EP1565321B1 - Materiau d'impression sensible a la chaleur et son utilisation - Google Patents

Materiau d'impression sensible a la chaleur et son utilisation Download PDF

Info

Publication number
EP1565321B1
EP1565321B1 EP03779990A EP03779990A EP1565321B1 EP 1565321 B1 EP1565321 B1 EP 1565321B1 EP 03779990 A EP03779990 A EP 03779990A EP 03779990 A EP03779990 A EP 03779990A EP 1565321 B1 EP1565321 B1 EP 1565321B1
Authority
EP
European Patent Office
Prior art keywords
heat
sensitive recording
recording material
material according
layer
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
EP03779990A
Other languages
German (de)
English (en)
Other versions
EP1565321A1 (fr
Inventor
Wolfgang Wagner
Gerhard Stork
Takao Masuda
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.)
Mitsubishi HiTech Paper Flensburg GmbH
Original Assignee
Mitsubishi HiTech Paper Flensburg GmbH
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 Mitsubishi HiTech Paper Flensburg GmbH filed Critical Mitsubishi HiTech Paper Flensburg GmbH
Publication of EP1565321A1 publication Critical patent/EP1565321A1/fr
Application granted granted Critical
Publication of EP1565321B1 publication Critical patent/EP1565321B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; 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
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; 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
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes

