NL2018248B1 - Paper composition for transfer printing - Google Patents

Paper composition for transfer printing Download PDF

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Publication number
NL2018248B1
NL2018248B1 NL2018248A NL2018248A NL2018248B1 NL 2018248 B1 NL2018248 B1 NL 2018248B1 NL 2018248 A NL2018248 A NL 2018248A NL 2018248 A NL2018248 A NL 2018248A NL 2018248 B1 NL2018248 B1 NL 2018248B1
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NL
Netherlands
Prior art keywords
paper
composition according
substrate
composition
paper composition
Prior art date
Application number
NL2018248A
Other languages
Dutch (nl)
Inventor
Godefridus Rops Johannes
Johannes Wesselink Bernardus
Original Assignee
Crown Van Gelder B V
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 Crown Van Gelder B V filed Critical Crown Van Gelder B V
Priority to NL2018248A priority Critical patent/NL2018248B1/en
Priority to PCT/NL2018/050054 priority patent/WO2018139925A1/en
Application granted granted Critical
Publication of NL2018248B1 publication Critical patent/NL2018248B1/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
    • B41M5/50—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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/003—Transfer printing
    • D06P5/004—Transfer printing using subliming dyes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/52—Cellulose; Derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/64—Inorganic compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22—Addition to the formed paper
    • D21H23/52—Addition to the formed paper by contacting paper with a device carrying the material
    • D21H23/56—Rolls
    • 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
    • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
    • B41M5/0256—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet the transferable ink pattern being obtained by means of a computer driven printer, e.g. an ink jet or laser printer, or by electrographic means
    • 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
    • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
    • B41M5/035—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic
    • 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
    • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
    • B41M5/035—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic
    • B41M5/0355—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic characterised by the macromolecular coating or impregnation used to obtain dye receptive properties
    • 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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
    • 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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
    • B41M5/395—Macromolecular additives, e.g. binders
    • 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
    • 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
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
    • 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
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)

Abstract

The present invention relates to a composition for surface treating a substrate, wherein the composition comprising a film forming agent, such as an organic polymer and a dye-fixing agent, said dye-fixing agent comprising a divalent metal. The composition of the present invention may be used for surface treating a substrate in order to provide a paper composition for transfer printing. The present invention further relates to a method of preparing such a composition, use of the paper composition in a transfer printing method and to a method for printing a surface of a support material other than paper by means of transfer printing using a substrate surface treated with the composition of the present invention.

Description

Octrooicentrum
Nederland
(21) Aanvraagnummer: 2018248 © Aanvraag ingediend: 27/01/2017 © 2018248 © BI OCTROOI © Int. CL:
B41M 3/12 (2017.01) D06P 5/28 (2017.01) D21H 19/52 (2017.01) D21H 19/54 (2017.01) D21H 19/62 (2017.01) D21H 19/64 (2017.01)
0 Aanvraag ingeschreven: © Octrooihouder(s):
07/08/2018 CROWN VAN GELDER B.V. te Velsen-Noord.
© Aanvraag gepubliceerd:
- © Uitvinder(s):
Johannes Godefridus Rops te Velsen-Noord.
© Octrooi verleend: Bernardus Johannes Wesselink
07/08/2018 te Velsen-Noord .
© Octrooischrift uitgegeven:
10/08/2018 © Gemachtigde:
ir. H.Th. van den Heuvel c.s.
te 's-Hertogenbosch.
© Paper composition for transfer printing © The present invention relates to a composition for surface treating a substrate, wherein the composition comprising a film forming agent, such as an organic polymer and a dye-fixing agent, said dye-fixing agent comprising a divalent metal. The composition of the present invention may be used for surface treating a substrate in order to provide a paper composition for transfer printing. The present invention further relates to a method of preparing such a composition, use of the paper composition in a transfer printing method and to a method for printing a surface of a support material other than paper by means of transfer printing using a substrate surface treated with the composition of the present invention.
NL Bl 2018248
Dit octrooi is verleend ongeacht het bijgevoegde resultaat van het onderzoek naar de stand van de techniek en schriftelijke opinie. Het octrooischrift komt overeen met de oorspronkelijk ingediende stukken.
Paper composition for transfer printing
The present invention relates to a paper composition for transfer printing. The present invention relates to a composition for surface treating a substrate, method for preparing such a composition and method for surface treating a substrate with the composition of the present invention. The present invention further relates to a paper composition and use of the paper composition in a transfer printing process. The present invention also relates to a method for printing the paper composition and subsequently printing the surface of a support material other than paper by means of transfer printing.
