EP3028866A1 - Recording material for thermal printing method - Google Patents

Recording material for thermal printing method Download PDF

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Publication number
EP3028866A1
EP3028866A1 EP14196562.4A EP14196562A EP3028866A1 EP 3028866 A1 EP3028866 A1 EP 3028866A1 EP 14196562 A EP14196562 A EP 14196562A EP 3028866 A1 EP3028866 A1 EP 3028866A1
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EP
European Patent Office
Prior art keywords
layer
recording material
material according
dye
gelatin
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
EP14196562.4A
Other languages
German (de)
French (fr)
Other versions
EP3028866B1 (en
Inventor
Dr. Christoph Kozlowski
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.)
Schoeller Technocell GmbH and Co KG
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Schoeller Technocell GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schoeller Technocell GmbH and Co KG filed Critical Schoeller Technocell GmbH and Co KG
Priority to ES14196562T priority Critical patent/ES2791719T3/en
Priority to EP14196562.4A priority patent/EP3028866B1/en
Priority to PL14196562T priority patent/PL3028866T3/en
Priority to US14/945,633 priority patent/US9604487B2/en
Priority to JP2015237210A priority patent/JP6077633B2/en
Priority to CN201510884557.0A priority patent/CN105667115B/en
Publication of EP3028866A1 publication Critical patent/EP3028866A1/en
Application granted granted Critical
Publication of EP3028866B1 publication Critical patent/EP3028866B1/en
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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
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
    • 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
    • B41M5/40—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
    • B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/506—Intermediate 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/02—Dye diffusion thermal transfer printing (D2T2)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/32—Thermal receivers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/36—Backcoats; Back layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer

Definitions

  • the invention relates to a recording material for the production of images in photo quality with thermal printing processes, in particular with a dye transfer process.
  • the method of thermal dye transfer is used to reproduce a digitally generated image in the form of a printed image whose image quality is adapted to the level of silver salt photography.
  • the digital image is selectively processed with respect to the primary colors cyan, magenta, yellow and black and converted into corresponding electrical signals, which are then converted into heat by means of the thermal head of a printer.
  • the dye sublimates from the donor layer of an ink ribbon (ink sheet) in contact with the recording material to be printed, and diffuses into the receiving layer of the recording material.
  • a recording material In order to obtain images of photo quality, a recording material needs good surface properties, low heat conductivity, good heat resistance, so-called compressibility (softness), which is important for ensuring good contact between the thermal head of the printer and the recording material, and good dimensional stability. Moreover, after printing, the recording material must have a good storage stability in order to prevent the migration of the dyes over time into and through the support and thus the deterioration of the image quality.
  • Recording materials for thermal transfer printing have been widely described. They essentially comprise a carrier, a dye-receiving layer and optionally further functional layers. By appropriate selection of the components of the recording material, the requirements placed on the material can be optimized.
  • Uncoated or coated papers can be used as the support, with synthetic resin-coated papers coated in particular with polyolefin or papers provided with a multilayer plastic film being considered particularly suitable. These carriers are for example described in EP 0 671 281 A1 . EP 0 681 922 A1 or EP 0 812 699 A1 ,
  • the dye-receiving layer contains a resin that has an affinity for the dye from the donor material.
  • a resin that has an affinity for the dye from the donor material.
  • plastics with ester compounds such as polyester resins, polyacrylic ester resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins
  • plastics with amide compounds such as polyamide resins
  • polyvinyl chloride and mixtures of the resins mentioned can be used.
  • copolymers which contain as main constituent at least one of the abovementioned polymers, e.g. Vinyl chloride / vinyl acetate copolymer.
  • anticurl layers can be used to counteract the curvature of the recording material after passing through the thermal printer.
  • plastic films which are laminated on the back side of the recording material are well suited for this purpose.
  • the problem of compressibility can be solved by applying an interlayer serving as a cushioning layer, as in FIG JP 02-274592 or JP 03-268998 described, be solved.
  • an interlayer serving as a cushioning layer as in FIG JP 02-274592 or JP 03-268998 described, be solved.
  • the in JP 04-21488 be described, containing an intermediate layer containing hollow microspheres.
  • This intermediate layer In addition, it has an insulating effect and helps to reduce the thermal conductivity.
  • a thermal imaging recording medium which has good temperature resistance and low thermal conductivity as well as good compressibility.
  • This object is achieved by means of a layer which consists of a gelatin derivatized with ethylenically unsaturated monomers, in particular a (meth) acrylated gelatin.
  • a disadvantage of this recording material is the high application weight of this layer. Because in order to achieve the required low thermal conductivity, layer thicknesses of 20 to 100 microns are necessary. However, the problem of dye migration into the depth of the recording material is not yet solved. A reduction of the dye migration can therefore be achieved by curing the layer in an additional operation using a Glättzylinders.
  • a recording material for thermal printing processes comprising a support and a dye-receiving layer equipped for thermal dye transfer, wherein a barrier layer is disposed between the support and the dye-receiving layer and the barrier layer contains gelatin and a water-dispersible polymeric binder, wherein gelatin and the water-dispersible polymeric binders are crosslinked together.
  • the gelatin in the barrier layer is preferably a non-chemically modified or non-derivatized gelatin.
  • a gelatin having an isoelectric point of 8 to 9, more preferably 8 to 8.5, can be used in the barrier layer.
  • the water-dispersible polymeric binder in the barrier layer is preferably a water-dispersible polyester / polyurethane copolymer.
  • a hydrophilic barrier is required.
  • Such a barrier may be a hydrophilic binder coat.
  • a disadvantage of such hydrophilic Binderstrichen is that the thermal printing in climates with high humidity, a so-called Mottle effect, i. a cloudiness in the printed image, occurs.
  • Mottle effect is achieved if the barrier layer contains a binder mixture of gelatin and polyester / polyurethane copolymer. It is also surprising that the aforementioned Mottle effect is avoided by this binder mixture after crosslinking. Consequently, a barrier layer containing gelatin and polyester / polyurethane copolymer not only permits the printing of images with low or mottle-free structures, but also a good to very good migration behavior of the recording material.
  • the mass ratio of gelatin to the water-dispersible polymeric binder in the barrier layer may be 80:20 to 40:60, more preferably 60:40 to 50:50.
  • the polyester polyurethanes used according to the invention are aliphatic polyester polyurethanes. They can be based on an aliphatic isocyanate having a modulus of elasticity of 100% according to DIN 53504 of 10 to 14 MPa, preferably 12 to 13 MPa. You can, for example, a melting range of 190 to 230 ° C, preferably 200 up to 220 ° C, on the Koflerbank. Suitable polyester polyurethanes can be used in anionic form as a dispersion. The solids content of the dispersion may be from 20 to 45% by weight, preferably from 28 to 40% by weight.
  • Films of the polyester polyurethane used according to the invention may have a microhardness according to DIN 53504 of about 95 ° Shore A.
  • the tensile strength of original such films according to DIN 53504 may be about 40 MPa and the elongation at break original according to DIN 53504 may be about 400%.
  • Such polyester polyurethanes are commercially available under the name NeoRez ® in different types.
  • crosslinking agents which allow crosslinking of a protein with a polyester-polyurethane copolymer can be used for this purpose.
  • Suitable crosslinking agents are, for example, imine groups or isocyanate group-containing compounds.
  • the crosslinking of both binders can be achieved with a combination of at least two crosslinking agents.
  • the first crosslinking agent may be an imine group-containing compound and the second crosslinking agent is preferably a compound having isocyanate groups.
  • the mass ratio of the imine group-containing crosslinking agent to the isocyanate group-containing crosslinking agent may be, for example, 6: 1 to 1: 1.
  • the amount of the crosslinking agent containing imine groups is 5 to 15% by weight, based on the total mass of the binders.
  • the amount of the isocyanate group-containing crosslinking agent in the barrier layer may be from 2 to 15% by weight, based on the total amount of the binders.
  • the total amount of crosslinking agent used according to the invention can be up to 40% by weight, based on the total mass of the binder.
  • the imine group-containing crosslinking agent is preferably a polyaziridine.
  • the isocyanate group-containing crosslinking agent is in particular a blocked isocyanate.
  • the blocking of the isocyanate can be effected by an oxime, which is split off under the action of temperature.
  • the gelatin becomes water-insoluble, and crosslinking of gelatin with the water-dispersible binder also takes place.
  • the barrier layer according to the invention may contain a pigment.
  • a pigment Particularly preferred are finely divided pigments which increase the opacity of the layer. Particularly suitable for this is titanium dioxide.
  • the amount of pigment may preferably be up to 30 wt .-%, but in particular 5 to 25 wt .-%, based on the mass of the dried layer.
  • the barrier layer according to the invention may optionally also contain other auxiliaries, for example anionic or nonionic surfactants, dyes, brighteners, lubricants, antiblocking agents and other conventional additives.
  • auxiliaries for example anionic or nonionic surfactants, dyes, brighteners, lubricants, antiblocking agents and other conventional additives.
  • the amount of auxiliaries may be from 0.01 to 5.0% by weight, in particular from 0.05 to 3.5% by weight, based on the weight of the dried layer.
  • the binders dissolved or dispersed in water are mixed together in the first step.
  • the pH can be adjusted to 7 to 7.5.
  • the pigment dispersion is added and mixed.
  • the addition of the crosslinking agent takes place. After a subsequent mixing process, the coating composition produced in this way is applied to the carrier material.
  • two crosslinking agents are added to the dispersion described above, wherein the addition of the second crosslinking agent can be carried out simultaneously with the addition of the first crosslinking agent or at a time interval thereto.
  • the coating composition for forming the barrier layer according to the invention can be applied in-line or off-line with all customary in papermaking application units, wherein the amount is chosen so that after drying the coating weight at most 3 g / m 2 , in particular 0.5 to 2.5 g / m 2 or according to a particularly preferred embodiment is 1 to 2 g / m 2 .
  • the carrier used according to the invention may contain or consist of an uncoated or a coated base paper.
  • base paper is understood as meaning an uncoated paper sized in the mass and / or a surface-sized paper.
  • a base paper may include pulp fibers, sizing agents such as alkylketene dimers, fatty acids and / or fatty acid salts, epoxidized fatty acid amides, alkenyl or alkyl succinic anhydride, wet strength agents such as polyamine-polyamide-epichlorohydrin, dry strength agents such as anionic, cationic or amphoteric polyamides or cationic starches, optical brighteners, fillers, pigments , Dyes, defoamers and other known in the paper industry tools may contain.
  • the base paper can be surface-sized.
  • Suitable sizing agents are polyvinyl alcohol or oxidized starch.
  • the base paper can be produced on a Fourdrinier or a Yankee paper machine (cylinder paper machine).
  • the basis weight of the base paper may be 50 to 250 g / m 2 , in particular 80 to 180 g / m 2 .
  • the raw paper can be used in uncompacted or compacted form (smoothed).
  • Particularly suitable are base papers having a density of 0.8 to 1.2 g / cm 3 , in particular 0.90 to 1.1 g / cm 3 .
  • pulp fibers for example, bleached hardwood kraft pulp (LBKP), bleached softwood kraft pulp (NBKP), bleached hardwood sulfite pulp (LBSP) or bleached softwood sulfite pulp (NBSP) can be used.
  • Pulp fibers derived from paper wastes can also be used.
  • the pulp fibers mentioned can also be used mixed and proportions of other fibers, for example of synthetic resin fibers, mixed.
  • pulp fibers are used from 100% hardwood pulp.
  • the mean fiber length of the unground pulp is preferably 0.5 to 0.85 mm (Kajaani measurement).
  • fillers for example, kaolins, calcium carbonate in its natural forms such as limestone, marble or dolomite stone, precipitated calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, silica, alumina and mixtures thereof can be used in the raw paper.
  • kaolins calcium carbonate in its natural forms such as limestone, marble or dolomite stone, precipitated calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, silica, alumina and mixtures thereof can be used in the raw paper.
  • a pigment-containing layer can be arranged on the base paper.
  • the pigment may be a metal oxide, silicate, carbonate, sulfide or sulfate.
  • the base paper or the coated base paper can be provided on both sides with synthetic resin layers.
  • the resin layers may preferably contain a thermoplastic polymer. Particularly suitable for this purpose are polyolefins, for example low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, 4-methylpentene-1 and mixtures thereof and polyesters, for example polycarbonates.
  • the front and / or rear synthetic resin layer contains at least 40 wt .-% HDPE having a density of more than 0.95 g / cm 3 , in particular 60 to 80 wt .-%.
  • Particularly preferred is a composition consisting of 65% by weight HDPE having a density greater than 0.95 g / cm 3 and 35% by weight LDPE having a density of less than 0.935 g / cm 3 .
  • the synthetic resin layers may contain white pigments such as titanium dioxide as well as other auxiliaries such as optical brighteners, dyes and dispersing aids.
  • antistatic substances in particular electrically conductive inorganic pigments, are added to the synthetic resin layers.
  • the coating weight of the synthetic resin layers may be 5 to 50 g / m 2 , in particular 5 to 30 g / m 2 , but preferably 10 to 20 g / m 2 .
  • the synthetic resin layer can be extruded onto the raw paper or the coated base paper in one layer or coextruded in a multilayered manner.
  • the extrusion coating can be carried out at machine speeds up to 600 m / min.
  • the carrier comprises a uncoated or coated base paper provided with a plastic film, the plastic film being laminated on the side facing the barrier layer (front side).
  • a polymeric layer preferably low density polyethylene (LDPE)
  • LDPE low density polyethylene
  • the thickness of the polyethylene layer is 6 to 15 g / m 2 , in particular 6 to 10 g / m 2 .
  • the plastic film preferably has a multilayer structure with a porous core layer and at least one pore-free surface layer. Particularly suitable for this purpose is a biaxially oriented polypropylene film with a thickness of 30 to 60 ⁇ m, in particular 35 to 50 ⁇ m, and an opacity of 70 to 90%, measured according to JIS-P-8148.
  • a single-layered or multi-layered plastic film in particular a biaxially oriented polypropylene film, can likewise be applied to the rear side.
  • the layer used according to the invention preferably contains a polymer selected from the group consisting of polyesters, polyacrylic acid esters, polycarbonates, styrene acrylates, vinyl homo- and / or vinyl copolymers. Particularly suitable are vinyl polymers such as polyvinyl chloride, vinyl chloride / acrylate copolymer, vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / vinyl acetate / vinylidene chloride.
  • the dye-receiving layer may contain an inorganic and / or organic pigment.
  • a finely divided inorganic pigment such as silica, alumina, alumina hydrate, aluminum silicate, calcium carbonate, zinc oxide, tin oxide, antimony oxide, titanium dioxide, indium oxide or a mixed oxide of these oxides.
  • the pigments may be present individually or as mixtures in the dye-receiving layer.
  • finely divided silicic acids in particular a finely dispersed silicic acid doped with aluminum, are contained in the layer.
  • the amount of the pigment in the dye-receiving layer may be 10 to 90% by weight, especially 30 to 70% by weight, based on the mass of the dried layer.
  • the finely divided pigment may have an average particle size of 10 nm to 2 ⁇ m.
  • the dye-receiving layer may also contain other adjuvants, for example, anionic or nonionic surfactants, matting agents, dyes, crosslinking agents, lubricants, antiblocking agents, and other conventional additives.
  • the amount of auxiliaries may be from 0.01 to 10% by weight, in particular from 0.05 to 5% by weight, based on the weight of the dried layer.
  • the coating composition for forming the dye-receiving layer can be applied in-line or off-line with all customary in papermaking application units, the amount is chosen so that after drying the coating weight of at most 5 g / m 2 , in particular 0.1 to 3 g / m 2 or, according to a particularly preferred embodiment, 0.3 to 1.0 g / m 2 .
  • the coating compositions for forming the barrier layer and the dye-receiving layer can be applied separately, ie first the coating composition produced to form the barrier layer is applied to the carrier material. In the next step, the coating composition for forming the ink-receiving layer is applied to the dried barrier layer and dried.
  • coating compositions described above can also be applied "wet-on-wet", for example with a multi-layer curtain coating unit.
  • a base paper A was made from eucalyptus pulp. For grinding, the pulp was ground as an approximately 5% aqueous suspension (thick matter) with the aid of a refiner to a freeness of 36 ° SR. The concentration of pulp fibers in the thin was 1 wt .-%, based on the mass of the pulp suspension.
  • the thin stock additives were added as cationic starch in an amount of 0.4 wt .-% as an alkyl ketene dimer neutral sizing agent (AKD) in an amount of 0.48 wt .-%, wet strength agents polyamine-polyamide-epichlorohydrin resin (Kymene ®) in an amount of 0.36 wt .-% and a natural CaCO 3 in an amount of 10 wt .-%.
  • the quantities are based on the pulp mass.
  • the thinstock whose pH was adjusted to about 7.5, was transferred from the head box to the wire of the paper machine, followed by sheet formation by dewatering the web in the wire section of the paper machine.
  • the base paper was painted on the front with a coating of a styrene-acrylate binder, starch and a pigment mixture of calcium carbonate and kaolin with a coating weight of 15 g / m 2 , dried, and then with a Calender smoothed.
  • the paper produced in this way has on the front side a Bekk smoothness of 800 seconds, measured according to DIN 53107.
  • the printed surface (front side) of the paper was laminated in the extruder after irradiation with a corona discharge with a three-layered biaxially oriented polypropylene film (HIPHANE BOPP, Hwaseung Industries Co., Ltd.) using a low-density polyethylene (LDPE) film. between the paper carrier material and the plastic film was extruded.
  • the thickness of the adhesion-promoting polyethylene film was 8 g / m 2 .
  • the cooling cylinder was chosen so that the resulting surface of the back has a roughness of 0.9 microns, measured as Rz value according to DIN 4768.
  • the support material obtained was then coated on the side coated with the plastic film with the coating compositions A1 to A6 according to the invention (25-gauge wire rod) and dried at 78 ° C. for three minutes.
  • the application rates of the coating compositions were chosen such that a dry application (barrier layer) was in each case 1.6 g / m 2 .
  • the dye-receiving coating B was applied to the barrier layers (15 wire bar) and dried (2 minutes, 78 ° C).
  • the application amount of the coating composition was chosen so that a dry application of 0.5 g / m 2 resulted.
  • the composition of the coating compositions is given below in Table 1.
  • coating slip B (dye-receiving layer)
  • the coating composition C 25-wire squeegee
  • the dye-absorbing coating composition B 15-wire bar
  • the coating of the barrier layer after drying was 1.6 g / m 2.
  • the application quantity of coating composition B was selected such that a dry application of 0.5 g / m 2 resulted.
  • the carrier material and the dye-receiving coating composition were as in Examples 1 to 6.
  • the compositions of the coating compositions C to G are shown in Table 2 below.
  • composition C D e F G Desalinated water 83.52 82.85 83,40 82.85 83,40 Gelatin Imagel ® AP 71979, 290 Bloom, Isoelektr.
  • the patterns are printed with the maximum color densities of yellow, cyan, magenta and black on the Mitsubishi CP-D70DW printer with standard donor ribbon.
  • the print size is 10 x 15 cm and the color areas are 1 x 1 cm.
  • These patterns are hung for 5 days at 80 ° C oven temperature. After 5 days, an evaluation of the dye penetration on the back of the printed pattern is made, this is done by means of school grades.
  • test results are summarized in the following Table 3. recording material migration grade mottle grade A1 Invention Example 1 1 2 A2 Invention Example 2 1 1 A3 Invention Example 3 2 2 A4 Invention Example 4 2 1.5 A5 Invention Example 5 5 1 A6 Invention Example 6 5 1 C Vergl.Bspl.1 1 4 D Vergl.Bspl.2 2 4 e Vergl.Bspl.3 3 3 F Vergl.Bspl.4 2.5 4 G Vergl.Bspl.5 4 3
  • the recording materials according to the invention after printing have a good to very good migration behavior for the dyes and no mottle effect.
  • all of the tested recording materials of the present invention show excellent color density of the transferred image.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Laminated Bodies (AREA)

Abstract

Ein Aufzeichnungsmaterial für thermische Druckverfahren mit einem Träger und einer für den thermischen Farbstofftransfer ausgerüsteten farbstoffaufnehmenden Schicht, wobei zwischen dem Träger und der farbstoffaufnehmenden Schicht eine Barriereschicht angeordnet ist und die Barriereschicht Gelatine und ein in Wasser dispergierbares polymeres Bindemittel enthält, worin Gelatine und das in Wasser dispergierbare polymere Bindemittel miteinander vernetzt sind, eignet sich zur Herstellung von fotoähnlichen Bildern mit sehr gutem Farbstoffmigrationsverhalten und ohne Mottle-Effekt.A thermal process recording material comprising a support and a dye-receiving layer for thermal dye transfer, wherein a barrier layer is disposed between the support and the dye-receiving layer and the barrier layer contains gelatin and a water-dispersible polymeric binder, wherein gelatin and water-dispersible polymeric binders are crosslinked with each other, is suitable for the production of photo-like images with very good dye migration behavior and no mottle effect.

Description

TECHNISCHES GEBIET DER ERFINDUNGTECHNICAL FIELD OF THE INVENTION

Die Erfindung betrifft ein Aufzeichnungsmaterial zur Herstellung von Bildern in Fotoqualität mit thermischen Druckverfahren, insbesondere mit einem Farbstoffübertragungsverfahren.The invention relates to a recording material for the production of images in photo quality with thermal printing processes, in particular with a dye transfer process.