Definitions

  • the invention relates to a heat-sensitive recording material having a substrate layer, to which a pigmented intermediate layer, a heat-sensitive recording layer containing color formers and color acceptors and a protective layer are applied in this order, and to the use of such a heat-sensitive recording material.
  • a heat-sensitive recording material of the type mentioned is for example from DE-A-101 08 982 known.
  • the well-known recording material has the task of guaranteeing a ticket as excellent Stkoventwertbarkeit; Furthermore, there was the demand for high environmental resistance of the known recording material with respect to water, fats, oils and plasticizers and good printability, inter alia, in offset printing.
  • the above-described recording material was able to convince in most applications, but the market requirements, especially with regard to printability, continued to increase, which is why the need for not only minor modifications but fundamental innovations existed.
  • thermosensitive recording material having one or more intermediate layers disposed between the recording layer and the substrate is known.
  • An intermediate layer contains particles of an oil-absorptive inorganic pigment.
  • fine hollow particles of a synthetic resin of styrene, Acryl.oder a copolymer of styrene and acrylic, optionally together with other inorganic pigment particles.
  • a particle size range (average diameter) of 0.75 ⁇ m to 1.5 ⁇ m is disclosed for the organic hollow particles.
  • Suitable inorganic pigments which may be added to the intermediate layer containing organic hollow particles include calcium and magnesium carbonate, silicon oxide, titanium oxide, kaolin and calcined kaolin. Lessons regarding a protective layer and the glass transition temperature of the organic hollow particles can not be found in this document.
  • thermosensitive recording material using a dye precursor dispersion whose dye precursor particles should not fall outside a range of 0.1 ⁇ m to 0.3 ⁇ m, allowing a proportion of not more than 1% for particles of 0.07 ⁇ m or less is.
  • a layer arranged between the recording layer and the substrate should preferably contain hollow particles of a thermoplastic resin, with a particle size of 2 ⁇ m to 10 ⁇ m in particular being considered preferred. Below a particle size of 2 microns production difficulties are expected.
  • coating compositions are proposed for the intermediate layer, which contain either calcined kaolin or organic hollow particles. With regard to a specific glass transition temperature, this document contains no statement.
  • the substrate of a recording paper for heat-sensitive or heat transfer recording having a security feature disposed in the substrate is known.
  • An intermediate layer provided on the substrate contains an inorganic pigment having an average particle size of 0.1 ⁇ m to 5 ⁇ m or organic particles having an average particle size of 0.5 ⁇ m to 30 ⁇ m.
  • a coating composition for an intermediate layer is disclosed which, in addition to styrene particles, also contains calcined kaolin and calcium carbonate. The document contains no information on the glass transition temperature of the organic particles.
  • an organic pigment is known whose particles are crosslinked and have multiple voids, ie multivoided particles. These particles are intended to circumvent the problems of multi-step production of spherical particles with only a single cavity.
  • the document discloses particle sizes of 0.1 to 2 microns, preferably from 0.5 to 1.5 microns.
  • inorganic pigments are also disclosed.
  • the particle size of the inorganic pigments or their mixing ratio to the particles of the organic pigment are not named.
  • a protective layer for covering the recording layer is given in a general form and without disclosure described the components to be used. In industrial practice, this disclosed organic pigment has hitherto gained no importance.
  • the intermediate layer of a thermosensitive recording material containing crosslinked polymer particles having a particle diameter of 0.2 to 5.0 ⁇ m and an inorganic pigment having an oil absorption of less than 170 ml / 100 g is described.
  • the document discloses a mixing ratio of organic polymer particles to inorganic pigment in the range of 1: 1 to 1: 9. With respect to the shape of the polymer particles, this document contains no information, nor is it disclosed whether they are particles having a cavity structure.
  • the effect of the intermediate layer is explained in the Scriptures in that the organic and inorganic pigment particles have a mutual effect and irregularities on the surface of the substrate used as a substrate are balanced or smoothed. Penetration of the recording layer-forming components should be suppressed so as to obtain a heat-insulating layer having a high void ratio.
