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WO2018139925A1 - Paper composition for transfer printing - Google Patents

Paper composition for transfer printing Download PDF

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Publication number
WO2018139925A1
WO2018139925A1 PCT/NL2018/050054 NL2018050054W WO2018139925A1 WO 2018139925 A1 WO2018139925 A1 WO 2018139925A1 NL 2018050054 W NL2018050054 W NL 2018050054W WO 2018139925 A1 WO2018139925 A1 WO 2018139925A1
Authority
WO
WIPO (PCT)
Prior art keywords
paper
composition
film forming
substrate
composition according
Prior art date
Application number
PCT/NL2018/050054
Other languages
French (fr)
Inventor
Johannes Godefridus ROPS
Bernardus Johannes WESSELINK
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.
Publication of WO2018139925A1 publication Critical patent/WO2018139925A1/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

Definitions

  • 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 with sublimable ink and subsequently transferring the sublimable ink to the surface of a support material other than paper by means of dye sublimation.
  • Transfer paper is used for indirectly printing support material made of fabric or other materials by first printing the paper and the transferring the mirror image to the surface of the receiving support material.
  • Support material may comprises polyester, in particular fabric, or material having a polyester coating.
  • a transfer printing method wherein the molecules of the dyes infuse into the support material, e.g. polyester, is commonly called dye sublimation printing.
  • common printing techniques e.g. Inkjet, flexographic, offset, intaglio, or rotary screen printing, a pattern, design or printing image is applied to the paper.
  • the ink is thin-fluid or in the form of a pasty mass.
  • the ink or paste contains sublimable components, i.e. sublimable dyes, which provide the colour of the ink or past.
  • sublimable dyes which provide the colour of the ink or past.
  • the sublimable dyes of the ink are subsequently transferred, in the transfer process, onto the surface that is eventually to be printed.
  • the temperatures common for transferring the dyes are within the range of from about 160°C to about 220°C.
  • transfer efficiency is typically measured in the field by visual comparison and based on colour measurement of the printed result.
  • 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%.
  • 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, preferably a cationic polymer selected from the group consisting of polyamines and polyimines, and the dye-fixing agent comprises a water soluble divalent metal salt.
  • the composition of the present invention does not comprise starch nanoparticles having an average particle size of 500 nm or less. It was found that by providing the composition of the present invention the transfer efficiency of a substrate surface treated with the composition of the present invention is significantly increased.
  • the porosity of the surface treated substrate is no longer subject to further restrictions.
  • the porosity of the surface treated substrate may be 100 ml/min or higher.
  • the concentration of the water soluble divalent metal salt in the composition is chosen such that after treating the substrate the divalent metal is present at an amount of at least 2.0 mmol/m 2 .
  • the concentration of the water soluble divalent metal salt can be less than 2.0 mmol/m 2 in case the film forming agent comprises a cationic polymer selected from the group consisting of polyamines and polyimines.
  • the dye-fixing agent comprised in the composition of the present invention is immobilising sublimable dyes in a fast and reliable manner on top of the surface of the treated substrate, while easily allowing the aqueous medium to be absorbed and thus enhancing the efficient release of the fixed sublimable dyes to any support material (other than paper) when heat and pressure is applied, without the need to have a very low porosity to prevent, so called, ghosting.
  • the term 'ghosting' is used to describe the process of sublimable dye migrating to the opposite side of the transfer paper and, as a result of, polluting the transfer equipment, depositing as a vague second print on another part of the support material.
  • water soluble divalent salts include, but are not limited to, calcium chloride, magnesium sulfate, calcium acetate, calcium acetate hydrate, calcium acetate monohydrate, magnesium acetate, magnesium acetate tetrahydrate, calcium propionate, calcium propionate hydrate, calcium gluconate monohydrate, and calcium formate and other such salts, anhydrous or hydrated forms.
  • the divalent metal may be a cation selected from the group consisting of Mg 2+ , Ca 2+ , Ba 2+ and Zn 2+ . Divalent cations such as Mg 2+ and Ca 2+ might be particularly useful. Combinations of cations may also be used.
  • divalent metal salts used in the composition include, but are not limited to, calcium chloride, calcium acetate, calcium nitrate, calcium pantothenate, magnesium chloride, magnesium acetate, magnesium nitrate, magnesium sulfate, barium chloride, barium nitrate, zinc chloride and zinc nitrate.