Transfer paper is used for printing textile and material provided with a polyester coating, in particular textile of polyester, and mixtures of polyester with other fibres. To this end, by means of common printing techniques, e.g. flexographic, offset, intaglio, or rotary screen printing, a pattern, design or printing image is applied to the paper. Depending on the printing technique, the ink is thin-fluid or in the form of a pasty mass. The ink or paste contains sublimable dye components. By means of heat, the sublimable components of the ink are subsequently transferred, in the transfer process, onto the surface that is eventually to be printed. In this process, the temperatures common for transferring the dyes are within the range of from about 160°C to about 220°C. During the transfer of the dyes in the ink, by means of heat and pressure, a portion of the dyes often stays behind on the paper. The extent to which the sublimable dye is transferred from the paper onto the textile during the transfer process is referred to as transfer efficiency.
Typically, the transfer efficiency of transfer papers is about 65%. An example of such a transfer paper is disclosed in European patent application no. EP 1 102 682 A1. EP’682 discloses a transfer paper suitable for ink-jet printing, provided, at least on the side to be printed, with a release or barrier layer, wherein the layer having a porosity of at most 100 ml/min.
The present invention provides a transfer paper having a transfer efficiency of at least 65%. In order to manufacture such a highly efficient transfer paper the present invention provides hereto a composition for surface treating a substrate, e.g. paper, comprising a film forming agent and a dye-fixing agent, wherein the film forming agent comprises an organic polymer. It was found that by providing a composition for surface treating a substrate wherein the dye-fixing agent comprises a divalent metal, the transfer efficiency of a substrate surface treated with the composition of the present invention is significantly increased. Further, it was found that by providing the composition of the present invention, the porosity of the surface treated substrate is no longer subject to further restrictions. In other words, the porosity of the surface treated substrate may be 100 ml/min or higher.
In fact, it was found that the significant difference in porosity of the transfer paper of the present invention (compared to the porosity of the substrate as disclosed in EP’682), results in a transfer paper having an excellent transfer efficiency in combination with excellent print quality. Without wishing to be bound by theory, it is believed that the divalent metal comprised in the composition of the present invention is firmly fixing sublimable dyes to the surface of the treated substrate and is able to release the fixed sublimable dyes to any support material (other than paper) when heat and pressure is applied. The divalent metal is thus acting as a, so called, anti-ghosting agent preventing any sublimable dye to be released to the opposite side of the treated surface of the substrate.
The divalent metal may be a salt selected from the group consisting of calcium chloride, magnesium chloride, calcium bromide, magnesium bromide, calcium nitrate, magnesium nitrate, calcium acetate and magnesium acetate. Preferably the divalent metal is a chloride salt, e.g. calcium chloride and/or magnesium chloride, since those divalent metal salts provide the greatest improvement in performance and they work efficiently on a cost-benefit basis. In addition to the above-identified divalent metal salts, a sulphate salt may be added as well, e.g. calcium sulphate and/or magnesium sulphate.
The organic polymer may be a hydrophilic polymer, preferably a polymer selected from the group consisting of polyvinyl alcohol, polydiallyldimethylammonium chloride, polyethylenimine, starch and cellulosic polymers including cellulose nitrate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose and carboxymethylcellulose. By providing a film forming agent being a hydrophilic polymer, the divalent metal is imbedded in the film forming layer formed by surface treating a substrate with the composition of the present invention. The use of polyvinyl alcohol, polydiallyldimethylammonium chloride and polyethylenimine is in particular preferred to reduce mottling (i.e. unevenness of the print optical density in a solid printed area). However, starch may be selected as a suitable hydrophilic polymer being a less expensive alternative.
The dye-fixing agent may further comprising a charged polymer, preferably a cationic polymer. The charged polymer may comprise a polyamine. Preferably diamine based polymers are used as cationic polymers, as they do not significantly influence the rheological properties of the surface treatment, as this is preferably controlled by the film forming agent. Excellent fixation of dyes and support of fixation of pigments is reached by diamine based polymers.
In addition to the film forming agent and dye-fixing agent, the composition may further comprise a surface sizing agent in order to produce a surface treated substrate with the composition of the present invention suitable for inkjet printing.
In order to provide excellent ink jet functionality, e.g. colour intensity, colour to colour bleed and mottle or print uniformity, the composition may further comprise a surface sizing agent such as modified starches, styrene maleic anhydride, styrene acrylic emulsion, styrene acrylic acid, ethylene acrylic acid, gelatine and polyurethane.
The composition of the present invention is preferably an aqueous solution. Preferably the aqueous solution is an acidic solution having a pH of between 1.0 and 8.0. More preferred the aqueous solution of the present invention has a pH of between 4.0 and 8.0. Even more preferred the aqueous solution of the present invention has a pH of between 4.5 and 7.5. Outside those preferred ranges the composition is less stable under storage conditions and may lose its effectiveness in uniform absorption and anchoring of the ink.
The composition of the present invention may have a viscosity of 5 to 900 mPa-s. Preferably the composition of the present invention may have a viscosity of 10 to 90 mPa-s.
The present invention also relates to a method for preparing the composition as described above, comprising the steps of mixing the film forming agent and dye fixing agent and dispersing the resulting mixture in an acidic aqueous medium. The acidic aqueous medium may comprises an acidic aqueous medium, wherein the acidic aqueous medium preferably having a pH of between 1.0 to 8.0. As already provided above, the pH may be between 4.0 and 8.0 or even between 4.5 and 7.5 to provide a composition which is stable under storage conditions.
