resin support.
  • Useful transparent organic resin supports include e.g. cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, polyvinylchloride film or poly-Alpha-olefin films such as polyethylene or polypropylene film.
  • the thickness of such organic resin film is preferably comprised between 0.07 and 0.35 mm.
  • the support is a polyethylene terephthalate layer provided with a subbing layer.
  • the layer containing the roughening agent can be the subbing layer itself applied to the support or can be an extra layer between the subbing layer and the metal layer.
  • Tis layer (b) can contain no binder at all but preferably it contains a binder.
  • Tis layer (b) can be coated in principle from an organic solvent or from an aqueous medium depending on the chemical nature of the binder.
  • Organic solvent-soluble binders include e.g. polymers derived from ⁇ , ⁇ -ethylenically unsaturated compounds such as e.g.
  • organic solvents can be used for dissolving and coating these polymers.
  • water-soluble binders coatable from an aqueous medium can be used, e.g. gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, gum arabic, casein, different kinds of water-soluble latices, etc.
  • the roughening agent is incorporated in the subbing layer applied to the polyester support, in other words this subbing layer constitutes layer (b).
  • This subbing layer can be applied before or after stretching of the polyester film support.
  • the polyester film support is preferably biaxially stretched at an elevated temperature of e.g. 70-120°C, reducing its thickness by about 1/2 to 1/9 or more and increasing its area 2 to 9 times. The stretching may be accomplished in two stages, transversal and longitudinal in either order or simultaneously.
  • the subbing layer is preferably applied by aqueous coating between the longitudinal and transversal stretch, in a thickness of 0.1 to 5 ⁇ m.
  • the subbing layer preferably contains, as described in European Patent Application EP 0 464 906, a homopolymer or copolymer of a monomer comprising covalently bound chlorine.
  • a homopolymer or copolymer of a monomer comprising covalently bound chlorine examples are e.g.
  • polyvinyl chloride polyvinylidene chloride, a copolymer of vinylidene chloride, an acrylic ester and itaconic acid, a copolymer of vinyl chloride and vinylidene chloride, a copolymer of vinyl chloride and vinyl acetate, a copolymer of butylacrylate vinyl acetate and vinyl chloride or vinylidene chloride, a copolymer of vinyl chloride, vinylidene chloride and itaconic acid, a copolymer of vinyl chloride, vinyl acetate and vinyl alcohol etc.
  • Polymers that are water dispersable are preferred since they allow aqueous coating of the subbing layer which is ecologically advantageous.
  • Said homopolymer or copolymer may be prepared by various polymerization methods of the constituting monomers.
  • the polymerization may be conducted in aqueous dispersion containing a catalyst and activator, e.g., sodium persulphate and meta sodium bisulphite, and an emulsifying and/or dispersing agent.
  • a catalyst and activator e.g., sodium persulphate and meta sodium bisulphite
  • an emulsifying and/or dispersing agent e.g., sodium persulphate and meta sodium bisulphite
  • the homopolymers or copolymers used with the present invention may be prepared by polymerization of the monomeric components in the bulk without added diluent, or the monomers may be reacted in appropriate organic solvent reaction media.
  • Chemical nature, concentration and particle distribution of the roughening agent must be chosen in such a way that a certain degree of uneveness can be introduced in the metal recording layer. It is shown that this uneveness can reduce the occurence of interference patterns because the reflectance gets more diffuse. It will be clear that the roughening agent must be closely packed in the layer.
  • the thickness of layer (b), the average particle size and the coverage of the roughening agent must be tuned to each other in such a way that a sufficient number of the roughening particles must protrude above the interface layer (b) / metal layer in order to induce local deformation spots into this metal layer.
  • the average particle size is too low the roughening agent will not be able to introduce uneveness in the metal layer.
  • the average particle size is too great too high a coverage will be required which would make layer (b) too thick. So it is clear that an optimal particle size should be chosen for the roughening agent and that this optimum will depend on the mechanical strenght of the metal layer and therefore on its thickness.
  • the average particle size of the roughening agent preferably ranges from 0.3 to 2.0 ⁇ m, and is most preferably about 1.0 ⁇ m.
  • the coverage of the roughening agent preferably ranges from 0.05 to 1.0 g/m2, and is most preferably about 0.6 g/m2.
  • the degree of roughness of layer (b) is best characterized by the so-called R a value.
  • This so-called average roughness value is defined as the arithmic average value of the absolute amounts of all the measured distances of the roughness profile from the middle line within the measured interval.
  • Layer (b) preferably has a R a value of at least 0.2 ⁇ m.
  • the roughening agent can be chosen from a wide variety of chemical classes and commercial products provided the particles chosen show an excellent mechanical and thermal stability.
  • Preferred roughening agents include following :
  • a thin intermediate layer can be applied between layer (b) and the metal recording layer for reasons of protection against physical damage.
  • the thin intermediate layer is coated together with layer (b) by slide hopper coating. It can contain the same kinds of binder as layer (b) at a coverage of lower than 1 g/m2 in order not to loose the roughening effect.
  • the metal recording layer is positioned immediately on top of layer (b) in order to get the full effect of the uneveness introduced by the roughening agent.
  • Possible metals for the recording layers in this invention include Mg, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Sn, As, Sb, Bi, Se, Te. These metals can be used alone or as a mixture or alloy of at least two metals therof. Due to their low melting point Mg, Zn, In, Sn, Bi and Te are preferred. The most preferred metal for the practice of this invention is Bi.
  • the metal recording layer may be applied on top of the layer containing the roughening agent by vapor deposition, sputtering, ion plating, chemical vapor deposition, electrolytic plating, or electroless plating.