  • Divalent metal salt might include CaCI 2 , MgCI 2 , MgS0 4 , Ca(N0 3 ) 2 , and Mg(N0 3 )2, including hydrated versions of these salts.
  • the water soluble divalent or multi-valent salt may be selected from the group consisting of calcium acetate, calcium acetate hydrate, calcium acetate monohydrate, magnesium acetate, magnesium acetate tetrahydrate, calcium propionate, calcium propionate hydrate, calcium gluconate monohydrate, calcium formate and combinations thereof.
  • any divalent metal salt having a solubility in water (at room temperature) of at least 0.01 mol/L, preferably having a solubility in water of at least 0.1 mol/L, are suitable for use in the composition of the present invention.
  • the water soluble divalent metal salt may be selected from the group consisting of calcium chloride, magnesium chloride, calcium bromide, magnesium bromide, calcium nitrate, magnesium nitrate, calcium acetate and magnesium acetate.
  • 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.
  • a sulphate salt may be added as well, e.g. calcium sulphate and/or magnesium sulphate.
  • the film forming agent may be selected from the group consisting of hydrophilic polymers, 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.
  • hydrophilic polymers 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.
  • starch may be selected as a suitable hydrophilic polymer being a less expensive alternative.
  • the composition may further comprise a charged polymer, preferably a cationic polymer.
  • the charged polymer may comprise a polyamine and/or polyimine.
  • diamine or diimine based polymers are used as cationic polymers, as they do not significantly influence the rheological properties of the surface treatment. Excellent fixation of dyes is reached by diamine based polymers. It was found that the use of a combination of cationic polymer and divalent metal salt results in a synergistic effect in enhancing transfer efficiency compared to the effect on transfer efficiency of the components not in combination with each other.
  • 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 ink jet printing.
  • a surface sizing agent such as modified starches, styrene maleic anhydride, styrene acrylic emulsion, styrene acrylic acid, ethylene acrylic acid, gelatine and
  • composition of the present invention is preferably an aqueous solution.
  • the aqueous solution is acidic or slightly alkaline 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 providing the film forming agent and the dye-fixing agent, mixing the film forming agent and dye-fixing agent in an acidic to slightly alkaline aqueous medium.
  • the medium preferably having a pH of between 1.0 to 8.0.
  • 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.
  • the method may further comprise mixing a surface sizing agent together with the film forming agent and dye-fixing agent.
  • a 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 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.
  • 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.
  • the method for surface treating a substrate e.g. a paper
  • 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 one 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.
  • the dry weight of the composition provided in step a) is 0.50 to 2.3 g/m 2 .
  • the dry weight of the composition provided in step a) is 0.70 to 2.0 g/m 2 , even more preferred 0.90 to 1 .8 g/m 2 .
  • the dry weight of the composition provided may vary.
  • the dry weight of the composition provided in step a) is preferably about 1 .1 to 1 .8 g/m 2
  • the dry weight of the composition provided in step a) is preferably about 1.1 g/m 2
  • 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, preferably a cationic polymer selected from the group consisting of polyamines and polyimines, and the dye-fixing agent comprises a divalent metal.
  • the film forming layer does not comprise starch nanoparticles having an average particle size of 500 nm or less.
  • the concentration of the divalent metal is present at an amount of at least 2.0 mmol/m 2 .
  • the concentration of the divalent metal can be less than 2.0 mmol/m 2 in case the film forming layer comprises a cationic polymer selected from the group consisting of polyamines and polyimines.
  • 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.
  • a paper composition wherein a film forming layer is applied to the surface of the substrate comprising an organic polymer, preferably a cationic polymer, and a divalent metal, sublimable dyes are immobilised on top of the surface of the paper composition comprising the film forming layer in a fast and efficient manner, whereas any further ink material, e.g. an aqueous medium such as water, is absorbed by the substrate. Because the sublimable dyes are quickly immobilised, excessive dot gain and uncontrolled conglomeration of dyes is stopped.
  • 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.
  • dye-fixing agent comprising a divalent metal, optionally in combination with a cationic polymer selected from the group consisting of polyamines and polyimines, embedded in the film forming layer acts as protective agent against ghosting as described above.
  • the divalent metal of the paper composition according to the present invention may be a salt as stated above.
  • 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.
  • the divalent metal is a chloride salt, e.g.
  • the film forming agent 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.
  • a film forming agent being a hydrophilic polymer
  • starch may be selected as a suitable hydrophilic polymer being a less expensive alternative.
  • the film forming layer may further comprising a charged polymer, preferably a cationic polymer.