In addition to mixing the film forming agent and dye-fixing agent, the method may further comprise mixing a surface sizing agent together with the film forming agent and dye-fixing agent. Any suitable surface sizing agent may be selected, for example surface sizing agents including modified starches, styrene maleic anhydride, styrene acrylic emulsion, styrene acrylic acid, ethylene acrylic acid, gelatine and polyurethane.
The composition of the present invention may be used for surface treating a substrate in order to obtain a transfer paper composition having excellent transfer efficiency and print quality. The method for surface treating a substrate, e.g. a paper-based substrate, comprises the steps of: a) providing the composition of the present invention; b) providing a substrate; c) surface treating the substrate provided in step b) with the composition provided in step a); and d) drying the treated substrate of step c).
The composition of the present invention may be applied to the substrate using any suitable technique for coating the surface of a substrate. Preferably, the composition of the present invention is applied to the substrate in step c) by using a roller coater, roller knife coater, blade coater, kiss roll coater, size press or film press.
The amount of the composition applied onto the surface of the substrate may be varied depending on the intended use of the surface treated substrate, i.e. the requirements set by the process wherein the surface treated substrate is used. In a preferred embodiment of the present invention, the dry weight of the composition provided in step a) is 0.50 to 2.3 g/m2. Preferably, the dry weight of the composition provided in step a) is 0.70 to 2.0 g/m2, even more preferred 0.90 to 1.8 g/m2. Depending on the film forming agents used, the dry weight of the composition provided may vary. For example, in case starch is used as film forming agent, the dry weight of the composition provided in step a) is preferably about 1.8 g/m2, whereas in case polyvinyl alcohol and polydiallyldimethylammonium chloride are used as film forming agent, the dry weight of the composition provided in step a) is preferably about 1.1 g/m2.
In another aspect the present invention relates to a paper composition for transfer printing obtainable by the method as described above, wherein the transfer efficiency is at least 65%, at least 70%, at least 75%, at least 80%, at least 85% or even at least 90%.
The present invention also relates to a paper composition for transfer printing comprising a substrate and a film forming layer applied to the surface of the substrate, said film forming layer comprises a film forming agent and a dye-fixing agent, wherein the film forming agent comprises an organic polymer, and wherein the dye-fixing agent comprises a divalent metal.
As already stated above, the paper composition provided by the present invention is suitable for transfer printing with an increased transfer efficiency when compared to the transfer papers disclosed in the prior art, e.g. EP'682. By providing a paper composition wherein a film forming layer is applied to the surface of the substrate comprising an organic polymer and a divalent metal, sublimable dyes are firmly fixed to the surface of the paper composition comprising the film forming layer whereas any further ink material, e.g. an aqueous medium such as water, is absorbed by the substrate. By absorption of the ink material by the substrate, wherein the sublimable dyes of the ink are fixed to the surface of the substrate, i.e. embedded in the film forming layer, the sublimable dyes are immobilised and, consequently, line growth (known as bleed or feathering) is further reduced resulting in high resolution of the printed image on the paper composition. The paper composition provided by the present invention thus results in a paper composition suitable for use in a transfer printing process having excellent transfer efficiency and print quality.
Even further, the divalent metal imbedded in the film forming layer act as antighosting agents preventing any sublimable dye to be released to the opposite side (non-treated surface) of the substrate.
The divalent metal of the paper composition according to the present invention may be a salt selected from the group consisting of calcium chloride, magnesium chloride, calcium bromide, magnesium bromide, calcium nitrate, magnesium nitrate, calcium acetate and magnesium acetate. Preferably the divalent metal is a chloride salt, e.g. calcium chloride and/or magnesium chloride, since those divalent metal salts provide the greatest improvement in performance and they work efficiently on a cost-benefit basis. In addition to the above-identified divalent metal salts, a sulphate salt may be added as well, e.g. calcium sulphate and/or magnesium sulphate.
The organic polymer may be a hydrophilic polymer, preferably a polymer selected from the group consisting of polyvinyl alcohol, polydiallyldimethylammonium chloride, polyethylenimine, starch and cellulosic polymers including cellulose nitrate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose and carboxymethylcellulose. By providing a film forming agent being a hydrophilic polymer, the divalent metal is imbedded in the film forming layer of the paper composition. The use of polyvinyl alcohol, polydiallyldimethylammonium chloride and polyethylenimine is in particular preferred to reduce mottling. However, starch may be selected as a suitable hydrophilic polymer being a less expensive alternative.
The dye-fixing agent may further comprising a charged polymer, preferably a cationic polymer. The charged polymer may comprise a polyamine. Preferably diamine based polymers are used as cationic polymers, as they do not significantly influence the rheological properties of the surface treatment, as this is preferably controlled by the film forming agent. Excellent fixation of dyes and support of fixation of pigments is reached by diamine based polymers.