  • Np-toluenesulfonylN '-3- (p-toluenesulfonyloxy) phenylurea is used for color-forming reaction with fluoran-based leuco dyes as a developer in association with at least one pigment contained in the heat-sensitive recording layer, comprising aluminum hydroxide, amorphous silica, Kaolin and talc, used.
  • an intermediate layer is disposed below the heat-sensitive recording layer.
  • the intermediate layer may contain a mixture of inorganic pigment and organic particles.
  • a protective layer may be disposed above the heat-sensitive recording layer.
  • a heat-sensitive recording material having a foamed portion having a minute gap in the intermediate layer is known from US 5,156,337 DE-A-39 01 234 known.
  • an intermediate layer is provided which contains an expandable plastic filler which comprises hollow particles of a thermoplastic material and a low boiling point solvent contained in these particles. Upon heating, the intermediate layer expands and certain voids are created.
  • an intermediate layer containing a blowing agent and a thermoplastic material has also been proposed. When heated, this creates an intermediate layer with a cellular structure.
  • the intermediate layer (s) after calendering should have a smoothness of at least 2000 Bekk seconds, a value of at least 2500 Bekk seconds is disclosed for the smoothness of the recording layer.
  • the intermediate layer may be applied to a basecoat covering the substrate containing inorganic pigment and binder.
  • inorganic pigment there is no disclosure in the document. Also, there are no indications in the document about the composition of a possible protective layer.
  • the US-A-5,919,729 relates to a heat-sensitive recording material with the broadest possible task aspects as already discussed EP-A-1 208 994 , As far as organic particles are concerned, they are those with a shell containing a plastic core, the core and shell should have different TG values. The organic particles are used as components of the recording layer, the protective layer and the back surface layer.
  • the inventors recognized after numerous attempts that, in restricting the considerations on the protective layer alone, the above-described task can not be solved. Rather, an intermediate layer to be positioned between the substrate and the heat-sensitive recording layer is also of great importance.
  • the thermal head initiating the color-forming reaction of the color formers with the color acceptors in the heat-sensitive recording layer causes the waxy constituents in the recording layer to melt.
  • a sealing the recording layer completely covering protective layer is provided to prevent adhesion of these waxy constituents as a melt on the thermal head.
  • an intermediate layer completely covering the substrate layer, which contains a pigment mixture of an inorganic and an organic pigment.
  • the inorganic pigments of this intermediate layer cause absorption of the melt. It is particularly advantageous if the pigments of the intermediate layer has an oil absorption of at least 80 cm3 / 100 g, and more preferably 100 cm3 / 100 g, determined according to the Japanese standard JIS K 5101, have. Calcined kaolin, calcium carbonate, silicon dioxide and kaolin have proven particularly useful due to their high absorbency. Also mixtures of several different types of inorganic pigments are conceivable.
  • organic pigments are to a particular extent conducive to a high heat softening capacity of the intermediate layer.
  • organic, so-called hollow body pigments have in their interior air, which is a good heat insulator.
  • the intermediate layer thus optimized as the heat reflection layer increases the response of the recording layer to heat, which remarkably increases the resolving power of the thermosensitive recording material and further raises the printing speed in the thermal printer.
  • the ratio between organic and inorganic pigment is a compromise of the effects caused by the two types of pigment, which is particularly advantageously solved when the pigment mixture to 15 to 50% by weight or better to 20 to 50 wt.% Of organic and 85 to 50 wt .-% or better to 80 to 50 wt .-% of inorganic pigment. It is very particularly preferred if the pigment mixture consists of 25 to 40% by weight of organic and 75 to 60% by weight of inorganic pigment.
  • the organic pigments have a wall of thermoplastic resin which preferably comprises (meth) acrylonitrile copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene acrylate, polyacrylonitrile or polyacrylic acid ester.
  • thermoplastic resin which preferably comprises (meth) acrylonitrile copolymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, styrene acrylate, polyacrylonitrile or polyacrylic acid ester.