HINTERGRUND DER ERFINDUNGBACKGROUND OF THE INVENTION

Das Verfahren der thermischen Farbstoffübertragung (TT) dient der Wiedergabe eines digital erzeugten Bilds in Form eines Druckbilds, dessen Bildqualität dem Niveau der Silbersalzfotografie angepasst ist. Das digitale Bild wird hinsichtlich der Grundfarben Cyan, Magenta, Gelb und Schwarz punktuell aufbereitet und in entsprechende elektrische Signale umgewandelt, die dann in Wärme mittels des Thermokopfs eines Druckers umgesetzt werden. Durch die Wärmeeinwirkung sublimiert der Farbstoff aus der Donorschicht eines im Kontakt mit dem zu bedruckenden Aufzeichnungsmaterial stehenden Farbbands (Farbblatts) und diffundiert in die Empfangsschicht des Aufzeichnungsmaterials.The method of thermal dye transfer (TT) is used to reproduce a digitally generated image in the form of a printed image whose image quality is adapted to the level of silver salt photography. The digital image is selectively processed with respect to the primary colors cyan, magenta, yellow and black and converted into corresponding electrical signals, which are then converted into heat by means of the thermal head of a printer. By the action of heat, the dye sublimates from the donor layer of an ink ribbon (ink sheet) in contact with the recording material to be printed, and diffuses into the receiving layer of the recording material.

Um Bilder von Fotoqualität zu erreichen, benötigt ein Aufzeichnungsmaterial gute Oberflächeneigenschaften, geringe Wärmeleitfähigkeit, gute Hitzebeständigkeit, eine sogenannte Kompressibilität (Weichheit), die wichtig zur Gewährleistung eines guten Kontakts zwischen dem Thermokopf des Druckers und dem Aufzeichnungsmaterial ist, und eine gute Dimensionsstabilität. Darüber hinaus muss das Aufzeichnungsmaterial nach dem Bedrucken eine gute Lagerbeständigkeit aufweisen, um die Migration der Farbstoffe über die Zeit in und durch den Träger und damit die Verschlechterung der Bildqualität zu verhindern.In order to obtain images of photo quality, a recording material needs good surface properties, low heat conductivity, good heat resistance, so-called compressibility (softness), which is important for ensuring good contact between the thermal head of the printer and the recording material, and good dimensional stability. Moreover, after printing, the recording material must have a good storage stability in order to prevent the migration of the dyes over time into and through the support and thus the deterioration of the image quality.

Aufzeichnungsmaterialien für den Thermotransferdruck sind vielfach beschrieben worden. Sie umfassen im Wesentlichen einen Träger, eine Farbstoffempfangsschicht und gegebenenfalls weitere Funktionsschichten. Durch entsprechende Auswahl der Komponenten des Aufzeichnungsmaterials können die an das Material gestellten Anforderungen optimiert werden.Recording materials for thermal transfer printing have been widely described. They essentially comprise a carrier, a dye-receiving layer and optionally further functional layers. By appropriate selection of the components of the recording material, the requirements placed on the material can be optimized.

Als Träger können unbeschichtete oder beschichtete Papiere eingesetzt werden, wobei kunstharzbeschichtete, insbesondere mit Polyolefin beschichtete Papiere oder mit einer mehrschichtigen Kunststofffolie versehene Papiere als besonders geeignet gelten. Diese Träger sind beispielsweise beschrieben in EP 0 671 281 A1 , EP 0 681 922 A1 oder EP 0 812 699 A1 .Uncoated or coated papers can be used as the support, with synthetic resin-coated papers coated in particular with polyolefin or papers provided with a multilayer plastic film being considered particularly suitable. These carriers are for example described in EP 0 671 281 A1 . EP 0 681 922 A1 or EP 0 812 699 A1 ,

Die Farbstoffempfangsschicht enthält ein Harz, das eine Affinität zum Farbstoff aus dem Donormaterial aufweist. Hierfür können beispielsweise Kunststoffe mit Esterverbindungen (wie Polyesterharze, Polyacrylsäureesterharze, Polycarbonatharze, Polyvinylacetatharze, Styrolacrylatharze), Kunststoffe mit Amidverbindungen (wie Polyamidharze), Polyvinylchlorid sowie Mischungen der erwähnten Harze verwendet werden. Es können aber auch Copolymere eingesetzt werden, die als Hauptbestandteil mindestens einen Vertreter der oben genannten Polymere enthalten, z.B. Vinylchlorid/Vinyl-acetat-Copolymer.The dye-receiving layer contains a resin that has an affinity for the dye from the donor material. For this purpose, for example, plastics with ester compounds (such as polyester resins, polyacrylic ester resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins), plastics with amide compounds (such as polyamide resins), polyvinyl chloride and mixtures of the resins mentioned can be used. However, it is also possible to use copolymers which contain as main constituent at least one of the abovementioned polymers, e.g. Vinyl chloride / vinyl acetate copolymer.

Als weitere Funktionsschichten können beispielsweise sogenannte Anticurl-Schichten eingesetzt werden, um der Wölbung des Aufzeichnungsmaterials nach einem Durchgang durch den Thermodrucker entgegenzuwirken. Dafür gut geeignet sind beispielsweise Kunststofffolien, die auf der Rückseite des Aufzeichnungsmaterials aufkaschiert werden.As further functional layers, for example so-called anticurl layers can be used to counteract the curvature of the recording material after passing through the thermal printer. For example, plastic films which are laminated on the back side of the recording material are well suited for this purpose.

Das Problem der Kompressibilität kann durch das Aufbringen einer die Funktion einer Polsterschicht erfüllenden Zwischenschicht, wie in JP 02-274592 oder JP 03-268998 beschrieben, gelöst werden. Alternativ dazu kann die in JP 04-21488 beschriebene, hohle Mikrokugeln enthaltende Zwischenschicht ein Lösungsweg sein. Diese Zwischenschicht hat zusätzlich eine isolierende Wirkung und trägt zur Verringerung der Wärmeleitfähigkeit bei.The problem of compressibility can be solved by applying an interlayer serving as a cushioning layer, as in FIG JP 02-274592 or JP 03-268998 described, be solved. Alternatively, the in JP 04-21488 be described, containing an intermediate layer containing hollow microspheres. This intermediate layer In addition, it has an insulating effect and helps to reduce the thermal conductivity.

In der WO 98/10939 A1 ist ein Aufzeichnungsmaterial für thermische Bildaufzeichnung beschrieben, welches eine gute Temperaturbeständigkeit und geringe Wärmeleitfähigkeit sowie eine gute Kompressibilität aufweist. Diese Aufgabe ist mit Hilfe einer Schicht gelöst, die aus einer mit ethylenisch ungesättigten Monomeren derivatisierten Gelatine, insbesondere einer (meth)acrylierten Gelatine, besteht. Nachteilig an diesem Aufzeichnungsmaterial ist das hohe Auftragsgewicht dieser Schicht. Denn um die erforderliche geringe Wärmeleitfähigkeit zu erreichen, sind Schichtdicken von 20 bis 100 µm notwendig. Das Problem der Farbstoffmigration in die Tiefe des Aufzeichnungsmaterials ist aber damit noch nicht gelöst. Eine Verringerung der Farbstoffmigration kann daher durch das Aushärten der Schicht in einem zusätzlichen Arbeitsgang mit Hilfe eines Glättzylinders erzielt werden.In the WO 98/10939 A1 there is described a thermal imaging recording medium which has good temperature resistance and low thermal conductivity as well as good compressibility. This object is achieved by means of a layer which consists of a gelatin derivatized with ethylenically unsaturated monomers, in particular a (meth) acrylated gelatin. A disadvantage of this recording material is the high application weight of this layer. Because in order to achieve the required low thermal conductivity, layer thicknesses of 20 to 100 microns are necessary. However, the problem of dye migration into the depth of the recording material is not yet solved. A reduction of the dye migration can therefore be achieved by curing the layer in an additional operation using a Glättzylinders.

ZUSAMMENFASSUNG DER ERFINDUNGSUMMARY OF THE INVENTION

Es ist daher Aufgabe der Erfindung, ein Aufzeichnungsmaterial bereitzustellen, das ein hinsichtlich der Farbstoffmigration verbessertes Verhalten unter Beibehaltung der übrigen, an ein Aufzeichnungsmaterial im thermischen Druckverfahren gestellten Erfordernisse aufweist.It is therefore an object of the invention to provide a recording material which has a respect to the dye migration improved behavior while maintaining the other requirements placed on a recording material in the thermal printing process requirements.

Gelöst wird diese Aufgabe durch eine Aufzeichnungsmaterial für thermische Druckverfahren mit einem Träger und einer für den thermischen Farbstofftransfer ausgerüsteten farbstoffaufnehmenden Schicht, wobei zwischen dem Träger und der farbstoffaufnehmenden Schicht eine Barriereschicht angeordnet ist und die Barriereschicht Gelatine und ein in Wasser dispergierbares polymeres Bindemittel enthält, worin Gelatine und das in Wasser dispergierbare polymere Bindemittel miteinander vernetzt sind.This object is achieved by a recording material for thermal printing processes comprising a support and a dye-receiving layer equipped for thermal dye transfer, wherein a barrier layer is disposed between the support and the dye-receiving layer and the barrier layer contains gelatin and a water-dispersible polymeric binder, wherein gelatin and the water-dispersible polymeric binders are crosslinked together.

BEVORZUGTE AUSFÜHRUNGSFORMEN DER ERFINDUNGPREFERRED EMBODIMENTS OF THE INVENTION

Die Gelatine in der Barriereschicht ist vorzugsweise eine nicht chemisch modifizierte oder nicht derivatisierte Gelatine. Vorzugsweise kann eine Gelatine mit einem isoelektrischen Punkt von 8 bis 9, besonders bevorzugt 8 bis 8,5 in der Barriereschicht eingesetzt werden.The gelatin in the barrier layer is preferably a non-chemically modified or non-derivatized gelatin. Preferably, a gelatin having an isoelectric point of 8 to 9, more preferably 8 to 8.5, can be used in the barrier layer.

Das in Wasser dispergierbare polymere Bindemittel in der Barriereschicht ist vorzugsweise ein wasserdispergierbares Polyester/Polyurethan-Copolymer.The water-dispersible polymeric binder in the barrier layer is preferably a water-dispersible polyester / polyurethane copolymer.