In addition to the film forming agent and dye-fixing agent, the paper composition may further comprise a sizing agent, e.g. a surface sizing agent and/or an internal sizing agent, in order to provide excellent ink jet functionality, e.g. colour intensity, colour to colour bleed, mottle or print uniformity and show thru. Suitable surface sizing agents may include modified starches, styrene maleic anhydride, styrene acrylic emulsion, styrene acrylic acid, ethylene acrylic acid, gelatine and polyurethane.
In a preferred embodiment, the substrate may comprise an internal sizing agent. It was found that by providing a substrate comprising an internal sizing agent, the transfer efficiency of the paper composition is further increased. The internal sizing agent may be selected from non-reactive and reactive sizing agents well known in the papermaking industry, e.g. rosin size, alkyl succinic anhydride, alkyl ethene dimer and the like, with varying chain lengths of the alkyl group to influence hydrofobicity of the bulk of the paper. A preferred internal sizing agent is selected from the group consisting of alkyl ethene dimer and alkyl succinic anhydride.
Without wishing to be bound by theory, it is believed that by providing a substrate comprising an internal sizing agent, the (hydrophilic) film forming layer applied onto the surface of the substrate does not penetrate the substrate as deep as compared to a film forming layer applied onto the surface of a substrate comprising less or no internal sizing agent at all. Even further, it is believed that by providing a more hydrophobic substrate, the retention time of the sublimable ink in the film forming layer is increased compared to a paper composition comprising a substrate having less or no internal sizing agent. By increasing the retention time of the sublimable ink in the film forming layer, the sublimable dyes do have more time to complex with the divalent metals embedded in the film forming layer. In other words, a higher sublimable dye-divalent metal binding efficacy is achieved by providing a paper composition comprising a substrate having an internal sizing agent. By providing a paper composition having a higher sublimable dye-divalent metal binding efficacy, the sublimable dye transfer efficiency is increased as well.
The substrate of the present invention may comprise a paper-based substrate. A paper-based substrate may include traditional papers, such as woody papers or non-woody papers, synthetic paper and regenerated paper. More generally, the terms ‘paper-based substrate' is meant to encompass a substrate based on cellulosic fibres and other known paper fibres. The substrate may be of any dimension, e.g. size or thickness or form, such as pulp, wet paper and dry paper. A substrate is meant to encompass plain paper or un-coated paper, writing paper, drawing paper, photobase paper, coated paper and the like. For example, a substrate may have a thickness of 0.05 mm to 0.75 mm, depending on a desired end application for the paper composition the substrate is used for.
Also, the substrate of the present invention may comprise at least 25 g/m2 paper, at least 35 g/m2 paper, at least 45 g/m2 paper or at least 55 g/m2 paper. Preferred ranges for the substrate are for example 25 to 150 g/m2 paper, 50 to 125 g/m2 paper and 55 to 90 g/m2 paper. It was found that even with paper compositions comprising a substrate having a low grammage, e.g. between 25 to 55 g/m2 paper, the paper compositions obtained are still suitable for use as transfer paper. For example, relatively good transfer printing results are already obtained by using a paper composition comprising a substrate having about 25 g/m2 paper, about 40 g/m2 paper or about 55 g/m2 paper.
The substrate of the paper composition of the present invention may comprise 0.50 to 2.00 kg/tonne internal sizing agent, preferably 0.75 to 1.50 kg/tonne, more preferably about 1.35 kg/tonne. By providing a substrate comprising a balanced amount of internal sizing agent, any waiving, due to the absorption of sublimable ink, of the paper composition is maintained within an acceptable range.
The paper composition of the present invention may have a porosity of at least 100 ml/min, preferably at least 150 ml/min, more preferably at least 200 ml/min. It was found that by providing a porous paper composition, the transfer efficiency is significantly higher than a paper composition being less porous, e.g. a paper composition typically used in the prior art such as disclosed by EP’682.
In order to obtain a paper composition having an optimal binding efficacy and, inherently, an optimal transfer efficiency, the paper composition preferably comprises between 0.05 to 1.00 g/m2 divalent metal, preferably between 0.08 to 0.75 g/m2 and more preferably between 0.30 to 0.60 g/m2 divalent metal.
It was further found that the ratio of divalent metal to film forming agent is further of influence for providing the most optimum paper composition having the highest transfer efficiency as possible. A preferred dry weight ratio of divalent metal to film forming agent is between 1 : 1 to 1 : 3.
Further it is noted that in a preferred embodiment, the surface of the substrate on the side to be printed is provided with the film forming layer. Optionally, the opposite surface of the substrate may be provided with the same film forming layer in order to further reduce the ‘ghosting effect’. However, such additional layer is not necessarily necessary. As already stated above, the film forming layer provided on the side to be printed have sufficient binding properties to bind the sublimable dyes on the treated surface of the paper composition.