  • Pigment mixtures of different organic pigments are conceivable.
  • a glass transition temperature greater than or equal to 100 ° C and preferably greater than or equal to 105 ° C was recognized as essential to the invention, because below these temperatures, an increased degree of yellowing was found.
  • an organic pigment is suitable which comprises spherical particles consisting of only one cavity surrounded by a wall.
  • the core of the particles is first filled with water, which volatilizes during the drying and smoothing of the intermediate layer by the action of temperature and pressure through the shell, thereby creating the cavity.
  • the particles retain, as much as possible, their original shape, volume, and diameter throughout this process.
  • the easiest way to measure the particle size of the organic pigments present in the intermediate layer in the as-supplied state of an aqueous dispersion before their incorporation into the intermediate layer is as a D 50 value.
  • the measurement of the particle size of the spherically shaped organic pigments after formation of the intermediate layer with a scanning electron microscope is possible, wherein the particle size of the organic pigments in the intermediate layer in a range of 0.75 microns to less than 1.5 microns, preferably in a range of 0.9 ⁇ m to 1.2 ⁇ m. Particle sizes below 0.75 ⁇ m ⁇ m, lies. Particle sizes below 0.75 microns prohibit due to rheological processing difficulties.
  • Particle sizes above 1.5 microns show too coarse-grained behavior and prevent a preferred leveling effect of the intermediate layer.
  • a particle size of less than 2 ⁇ m, determined as D 50 value is particularly recommended.
  • Pigments which have a particle size distribution of from 34 to 40% by weight of less than 1 ⁇ m and from 57 to 63% by weight of less than 2 ⁇ m have proved to be advantageous.
  • Another suitable particle size distribution results when 88% by weight is less than 1 ⁇ m.
  • the ratio of the particle size of the organic pigment to the particle size of the inorganic pigment is in a range from 1: 0.38 to 1: 1.5.
  • the intermediate layer further comprises a binder selected from the group consisting of polyvinyl alcohol, styrene-butadiene latex, starch, carboxymethyl cellulose, cellulose derivatives, with Styroj-butadiene latex being particularly preferred.
  • a binder selected from the group consisting of polyvinyl alcohol, styrene-butadiene latex, starch, carboxymethyl cellulose, cellulose derivatives, with Styroj-butadiene latex being particularly preferred.
  • the binder content in the intermediate layer preferably consists of 69 to 76 wt .-% of styrene-butadiene latex.
  • an intermediate layer positioned between the substrate layer and the heat-sensitive recording layer can make a positive contribution to equalization of the substrate layer surface, thus reducing the mass of coating color necessarily required for the heat-sensitive recording layer.
  • To order the intermediate layer offer so far preferably equalizing commissioned works such as roller blade and doctor blade or blade.
  • the formation of the intermediate layer with a basis weight in a range of 5 g / m 2 to 20 g / m 2 and more preferably between 7g / m 2 and 10 g / m 2 .
  • the heat-sensitive recording material according to the invention contains in its protective layer at least one polyvinyl alcohol and a crosslinking aid.
  • the polyvinyl alcohol of the protective layer is modified with carboxyl or silanol groups.
  • Such a protective layer has a high affinity with respect to the preferably UV-crosslinking printing ink used in the offset printing process, which decisively helps to meet the requirement for improved printability within the offset printing. It is also conceivable to use mixtures of different carboxyl-group- or silanol-modified polyvinyl alcohols.
  • Suitable crosslinking aids in the protective layer are in particular those which are selected from the group comprising: boric acid, polyamine, epoxy resin, dialdehyde, formaldehyde oligomers, epiochlorohydrin resin, dimethylurea, melamine-formaldehyde. It is also possible to use mixtures of different crosslinking aids.
  • the ratio of the weight percent of the modified polyvinyl alcohol to the crosslinking aid ranges from 20: 1 to 5: 1, and preferably within the range of 12: 1 to 7: 1 a ratio of the modified polyvinyl alcohol to the crosslinking aid of 100 parts by volume has proved to be 15 to 30 parts by volume.
  • the protective layer additionally contains an inorganic pigment. It is particularly advisable if the inorganic pigment is selected from the group comprising silicon dioxide, aluminum hydroxide, calcium carbonate, kaolin or a mixture of said inorganic pigments.