  • the recording layer is preferably provided by vapor deposition in vacuo. A method and an apparatus for such a deposition are disclosed in EP 0 384 041.
  • the thickness of this Bi layer is preferably comprised between 0.1 and 0.6 ⁇ m. When this thickness is too low the recorded images do not have sufficient density. When on the other hand the thickness is too high the sensitivity tends to decrease and the minimal density, i.e. the density after laser recording on the exposed areas tends to be higher.
  • this protective element comprises a transparent organic resin, acting as cover sheet, and an adhesive layer.
  • a method for applying such a protective element by lamination in the same vacuum environment as wherein the deposition of the metal layer took place is disclosed in EP 0 384 041, cited above.
  • the cover sheet can be chosen from the group of polymeric resins usable for the support of the heat mode element.
  • the cover sheet is also polyethylene terephthalate but preferably substantially thinner than the polyethylene terephthalate of the support.
  • a layer of a pressure-sensitive adhesive resin can be used for the adherence of the hard protective outermost resin layer to the heat mode recording layer.
  • a layer of a pressure-sensitive adhesive resin can be used for the adherence of the hard protective outermost resin layer to the heat mode recording layer.
  • a layer of a pressure-sensitive adhesive resin is described in US-P 4,033,770 for use in the production of adhesive transfers (decalcomanias) by the silver complex diffusion transfer process. in the Canadian Patent 728,607 and in the United States Patent 3,131,106.
  • Pressure-sensitive adhesives are usually composed of (a) thermoplastic polymer(s) having some elasticity and tackiness at room temperature (about 20°C), which is controlled optionally with a plasticizer and/or tackifying resin.
  • a thermoplastic polymer is completely plastic if there is no recovery on removal of stress and completely elastic if recovery is instantaneous and complete.
  • Particularly suitable pressure-sensitive adhesives are selected from the group of polyterpene resins, low density polyethylene, a copoly(ethylene/vinyl acetate), a poly(C1-C16)alkyl acrylate, a mixture of poly(C1-C16)alkyl acrylate with polyvinyl acetate, and copoly(vinylacetate-acrylate) being tacky at 20°C.
  • an intrinsically non-tacky polymer may be tackified by the adding of a tackifying substance, e.g. plasticizer or other tackifying resin.
  • a tackifying substance e.g. plasticizer or other tackifying resin.
  • tackifying resins examples include the terpene tackifying resins described in the periodical "Adhesives Age", Vol. 31, No. 12, November 1988, p. 28-29.
  • the protective element is laminated or adhered to the heat-mode recording layer by means of a heat-sensitive also called heat-activatable adhesive layer or thermoadhesive layer, examples of which are described also in US-P 4,033,770.
  • a heat-sensitive also called heat-activatable adhesive layer or thermoadhesive layer
  • the laminating material consisting of adhesive layer and abrasion resistant protective layer and/or the recording web material to be protected by lamination are heated in their contacting area to a temperature beyond the softening point of the adhesive. Heat may be supplied by electrical energy to at least one of the rollers between which the laminate is formed or it may be supplied by means of infra-red radiation.
  • the laminating may proceed likewise by heat generated by high-frequency micro-waves as described e.g. in published EP-A 0 278 818 directed to a method for applying a plastic covering layer to documents.
  • the adhesive layer may be heat-curable or ultra-violet radiation curable.
  • heat-curable organic resins and curing agents therefore reference is made e.g. to the above mentioned “Handbook of Adhesive Raw Materials", and for UV curable resin layers reference is made e.g. to "UV Curing: Science and Technology” - Technology Marketing Corporation. 642 Westover Road - Stanford - Connecticut - USA - 06902 (1979).
  • UV curable resin layers reference is made e.g. to "UV Curing: Science and Technology” - Technology Marketing Corporation. 642 Westover Road - Stanford - Connecticut - USA - 06902 (1979).
  • heat mode recording with a meltable metal layer preference is given to an easily deformable adhesive layer so that it does not form a hindrance for the formation of small metal globules in the areas of the recording layer struck by high intensity radiation energy laser energy.
  • the easy deformability of the adhesive interlayer is in favour of recording sensitivity.
  • dimensional stability is of utmost importance.
  • Fields of application where the requirements for dimensional stability are very stringent are e.g. those where the heat moded image serves as an intermediate for the exposure of a lithographic printing plate, or as a master mask for the production of microelectronic integrated circuits or printed circuit boards (PCB) .
  • PCB printed circuit boards
  • one or more barrier layers can be applied onto the heat mode recording element retarding the uptake of water vapour as disclosed in European Patent Application Appl. No. 93201366, filed 12 May, 1993.
  • this barrier layer is a vapour-deposited glass layer substantially composed of SiO x , x ranging from 1.2.to 1.8.
  • a barrier layer can be applied to one of or to both outermost sides of the complete finished heat mode element of the present invention, or to one of or to both sides of the support of the recording element before the element is further produced.
  • any laser can be used which provides enough energy needed for the production of sufficient heat for this particular process of image formation.
  • a powerful infra-red laser is used.
  • a Nd-YLF laser is used emitting at 1053 nm.
  • a bismuth layer of 0.3 ⁇ m thickness was applied by vacuum-deposition (vacuum of 10 ⁇ 2 Pa) in a Leybold apparatus, after a weak corona discharge of 0.05 Ampère.
  • a protective element consisting of a 8 ⁇ m thick adhesive layer containing copoly(butylacrylate-vinylacetate), and of a cover sheet being a 12 ⁇ m thick polyethylene terephthalate foil.
  • the macroscopic homogeneity was defined as the minimal laser power at which the full areas and lines showed no interference patterns or interference fringes any more. These values are summarized in table 2 : TABLE 2 element homogeneity full areas lines R-1 > 1330 > 1330 R-2 > 1330 > 1330 I-1 1200-1260 > 1330 I-2 1110-1200 1110-1200