A further aspect of the present invention relates to the use of the paper composition of the present invention. The paper composition may be applied as a transfer paper in a method for printing a surface of a support material other than paper, by means of transfer printing. Preferably, the transfer printing method comprises thermal sublimation.
The support material other than paper may include any type of material suitable for use in a transfer printing process. Preferred support materials comprises textile and/or polyester.
The present invention also relates to a method for printing the paper composition according to the present invention, comprising the steps of: i) providing a paper composition as described above; ii) providing an aqueous dispersion of a sublimable ink; and iii) printing of the film forming layered side of the paper composition provided in step i) with the aqueous dispersion provided in step ii). The printing step iii) is preferably performed by using an inkjet printer. The present invention thus provides a fast and reliable method in printing the paper composition with a sublimable ink for further use in a transfer printing process.
The present invention further relates to a method for printing a surface of a support material other than paper, comprising the steps of: iv) providing a paper composition printed with an aqueous dispersion of a sublimable ink as described above; v) providing a support material other than paper; and vi) transferring the sublimable ink to the surface of the support material.
As already stated above, the support material may comprise textile and/or polyester. Also, the transfer of the sublimable ink to the surface of the support material in step vi) is preferably performed by using thermal sublimation.
The invention will now be further illustrated with reference to the following examples.
Examples
The transfer efficiency, print quality (black optical density) and uniformity (feathering) was measured of 7 paper compositions. The results are shown in table
1.
Table 1. Measured transfer efficiency, print quality and uniformity of 7 paper compositions.
Paper composition
1 2 3 4 5 6 7
Weight paper (g/m2) 90 80 90 90 70 70 55
Internal sizing agent (kg/tonne) - 0.75 0.90 - 0.75 - 1.4
Divalent salt (g/m2) - - 0.3 - 0.5 0.3 0.6
Coating yield (g/m2) - - 2.1 0.4 0.9 0.7 1.1
Roughness Bendtsen (ml/min) 200 200 100 100 22 22 100
Porosity Bendtsen (ml/min) >1000 >1000 >200 >200 >100 >100 >200
Transfer efficiency - + ++ - +++ ++ ++++
Print quality - + ++ + +++ ++ +++
Uniformity + - ++ + +++ ++ +++
The transfer efficiency, print quality and uniformity in table 1 is scored using the following scoring system:
- = no result at all;
+ = bad result;
++ = reasonable result;
+++ = good result; and
++++ = excellent result.
It is noted that a ‘++’ score for transfer efficiency corresponds to a transfer efficiency of at least 65%, whereas a “++++’ score for transfer efficiency corresponds to a transfer efficiency of at least 90%.
Given the results provided in table 1, it can be concluded that the addition of an internal sizing agent did result in an increase of transfer efficiency and print quality (see: paper composition 1 compared to paper composition 2 and paper composition 6 compared to paper compositions 5 and 7).
Even further, it can be concluded that by providing a coating layer (without comprising a divalent metal) did result in an increase of print quality and uniformity (see: paper composition 1 compared to paper composition 4).
Also, it is shown that by adding a divalent metal to the coating layer, the transfer efficiency, print quality and uniformity is significantly increased (see: paper compositions 1,2 and 4 compared to paper compositions 3, 5, 6 and 7). It is noted that the transfer efficiency, print quality and uniformity is increased significantly by using a divalent salt irrespective the presence of an internal sizing agent (see: paper composition 4 compared to paper compositions 3 and 6).

Claims (10)

ConclusiesConclusions 1. Samenstelling voor het behandelen van het oppervlak van een substraat, omvattende:A composition for treating the surface of a substrate, comprising: 5 - een filmvormend middel; en een kleurstofbindend middel, waarbij het filmvormend middel een organische polymeer omvat, met het kenmerk dat het kleurstofbindend middel een tweewaardig metaal omvat.5 - a film-forming agent; and a dye-binding agent, wherein the film-forming agent comprises an organic polymer, characterized in that the dye-binding agent comprises a divalent metal. 1010 2. Samenstelling volgens conclusie 1, met het kenmerk dat het tweewaardig metaal een zout is dat wordt gekozen uit calciumchloride, magnesiumchloride, calciumbromide, magnesiumbromide, calciumnitraat, magnesiumnitraat, calciumacetaat en magnesiumacetaat, bij voorkeur wordt gekozen uit calciumchloride en magnesiumchloride.Composition according to claim 1, characterized in that the divalent metal is a salt selected from calcium chloride, magnesium chloride, calcium bromide, magnesium bromide, calcium nitrate, magnesium nitrate, calcium acetate and magnesium acetate, preferably selected from calcium chloride and magnesium chloride. 