  • the protective layer which can be formed as single-layer as economically as possible with a basis weight in a range of 1.5 g / m 2 to 6 g / m 2 and especially between 1.8 g / m 2 and 3 g / m 2 , It has been found to be advantageous to have a smoothness of the protective layer in the range of 500 and preferably from 800 or better still 1,000 Bekk seconds (sec) to less than 3,000 Bekk-sec. In particular, values of 1,000 Bekk-sec to less than 2,500 Bekk-sec and most preferably from 1,200 Bekk-sec to 2,000 Bekk-sec are suitable.
  • the gloss of the protective layer is largely determined by the type of smoothing and the friction surfaces and their materials influencing the friction in the calender and calender.
  • a preferred range is between 30% and 50%, and most preferably between 40% and 48%, measured according to Tappi 450 or ISO 2813 at a reflection angle of 75 °.
  • Another preferred range is between 10% and 15%, determined according to the same rules and parameters.
  • a particularly good printability for the offset printing process is present when the protective layer of the new heat-sensitive recording material has the lowest possible polar fraction of the surface tension to be determined as the sum of disperse and polar fraction.
  • the surface tension is determined according to Owens Wendt as in Journal of Applied Polymer Science, Vol. 13, 1969, pages 1741-1747: Estimation of the Surface Free Energy of Polymers; DK Owens, RC Wendt noted s.
  • a suitable range for the measurements of the polar component of the surface tension is above zero and below 15 mN / m (milli-Newton per meter).
  • a polar fraction of the surface tension is particularly preferably less than 10 mN / m.
  • a non-surface treated base paper is to be understood as meaning a base paper not treated in a size press or coater.
  • films of, for example, polyolefin and polyolefin-coated papers are possible as a substrate layer to the same extent, without such an embodiment having an exclusive character.
  • the recording material according to the invention has a backside coating which is applied to the substrate layer side which is opposite to the side provided with the layer sequence of at least the intermediate layer, heat-sensitive recording layer and protective layer.
  • a backside coating is used for example in the DE-A-197 48 258 proposed and then serves an improved back-printability of the recording sheet in the offset and flexographic printing process and an improved barrier effect of the back to plasticizers, oils and fats.
  • Order volumes in a range of 1 g / m 2 to 3 g / m 2 and especially between 1.5 g / m 2 and 2.5 g / m 2 have proved to be advantageous.
  • a paper web made of a mixture of bleached and ground softwood sulphate pulp and eucalyptus pulp having a weight per unit area of 63 g / m.sup.2 with the addition of customary blending substances in customary amounts is produced on a fourdrinier paper machine as the substrate layer.
  • the substrate layer On-line within the paper machine, the substrate layer is provided at the front by means of a blade applicator with an intermediate layer of 9 g / m 2 , which completely covers the substrate layer.
  • the intermediate layer comprises a pigment mixture of 30% by weight (atro) organic pigment having a particle size (D 50 ) of 1 ⁇ m and 70% by weight (atro) calcined kaolin having a particle size (D 50 ) of 0.9 ⁇ m and an oil absorption of 110 cm 3 / 100g.
  • the organic pigment has a glass transition value of 105 ° C.
  • the intermediate layer further comprises a binder mixture of 75% by weight of styrene-butadiene latex and 25% by weight of starch.
  • a heat-sensitive recording layer is coated on the interlayer with a fluoran color former and 4 - [(4- (1-methylethoxy) phenyl) sulfonyl) phenol as a color acceptor, both having a particle size of 0, 9 ⁇ m.
  • a protective layer completely covering the recording layer of 2 g / m 2 is coated with a silanol-modified polyvinyl alcohol and a mixture of an epichlorohydrin resin and a dialdehyde crosslinking agent.
  • the ratio of the silanol-modified polyvinyl alcohol to the mixture of the crosslinking aids is 100 parts by volume to 23 parts by volume.
  • the protective layer further comprises aluminum hydroxide as a pigment.
  • thermosensitive recording material thus produced in the first example has a caliper of 1800 after its calendering Bekk seconds and a gloss value of 40%, measured according to Tappi Standard 450 or ISO 2813 at a reflection angle of 75 °.
  • the polar fraction of the surface tension is below 10 mN / m, more precisely in the first example at 9.57 and in the second example at 9.89 mN / m.
  • novel recording materials produced in this way have a high environmental stability and outstanding offset printability.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Laminated Bodies (AREA)