Landscapes

  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

A heat mode recording element is disclosed comprising a metal recording layer, preferably a bismuth layer, and a layer containing a roughening agent underneath the metal layer. An image is formed by exposure with intense laser light and the presence of the roughening agent reduces or eliminates interference patterns.

Description

    1. Field of the invention.
  • The present invention relates to an improved heat mode recording element containing a thin metal recording layer.
  • 2. Background of the invention.
  • Recording materials have been disclosed on which records are made thermally by the use of intense radiation like laser beams having a high energy density. In such thermal recording or heat mode recording materials information is recorded by creating differences in reflection and/or in transmission optical density on the recording layer. The recording layer has high optical density and absorbs radiation beams which impinge thereon. The conversion of radiation into heat brings about a local temperature rise, causing a thermal change such as evaporation or ablation to take place in the recording layer. As a result, the irradiated parts of the recording layer are totally or partially removed, and a difference in optical density is formed between the irradiated parts and the unirradiated parts (cf. US Pat. Nos. 4,216,501, 4,233,626, 4,188,214 and 4,291,119 and British Pat. No. 2,026,346)
  • The recording layer of such heat mode recording materials is usually made of metals, dyes, or polymers. Recording materials like this are described in 'Electron, Ion and Laser Beam Technology", by M. L. Levene et al.; The Proceedings of the Eleventh Symposium (1969); "Electronics" (Mar. 18, 1968) , P. 50; "The Bell System Technical Journal", by D. Maydan, Vol. 50 (1971), P. 1761; and "Science", by C. O. Carlson, Vol. 154 (1966), P. 1550.
  • Recording on such thermal recording materials is usually accomplished by converting the information to be recorded into electrical time series signals and scanning the recording material with a laser beam which is modulated in accordance with the signals. This method is advantageous in that recording images can be obtained on real time (i.e. instantaneously). Recording materials of this type are called "direct read after write" (DRAW) materials. DRAW recording materials can be used as a medium for recording an imagewise modulated laser beam to produce a human readable or machine readable record. Human readable records are e.g. micro-images that can be read on enlargement and projection. An example of a machine readable DRAW recording material is the optical disc. To date for the production of optical discs tellurium and its alloys have been used most widely to form highly reflective thin metal films wherein heating with laser beam locally reduces reflectivity by pit formation (ref. e.g. the periodical 'Physik in unserer Zeit', 15. Jahrg. 1984/Nr. 5, 129-130 the article "Optische Datenspeicher" by Jochen Fricke). Tellurium is toxic and has poor archival properties because of its sensitivity to oxygen and humidity. Other metals suited for use in DRAW heat-mode recording are given in US-P-4499178 and US-P-4388400. To avoid the toxicity problem other relatively low melting metals such as bismuth have been introduced in the production of a heat-mode recording layer. By exposing such a recording element very shortly by pulses of a high-power laser the radiation is converted into heat on striking the bismuth layer surface. As a result the writing spot ablates or melts a small amount of the bismuth layer. On melting the layer contracts on the heated spot by surface tension thus forming small cavitations or holes. As a result light can pass through these cavitations and the density is lowered to a certain Dmin value depending on the laser energy irradiated.
  • Heat mode recording materials usually do not require development and fixing processes and do not require darkroom operations because of their insensitivity to room light. Therefore they constitute a valuable alternative to conventional photosensitive materials based on silver halide emulsions, e.g. for phototype-setting or image-setting applications. As is generally known silver halide materials have the advantage of high potential intrinsic sensitivity and excellent image quality. On the other hand they show the drawback of requiring several wet processing steps employing chemical ingredients which are suspect from an ecological point of view. For instance the commonly used developing agent hydroquinone is allergenic and the biodegradation of disposed phenidone is too slow. As a consequence it is undesirable that depleted solutions of this kind would be discharged into the public sewerage; they have to be collected and destroyed by combustion, a cumbersome and expensive process.
  • However, recording elements based on a thin metal layer show the drawback that the thin metal film may reflect more than 50 % of the laser radiation, wasting the energy of the laser radiation. Accordingly, such material may require a substantial amount of energy for recording. Therefore, a high output laser light source is required if records are to be made by high-speed scanning. Methods to reduce reflectance are proposed in the Japanese Unexamined Patent Publications Nos. 40479/71 and 74632/76. However the proposed solutions have other drawbacks. Moreover, due to the high specular reflectance interference patterns arise with periods depending on the thickness of the protective cover usually present to protect the scratch-sensitive metal layer. As a consequence of these interference phenomena the finished image has an uneven and splodgy appearance.
  • It is an object of the present invention to provide an improved heat mode recording element based on a thin metal layer which shows reduced or no interference patterns on laser recording.
  • It is a further object of the present invention to provide a method for the formation of a heat mode image which has no uneven or splodgy appearance.
  • 3. Summary of the invention.
  • The objects of the present invention are realized by providing a heat mode recording element comprising, in order :
    • (a) a support,
    • (b) a layer containing a roughening agent,
    • (c) a metal recording layer,
    • (d) a protective element.
  • In a preferred embodiment the metal layer is a vacuum-deposited thin bismuth layer having a thickness preferably comprised between 0.1 and 0.6 µm. The average particle size of the roughening agent preferably ranges between 0.3 and 2.0 µm, most preferably around 1.0 µm. A preferred roughening agent is composed of polymethylmethacrylate beads.
  • The layer containing the roughening agent can be the subbing layer of the support or can be an extra layer between the subbing layer and the metal layer.
  • The protective element preferably comprises a cover sheet and an adhesive layer.