Zur Verringerung der Migration von hydrophoben Farbstoffen aus der farbstoffaufnehmenden Schicht ist eine hydrophile Barriere erforderlich. Eine solche Barriere kann ein hydrophiler Binderstrich sein kann. Nachteilig an solchen hydrophilen Binderstrichen ist jedoch, dass beim Thermodruck in Klimata mit hoher Luftfeuchtigkeit ein sogenannter Mottle-Effekt, d.h. eine Wolkigkeit im Druckbild, auftritt. Überraschend hat sich herausgestellt, dass eine gute Barrierewirkung erzielt wird, wenn die Barriereschicht ein Bindemittelgemisch aus Gelatine und Polyester/PolyurethanCopolymer enthält. Überraschend ist ferner, dass durch dieses Bindemittelgemisch nach Vernetzung der zuvor erwähnte Mottle-Effekt vermieden wird. Eine Barriereschicht, enthaltend Gelatine und Polyester/Polyurethan-Copolymer, erlaubt folglich nicht nur das Drucken von Bildern mit geringem bzw. von Mottle freien Strukturen, sondern auch ein gutes bis sehr gutes Migrationsverhalten des Aufzeichnungsmaterials.To reduce the migration of hydrophobic dyes from the dye-receiving layer, a hydrophilic barrier is required. Such a barrier may be a hydrophilic binder coat. A disadvantage of such hydrophilic Binderstrichen, however, is that the thermal printing in climates with high humidity, a so-called Mottle effect, i. a cloudiness in the printed image, occurs. Surprisingly, it has been found that a good barrier effect is achieved if the barrier layer contains a binder mixture of gelatin and polyester / polyurethane copolymer. It is also surprising that the aforementioned Mottle effect is avoided by this binder mixture after crosslinking. Consequently, a barrier layer containing gelatin and polyester / polyurethane copolymer not only permits the printing of images with low or mottle-free structures, but also a good to very good migration behavior of the recording material.

Vorzugsweise kann das Massenverhältnis von Gelatine zu dem wasserdispergierbaren polymeren Bindemittel in der Barriereschicht 80:20 bis 40:60, besonders bevorzugt 60:40 bis 50:50, betragen.Preferably, the mass ratio of gelatin to the water-dispersible polymeric binder in the barrier layer may be 80:20 to 40:60, more preferably 60:40 to 50:50.

Die erfindungsgemäß eingesetzten Polyesterpolyurethane sind aliphatische Polyesterpolyurethane. Sie können auf einen aliphatischen Isocyanat mit einem E-Modul 100% gemäß DIN 53504 von 10 bis 14 MPa, vorzugsweise12 bis 13 MPa basieren. Sie können beispielsweise einen Schmelzbereich von 190 bis 230 °C, vorzugsweise 200 bis 220 °C, auf der Koflerbank aufweisen. Geeignete Polyesterpolyurethane können in anionischer Form als Dispersion eingesetzt werden. Der Feststoffanteil der Dispersion kann 20 bis 45 Gew.-%, vorzugsweise 28 bis 40 Gew.-%, betragen. Filme aus dem erfindungsgemäß eingesetzten Polyesterpolyurethan können eine Microhärte gemäß DIN 53504 von etwa 95° Shore A aufweisen. Die Zugfestigkeit Original solcher Filme nach DIN 53504 kann etwa 40 MPa und die Bruchdehnung Original nach DIN 53504 kann etwa 400% betragen. Solche Polyesterpolyurethane sind im Handel unter der Bezeichnung NeoRez® in verschieden Typen erhältlich.The polyester polyurethanes used according to the invention are aliphatic polyester polyurethanes. They can be based on an aliphatic isocyanate having a modulus of elasticity of 100% according to DIN 53504 of 10 to 14 MPa, preferably 12 to 13 MPa. You can, for example, a melting range of 190 to 230 ° C, preferably 200 up to 220 ° C, on the Koflerbank. Suitable polyester polyurethanes can be used in anionic form as a dispersion. The solids content of the dispersion may be from 20 to 45% by weight, preferably from 28 to 40% by weight. Films of the polyester polyurethane used according to the invention may have a microhardness according to DIN 53504 of about 95 ° Shore A. The tensile strength of original such films according to DIN 53504 may be about 40 MPa and the elongation at break original according to DIN 53504 may be about 400%. Such polyester polyurethanes are commercially available under the name NeoRez ® in different types.

Die erfindungsgemäß erzielte vorteilhafte Wirkung hinsichtlich des Migrationsverhaltens des Farbstoffs wird durch eine Vernetzung beider Bindertypen mit Hilfe eines Vernetzungsmittels erzielt. Grundsätzlich können hierzu Vernetzungsmittel verwendet werden, die eine Vernetzung eines Proteins mit einem Polyesterpolyurethan-Copolymer ermöglichen.The advantageous effect achieved according to the invention with regard to the migration behavior of the dye is achieved by crosslinking of both types of binder with the aid of a crosslinking agent. In principle, crosslinking agents which allow crosslinking of a protein with a polyester-polyurethane copolymer can be used for this purpose.

Geeignete Vernetzungsmittel sind beispielsweise Imin-Gruppen oder Isocyanat-Gruppen enthaltende Verbindungen. In einer bevorzugten Ausführungsform der Erfindung kann die Vernetzung beider Bindemittel mit einer Kombination von mindestens zwei Vernetzungsmitteln erzielt werden. Das erste Vernetzungsmittel kann eine Imin-Gruppen enthaltende Verbindung sein und das zweite Vernetzungsmittel vorzugsweise eine Verbindung mit Isocyanat-Gruppen. In diesem Fall kann das Massenverhältnis des Imin-Gruppen enthaltenden Vernetzungsmittels zu dem Isocyanat-Gruppen enthaltenden Vernetzungsmittel beispielsweise 6:1 bis 1:1 betragen.Suitable crosslinking agents are, for example, imine groups or isocyanate group-containing compounds. In a preferred embodiment of the invention, the crosslinking of both binders can be achieved with a combination of at least two crosslinking agents. The first crosslinking agent may be an imine group-containing compound and the second crosslinking agent is preferably a compound having isocyanate groups. In this case, the mass ratio of the imine group-containing crosslinking agent to the isocyanate group-containing crosslinking agent may be, for example, 6: 1 to 1: 1.

Die Menge des Imin-Gruppen enthaltenden Vernetzungsmittels 5 bis 15 Gew.-%, bezogen auf die Gesamtmasse der Bindemittel, betragen.The amount of the crosslinking agent containing imine groups is 5 to 15% by weight, based on the total mass of the binders.

Die Menge des Isocyanat-Gruppen enthaltenden Vernetzungsmittels in der Barriereschicht kann 2 bis 15 Gew.-%, bezogen auf die Gesamtmenge der Bindemittel, betragen. Die Gesamtmenge des erfindungsgemäß eingesetzten Vernetzungsmittels kann bis zu 40 Gew.-% betragen, bezogen auf die Gesamtmasse der Bindemittel.The amount of the isocyanate group-containing crosslinking agent in the barrier layer may be from 2 to 15% by weight, based on the total amount of the binders. The total amount of crosslinking agent used according to the invention can be up to 40% by weight, based on the total mass of the binder.

Das Imin-Gruppen enthaltendes Vernetzungsmittel ist vorzugsweise ein Polyaziridin. Bei dem Isocyanat-Gruppen enthaltenden Vernetzungsmittel handelt es sich insbesondere um ein blockiertes Isocyanat. Die Blockierung des Isocyanats kann durch ein Oxim erfolgen, das unter Temperatureinwirkung abgespalten wird. Durch die Vernetzung wird die Gelatine wasserunlöslich, und es erfolgt auch eine Vernetzung von Gelatine mit dem in Wasser dispergierbaren Bindemittel.The imine group-containing crosslinking agent is preferably a polyaziridine. The isocyanate group-containing crosslinking agent is in particular a blocked isocyanate. The blocking of the isocyanate can be effected by an oxime, which is split off under the action of temperature. As a result of the crosslinking, the gelatin becomes water-insoluble, and crosslinking of gelatin with the water-dispersible binder also takes place.

In einer weiteren Ausgestaltung der Erfindung kann die erfindungsgemäße Barriereschicht ein Pigment enthalten. Besonders bevorzugt sind feinteilige Pigmente, die die Opazität der Schicht erhöhen. Hierzu besonders gut geeignet ist Titandioxid. Die Pigmentmenge kann vorzugsweise bis 30 Gew.-% betragen, insbesondere jedoch 5 bis 25 Gew.-%, bezogen auf die Masse der getrockneten Schicht.In a further embodiment of the invention, the barrier layer according to the invention may contain a pigment. Particularly preferred are finely divided pigments which increase the opacity of the layer. Particularly suitable for this is titanium dioxide. The amount of pigment may preferably be up to 30 wt .-%, but in particular 5 to 25 wt .-%, based on the mass of the dried layer.

Die erfindungsgemäße Barriereschicht kann gegebenenfalls auch weitere Hilfsmittel enthalten, beispielsweise anionische oder nichtionische oberflächenaktive Mittel, Farbstoffe, Aufheller, Gleitmittel, Antiblocking-Mittel und andere übliche Additive. Die Menge der Hilfsmittel kann 0,01 bis 5,0 Gew.-%, insbesondere 0,05 bis 3,5 Gew.-%, bezogen auf die Masse der getrockneten Schicht, betragen.The barrier layer according to the invention may optionally also contain other auxiliaries, for example anionic or nonionic surfactants, dyes, brighteners, lubricants, antiblocking agents and other conventional additives. The amount of auxiliaries may be from 0.01 to 5.0% by weight, in particular from 0.05 to 3.5% by weight, based on the weight of the dried layer.

Bei der Herstellung der erfindungsgemäßen Beschichtungsmasse zur Bildung der Barriereschicht werden im ersten Schritt die in Wasser gelösten oder dispergierten Bindemittel miteinander vermischt. Der pH-Wert kann auf 7 bis 7,5 eingestellt werden. Die Pigmentdispersion wird zugegeben und vermischt. Im zweiten Schritt erfolgt die Zugabe des Vernetzungsmittels. Nach einem darauffolgenden Mischvorgang wird die auf diese Weise erzeugte Beschichtungsmasse auf das Trägermaterial aufgetragen.In the preparation of the coating composition of the invention for forming the barrier layer, the binders dissolved or dispersed in water are mixed together in the first step. The pH can be adjusted to 7 to 7.5. The pigment dispersion is added and mixed. In the second step, the addition of the crosslinking agent takes place. After a subsequent mixing process, the coating composition produced in this way is applied to the carrier material.

In einer bevorzugten Ausgestaltung der Erfindung werden der oben beschriebenen Dispersion zwei Vernetzungsmittel zugegeben, wobei die Zugabe des zweiten Vernetzungsmittels gleichzeitig mit der Zugabe des ersten Vernetzungsmittels oder in einem zeitlichen Abstand dazu erfolgen kann.In a preferred embodiment of the invention, two crosslinking agents are added to the dispersion described above, wherein the addition of the second crosslinking agent can be carried out simultaneously with the addition of the first crosslinking agent or at a time interval thereto.