Claims (23)

  1. Matériau d'enregistrement thermosensible ayant une couche de substrat, sur laquelle on a appliqué des couches dans l'ordre suivant :
    - une couche intermédiaire pigmentée avec un mélange de pigments formé d'un pigment inorganique et d'un pigment creux organique,
    - le pigment creux organique de la couche intermédiaire pigmentée ayant une température de transition vitreuse supérieure ou égale à 100 °C et une taille particulaire (D50) dans une plage de 0,75 µm à moins de 1,5 µm,
    - une couche d'enregistrement thermosensible contenant des agents chromogènes et des accepteurs de couleur et
    - une couche protectrice contenant un alcool polyvinylique modifié par des groupements carboxyle ou silanol et un adjuvant de réticulation,
    caractérisé par la combinaison des caractéristiques suivantes :
    - chaque couche appliquée recouvre complètement la couche sur laquelle elle a été appliquée,
    - les particules du pigment creux organique, initialement remplies d'eau, présentent leur forme sphérique initiale avec leur diamètre initial après séchage et lissage de la couche intermédiaire pigmentée qui les contient,
    - le rapport de l'alcool polyvinylique modifié à l'agent de réticulation, indiqué respectivement en % en poids, se situe dans une plage de 20:1 à 5:1.
  2. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que le rapport de l'alcool polyvinylique modifié à l'agent de réticulation, indiqué respectivement en % en poids, se situe dans une plage de 12:1 à 7:1.
  3. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 et 2, caractérisé en ce que le pigment organique a une température de transition vitreuse supérieure ou égale à 105 °C.
  4. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le pigment organique de la couche intermédiaire a une taille particulaire (D50) dans une plage de 0,9 µm à 1,2 µm.
  5. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le pigment organique de la couche intermédiaire comprend des particules qui sont constituées uniquement d'un espace creux entouré d'une paroi.
  6. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le pigment inorganique de la couche intermédiaire présente une absorption d'huile d'au moins 80 cm3/100 g, déterminée selon la norme japonaise JIS K 5101.
  7. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le pigment inorganique de la couche intermédiaire présente une absorption d'huile d'au moins 100 cm3/100 g, déterminée selon la norme japonaise JIS K 5101.
  8. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 7, caractérisé en ce que l'on choisit le pigment inorganique de la couche intermédiaire parmi un ou plusieurs des pigments mentionnés ci-après : kaolin calciné, carbonate de calcium, dioxyde de silicium et kaolin.
  9. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le pigment inorganique de la couche intermédiaire présente une taille particulaire (D50) inférieure à 2 µm.
  10. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le rapport de la taille particulaire du pigment organique à celle du pigment inorganique se situe dans une plage de 1:0,38 à 1:1,5.
  11. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le mélange de pigments est constitué de pigment organique à raison de 15 à 50 % en poids et de pigment inorganique à raison de 85 à 50 % en poids.
  12. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 11, caractérisé en ce que la couche intermédiaire contient un ou plusieurs des agents liants mentionnés ci-après : l'alcool polyvinylique, le latex de styrène-butadiène, l'amidon, la carboxyméthylcellulose et des dérivés de cellulose.
  13. Matériau d'enregistrement thermosensible selon la revendication 12, caractérisé en ce que l'agent liant est constitué de latex de styrène-butadiène pour 69 à 76 % en poids.
  14. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 13, caractérisé en ce que l'adjuvant de réticulation de la couche protectrice est choisi dans le groupe comprenant l'acide borique, une polyamine, une résine époxy, un dialdéhyde, des oligomères de formaldéhyde, une résine épichlorhydrine, la diméthylurée et la mélamineformaldéhyde.
  15. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 14, caractérisé en ce que la couche protectrice contient un pigment inorganique.
  16. Matériau d'enregistrement thermosensible selon la revendication 15, caractérisé en ce que le pigment inorganique de la couche protectrice est choisi dans le groupe comprenant le dioxyde de silicium, l'hydroxyde d'aluminium, le carbonate de calcium et le kaolin.
  17. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 16, caractérisé en ce que la couche protectrice présente une valeur de la fraction polaire de la tension de surface dans une plage de 0 à 15 mN/m.
  18. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 17, caractérisé en ce que la couche de substrat est constituée de papier.
  19. Matériau d'enregistrement thermosensible selon la revendication 18, caractérisé en ce que le papier est un papier support de couchage brut non traité en surface.
  20. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 19, caractérisé en ce que la couche protectrice présente un lissage Bekk dans une plage supérieure ou égale à 1000 secondes Bekk à moins de 3000 secondes Bekk.
  21. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 20, caractérisé en ce que la couche protectrice présente une valeur de brillance dans une plage de 30 % à 50 %, mesurée selon la norme Tappi 450 ou ISO 2813 (angle de réflexion de 75 °).
  22. Matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 20, caractérisé en ce que la couche protectrice présente une valeur de brillance dans une plage de 10 % à 15 %, mesurée selon la norme Tappi 450 ou ISO 2813 (angle de réflexion de 75 °).
  23. Utilisation d'un matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 22 sous la forme d'un ticket.
EP03779990A 2002-11-19 2003-11-19 Materiau d'impression sensible a la chaleur et son utilisation Expired - Lifetime EP1565321B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10254070 2002-11-19
DE10254070A DE10254070A1 (de) 2002-11-19 2002-11-19 Wärmeempfindliches Aufzeichnungsmaterial und seine Verwendung
PCT/EP2003/012939 WO2004045862A1 (fr) 2002-11-19 2003-11-19 Matériau d'impression sensible à la chaleur et son utilisation