  • 4. Detailed description of the invention.
  • The different elements constituting the heat mode recording material of the present invention will now be explained in more detail.
  • Although the support of the heat mode element can in principle be an opaque paper base preference is given to a transparent organic resin support. Useful transparent organic resin supports include e.g. cellulose nitrate film, cellulose acetate film, polyvinylacetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, polyvinylchloride film or poly-Alpha-olefin films such as polyethylene or polypropylene film. The thickness of such organic resin film is preferably comprised between 0.07 and 0.35 mm. In a most preferred embodiment of the present invention the support is a polyethylene terephthalate layer provided with a subbing layer.
  • The layer containing the roughening agent can be the subbing layer itself applied to the support or can be an extra layer between the subbing layer and the metal layer.
  • In principle layer (b) can contain no binder at all but preferably it contains a binder. Tis layer (b) can be coated in principle from an organic solvent or from an aqueous medium depending on the chemical nature of the binder. Organic solvent-soluble binders include e.g. polymers derived from α,β-ethylenically unsaturated compounds such as e.g. polymethyl methacrylate polyvinyl chloride, a vinylidene chloride-vinyl chloride copolymer polyvinyl acetate, a vinyl acetate-vinyl chloride copolymer, a vinylidene chloride-acrylonitrile copolymer, a styrene-acrylonitrile copolymer chlorinated polyethylene, chlorinated polypropylene, a polyester, a polyamide, polyvinylbutyral etc. Several organic solvents can be used for dissolving and coating these polymers. On the other hand water-soluble binders coatable from an aqueous medium can be used, e.g. gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, gum arabic, casein, different kinds of water-soluble latices, etc.
  • In a preferred embodiment the roughening agent is incorporated in the subbing layer applied to the polyester support, in other words this subbing layer constitutes layer (b). This subbing layer can be applied before or after stretching of the polyester film support. The polyester film support is preferably biaxially stretched at an elevated temperature of e.g. 70-120°C, reducing its thickness by about 1/2 to 1/9 or more and increasing its area 2 to 9 times. The stretching may be accomplished in two stages, transversal and longitudinal in either order or simultaneously. The subbing layer is preferably applied by aqueous coating between the longitudinal and transversal stretch, in a thickness of 0.1 to 5 µm. In case of a bismuth recording layer the subbing layer preferably contains, as described in European Patent Application EP 0 464 906, a homopolymer or copolymer of a monomer comprising covalently bound chlorine. Examples of said homopolymers or copolymers suitable for use in the subbing layer are e.g. polyvinyl chloride, polyvinylidene chloride, a copolymer of vinylidene chloride, an acrylic ester and itaconic acid, a copolymer of vinyl chloride and vinylidene chloride, a copolymer of vinyl chloride and vinyl acetate, a copolymer of butylacrylate vinyl acetate and vinyl chloride or vinylidene chloride, a copolymer of vinyl chloride, vinylidene chloride and itaconic acid, a copolymer of vinyl chloride, vinyl acetate and vinyl alcohol etc.. Polymers that are water dispersable are preferred since they allow aqueous coating of the subbing layer which is ecologically advantageous.
  • Said homopolymer or copolymer may be prepared by various polymerization methods of the constituting monomers. For example, the polymerization may be conducted in aqueous dispersion containing a catalyst and activator, e.g., sodium persulphate and meta sodium bisulphite, and an emulsifying and/or dispersing agent. Alternatively, the homopolymers or copolymers used with the present invention may be prepared by polymerization of the monomeric components in the bulk without added diluent, or the monomers may be reacted in appropriate organic solvent reaction media.
  • The roughening agent incorporated in layer (b) - for many actual substances this term will be equivalent to the more familiar terms "matting agent" or "spacing agent", but the term is chosen for its functional aspect - must fulfil several requirements for the successful practice of the present invention. Chemical nature, concentration and particle distribution of the roughening agent must be chosen in such a way that a certain degree of uneveness can be introduced in the metal recording layer. It is shown that this uneveness can reduce the occurence of interference patterns because the reflectance gets more diffuse. It will be clear that the roughening agent must be closely packed in the layer. It will also be easily understood that the thickness of layer (b), the average particle size and the coverage of the roughening agent must be tuned to each other in such a way that a sufficient number of the roughening particles must protrude above the interface layer (b) / metal layer in order to induce local deformation spots into this metal layer. When the average particle size is too low the roughening agent will not be able to introduce uneveness in the metal layer. When the average particle size is too great too high a coverage will be required which would make layer (b) too thick. So it is clear that an optimal particle size should be chosen for the roughening agent and that this optimum will depend on the mechanical strenght of the metal layer and therefore on its thickness. For the preferred embodiment of a bismuth layer with a thickness of about 0.3 µm the average particle size of the roughening agent preferably ranges from 0.3 to 2.0 µm, and is most preferably about 1.0 µm. In this case the coverage of the roughening agent preferably ranges from 0.05 to 1.0 g/m², and is most preferably about 0.6 g/m².
  • It will also be clear that the optimal amount/m² of the binder will be dependent on the average particle size of the roughening agent.
  • The degree of roughness of layer (b) is best characterized by the so-called Ra value. This so-called average roughness value is defined as the arithmic average value of the absolute amounts of all the measured distances of the roughness profile from the middle line within the measured interval. Layer (b) preferably has a Ra value of at least 0.2 µm.
  • The roughening agent can be chosen from a wide variety of chemical classes and commercial products provided the particles chosen show an excellent mechanical and thermal stability. Preferred roughening agents include following :
    • the spherical polymeric beads disclosed in US 4,861,818 ;
    • the alkali-soluble beads of US 4,906,560 and EP 0 584 407 ;
    • the insoluble polymeric beads disclosed in EP 0 466 982 ;
    • polymethylmethacrylate beads ;
    • copolymers of methacrylic acid with methyl- or ethylmethacrylate ;