  • the charged polymer may comprise a polyamine and/or polyimine.
  • diamine or diimine based polymers are used as cationic polymers, as they do not significantly influence the rheological properties of the surface treatment. Excellent fixation of dyes is reached by diamine based polymers. It was found that the use of a combination of cationic polymer and divalent metal salt results in a synergistic effect in enhancing transfer efficiency compared to the effect on transfer efficiency of the components not in combination with each other.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • a higher sublimable dye-divalent metal binding efficacy is achieved by providing a paper composition comprising a substrate having an internal sizing agent.
  • a paper composition having a higher sublimable dye-divalent metal binding efficacy optionally in combination with a cationic polymer selected from the group consisting of polyamines polyimines, 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 wood free papers, synthetic paper and regenerated paper. More generally, the terms 'paper-based substrate' is meant to encompass a substrate based on cellulosic and/or lingo 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.
  • a substrate may have a thickness of 0.025 mm to 0.75 mm, depending on a desired end application for the paper composition the substrate is used for.
  • the substrate of the present invention may comprise at least 25 g/m 2 paper, at least 35 g/m 2 paper, at least 45 g/m 2 paper or at least 55 g/m 2 paper.
  • Preferred ranges for the substrate are for example 25 to 150 g/m 2 paper, 40 to 125 g/m 2 paper and 45 to 90 g/m 2 paper. It was found that even with paper compositions comprising a substrate having a low grammage, e.g. between 25 to 55 g/m 2 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/m 2 paper, about 40 g/m 2 paper or about 55 g/m 2 paper.
  • the substrate of the paper composition of the present invention may comprise 0.20 to 2.00 kg/tonne internal sizing agent, preferably 0.50 to 1.70 kg/tonne, more preferably 0.70 to 1 .50 kg/tonne.
  • 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. In an embodiment of the present invention the paper composition may have a porosity between 120 and 300 ml/min, more preferably between 130 and 280 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.
  • the paper composition preferably comprises at least 2.0 mmol/m 2 divalent metal, preferably between 2.5 to 10 mmol/m 2 divalent metal, preferably between 3.0 to 7.0 mmol/m 2 and more preferably between 4.0 to 6.0 mmol/m 2 divalent metal. In a particular preferred embodiment, the paper composition comprises about 5.5 mmol/m 2 divalent metal.
  • a preferred dry weight (g/m 2 ) ratio of divalent metal to film forming agent is between 2 : 1 to 1 : 4, preferably 3 : 2 to 1 : 3.
  • the preferred dry weight (g/m 2 ) ratio of water soluble divalent metal salt to film forming agent is between 1 : 1 to 1 : 3, preferably about 1 : 2.
  • the surface of the substrate on the side to be printed is provided with the film forming layer of the present invention.
  • the opposite surface of the substrate may be provided with the same or a similar film forming layer in order to further reduce the 'ghosting effect'.
  • additional layer is not necessarily required.
  • the film forming layer provided on the side to be printed has sufficient binding properties to retain the sublimable dyes on the treated surface of the paper composition and to prevent migration of the sublimable dyes through the substrate.
  • 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.
  • the transfer printing method comprises thermal dye 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 polyester or materials coated with 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
  • the support material may comprise polyester or material coated with polyester.
  • the transfer of the sublimable ink to the surface of the support material in step vi) is preferably performed by using thermal dye
  • Paper compositions (A-E) without internal sizing agent and paper composition (F- M) with internal sizing agent were printed with dye sublimation ink, transferred onto a fabric comprising polyester and the transfer print was evaluated for transfer efficiency (in descending order or importance of L * value green, a * value red and L * value blue), print uniformity (visual appearance of mottle) and print quality (visual appearance of print definition and feathering).
  • the Roughness Bendtsen and Porosity Bendtsen of the paper compositions was measured using, respectively, ISO 8791 -2:2013 and ISO 5636-3:2013 methods.
  • a '++' score for transfer efficiency corresponds to a transfer efficiency of at least 65%
  • a '++++' score for transfer efficiency corresponds to a transfer efficiency of at least 90%.
  • Table 1 Measured and visually inspected transfer efficiency, print quality and uniformity of surface treated and surface untreated paper compositions without internal sizing agent.
  • Table 2 Measured and visually inspected transfer efficiency, print quality and uniformity of surface treated and surface untreated paper compositions with internal sizing agent.