Die Beschichtungsmasse zur Bildung der erfindungsgemäßen Barriereschicht kann mit allen in der Papierherstellung üblichen Auftragsaggregaten inline oder offline aufgebracht werden, wobei die Menge so gewählt wird, dass nach dem Trocknen das Auftragsgewicht höchstens 3 g/m2, insbesondere 0,5 bis 2,5 g/m2 oder gemäß einer besonders bevorzugten Ausführungsform 1 bis 2 g/m2 beträgt.The coating composition for forming the barrier layer according to the invention can be applied in-line or off-line with all customary in papermaking application units, wherein the amount is chosen so that after drying the coating weight at most 3 g / m 2 , in particular 0.5 to 2.5 g / m 2 or according to a particularly preferred embodiment is 1 to 2 g / m 2 .

Der erfindungsgemäß eingesetzte Träger kann ein unbeschichtetes oder ein gestrichenes Rohpapier enthalten oder aus einem solchen bestehen.The carrier used according to the invention may contain or consist of an uncoated or a coated base paper.

Für die Zwecke der Erfindung versteht man unter dem Begriff Rohpapier ein in der Masse geleimtes unbeschichtetes Papier und/oder ein oberflächengeleimtes Papier. Ein Rohpapier kann neben Zellstofffasern, Leimungsmittel wie Alkylketendimeren, Fettsäuren und/oder Fettsäuresalze, epoxydierte Fettsäureamide, Alkenyl- oder Alkylbernsteinsäureanhydrid, Nassfestmittel wie Polyamin-Polyamid-Epichlorhydrin, Trockenfestmittel wie anionische, kationische oder amphotere Polyamide oder kationische Stärken, optische Aufheller, Füllstoffe, Pigmente, Farbstoffe, Entschäumer und weitere in der Papierindustrie bekannte Hilfsmittel enthalten kann. Das Rohpapier kann oberflächengeleimt sein. Hierzu geeignete Leimmittel sind beispielsweise Polyvinylalkohol oder oxydierte Stärke. Das Rohpapier kann auf einer Fourdrinier- oder einer Yankee-Papiermaschine(Zylinder-Papiermaschine) hergestellt werden. Das Flächengewicht des Rohpapiers kann 50 bis 250 g/m2, insbesondere 80 bis 180 g/m2 betragen. Das Rohpapier kann in unverdichteter oder verdichteter Form (geglättet) eingesetzt werden. Besonders gut geeignet sind Rohpapiere mit einer Dichte von 0,8 bis 1,2 g/cm3, insbesondere 0,90 bis 1,1 g/cm3. Als Zellstofffasern können beispielsweise gebleichter Hartholz-Kraftzellstoff (LBKP), gebleichter Nadelholz-Kraftzellstoff (NBKP), gebleichter Laubholzsulfitzellstoff (LBSP) oder gebleichter Nadelholzsulfitzellstoff (NBSP) eingesetzt werden. Es können auch aus Papierabfällen gewonnene Zellstofffasern verwendet werden. Die genannten Zellstofffasern können auch gemischt eingesetzt werden und Anteile anderer Fasern, zum Beispiel von Kunstharzfasern, zugemischt werden. Bevorzugt jedoch werden Zellstofffasern aus 100% Laubholzzellstoff eingesetzt. Die mittlere Faserlänge des ungemahlenen Zellstoffs beträgt vorzugsweise 0,5 bis 0,85 mm (Kajaani-Messung).For the purposes of the invention, the term base paper is understood as meaning an uncoated paper sized in the mass and / or a surface-sized paper. A base paper may include pulp fibers, sizing agents such as alkylketene dimers, fatty acids and / or fatty acid salts, epoxidized fatty acid amides, alkenyl or alkyl succinic anhydride, wet strength agents such as polyamine-polyamide-epichlorohydrin, dry strength agents such as anionic, cationic or amphoteric polyamides or cationic starches, optical brighteners, fillers, pigments , Dyes, defoamers and other known in the paper industry tools may contain. The base paper can be surface-sized. Examples of suitable sizing agents are polyvinyl alcohol or oxidized starch. The base paper can be produced on a Fourdrinier or a Yankee paper machine (cylinder paper machine). The basis weight of the base paper may be 50 to 250 g / m 2 , in particular 80 to 180 g / m 2 . The raw paper can be used in uncompacted or compacted form (smoothed). Particularly suitable are base papers having a density of 0.8 to 1.2 g / cm 3 , in particular 0.90 to 1.1 g / cm 3 . As pulp fibers, for example, bleached hardwood kraft pulp (LBKP), bleached softwood kraft pulp (NBKP), bleached hardwood sulfite pulp (LBSP) or bleached softwood sulfite pulp (NBSP) can be used. Pulp fibers derived from paper wastes can also be used. The pulp fibers mentioned can also be used mixed and proportions of other fibers, for example of synthetic resin fibers, mixed. Preferably, however, pulp fibers are used from 100% hardwood pulp. The mean fiber length of the unground pulp is preferably 0.5 to 0.85 mm (Kajaani measurement).

Als Füllstoff können beispielsweise Kaoline, Calciumcarbonat in seinen natürlichen Formen wie Kalkstein, Marmor oder Dolomitstein, gefälltes Calciumcarbonat, Calciumsulfat, Bariumsulfat, Titandioxid, Talkum, Silica, Aluminiumoxid und deren Gemische im Rohpapier eingesetzt werden.As fillers, for example, kaolins, calcium carbonate in its natural forms such as limestone, marble or dolomite stone, precipitated calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, silica, alumina and mixtures thereof can be used in the raw paper.

In einer besonderen Ausführungsform der Erfindung kann auf dem Rohpapier eine pigmenthaltige Schicht angeordnet sein. Das Pigment kann ein Metalloxid, Silikat, Carbonat, Sulfid oder Sulfat sein. Besonders gut geeignet sind Pigmente wie Kaoline, Talkum, Calciumcarbonat und/oder Bariumsulfat. Als besonders vorteilhaft erwies sich ein Calciumcarbonat mit einem d50%-Wert in der Teilchengröße von etwa 0,7 µm.In a particular embodiment of the invention, a pigment-containing layer can be arranged on the base paper. The pigment may be a metal oxide, silicate, carbonate, sulfide or sulfate. Particularly suitable are pigments such as kaolins, talc, calcium carbonate and / or barium sulfate. Particularly advantageous proved to be a calcium carbonate with a d50% value in the particle size of about 0.7 microns.

In einer weiteren Ausführungsform der Erfindung kann das Rohpapier oder das gestrichene Rohpapier beidseitig mit Kunstharzschichten versehen sein. Die Kunstharzschichten (vorderseitige und/oder rückseitige Kunstharzschicht) können vorzugsweise ein thermoplastisches Polymer enthalten. Insbesondere geeignet hierfür sind Polyolefine, beispielsweise Polyethylen niedriger Dichte (LDPE), Polyethylen hoher Dichte (HDPE), Polypropylen, 4-Methylpenten-1 und deren Gemische sowie Polyester, beispielsweise Polycarbonate.In a further embodiment of the invention, the base paper or the coated base paper can be provided on both sides with synthetic resin layers. The resin layers (front and / or back resin layer) may preferably contain a thermoplastic polymer. Particularly suitable for this purpose are polyolefins, for example low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene, 4-methylpentene-1 and mixtures thereof and polyesters, for example polycarbonates.

In einer weiteren besonders bevorzugten Ausgestaltung der Erfindung enthält die vorderseitige und/oder rückseitige Kunstharzschicht mindestens 40 Gew.-% HDPE mit einer Dichte von mehr als 0,95 g/cm3, insbesondere 60 bis 80 Gew.-%. Besonders bevorzugt ist eine Zusammensetzung, die aus 65 Gew.-% HDPE mit einer Dichte von mehr als 0,95 g/cm3 und 35 Gew.-% LDPE mit einer Dichte von weniger als 0,935 g/cm3 besteht.In a further particularly preferred embodiment of the invention, the front and / or rear synthetic resin layer contains at least 40 wt .-% HDPE having a density of more than 0.95 g / cm 3 , in particular 60 to 80 wt .-%. Particularly preferred is a composition consisting of 65% by weight HDPE having a density greater than 0.95 g / cm 3 and 35% by weight LDPE having a density of less than 0.935 g / cm 3 .

Die Kunstharzschichten können Weißpigmente wie Titandioxid sowie weitere Hilfsstoffe wie optische Aufheller, Farbstoffe und Dispergierhilfsmittel enthalten. In einer besonderen Ausgestaltungsform der Erfindung werden antistatisch wirkende Substanzen, insbesondere elektrisch leitfähige anorganische Pigmente, zu den Kunstharzschichten zugefügt.The synthetic resin layers may contain white pigments such as titanium dioxide as well as other auxiliaries such as optical brighteners, dyes and dispersing aids. In a particular embodiment of the invention, antistatic substances, in particular electrically conductive inorganic pigments, are added to the synthetic resin layers.

Das Auftragsgewicht der Kunstharzschichten kann 5 bis 50 g/m2, insbesondere 5 bis 30 g/m2, bevorzugt jedoch 10 bis 20 g/m2, betragen. Die Kunstharzschicht kann auf das Rohpapier oder das gestrichene Rohpapier einschichtig extrudiert oder mehrschichtig coextrudiert werden. Die Extrusionsbeschichtung kann mit Maschinengeschwindigkeiten bis 600 m/min erfolgen.The coating weight of the synthetic resin layers may be 5 to 50 g / m 2 , in particular 5 to 30 g / m 2 , but preferably 10 to 20 g / m 2 . The synthetic resin layer can be extruded onto the raw paper or the coated base paper in one layer or coextruded in a multilayered manner. The extrusion coating can be carried out at machine speeds up to 600 m / min.

In einer bevorzugten Ausgestaltung der Erfindung enthält der Träger ein mit einer Kunststofffolie versehenes unbeschichtetes oder gestrichenes Rohpapier, wobei die Kunststofffolie auf der der Barriereschicht zugewandten Seite (Vorderseite) aufkaschiert ist. Dabei wird eine polymere Schicht, vorzugsweise Polyethylen niedriger Dichte (LDPE), zwischen das Rohpapier und die Kunststofffolie extrudiert. Die Dicke der Polyethylenschicht beträgt 6 bis 15 g/m2, insbesondere 6 bis 10 g/m2. Die Kunststofffolie weist vorzugsweise eine mehrschichtige Struktur mit einer porösen Kernschicht und mindestens einer porenfreien Oberflächenschicht auf. Hierfür besonders gut geeignet ist eine biaxial orientierte Polypropylenfolie mit einer Dicke von 30 bis 60 µm, insbesondere 35 bis 50 µm, und einer Opazität von 70 bis 90%, gemessen nach JIS-P-8148.In a preferred embodiment of the invention, the carrier comprises a uncoated or coated base paper provided with a plastic film, the plastic film being laminated on the side facing the barrier layer (front side). In this case, a polymeric layer, preferably low density polyethylene (LDPE), is extruded between the base paper and the plastic film. The thickness of the polyethylene layer is 6 to 15 g / m 2 , in particular 6 to 10 g / m 2 . The plastic film preferably has a multilayer structure with a porous core layer and at least one pore-free surface layer. Particularly suitable for this purpose is a biaxially oriented polypropylene film with a thickness of 30 to 60 μm, in particular 35 to 50 μm, and an opacity of 70 to 90%, measured according to JIS-P-8148.