    • TOSPEARL siloxane particles (e.g. types T105, T108, T103, T120) marketed by Toshiba Co ;
    • SEAHOSTAR polysiloxane - silica particles (e.g. type KE-P50) marketed by Nippon Shokubai Co ;
    • ROPAQUE particles, being polymeric hollow spherical core/sheat beads, marketed by Rohm and Haas Co, and described e.g. is US-P's 4,427,836, 4,468,498 and 4,469,825 ;
    • ABD PULVER, marketed by BASF AG ;
    • CHEMIPEARL, spherical poymeric particles, marketed by Misui Petrochemical Industries, Ltd.
  • In principle, a thin intermediate layer can be applied between layer (b) and the metal recording layer for reasons of protection against physical damage. In this case the thin intermediate layer is coated together with layer (b) by slide hopper coating. It can contain the same kinds of binder as layer (b) at a coverage of lower than 1 g/m² in order not to loose the roughening effect. However in a preferred embodiment there is no such an intermediate layer and the metal recording layer is positioned immediately on top of layer (b) in order to get the full effect of the uneveness introduced by the roughening agent.
  • Possible metals for the recording layers in this invention include Mg, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd, Ir, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Si, Ge, Sn, As, Sb, Bi, Se, Te. These metals can be used alone or as a mixture or alloy of at least two metals therof. Due to their low melting point Mg, Zn, In, Sn, Bi and Te are preferred. The most preferred metal for the practice of this invention is Bi.
  • The metal recording layer may be applied on top of the layer containing the roughening agent by vapor deposition, sputtering, ion plating, chemical vapor deposition, electrolytic plating, or electroless plating. In the preferred case of Bi the recording layer is preferably provided by vapor deposition in vacuo. A method and an apparatus for such a deposition are disclosed in EP 0 384 041.
  • The thickness of this Bi layer is preferably comprised between 0.1 and 0.6 µm. When this thickness is too low the recorded images do not have sufficient density. When on the other hand the thickness is too high the sensitivity tends to decrease and the minimal density, i.e. the density after laser recording on the exposed areas tends to be higher.
  • Since the metal layer is very sensitive to mechanical damage a protective element must be provided on top of the metal layer. In a preferred embodiment this protective element comprises a transparent organic resin, acting as cover sheet, and an adhesive layer. A method for applying such a protective element by lamination in the same vacuum environment as wherein the deposition of the metal layer took place is disclosed in EP 0 384 041, cited above. The cover sheet can be chosen from the group of polymeric resins usable for the support of the heat mode element. In a preferred embodiment the cover sheet is also polyethylene terephthalate but preferably substantially thinner than the polyethylene terephthalate of the support.
  • For the adherence of the hard protective outermost resin layer to the heat mode recording layer preferably a layer of a pressure-sensitive adhesive resin can be used. Examples of such resins are described in US-P 4,033,770 for use in the production of adhesive transfers (decalcomanias) by the silver complex diffusion transfer process. in the Canadian Patent 728,607 and in the United States Patent 3,131,106.
  • Pressure-sensitive adhesives are usually composed of (a) thermoplastic polymer(s) having some elasticity and tackiness at room temperature (about 20°C), which is controlled optionally with a plasticizer and/or tackifying resin. A thermoplastic polymer is completely plastic if there is no recovery on removal of stress and completely elastic if recovery is instantaneous and complete.
  • Particularly suitable pressure-sensitive adhesives are selected from the group of polyterpene resins, low density polyethylene, a copoly(ethylene/vinyl acetate), a poly(C₁-C₁₆)alkyl acrylate, a mixture of poly(C₁-C₁₆)alkyl acrylate with polyvinyl acetate, and copoly(vinylacetate-acrylate) being tacky at 20°C.
  • In the production of a pressure-adhesive layer an intrinsically non-tacky polymer may be tackified by the adding of a tackifying substance, e.g. plasticizer or other tackifying resin.
  • Examples of suitable tackifying resins are the terpene tackifying resins described in the periodical "Adhesives Age", Vol. 31, No. 12, November 1988, p. 28-29.
  • According to another embodiment the protective element is laminated or adhered to the heat-mode recording layer by means of a heat-sensitive also called heat-activatable adhesive layer or thermoadhesive layer, examples of which are described also in US-P 4,033,770. In such embodiment the laminating material consisting of adhesive layer and abrasion resistant protective layer and/or the recording web material to be protected by lamination are heated in their contacting area to a temperature beyond the softening point of the adhesive. Heat may be supplied by electrical energy to at least one of the rollers between which the laminate is formed or it may be supplied by means of infra-red radiation. The laminating may proceed likewise by heat generated by high-frequency micro-waves as described e.g. in published EP-A 0 278 818 directed to a method for applying a plastic covering layer to documents.
  • A survey of pressure and/or heat-sensitive adhesives is given by J. Shields in "Adhesives Handbook", 3rd. ed. (1984) , Butterworths - London, Boston, and by Ernest W. Flick in "Handbook of Adhesive Raw Materials" (1982), Noyens Publications, Park Ridge, New Jersey - USA.
  • The adhesive layer may be heat-curable or ultra-violet radiation curable. For heat-curable organic resins and curing agents therefore reference is made e.g. to the above mentioned "Handbook of Adhesive Raw Materials", and for UV curable resin layers reference is made e.g. to "UV Curing: Science and Technology" - Technology Marketing Corporation. 642 Westover Road - Stanford - Connecticut - USA - 06902 (1979). However, in heat mode recording with a meltable metal layer preference is given to an easily deformable adhesive layer so that it does not form a hindrance for the formation of small metal globules in the areas of the recording layer struck by high intensity radiation energy laser energy. The easy deformability of the adhesive interlayer is in favour of recording sensitivity.