Publications (2)

Publication Number Publication Date
EP1565321A1 EP1565321A1 (fr) 2005-08-24
EP1565321B1 true EP1565321B1 (fr) 2007-10-10

Family

ID=32308599

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03779990A Expired - Lifetime EP1565321B1 (fr) 2002-11-19 2003-11-19 Materiau d'impression sensible a la chaleur et son utilisation

Country Status (6)

Country Link
EP (1) EP1565321B1 (fr)
AT (1) ATE375258T1 (fr)
AU (1) AU2003288116A1 (fr)
DE (2) DE10254070A1 (fr)
ES (1) ES2295669T3 (fr)
WO (1) WO2004045862A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2431660A (en) * 2005-10-28 2007-05-02 Sun Chemical Ltd Thermally resistant gas barrier lamella
DE102018101109A1 (de) * 2018-01-18 2019-07-18 Mitsubishi Hitec Paper Europe Gmbh Wärmeempfindliches Aufzeichnungsmaterial umfassend eine Mehrzahl von Submikrometerpartikeln mit monomodaler Partikelgrößenverteilung

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8729399D0 (en) * 1987-12-17 1988-02-03 Tioxide Group Plc Polymeric particles & their preparation
JP2809229B2 (ja) 1988-05-12 1998-10-08 三菱製紙株式会社 感熱記録材料
DE3901234A1 (de) 1989-01-23 1990-07-26 Ricoh Kk Waermeempfindliches aufzeichnungsmaterial
US4929590A (en) 1989-03-02 1990-05-29 Ricoh Company, Ltd. Thermosensitive recording material
JPH05318927A (ja) 1992-05-15 1993-12-03 Nippon Paper Ind Co Ltd 感熱記録シート
FR2742380B1 (fr) * 1995-12-15 1999-01-29 Ricoh Kk Support d'enregistrement thermosensible a couche protectrice
DE19748258A1 (de) 1997-10-31 1999-05-06 Stora Spezialpapiere Gmbh Wärmeempfindlicher Aufzeichnungsbogen
DE60101870T2 (de) 2000-07-11 2004-11-04 Oji Paper Co., Ltd. Fälschungssicheres Aufzeichnungspapier und Papierträger
DE60102055T3 (de) * 2000-11-24 2012-03-29 Oji Paper Co., Ltd. Wärmeempfindliches Aufzeichnungsmaterial
EP1231073B1 (fr) * 2001-02-09 2004-07-21 Oji Paper Co., Ltd. Matériau pour l'enregistrement thermosensible et procédé pour sa fabrication
DE10108982A1 (de) 2001-02-23 2002-09-12 Mitsubishi Hitec Paper Flensbu Wärmeempfindliches Aufzeichnungsmaterial und seine Verwendung
CA2350633A1 (fr) 2001-03-01 2002-09-01 Rohm And Haas Company Materiau d'enregistrement thermosensible
EP1243437B1 (fr) 2001-03-23 2004-11-17 Ricoh Company, Ltd. Dispersion de colorant leuco et matériau thermosensible utilisant ladite dispersion

Also Published As

Publication number Publication date
ES2295669T3 (es) 2008-04-16
ATE375258T1 (de) 2007-10-15
DE10254070A1 (de) 2004-06-09
WO2004045862A1 (fr) 2004-06-03
DE50308369D1 (de) 2007-11-22
AU2003288116A1 (en) 2004-06-15
EP1565321A1 (fr) 2005-08-24

Similar Documents

Publication Publication Date Title
DE3934014C2 (fr)
DE69310107T3 (de) Aufzeichnungsblatt für Tintenstrahlschreiber und Verfahren zu seiner Herstellung
EP3109059B1 (fr) Materiel d'enregistrement sensible a la chaleur
EP2993055B1 (fr) Matériel d'enregistrement sensible à la chaleur en forme de bande doté d'une couche de protection
DE2905825A1 (de) Waermeempfindliches aufzeichnungsmaterial
EP2993054B1 (fr) Matériel d'enregistrement sensible à la chaleur en forme de bande ayant au moins deux couches
EP1048480A1 (fr) Matériau pour l'impression par jet d'encre contenant des couches de pigmentées
EP2043876B1 (fr) Matériau d'enregistrement thermosensible
DE3239187A1 (de) Waermeempfindliche aufzeichnungsblaetter
EP3237219A1 (fr) Matériau d'enregistrement thermosensible pour l'impression offset
DE3239198A1 (de) Waermeempfindliche aufzeichnungspapiere
DE60103194T2 (de) Tintenstrahl-druckverfahren
DE60010542T2 (de) Tintenstrahlaufzeichnungsmaterial mit verbesserter Lichtechtheit
DE60222210T2 (de) Wärmeempfindliches Aufzeichnungsmaterial
EP2033801B1 (fr) Matériau d'enregistrement sensible à la chaleur
DE69822707T2 (de) Tintenstrahlaufzeichnungsschicht
EP2076398B1 (fr) Materiau d'impression a jet d'encre dote d'une couche arriere perforee en resine synthetique
EP1565321B1 (fr) Materiau d'impression sensible a la chaleur et son utilisation
DE3504730A1 (de) Waermeempfindliches und waermeuebertragungs-aufzeichnungsblatt mit druckempfindlichkeit
DE60008610T2 (de) Beidseitiges Aufzeichnungsmedium
WO2022262908A2 (fr) Matériaux d'impression thermosensibles
DE10057083A1 (de) Tintenstrahl-Aufzeichnungsmaterial für eine nicht-wässerige Tinte
EP1543984B1 (fr) Matériau d'enregistrement sensible à la chaleur pour l'impression recto-verso
EP1527900B1 (fr) Matériau pour l'enregistrement par la chaleur, son utilisation et méthode pour sa fabrication
EP2070714B1 (fr) Procédé de fabrication d'un matériel d'enregistrement sensible à la chaleur