In einer weiteren Ausgestaltungsform der Erfindung kann auf der Rückseite ebenfalls eine einschichtige oder mehrschichtige Kunststofffolie, insbesondere eine biaxial orientierte Polypropylenfolie aufgetragen werden.In a further embodiment of the invention, a single-layered or multi-layered plastic film, in particular a biaxially oriented polypropylene film, can likewise be applied to the rear side.

Als farbstoffaufnehmende Schicht eignet sich grundsätzlich jede aus dem Stand der Technik für thermische Übertragungsverfahren bekannte Farbempfangsschicht. Die erfindungsgemäß eingesetzte Schicht enthält vorzugsweise ein aus der Gruppe der Polyester, Polyacrylsäureester, Polycarbonate, Styrolacrylate, Vinyl-Homo- und/oder Vinyl-Copolymere ausgewähltes Polymer. Insbesondere gut geeignet sind Vinylpolymere wie Polyvinylchlorid, Vinylchlorid/Acrylat-Copolymer, Vinylchlorid/Vinylacetat-Copolymer und/oder Vinylchlorid/Vinylacetat/Vinylidenchlorid.As the dye-receiving layer, basically any color-receiving layer known in the art for thermal transfer processes is suitable. The layer used according to the invention preferably contains a polymer selected from the group consisting of polyesters, polyacrylic acid esters, polycarbonates, styrene acrylates, vinyl homo- and / or vinyl copolymers. Particularly suitable are vinyl polymers such as polyvinyl chloride, vinyl chloride / acrylate copolymer, vinyl chloride / vinyl acetate copolymer and / or vinyl chloride / vinyl acetate / vinylidene chloride.

In einer weiteren Ausgestaltung der Erfindung kann die farbstoffaufnehmende Schicht ein anorganisches und/oder organisches Pigment enthalten. Besonders gut geeignet ist ein feinteiliges anorganisches Pigment, beispielsweise Siliciumdioxid, Aluminiumoxid, Aluminiumoxidhydrat, Aluminiumsilicat, Calciumcarbonat, Zinkoxid, Zinnoxid, Antimonoxid, Titandioxid, Indiumoxid oder ein Mischoxid dieser Oxide. Die Pigmente können einzeln oder als Mischungen in der farbstoffaufnehmenden Schicht vorhanden sein. In einer bevorzugten Ausgestaltung der Erfindung sind feinteilige Kieselsäuren, insbesondere eine mit Aluminium dotierte feindisperse Kieselsäure in der Schicht enthalten.In a further embodiment of the invention, the dye-receiving layer may contain an inorganic and / or organic pigment. Particularly suitable is a finely divided inorganic pigment, such as silica, alumina, alumina hydrate, aluminum silicate, calcium carbonate, zinc oxide, tin oxide, antimony oxide, titanium dioxide, indium oxide or a mixed oxide of these oxides. The pigments may be present individually or as mixtures in the dye-receiving layer. In a preferred embodiment of the invention finely divided silicic acids, in particular a finely dispersed silicic acid doped with aluminum, are contained in the layer.

Die Menge des Pigments in der farbstoffaufnehmenden Schicht kann 10 bis 90 Gew.-%, insbesondere 30 bis 70 Gew.-% betragen, bezogen auf die Masse der getrockneten Schicht.The amount of the pigment in the dye-receiving layer may be 10 to 90% by weight, especially 30 to 70% by weight, based on the mass of the dried layer.

Das feinteilige Pigment kann eine eine mittlere Teilchengröße von 10 nm bis 2 µm aufweisen.The finely divided pigment may have an average particle size of 10 nm to 2 μm.

Die farbstoffaufnehmende Schicht kann gegebenenfalls auch weitere Hilfsmittel enthalten, beispielsweise anionische oder nichtionische oberflächenaktive Mittel, Mattierungsmittel, Farbstoffe, Vernetzungsmittel, Gleitmittel, Antiblocking-Mittel und andere übliche Additive. Die Menge der Hilfsmittel kann 0,01 bis 10 Gew.-%, insbesondere 0,05 bis 5 Gew.-%, bezogen auf die Masse der getrockneten Schicht, betragen.Optionally, the dye-receiving layer may also contain other adjuvants, for example, anionic or nonionic surfactants, matting agents, dyes, crosslinking agents, lubricants, antiblocking agents, and other conventional additives. The amount of auxiliaries may be from 0.01 to 10% by weight, in particular from 0.05 to 5% by weight, based on the weight of the dried layer.

Die Beschichtungsmasse zur Bildung der farbstoffaufnehmenden Schicht kann mit allen in der Papierherstellung üblichen Auftragsaggregaten inline oder offline aufgebracht werden, wobei die Menge so gewählt wird, dass nach dem Trocknen das Auftragsgewicht höchstens 5 g/m2, insbesondere 0,1 bis 3 g/m2 oder gemäß einer besonders bevorzugten Ausführungsform 0,3 bis 1,0 g/m2 beträgt.The coating composition for forming the dye-receiving layer can be applied in-line or off-line with all customary in papermaking application units, the amount is chosen so that after drying the coating weight of at most 5 g / m 2 , in particular 0.1 to 3 g / m 2 or, according to a particularly preferred embodiment, 0.3 to 1.0 g / m 2 .

Die Beschichtungsmassen zur Bildung der Barriereschicht und der farbstoffaufnehmenden Schicht können getrennt aufgetragen werden, d.h. zunächst wird die zur Bildung der Barriereschicht erzeugte Beschichtungsmasse auf das Trägermaterial aufgetragen. Im nächsten Schritt wird auf die getrocknete Barriereschicht die Beschichtungsmasse zur Bildung der Tintenaufnahmeschicht aufgetragen und getrocknet.The coating compositions for forming the barrier layer and the dye-receiving layer can be applied separately, ie first the coating composition produced to form the barrier layer is applied to the carrier material. In the next step, the coating composition for forming the ink-receiving layer is applied to the dried barrier layer and dried.

Die oben beschriebenen Beschichtungsmassen können aber auch "nass-in-nass" zum Beispiel mit einem Mehrschichtvorhang-Beschichtungsaggregat aufgetragen werden.However, the coating compositions described above can also be applied "wet-on-wet", for example with a multi-layer curtain coating unit.

Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung.The following examples serve to further illustrate the invention.

BEISPIELEEXAMPLES Beispiel 1 - Herstellung eines Rohpapiers Example 1 - Preparation of a base paper

Ein Rohpapier A wurde aus Eukalyptus-Zellstoff hergestellt. Zur Mahlung wurde der Zellstoff als etwa 5 %ige wässrige Suspension (Dickstoff) mit Hilfe eines Refiners auf einen Mahlgrad von 36 °SR gemahlen. Die Konzentration der Zellstofffasern im Dünnstoff betrug 1 Gew.-%, bezogen auf die Masse der Zellstoffsuspension. Dem Dünnstoff wurden Zusatzstoffe zugesetzt wie kationische Stärke in einer Menge von 0,4 Gew.-%, als ein neutrales Leimungsmittel Alkylketendimer (AKD)in einer Menge von 0,48 Gew.-%, Nassfestmittel Polyamin-Polyamid-Epichlorhydrinharz (Kymene®) in einer Menge von 0,36 Gew.-% und ein natürliches CaCO3 in einer Menge von 10 Gew.-%. Die Mengenangaben beziehen sich auf die Zellstoffmasse. Der Dünnstoff, dessen pH-Wert auf etwa 7,5 eingestellt wurde, wurde vom Stoffauflauf auf das Sieb der Papiermaschine gebracht, worauf die Blattbildung unter Entwässerung der Bahn in der Siebpartie der Papiermaschine erfolgte. In der Pressenpartie der Papiermaschine erfolgte die weitere Entwässerung der Papierbahn auf einen Wassergehalt von 60 Gew.-%, bezogen auf das Bahngewicht. Die weitere Trocknung erfolgte in der Trockenpartie der Papiermaschine mit beheizten Trockenzylindern. Es entstand ein Rohpapier mit einem Flächengewicht von 132 g/m2 und einer Feuchte von etwa 7%.A base paper A was made from eucalyptus pulp. For grinding, the pulp was ground as an approximately 5% aqueous suspension (thick matter) with the aid of a refiner to a freeness of 36 ° SR. The concentration of pulp fibers in the thin was 1 wt .-%, based on the mass of the pulp suspension. The thin stock additives were added as cationic starch in an amount of 0.4 wt .-% as an alkyl ketene dimer neutral sizing agent (AKD) in an amount of 0.48 wt .-%, wet strength agents polyamine-polyamide-epichlorohydrin resin (Kymene ®) in an amount of 0.36 wt .-% and a natural CaCO 3 in an amount of 10 wt .-%. The quantities are based on the pulp mass. The thinstock, whose pH was adjusted to about 7.5, was transferred from the head box to the wire of the paper machine, followed by sheet formation by dewatering the web in the wire section of the paper machine. In the press section of the paper machine, the further dewatering of the paper web was carried out to a water content of 60% by weight, based on the web weight. Further drying took place in the dryer section of the paper machine with heated drying cylinders. The result was a base paper with a basis weight of 132 g / m 2 and a humidity of about 7%.

Das Rohpapier wurde auf der Vorderseite mit einer Streichmasse aus einem Styrolacrylat-Binder, Stärke und einer Pigmentmischung aus Calciumcarbonat und Kaolin mit einem Auftragsgewicht von 15 g/m2 gestrichen, getrocknet und anschließend mit einem Kalander geglättet. Das auf diese Weise erzeugte Papier weist auf der Vorderseite eine Bekk-Glätte von 800 Sekunden, gemessen nach DIN 53107, auf.The base paper was painted on the front with a coating of a styrene-acrylate binder, starch and a pigment mixture of calcium carbonate and kaolin with a coating weight of 15 g / m 2 , dried, and then with a Calender smoothed. The paper produced in this way has on the front side a Bekk smoothness of 800 seconds, measured according to DIN 53107.