  • For several applications of a heat mode DRAW material such as the one of the present invention the dimensional stability is of utmost importance. Fields of application where the requirements for dimensional stability are very stringent are e.g. those where the heat moded image serves as an intermediate for the exposure of a lithographic printing plate, or as a master mask for the production of microelectronic integrated circuits or printed circuit boards (PCB) . To improve the dimensional stablility one or more barrier layers can be applied onto the heat mode recording element retarding the uptake of water vapour as disclosed in European Patent Application Appl. No. 93201366, filed 12 May, 1993. In a preferred embodiment this barrier layer is a vapour-deposited glass layer substantially composed of SiOx, x ranging from 1.2.to 1.8. Such a barrier layer can be applied to one of or to both outermost sides of the complete finished heat mode element of the present invention, or to one of or to both sides of the support of the recording element before the element is further produced.
  • For the formation of a heat mode image using the element of the present invention any laser can be used which provides enough energy needed for the production of sufficient heat for this particular process of image formation. In a preferred embodiment a powerful infra-red laser is used. Most preferably a Nd-YLF laser is used emitting at 1053 nm.
  • The present invention will be illustrated now by the following example without however being limited thereto.
  • EXAMPLE - preparation of heat mode recording elements
  • The following substrates for the deposition of a bismuth layer were prepared :
    • reference 1 (R-1) : this substrate consisted of a polyethylene terphthalate support sheet subbed with a layer containing 0.16 g/m² of a copolymer consisting of 88 mole % of vinylidene chloride, 10 mole % of methylacrylate and 2 mole % of itaconic acid, serving as a binder, and also containing 0.04 g/m² of SiO₂ with an average particle size of 0.1 µm. A backing layer was also present containing, as antistatic element 5.2 mg/m² of an epoxysilane hydrolyzed in polysulphonic acid, and 5 mg/m² of SiO₂ with an average particle size of 0.1 µm. This reference 1 element was taken from current manufacturing by Agfa-Gevaert N.V. ;
    • reference 2 (R-2) : an aqueous coating solution was prepared containing the same copolymer consisting of 88 mole % of vinylidene chloride, 10 mole % of methylacrylate and 2 mole % of itaconic acid, serving as a binder, and two conventional commercial wetting agents. This solution was coated on top of a subbed polyethylene terephthalate substrate corresponding to reference 1. After drying this extra layer contained 0.45 g/m² of the copolymer ;
    • invention 1 (I-1) : this substrate was similar to reference 2 with the exception that the extra layer contained only 0.16 g/m² of the copolymeric binder and 0.09 g/m² of roughening agent ROPAQUE OP62 LO, having an average particle size of 0.5 µm, purchased from Rohm and Haas Co.
    • invention 2 (I-2) : this substrate was similar to reference 2 with the exception that the extra layer further contained a roughening agent consisting of polymethylmethacrylate beads, having an average particle size diameter of 1.0 µm, at a coverage of 0.59 g/m².
  • To these four substrates a bismuth layer of 0.3 µm thickness was applied by vacuum-deposition (vacuum of 10⁻² Pa) in a Leybold apparatus, after a weak corona discharge of 0.05 Ampère. To the bismuth layer was laminated in vacuo a protective element consisting of a 8 µm thick adhesive layer containing copoly(butylacrylate-vinylacetate), and of a cover sheet being a 12 µm thick polyethylene terephthalate foil.
  • - image formation and evaluation of image quality
  • The four recording elements were exposed by means of a high-power internal drum laser recorder with following characteristics :
    • laser type : Nd-YLF laser ;
    • wavelenght : 1053 nm ;
    • spot diameter (1/e²) : 18 µm ;
    • pitch : 10.58 µm ;
    • velocity of the rotating scanning mirror : 1663 rpm ;
    • drum radius : 188.6 mm ;
       The elements were exposed through the protective laminate side. Full areas and separate scan lines (1 on / 10 off) were exposed at different laser powers ranging between 480 mW and 1330 mW. The obtained image quality was evaluated as follows. (a) Dmax and Dmin
  • The densities of exposed and unexposed full areas were measured with a MACKBETH TD904 densitometer equipped with a UV-filter and a measuring spot of 3 mm. The results (mean values of different measurements, expressed in thousands) are summarized in table 1. TABLE 1
    element Dmax Dmin
    480 mW 700 mW 900 mW 1110 mW 1260 mW 1330 mW
    R-1 362 290 133 53 37 30 29
    R-2 390 345 98 46 35 31 32
    I-1 380 332 142 49 34 32 31
    I-2 289 233 108 49 34 32 31
  • From table 1 it is clear that at least a laser power output, measured on the recording element plane, of 1110 mW is necessary to get a maximal density differentiation between exposed and unexposed areas. At this and above this power the presence or absence of a roughening agent has little influence on Dmin.
  • (b) macroscopic evaluation of homogeneity
  • The macroscopic homogeneity was defined as the minimal laser power at which the full areas and lines showed no interference patterns or interference fringes any more. These values are summarized in table 2 : TABLE 2
    element homogeneity
    full areas lines
    R-1 > 1330 > 1330
    R-2 > 1330 > 1330
    I-1 1200-1260 > 1330
    I-2 1110-1200 1110-1200
  • The interference phenomena disappeared at a lower laser power when the recording elements contained a roughening agent. The best result was obtained with roughening agent polymethylmethacrylate having an average grain size of 1.0 µm.
  • (c) microscopic evaluation of homogeneity
  • The recorded full areas and lines were enlarged 100 fold by means of a Nikon microscope and photographed so that individual scan lines became visible.
  • An arbitrary qualification ranging from 0 to 5 was assigned to the physical quality of the recorded full areas at 1200 mW power and 1330 mW power. This qualification range had following meaning :
    • 1 : inhomogeneous, very intense interference spots ;
    • 2 : inhomogeneous, rather intense interference spots ;
    • 3 : rather homogeneous, still slight interference ;
    • 4 : practically completely homogeneous ; sometimes very slight interference ;
    • 5 : very homogeneous ; no interference.
  • The quality results are summarized in table 3 : TABLE 3
    element quality at 1200 mw quality at 1330 mW
    R-1 1 2
    R-2 2 3
    I-1 4 5
    I-2 5 5
  • The table clearly illustrates the superior results obtained with the elements according to the present invention.
  • The recorded lines showed local variations in width due to local variations of laser power as a consequence of interference. Table 4 summarizes the minimal and maximal values of the line width (in µm) obtained with laser powers varying between 1110 and 1330 mW. TABLE 4
    Power elements
    R-1 min-max R-2 min-max I-1 min-max I-2 min-max
    1010 0 - 8 0 - 8 7 - 10 7 - 9
    1110 0 - 8 5 - 11 7 - 10 8 - 9
    1200 3 - 10 7 - 11 7 - 11 9.5-10
    1260 5 - 11 7 - 11 9 - 12 10 - 11
    1300 7-11.5 10 - 12 11 - 13 11-11.5
    1330 7 - 12 10 - 12 11 - 13 11 - 12
  • It is clear from the table that the difference between minimal and maximal line width is smaller with the elements according to the invention.