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

17P Request for examination filed

Effective date: 20050620

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 50308369

Country of ref document: DE

Date of ref document: 20071122

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20080113

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2295669

Country of ref document: ES

Kind code of ref document: T3

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: 20071010

Ref country code: SE

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: 20080110

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

Ref country code: PT

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: 20080310

Ref country code: BG

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: 20080110

ET Fr: translation filed
REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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

Ref country code: MC

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

Effective date: 20071130

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

Ref country code: DK

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: 20071010

Ref country code: CZ

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: 20071010

Ref country code: CH

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

Effective date: 20071130

Ref country code: LI

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

Effective date: 20071130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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

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

Ref country code: SK

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: 20071010

Ref country code: RO

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: 20071010

26N No opposition filed

Effective date: 20080711

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

Ref country code: IE

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: 20071010

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

Ref country code: EE

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: 20071010

Ref country code: GR

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: 20080111

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

Ref country code: AT

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

Effective date: 20071119

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

Ref country code: SI

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: 20071010

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

Ref country code: CY

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: 20071010

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

Ref country code: LU

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

Effective date: 20071119

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

Ref country code: TR

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: 20071010

Ref country code: HU

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: 20080411

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 50308369

Country of ref document: DE

Owner name: MITSUBISHI HITEC PAPER EUROPE GMBH, DE

Free format text: FORMER OWNER: MITSUBISHI HITEC PAPER FLENSBURG GMBH, 24941 FLENSBURG, DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: MITSUBISHI HITEC PAPER EUROPE GMBH

Effective date: 20181108

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20181105 AND 20181107

REG Reference to a national code

Ref country code: BE

Ref legal event code: PD

Owner name: MITSUBISHI HITEC PAPER EUROPE GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), FUSION; FORMER OWNER NAME: MITSUBISHI HITEC PAPER FLENSBURG GMBH

Effective date: 20181031

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

Ref country code: FI

Payment date: 20191125

Year of fee payment: 17

Ref country code: DE

Payment date: 20191128

Year of fee payment: 17

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

Ref country code: BE

Payment date: 20191122

Year of fee payment: 17

Ref country code: IT

Payment date: 20191129

Year of fee payment: 17

Ref country code: ES

Payment date: 20191211

Year of fee payment: 17

Ref country code: FR

Payment date: 20191124

Year of fee payment: 17

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

Ref country code: GB

Payment date: 20191122

Year of fee payment: 17

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 50308369

Country of ref document: DE

REG Reference to a national code

Ref country code: FI

Ref legal event code: MAE

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

Effective date: 20201119

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

Ref country code: FI

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

Effective date: 20201119

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201130

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: 20201130

Ref country code: IT

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

Effective date: 20201119

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: 20210601

Ref country code: GB

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

Effective date: 20201119

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220202

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

Ref country code: ES

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

Effective date: 20201120

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

Ref country code: BE

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

Effective date: 20201130