Die zur Bedruckung vorgesehene Oberfläche (Vorderseite) des Papiers wurde nach Bestrahlung mit einer Corona-Entladung mit einer dreischichtigen biaxial orientierten Polypropylen-Folie (HIPHANE BOPP, Hwaseung Industries Co. Ltd) im Extruder laminiert, wobei ein Film aus Polyethylen niedriger Dichte (LDPE) zwischen das Papierträgermaterial und die Kunststofffolie extrudiert wurde. Die Dicke des haftvermittelnden Polyethylenfilms betrug 8 g/m2. Die der zu bedruckenden Seite gegenüberliegende Seite (Rückseite) des Papiers wurde mit einem Polyethylengemisch aus 30 Gew.-% eines Polyethylens niedriger Dichte (LDPE, d=0,923 g/cm3) und 70 Gew.-% eines Polyethylens hoher Dichte (HDPE, d=0,964 g/cm3) mit einem Auftragsgewicht von 40 g/m2 im Extruder beschichtet. Der Kühlzylinder wurde so gewählt, dass die resultierende Oberfläche der Rückseite eine Rauhigkeit von 0,9 µm aufweist, gemessen als Rz-Wert nach DIN 4768.The printed surface (front side) of the paper was laminated in the extruder after irradiation with a corona discharge with a three-layered biaxially oriented polypropylene film (HIPHANE BOPP, Hwaseung Industries Co., Ltd.) using a low-density polyethylene (LDPE) film. between the paper carrier material and the plastic film was extruded. The thickness of the adhesion-promoting polyethylene film was 8 g / m 2 . The side (back) of the paper opposite the print side was coated with a polyethylene blend of 30% by weight of a low density polyethylene (LDPE, d = 0.923 g / cm 3 ) and 70% by weight of a high density polyethylene (HDPE, d = 0.964 g / cm 3 ) coated with an application weight of 40 g / m 2 in the extruder. The cooling cylinder was chosen so that the resulting surface of the back has a roughness of 0.9 microns, measured as Rz value according to DIN 4768.

Das erhaltene Trägermaterial wurde anschließend auf der mit der Kunststofffolie beschichteten Seite mit den erfindungsgemäßen Streichmassen A1 bis A6 beschichtet (25iger Drahtrakel) und drei Minuten lang bei 78°C getrocknet. Die Auftragsmengen der Streichmassen wurden dabei so gewählt, dass sich ein Trockenauftrag (Barriereschicht) jeweils von 1,6 g/m2 ergab.The support material obtained was then coated on the side coated with the plastic film with the coating compositions A1 to A6 according to the invention (25-gauge wire rod) and dried at 78 ° C. for three minutes. The application rates of the coating compositions were chosen such that a dry application (barrier layer) was in each case 1.6 g / m 2 .

Im nächsten Schritt wurde auf die Barriereschichten die farbstoffaufnehmende Streichmasse B aufgetragen (15er Drahtrakel) und getrocknet (2 Minuten, 78°C). Die Auftragsmenge der Streichmasse wurde dabei so gewählt, dass sich ein Trockenauftrag von 0,5 g/m2 ergab. Die Zusammensetzung der Streichmassen ist nachfolgend in Tabelle 1 angegeben.In the next step, the dye-receiving coating B was applied to the barrier layers (15 wire bar) and dried (2 minutes, 78 ° C). The application amount of the coating composition was chosen so that a dry application of 0.5 g / m 2 resulted. The composition of the coating compositions is given below in Table 1.

Streichmassen A1 bis A6Coatings A1 to A6

Zusammensetzungcomposition A1A1 A2A2 A3A3 A4A4 A5A5 A6A6 Entsalztes WasserDesalinated water 82,7082.70 82,3782.37 81,4581.45 80,6380.63 79,8179.81 78,3478.34 Gelatine
Imagel® AP 71979,
290 Bloom,Isoel.Pkt.=8
Gelita AGgelatin
Imagel ® AP 71979,
290 Bloom, Isoel.Point = 8
Gelita AG 5,805.80 5,805.80 3,633.63 3,633.63 0,730.73 0,730.73 NH3-Lösung, 5%igNH 3 solution, 5% 1,201.20 1,201.20 0,750.75 0,750.75 0,150.15 0,150.15 TiO2
Ti-Pure RPS Vantage 71%ig in Wasser, DuPontTiO 2
Ti-Pure RPS Vantage 71% in water, DuPont 2,912.91 2,912.91 2,912.91 2,912.91 2,912.91 2,912.91 Optischer Aufheller
Leucophor® U0, 25%ig
Archroma InternationalOptical brightener
Leucophor® ® U0, 25% strength
Archroma International 1,301.30 1,301.30 1,301.30 1,301.30 1,301.30 1,301.30 Polyesterpolyurethan
PU-Coat DMP 105, 40%ig in Wasser, Baumeister Chemicals & Consulting GmbH & Co. KGpolyester polyurethane
PU-Coat DMP 105, 40% in water, Baumeister Chemicals & Consulting GmbH & Co. KG 3,263.26 3,263.26 8,168.16 8,168.16 14,6814.68 14,6814.68 Netzmittel
Capstone® FS 30, 25%ig in Wasser, DuPontwetting agent
Capstone ® FS 30, 25% in water, DuPont 0,070.07 0,070.07 0,070.07 0,070.07 0,070.07 0,070.07 Polyaziridin
PZ-33, 50%ig in IPA
Flevo Chemie B.V.polyaziridine
PZ-33, 50% in IPA
Flevo Chemie BV 2,762.76 2,762.76 1,731.73 1,731.73 0,350.35 0,350.35 Blockiertes Polyisocyanat,
TexiCross® Al45, 40%ig in Wasser, Baumeister Chemicals & Consulting GmbH & Co. KGBlocked polyisocyanate,
TexiCross ® AL45, 40% in water, builder Chemicals & Consulting GmbH & Co. KG -- 0,330.33 -- 0,820.82 -- 1,471.47

Streichmassecoating slip B (Farbstoffaufnehmende Schicht)B (dye-receiving layer)

31,70 g einer Vinylchlorid/Acrylat-Compolymerdispersion mit einem Feststoffgehalt von 56 Gew.% (PrintRite® DP 281.E, Hersteller Lubrizol) und 13,58 g einer Vinylchlorid/Vinylace-tat/Vinylidenchlorid-Dispersion mit einem Feststoffgehalt von 56 Gew.-% (Vycar® 577 E, Hersteller Lubrizol) wurden mit 3,15 g einer 30%igen wäßrigen Suspension von kolloidaler Kieselsäure (Ludox® AM X4931, Hersteller Grace), 0,95 g Polydimethylsiloxan (TegoGlide® 482, Hersteller Evonik Industries), 0,25 g eines Entschäumungsmittels (Tego Foamex® 825, Hersteller Evonik Industries), 0,08 g einer oberflächenaktiven Substanz (Capstone® FS 30, 25%ig, Hersteller DuPont) und 50,29 g Wasser gemischt.31.70 g of a vinyl chloride / acrylate Compolymerdispersion with a solids content of 56 wt.% (PrintRite ® DP 281.E, manufacturer Lubrizol) and 13.58 g of a vinyl chloride / vinyl acetate / vinylidene chloride dispersion having a solids content of 56 wt .-% (VYCAR ® 577 e, manufacturer Lubrizol) were mixed with 3.15 g of a 30% aqueous suspension of colloidal silica (Ludox AM ® X4931, manufacturer Grace), 0.95 g of polydimethylsiloxane (TegoGlide ® 482, manufacturer Evonik Industries ), 0.25 g of a defoamer (Tego Foamex 825 ®, manufacturer Evonik Industries), 0.08 g of a surfactant mixed (Capstone ® FS 30, 25% pure, available from DuPont) and 50.29 g of water.

Vergleichsbeispiel 1Comparative Example 1

Auf die Vorderseite des in den Beispielen 1 bis 6 verwendeten Trägermaterials wurde zunächst die zur Bildung der Barriereschicht vorgesehene Beschichtungsmasse C (25iger Drahtrakel) aufgetragen, die nach Trocknung (3 Minuten, 78°C) mit der farbstoffaufnehmenden Beschichtungsmasse B (15er Drahtrakel beschichtet wurde. Der Auftrag der Barriereschicht betrug nach Trocknung 1,6 g/m2. Die Auftragsmenge der Streichmasse B wurde dabei so gewählt, dass sich ein Trockenauftrag von 0,5 g/m2 ergab.On the front side of the carrier material used in Examples 1 to 6, the coating composition C (25-wire squeegee) provided for the formation of the barrier layer was first coated after drying (3 minutes, 78 ° C.) with the dye-absorbing coating composition B (15-wire bar). The coating of the barrier layer after drying was 1.6 g / m 2. The application quantity of coating composition B was selected such that a dry application of 0.5 g / m 2 resulted.

Vergleichsbeispiele 2 bis 5Comparative Examples 2 to 5

Zur Bildung der Barriereschicht wurden die Beschichtungsmassen D (Vergleichsbeispiel 2), E (Vergleichsbeispiel 3), F (Vergleichsbeispiel 4) und G (Vergleichsbeispiel G) eingesetzt. Das Trägermaterial und die farbstoffaufnehmende Beschichtungsmasse waren wie in den Beispielen 1 bis 6. Die Zusammensetzungen der Streichmassen C bis G sind nachfolgend in Tabelle 2 angegeben. Zusammensetzung C D E F G Entsalztes Wasser 83,52 82,85 83,40 82,85 83,40 Gelatine Imagel® AP 71979, 290 Bloom, Isoelektr. Punkt =8, Gelita AG 7,25 5,80 2,94 5,80 2,94 NH3-Lösung, 5%ig 1,50 1,50 1,50 1,50 1,50 TiO2 Ti-Pure RPS Vantage 71%ig in Wasser, DuPont 2,91 2,91 2,91 2,91 2,91 Optischer Aufheller Leucophor® UO, 25%ig Archroma International 1,30 1,30 1,30 1,30 1,30 Acryl/Methacrylsäureester-Copolymer Thyon® SF 10, 46,5%ig in Wasser, Ecronova Polym. GmbH - 2,81 7,02 - - Polyesterpolyurethan NeoRez® R 600, 33%ig in Wasser, DSM Neoresins - - - 2,81 7,02 Netzmittel Capstone® FS 30, 25%ig in Wasser, DuPont 0,07 0,07 0,07 0,07 0,07 Polyaziridin PZ-33, 50%ig in IPA Flevo Chemie B.V. 3,45 2,76 0,86 2,76 0,86 The coating compositions D (Comparative Example 2), E (Comparative Example 3), F (Comparative Example 4) and G (Comparative Example G) were used to form the barrier layer. The carrier material and the dye-receiving coating composition were as in Examples 1 to 6. The compositions of the coating compositions C to G are shown in Table 2 below. composition C D e F G Desalinated water 83.52 82.85 83,40 82.85 83,40 Gelatin Imagel ® AP 71979, 290 Bloom, Isoelektr. Point = 8, Gelita AG 7.25 5.80 2.94 5.80 2.94 NH 3 solution, 5% 1.50 1.50 1.50 1.50 1.50 TiO 2 Ti-Pure RPS Vantage 71% in water, DuPont 2.91 2.91 2.91 2.91 2.91 Optical brightener Leucophor ® UO, 25% Archroma International 1.30 1.30 1.30 1.30 1.30 Acrylic / methacrylic acid ester copolymer Thyon ® SF 10, 46.5% in water, Ecronova Polym. GmbH - 2.81 7.02 - - Polyurethane NeoRez ® R 600, 33% in water, DSM neoresins - - - 2.81 7.02 Wetting agents Capstone ® FS 30, 25% in water, DuPont 0.07 0.07 0.07 0.07 0.07 Polyaziridine PZ-33, 50% in IPA Flevo Chemie BV 3.45 2.76 0.86 2.76 0.86

Die gemäß den Beispielen und Vergleichsbeispielen erhaltenen Aufzeichnungsmaterialien wurden den nachstehend beschriebenen Prüfungen unterzogen.The recording materials obtained in Examples and Comparative Examples were subjected to the tests described below.