Claims (14)

  1. Heat mode recording element comprising, in order :
    (a) a support,
    (b) a layer containing a roughening agent,
    (c) a metal recording layer,
    (d) a protective element.
  2. Heat mode recording element according to claim 1 wherein said layer containing a roughening agent has a Ra value of at least 0.2 µm.
  3. Heat mode recording element according to claim 1 or 2 wherein said roughening agent has an average particle size between 0.3 and 2.0 µm.
  4. Heat mode recording element according to claim 3 wherein said roughening agent having an average particle size between 0.3 and 2.0 µm is present in layer (b) at a coverage between 0.05 and 1.0 g/m².
  5. Heat mode recording element according to any of claims 1 to 4 wherein said roughening agent is polymethylmethacrylate.
  6. Heat mode recording element according to any of claims 1 to 5 wherein said metal recording layer is a bismuth layer.
  7. Heat mode recording element according to claim 6 wherein said bismuth layer has a thickness between 0.05 and 0.6 µm.
  8. Heat mode recording element according to any of claims 1 to 7 wherein said support is provided with a subbing layer and said layer (b) containing a roughening agent is said subbing layer.
  9. Heat mode recording element according to any of claims 1 to 8 wherein said protective element comprises a polymeric cover sheet or layer being a transparent polymeric resin, and an adhesive layer.
  10. Method for the formation of a heat mode image comprising exposing information-wise by intense laser radiation a heat mode recording element according to any of claims 1 to 9.
  11. Method according to claim 10 wherein said intense laser radiation is produced by an infra-red laser.
  12. Method according to claim 11 wherein said infra-red laser is a Nd-YLF laser emitting at 1053 nm.
  13. Use of the heat mode image obtained according to the method of any of claims 10, 11, or 12 as a master for the production of printed circuit boards or microelectronic integrated circuits.
  14. Use of the heat mode image obtained according to the method of any of claims 10, 11, or 12 as a master for the exposure of a printing plate.
EP19950201166 1994-05-25 1995-05-08 Heat mode recording element Expired - Lifetime EP0684145B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19950201166 EP0684145B1 (en) 1994-05-25 1995-05-08 Heat mode recording element

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP94201472 1994-05-25
EP94201472 1994-05-25
EP19950201166 EP0684145B1 (en) 1994-05-25 1995-05-08 Heat mode recording element

Publications (2)

Publication Number Publication Date
EP0684145A1 true EP0684145A1 (en) 1995-11-29
EP0684145B1 EP0684145B1 (en) 1998-08-12

Family

ID=26136284

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19950201166 Expired - Lifetime EP0684145B1 (en) 1994-05-25 1995-05-08 Heat mode recording element

Country Status (1)