3. Samenstelling volgens conclusie 1 of 2, met het kenmerk dat het organische polymeer een hydrofiele polymeer omvat.Composition according to claim 1 or 2, characterized in that the organic polymer comprises a hydrophilic polymer. 4. Samenstelling volgens conclusie 3, met het kenmerk dat de hydrofielComposition according to claim 3, characterized in that the hydrophilic 20 polymeer wordt gekozen uit polyvinylalcohol, polydiallyldimethylammoniumchloride, polyethyleenimine, zetmeel en cellulose polymeren met inbegrip van cellulosenitraat, celluloseacetaat butyraat, methylcellulose, ethyl cellulose en carboxymethylcellulose.Polymer is selected from polyvinyl alcohol, polydialyl dimethyl ammonium chloride, polyethylene imine, starch and cellulose polymers including cellulose nitrate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose and carboxymethyl cellulose. 25 5. Samenstelling volgens één der voorgaande conclusies, met het kenmerk dat het kleurstofbindend middel een geladen polymeer, bij voorkeur een kationisch polymeer, omvat.5. A composition according to any one of the preceding claims, characterized in that the dye-binding agent comprises a charged polymer, preferably a cationic polymer. 6. Samenstelling volgens één der voorgaande conclusies, met het kenmerk 30 dat de samenstelling een apprêteermiddel omvat.6. A composition according to any one of the preceding claims, characterized in that the composition comprises an sizing agent. 7. Samenstelling volgens één der voorgaande conclusies, met het kenmerk dat de samenstelling een waterige oplossing omvat.Composition according to any one of the preceding claims, characterized in that the composition comprises an aqueous solution. 8. Samenstelling volgens één der voorgaande conclusies, met het kenmerk dat de waterige oplossing een zure waterige oplossing omvat, waarbij de zure waterige oplossing een pH van 1,0 tot 8,0 heeft, bij voorkeur een pH van 4,0 tot 8,0, bij meer voorkeur een pH van 4,5 tot 7,5.Composition according to any one of the preceding claims, characterized in that the aqueous solution comprises an acidic aqueous solution, wherein the acidic aqueous solution has a pH of 1.0 to 8.0, preferably a pH of 4.0 to 8, 0, more preferably a pH of 4.5 to 7.5. 9. Samenstelling volgens één der voorgaande conclusies, met het kenmerk dat de samenstelling een viscositeit van 5 tot 900 mPa-s heeft, bij voorkeur 10 tot 90 mPa-s.A composition according to any one of the preceding claims, characterized in that the composition has a viscosity of 5 to 900 mPa-s, preferably 10 to 90 mPa-s. 10. Werkwijze voor de bereiding van de samenstelling volgens één der voorgaande conclusies, omvattende de stappen:A method for the preparation of the composition according to any one of the preceding claims, comprising the steps of: het mengen van het filmvormend middel en het kleurstof bindend middel; en het dispergeren van het verkregen mengsel in een waterig medium.mixing the film-forming agent and the dye-binding agent; and dispersing the resulting mixture in an aqueous medium. 11. Werkwijze volgens conclusie 10, met het kenmerk dat het waterig medium een zuur waterig medium omvat, waarbij het zure waterige medium een pH van 1,0 tot 8,0 heeft, bij voorkeur een pH van 4,0 tot 8,0, bij meer voorkeur een pH van 4,5 tot 7,5.A method according to claim 10, characterized in that the aqueous medium comprises an acidic aqueous medium, wherein the acidic aqueous medium has a pH of 1.0 to 8.0, preferably a pH of 4.0 to 8.0, more preferably a pH of 4.5 to 7.5. 12. Werkwijze volgens conclusie 10 of 11, met het kenmerk dat stap a) verder het mengen van een appreteermiddel omvat.A method according to claim 10 or 11, characterized in that step a) further comprises mixing a sizing agent. 13. Werkwijze voor het behandelen van het oppervlak van een substraat, omvattende de stappen:A method for treating the surface of a substrate, comprising the steps of: a) het verschaffen van een samenstelling volgens één der conclusies 1 -9;a) providing a composition according to any one of claims 1-9; b) het verschaffen van een substraat;b) providing a substrate; c) het aanbrengen van de in stap a) verschafte samenstelling op het oppervlak van het in stap b) verschafte substraat; enc) applying the composition provided in step a) to the surface of the substrate provided in step b); and d) het drogen van het in stap c) behandelde substraat.d) drying the substrate treated in step c). 14. Werkwijze volgens conclusie 13, met het kenmerk dat in stap c) de samenstelling wordt aangebracht op het substraat middels een lakwals, rolmes coater, rakel coater, likrol coater, lijmpers of filmpers.A method according to claim 13, characterized in that in step c) the composition is applied to the substrate by means of a lacquer roller, roller knife coater, doctor blade coater, likrol roller coater, size press or film press. 