FarbstoffmigrationsprüfungDye migration test

Die Muster werden mit den maximalen Farbdensitäten von Gelb, Cyan, Magenta und Schwarz auf dem Drucker CP-D70DW von Mitsubishi mit Standard-Donorband gedruckt. Das Druckformat ist 10 x 15 cm und die Farbflächensind 1 x 1 cm groß. Diese Muster werden für 5 Tage bei 80°C Ofentemperatur eingehängt. Nach 5 Tagen wird eine Beurteilung des Farbstoffdurchschlags auf der Rückseite des bedruckten Musters vorgenommen, diese erfolgt mittels Schulnoten.The patterns are printed with the maximum color densities of yellow, cyan, magenta and black on the Mitsubishi CP-D70DW printer with standard donor ribbon. The print size is 10 x 15 cm and the color areas are 1 x 1 cm. These patterns are hung for 5 days at 80 ° C oven temperature. After 5 days, an evaluation of the dye penetration on the back of the printed pattern is made, this is done by means of school grades.

Die Bewertung wird wie folgt vorgenommen: Kein Farbdurchlag auf der Rückseite wird als Note 1, starker und großflächiger Farbdurchschlag wird als Note 5 bewertet. Dazu erfolgt die relative Abstufung von Note 1 bis Note 5.The evaluation is carried out as follows: No color bleed on the back is rated as grade 1, strong and large color bleed is rated as grade 5. For this, the relative graduation from grade 1 to grade 5 takes place.

Mottle-Bewertung (Wolkigkeit)Mottle rating (cloudiness)

Muster und Drucker CP-D70DW von Mitsubishi werden 12h lang bei 40°C und 80% relativer Luftfeuchtigkeit vorkonditioniert. Anschließend wird beim bestehenden Klima ein 10x15 cm vollflächiger Schwarzdruck durchgeführt. Die Mottle-Bewertung der Muster erfolgt in Schulnoten von 1-5. Die Schulnote 1 bedeutet kein Mottle und Schulnote 5 bedeutet starkes Mottle. Die Notenabstufung zwischen 1-5 erfolgt relativ zu den Noten 1 und Noten 5.Mitsubishi's CP-D70DW samples and printers are preconditioned for 12 hours at 40 ° C and 80% relative humidity. Subsequently, in the existing climate, a 10x15 cm full-scale black print is performed. The mottle rating of the patterns is in grades 1-5. The grade 1 means no mottle and grade 5 means strong mottle. Grades between 1-5 are relative to grades 1 and 5.

Die Prüfergebnisse sind in der folgenden Tabelle 3 zusammengefasst. Aufzeichnungsmaterial Migration
Note Mottle
Note A1 Erfindung Beispiel 1 1 2 A2 Erfindung Beispiel 2 1 1 A3 Erfindung Beispiel 3 2 2 A4 Erfindung Beispiel 4 2 1,5 A5 Erfindung Beispiel 5 5 1 A6 Erfindung Beispiel 6 5 1 C Vergl.Bspl.1 1 4 D Vergl.Bspl.2 2 4 E Vergl.Bspl.3 3 3 F Vergl.Bspl.4 2,5 4 G Vergl.Bspl.5 4 3 The test results are summarized in the following Table 3. recording material migration
grade mottle
grade A1 Invention Example 1 1 2 A2 Invention Example 2 1 1 A3 Invention Example 3 2 2 A4 Invention Example 4 2 1.5 A5 Invention Example 5 5 1 A6 Invention Example 6 5 1 C Vergl.Bspl.1 1 4 D Vergl.Bspl.2 2 4 e Vergl.Bspl.3 3 3 F Vergl.Bspl.4 2.5 4 G Vergl.Bspl.5 4 3

Es zeigt sich, dass die erfindungsgemäßen Aufzeichnungsmaterialien nach dem Bedrucken ein gutes bis sehr gutes Migrationsverhalten für die Farbstoffe und keinen Mottle-Effekt aufweisen. Alle geprüften erfindungsgemäßen Aufzeichungsmaterialien zeigen darüber hinaus eine hervorragende Farbdichte des übertragenen Bilds.It turns out that the recording materials according to the invention after printing have a good to very good migration behavior for the dyes and no mottle effect. In addition, all of the tested recording materials of the present invention show excellent color density of the transferred image.

Claims (13)

Aufzeichnungsmaterial für thermische Druckverfahren mit einem Träger und einer für den thermischen Farbstofftransfer ausgerüsteten farbstoffaufnehmenden Schicht, dadurch gekennzeichnet, dass zwischen dem Träger und der farbstoffaufnehmenden Schicht eine Barriereschicht angeordnet ist und die Barriereschicht Gelatine und ein in Wasser dispergierbares polymeres Bindemittel enthält, worin Gelatine und das in Wasser dispergierbare polymere Bindemittel miteinander vernetzt sind.A thermal printing material recording medium comprising a support and a dye-receiving layer provided for thermal dye transfer, characterized in that a barrier layer is disposed between the support and the dye-receiving layer and the barrier layer contains gelatin and a water-dispersible polymeric binder, wherein gelatin and the like described in U.S. Pat Water-dispersible polymeric binders are crosslinked with each other. Aufzeichnungsmaterial nach Anspruch 1, dadurch gekennzeichnet, dass die Vernetzung der miteinander vernetzten Bindemittel durch mindestens zwei verschiedene Vernetzungsmittel erfolgt ist.Recording material according to claim 1, characterized in that the crosslinking of the crosslinked binders is carried out by at least two different crosslinking agents. Aufzeichnungsmaterial nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Gelatine eine nicht derivatisierte Gelatine ist.A recording material according to claim 1 or 2, characterized in that the gelatin is a non-derivatized gelatin. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das wasserdispergierbare polymere Bindemittel ein Polyesterpolyurethan-Copolymer ist.Recording material according to one of Claims 1 to 3, characterized in that the water-dispersible polymeric binder is a polyester-polyurethane copolymer. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Massenverhältnis Gelatine zu dem in Wasser dispergierbaren Bindemittel 80:20 bis 40:60 beträgt.A recording material according to any one of claims 1 to 4, characterized in that the mass ratio of gelatin to the water-dispersible binder is 80:20 to 40:60. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Vernetzungsmittel eine Imin-Gruppen enthaltende Verbindung und eine Isocyanat-Gruppen enthaltende Verbindung sind, wobei das Massenverhältnis beider Verbindungen 1:1 bis 6:1 beträgt.A recording material according to any one of claims 1 to 5, characterized in that the crosslinking agents are an imine group-containing compound and an isocyanate group-containing compound, wherein the mass ratio of both compounds is 1: 1 to 6: 1. Aufzeichnungsmaterial nach Anspruch 6, dadurch gekennzeichnet, dass das Imin-Gruppen enthaltende Vernetzungsmittel ein Polyaziridin ist.A recording material according to claim 6, characterized in that the imine group-containing crosslinking agent is a polyaziridine. Aufzeichnungsmaterial nach einem der Ansprüche 6 oder 7, dadurch gekennzeichnet, dass das Isocyanat-Gruppen enthaltende Vernetzungsmittel ein blockiertes Isocyanat ist.Recording material according to one of claims 6 or 7, characterized in that the isocyanate group-containing crosslinking agent is a blocked isocyanate. Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das Trägermaterial ein unbeschichtetes Rohpapier oder ein gestrichenes Rohpapier enthält und auf der der Barriereschicht zugewandten Seite eine Kunstharzschicht aufweist.Recording material according to one of Claims 1 to 8, characterized in that the carrier material contains an uncoated base paper or a coated base paper and has a synthetic resin layer on the side facing the barrier layer. Aufzeichnungsschicht nach Anspruch 9, dadurch gekennzeichnet, dass die Kunstharzschicht eine extrudierte Polyolefinschicht oder eine aufkaschierte Polymerfolie ist.A recording layer according to claim 9, characterized in that the synthetic resin layer is an extruded polyolefin layer or a laminated polymer film. Aufzeichnungsschicht nach Anspruch 10, dadurch gekennzeichnet, dass die Polymerfolie eine biaxial orientierte Polypropylenfolie mit einer porösen Kernschicht und mindestens einer porenfreien Oberflächenschicht ist.A recording layer according to claim 10, characterized in that the polymer film is a biaxially oriented polypropylene film having a porous core layer and at least one pore-free surface layer. Aufzeichnungsmaterial nach mindestens einem der Ansprüche 10 bis 11,
dadurch gekennzeichnet, dass zwischen der Kunstharzschicht und der Barriereschicht eine Polyethylenschicht angeordnet ist.Recording material according to at least one of claims 10 to 11,
characterized in that a polyethylene layer is arranged between the synthetic resin layer and the barrier layer. Aufzeichnungsmaterial nach mindestens einem der Ansprüche 1 bis 12 dadurch gekennzeichnet, dass die farbstoffaufnehmende Schicht Polymer mit Affinität zu den Farbstoffen des Donormaterials, ein feinteiliges anorganisches Pigment und gegebenenfalls weitere Hilfsmittel enthält.Recording material according to at least one of claims 1 to 12, characterized in that the dye-receiving layer polymer with affinity for the dyes of the donor material, a finely divided inorganic pigment and optionally further auxiliaries.
EP14196562.4A 2014-12-05 2014-12-05 Recording material for thermal printing method Active EP3028866B1 (en)

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ES14196562T ES2791719T3 (en) 2014-12-05 2014-12-05 Record material for thermal printing procedures
EP14196562.4A EP3028866B1 (en) 2014-12-05 2014-12-05 Recording material for thermal printing method
PL14196562T PL3028866T3 (en) 2014-12-05 2014-12-05 Recording material for thermal printing method
US14/945,633 US9604487B2 (en) 2014-12-05 2015-11-19 Recording material for thermal printing methods
JP2015237210A JP6077633B2 (en) 2014-12-05 2015-12-04 Recording material for thermal printing
CN201510884557.0A CN105667115B (en) 2014-12-05 2015-12-04 For the recording materials of thermal printing method

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US20160159126A1 (en) 2016-06-09
CN105667115B (en) 2018-05-29
CN105667115A (en) 2016-06-15
JP2016107641A (en) 2016-06-20
ES2791719T3 (en) 2020-11-05
JP6077633B2 (en) 2017-02-08
US9604487B2 (en) 2017-03-28
EP3028866B1 (en) 2020-04-29

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