Country Link
EP (1) EP0684145B1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998016397A1 (en) * 1996-10-11 1998-04-23 Schreiner Etiketten Und Selbstklebetechnik Gmbh & Co. Foil capable of being inscribed by a laser beam
EP0886268A1 (en) * 1997-06-18 1998-12-23 Agfa-Gevaert N.V. Heat mode recording element based on a thin metallic recording layer
US5989777A (en) * 1997-06-18 1999-11-23 Agfa-Gevaert, N. V. Heat mode recording element based on a thin metallic recording layer
EP0982718A1 (en) * 1998-08-28 2000-03-01 Agfa-Gevaert N.V. Heat mode recording element with two antistatic layers
EP1004454A1 (en) * 1998-11-26 2000-05-31 Konica Corporation Thermal transfer image forming material
US6692895B2 (en) 2001-05-25 2004-02-17 3M Innovative Properties Company Imageable article and method of imaging

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5729493A (en) * 1980-07-30 1982-02-17 Honshu Paper Co Ltd Discharge recording medium
EP0293778A2 (en) * 1987-05-30 1988-12-07 Kuraray Co., Ltd. Optical recording medium and recording process utilizing the same
JPH03297688A (en) * 1990-04-16 1991-12-27 Toppan Printing Co Ltd Thermosensitive recording card
JPH03297698A (en) * 1990-04-16 1991-12-27 Toppan Printing Co Ltd Card and manufacture thereof
EP0573092A1 (en) * 1992-06-05 1993-12-08 Agfa-Gevaert N.V. A method for obtaining an image using a heat mode recording material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5729493A (en) * 1980-07-30 1982-02-17 Honshu Paper Co Ltd Discharge recording medium
EP0293778A2 (en) * 1987-05-30 1988-12-07 Kuraray Co., Ltd. Optical recording medium and recording process utilizing the same
JPH03297688A (en) * 1990-04-16 1991-12-27 Toppan Printing Co Ltd Thermosensitive recording card
JPH03297698A (en) * 1990-04-16 1991-12-27 Toppan Printing Co Ltd Card and manufacture thereof
EP0573092A1 (en) * 1992-06-05 1993-12-08 Agfa-Gevaert N.V. A method for obtaining an image using a heat mode recording material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9207, Derwent World Patents Index; AN 92-053752 *
PATENT ABSTRACTS OF JAPAN vol. 16, no. 137 (M - 1231) 7 April 1992 (1992-04-07) *
PATENT ABSTRACTS OF JAPAN vol. 6, no. 93 (M - 133) 29 May 1982 (1982-05-29) *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998016397A1 (en) * 1996-10-11 1998-04-23 Schreiner Etiketten Und Selbstklebetechnik Gmbh & Co. Foil capable of being inscribed by a laser beam
US6066437A (en) * 1996-10-11 2000-05-23 Schreiner Etiketten Und Selbstklebetechnik Gmbh & Co. Film which can be lettered using a laser beam
EP0886268A1 (en) * 1997-06-18 1998-12-23 Agfa-Gevaert N.V. Heat mode recording element based on a thin metallic recording layer
US5989777A (en) * 1997-06-18 1999-11-23 Agfa-Gevaert, N. V. Heat mode recording element based on a thin metallic recording layer
EP0982718A1 (en) * 1998-08-28 2000-03-01 Agfa-Gevaert N.V. Heat mode recording element with two antistatic layers
EP1004454A1 (en) * 1998-11-26 2000-05-31 Konica Corporation Thermal transfer image forming material
US6383621B1 (en) 1998-11-26 2002-05-07 Konica Corporation Thermal transfer image forming material
US6692895B2 (en) 2001-05-25 2004-02-17 3M Innovative Properties Company Imageable article and method of imaging

Also Published As

Publication number Publication date
EP0684145B1 (en) 1998-08-12

Similar Documents

Publication Publication Date Title
US4587198A (en) Dye transfer image process
US5147490A (en) Process for the production of a heat-mode recording material
EP0280531A2 (en) Optical information recording carrier
GB2029267A (en) Thermal recording elements
NL8303893A (en) INFORMATION REGISTRATION MEDIUM.
US5656410A (en) Process for producing a protected heat-mode recording material
EP0684145B1 (en) Heat mode recording element
JPS62219247A (en) Optical recording medium and optical recording method thereof
JPS6099699A (en) Optical recording medium for information
US5962181A (en) Process for the preparation of a metal heat mode recording element
US6309808B1 (en) Heat mode recording element
EP0709227B1 (en) Method for the formation of an improved image
EP0687569B1 (en) Process for producing a protected heat-mode recording material
EP1043720A1 (en) Heat mode recording element based on a thin metal layer
EP0886268B1 (en) Heat mode recording element based on a thin metallic recording layer
US5989777A (en) Heat mode recording element based on a thin metallic recording layer
EP0875889B1 (en) Thin metal recording layer coated from aqueous medium
EP0803376B1 (en) Process for the preparation of a metal heat mode recording element
US6132927A (en) Thin metal recording layer coated from aqueous medium
EP0982718B1 (en) Heat mode recording element with two antistatic layers
JP2879142B2 (en) Method for producing metal heat mode recording material
EP0697967B1 (en) Thermosensitive recording material
EP0741643B1 (en) Laminar imaging medium utilizing crosslinked borated polymeric binder
JP2591941B2 (en) Optical recording method and optical recording medium
JPS59231526A (en) Image forming article

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB NL

17P Request for examination filed

Effective date: 19960529

17Q First examination report despatched

Effective date: 19970113

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980812

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19980812

REF Corresponds to:

Ref document number: 69503968

Country of ref document: DE

Date of ref document: 19980917

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: 746

Effective date: 19990812

REG Reference to a national code

Ref country code: FR

Ref legal event code: D6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20000505

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000509

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010508

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020131

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20030423

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041201