15. Werkwijze volgens conclusie 13 of 14, met het kenmerk dat het drooggewicht van de in stap a) verschafte samenstelling 0,50 tot 2,3 g/m2 bedraagt, bij voorkeur 0,70 tot 2,0 g/m2, bij meer voorkeur 0,90 tot 1,8 g/m2.Method according to claim 13 or 14, characterized in that the dry weight of the composition provided in step a) is 0.50 to 2.3 g / m 2 , preferably 0.70 to 2.0 g / m 2 , more preferably 0.90 to 1.8 g / m 2 . 5 16. Papiersamenstelling voor transferdruk verkrijgbaar middels de werkwijze volgens één der conclusies 13-15, met het kenmerk dat het transferrendement ten minste 65% bedraagt.16. Paper composition for transfer printing obtainable by the method according to one of claims 13-15, characterized in that the transfer efficiency is at least 65%. 17. Papiersamenstelling voor transferdruk omvattende:A paper composition for transfer printing comprising: 10 - een substraat; en een op het oppervlak van het substraat aangebrachte filmvormende laag omvattende een filmvormend middel en een kleurstofbindend middel, waarbij het filmvormend middel een organische polymeer omvat, met het kenmerk dat het kleurstofbindend middel een tweewaardig metaal omvat.10 - a substrate; and a film-forming layer applied to the surface of the substrate comprising a film-forming agent and a dye-binding agent, wherein the film-forming agent comprises an organic polymer, characterized in that the dye-binding agent comprises a divalent metal. 18. Papiersamenstelling volgens conclusie 17, met het kenmerk dat het tweewaardig metaal een zout is dat wordt gekozen uit calciumchloride, magnesiumchloride, calciumbromide, magnesiumbromide, calciumnitraat, magnesiumnitraat, calcium acetaat en magnesiumacetaat, bij voorkeur wordtA paper composition according to claim 17, characterized in that the divalent metal is a salt selected from calcium chloride, magnesium chloride, calcium bromide, magnesium bromide, calcium nitrate, magnesium nitrate, calcium acetate and magnesium acetate, preferably 20 gekozen uit calciumchloride en magnesiumchloride.Selected from calcium chloride and magnesium chloride. 19. Papiersamenstelling volgens conclusie 17 of 18, met het kenmerk dat het organische polymeer een hydrofiele polymeer omvat.Paper composition according to claim 17 or 18, characterized in that the organic polymer comprises a hydrophilic polymer. 25 20. Papiersamenstelling volgens conclusie 19, met het kenmerk dat de hydrofiel polymeer wordt gekozen uit polyvinylalcohol, polydiallyldimethylammoniumchloride, polyethyleenimine, zetmeel en cellulose polymeren met inbegrip van cellulosenitraat, celluloseacetaat butyraat, methylcellulose, ethyl cellulose en carboxymethylcellulose.20. A paper composition according to claim 19, characterized in that the hydrophilic polymer is selected from polyvinyl alcohol, polydiallyldimethylammonium chloride, polyethylene imine, starch and cellulose polymers including cellulose nitrate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose and carboxymethyl cellulose. 21. Papiersamenstelling volgens één der conclusies 17-20, met het kenmerk dat het kleurstofbindend middel een geladen polymeer, bij voorkeur een kationisch polymeer, omvat.A paper composition according to any one of claims 17-20, characterized in that the dye-binding agent comprises a charged polymer, preferably a cationic polymer. 22. Papiersamenstelling volgens één der conclusies 17-21, met het kenmerk dat de samenstelling een apprêteermiddel omvat.Paper composition according to any one of claims 17-21, characterized in that the composition comprises an extractant. 23. Papiersamenstelling volgens één der conclusies 16-22, met het kenmerkPaper composition according to one of claims 16 to 22, characterized in that 5 dat het substraat een op papier gebaseerd substraat omvat.5 that the substrate comprises a paper-based substrate. 24. Papiersamenstelling volgens één der conclusies 16-23, met het kenmerk dat het substraat ten minste 25 g/m2 papier omvat, ten minste 40 g/m2 of ten minste 55 tot 90 g/m2.A paper composition according to any one of claims 16 to 23, characterized in that the substrate comprises at least 25 g / m 2 of paper, at least 40 g / m 2 or at least 55 to 90 g / m 2 . 25. Papiersamenstelling volgens één der conclusies 16-24, met het kenmerk dat het substraat een intern apprêteermiddel omvat.The paper composition according to any of claims 16 to 24, characterized in that the substrate comprises an internal sizing agent. 26. Papiersamenstelling volgens conclusie 25, met het kenmerk dat het internPaper composition according to claim 25, characterized in that it is internal 15 apprêteermiddel wordt gekozen uit alkylketeendimeer en alkenylbarnsteenzuuranhydride.Sizing agent is selected from alkyl ketone dimer and alkenyl succinic anhydride. 27. Papiersamenstelling volgens conclusie 25 of 26, met het kenmerk dat het substraat 0,50 tot 2,00 kg/ton intern apprêteermiddel omvat, bij voorkeur 0,75 totA paper composition according to claim 25 or 26, characterized in that the substrate comprises 0.50 to 2.00 kg / ton of internal sizing agent, preferably 0.75 to 20 1,50 kg/ton, bij meer voorkeur ongeveer 1,35 kg/ton.1.50 kg / ton, more preferably about 1.35 kg / ton. 28. Papiersamenstelling volgens één der conclusies 16-27, met het kenmerk dat de porositeit van de papiersamenstelling ten minste 100 ml/min bedraagt, bij voorkeur ten minste 150 ml/min, bij meer voorkeur ten minste 200 ml/min.A paper composition according to any one of claims 16-27, characterized in that the porosity of the paper composition is at least 100 ml / min, preferably at least 150 ml / min, more preferably at least 200 ml / min. 29. Papiersamenstelling volgens één der conclusies 16-28, met het kenmerk dat de papiersamenstelling 0,05 tot 1,00 g/m2 tweewaardig metaal omvat, bij voorkeur 0,08 tot 0,75 g/m2, bij meer voorkeur 0,30 tot 0,60 g/m2.A paper composition according to any one of claims 16-28, characterized in that the paper composition comprises 0.05 to 1.00 g / m 2 divalent metal, preferably 0.08 to 0.75 g / m 2 , more preferably 0 , 30 to 0.60 g / m 2 . 30 30. Papiersamenstelling volgens één der conclusies 16-29, met het kenmerk dat de verhouding van het tweewaardig metaal en het filmvormende middel 1 : 1 tot 1 :3 bedraagt.30. A paper composition according to any one of claims 16-29, characterized in that the ratio of the divalent metal and the film-forming agent is 1: 1 to 1: 3. 31. Papiersamenstelling volgens één der conclusies 16-30, met het kenmerkA paper composition according to any one of claims 16-30, characterized in that 35 dat het oppervlak van de te bedrukken zijde van het substraat is voorzien van de filmvormende laag.35 that the surface of the side of the substrate to be printed is provided with the film-forming layer. 32. Gebruik van de papiersamenstelling volgens één der conclusies 16-31 voor toepassing als transferpapier in een werkwijze voor het bedrukken van eenUse of the paper composition according to any of claims 16 to 31 for use as a transfer paper in a method of printing a paper 5 oppervlak van een dragermateriaal, anders dan papier, middels transferdruk.5 surface of a carrier material, other than paper, by transfer printing. 33. Gebruik volgens conclusie 32, met het kenmerk dat de werkwijze thermische sublimatie omvat.Use according to claim 32, characterized in that the method comprises thermal sublimation. 10 34. Gebruik volgens conclusie 32 of 33, met het kenmerk dat het dragermateriaal textiel omvat.34. Use as claimed in claim 32 or 33, characterized in that the carrier material comprises textile. 35. Gebruik volgens één der conclusies 32-34, met het kenmerk dat het dragermateriaal polyester omvat.Use according to any one of claims 32 to 34, characterized in that the carrier material comprises polyester. 36. Werkwijze voor het bedrukken van de papiersamenstelling volgens één der conclusies 16-31, omvattende de stappen:A method for printing on the paper composition according to any of claims 16-31, comprising the steps of: i. het verschaffen van een papiersamenstelling volgens één der conclusies 16-31;i. providing a paper composition according to any of claims 16-31; 20 ii. het verschaffen van een waterige dispersie van een sublimeerbare inkt; en iii. het bedrukken van de van filmvormende laag voorziene zijde van de in stap i verschafte papiersamenstelling met de in stap ii verschafte waterige dispersie.Ii. providing an aqueous dispersion of a sublimable ink; and iii. printing the film-coated side of the paper composition provided in step i with the aqueous dispersion provided in step ii. 37. Werkwijze volgens conclusie 36, met het kenmerk dat stap iii wordtThe method according to claim 36, characterized in that step iii 25 uitgevoerd met behulp van een inkjetprinter.25 performed with the aid of an inkjet printer. 38. Werkwijze voor het bedrukken van een oppervlak van een dragermateriaal anders dan papier, omvattende de stappen:38. A method for printing on a surface of a carrier material other than paper, comprising the steps of: iv. het verschaffen van een met een waterige dispersie van een sublimeerbareiv. providing a sublimable with an aqueous dispersion 30 inkt bedrukte papiersamenstelling volgens de werkwijze volgens conclusie 36 of 37;An ink-printed paper composition according to the method according to claim 36 or 37; v. het verschaffen van een dragermateriaal anders dan papier;v. providing a carrier material other than paper; vi. het transfereren van de sublimeerbare inkt op het oppervlak van het dragermateriaal.vi. transferring the sublimable ink to the surface of the carrier material. 39. Werkwijze volgens conclusie 38, met het kenmerk dat het dragermateriaal textiel omvat.A method according to claim 38, characterized in that the carrier material comprises textile. 40. Werkwijze volgens conclusie 38 of 39, met het kenmerk dat hetA method according to claim 38 or 39, characterized in that the 5 dragermateriaal polyester omvat.Carrier material comprises polyester. 41. Werkwijze volgens één der conclusies 38-40, met het kenmerk dat stap vi thermische sublimatie betreft.A method according to any one of claims 38-40, characterized in that step vi relates to thermal sublimation.
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