  • composition B efficient transfer paper
  • composition C comprising 0.17 g/m 2 divalent salt (corresponds to 1 .50 mmol/m 2 divalent salt/divalent metal) and a cationic polymer also showed good results on transfer efficiency, whereas a similar composition (not included in table 1 ) comprising 0.18 g/m 2 divalent metal salt (corresponds to 1.62 mmol/m 2 divalent salt/divalent metal) with a coating not comprising a cationic polymer, showed bad results on transfer efficiency.
  • the amount of divalent metal may be varied to result in a transfer paper having at least 65% of transfer efficiency.
  • the presence of an internal sizing agent did result in an increase of transfer efficiency providing paper compositions with a transfer efficiency of at least 90%

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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, preferably a cationic polymer selected from the group consisting of polyamines and polyimines, 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

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 with sublimable ink and subsequently transferring the sublimable ink to the surface of a support material other than paper by means of dye sublimation.
Transfer paper is used for indirectly printing support material made of fabric or other materials by first printing the paper and the transferring the mirror image to the surface of the receiving support material. Support material may comprises polyester, in particular fabric, or material having a polyester coating. A transfer printing method wherein the molecules of the dyes infuse into the support material, e.g. polyester, is commonly called dye sublimation printing. To this end, by means of common printing techniques, e.g. Inkjet, 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 components, i.e. sublimable dyes, which provide the colour of the ink or past. By means of heat and pressure, the sublimable dyes 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. Transfer efficiency is typically measured in the field by visual comparison and based on colour measurement of the printed result.
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, preferably a cationic polymer selected from the group consisting of polyamines and polyimines, and the dye-fixing agent comprises a water soluble divalent metal salt. The composition of the present invention does not comprise starch nanoparticles having an average particle size of 500 nm or less. It was found that by providing the composition of the present invention 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. It was found that in case the film forming agent comprises an organic polymer, not being a polyamine and/or polyimine, the concentration of the water soluble divalent metal salt in the composition is chosen such that after treating the substrate the divalent metal is present at an amount of at least 2.0 mmol/m2. The concentration of the water soluble divalent metal salt can be less than 2.0 mmol/m2 in case the film forming agent comprises a cationic polymer selected from the group consisting of polyamines and polyimines.
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. Further it was found that the substrate treated with the composition of the present invention resulted in a transfer paper having quick, rub free, dye fixation during printing of the transfer paper. Without wishing to be bound by theory, it is believed that the dye-fixing agent comprised in the composition of the present invention is immobilising sublimable dyes in a fast and reliable manner on top of the surface of the treated substrate, while easily allowing the aqueous medium to be absorbed and thus enhancing the efficient release of the fixed sublimable dyes to any support material (other than paper) when heat and pressure is applied, without the need to have a very low porosity to prevent, so called, ghosting. The term 'ghosting' is used to describe the process of sublimable dye migrating to the opposite side of the transfer paper and, as a result of, polluting the transfer equipment, depositing as a vague second print on another part of the support material.
Examples of water soluble divalent salts include, but are not limited to, calcium chloride, magnesium sulfate, calcium acetate, calcium acetate hydrate, calcium acetate monohydrate, magnesium acetate, magnesium acetate tetrahydrate, calcium propionate, calcium propionate hydrate, calcium gluconate monohydrate, and calcium formate and other such salts, anhydrous or hydrated forms. The divalent metal may be a cation selected from the group consisting of Mg2+, Ca2+, Ba2+ and Zn2+. Divalent cations such as Mg2+ and Ca2+ might be particularly useful. Combinations of cations may also be used.
Specific examples of the divalent metal salts used in the composition include, but are not limited to, calcium chloride, calcium acetate, calcium nitrate, calcium pantothenate, magnesium chloride, magnesium acetate, magnesium nitrate, magnesium sulfate, barium chloride, barium nitrate, zinc chloride and zinc nitrate. Divalent metal salt might include CaCI2, MgCI2, MgS04, Ca(N03)2, and Mg(N03)2, including hydrated versions of these salts. In some examples, the water soluble divalent or multi-valent salt may be selected from the group consisting of calcium acetate, calcium acetate hydrate, calcium acetate monohydrate, magnesium acetate, magnesium acetate tetrahydrate, calcium propionate, calcium propionate hydrate, calcium gluconate monohydrate, calcium formate and combinations thereof. In general, any divalent metal salt having a solubility in water (at room temperature) of at least 0.01 mol/L, preferably having a solubility in water of at least 0.1 mol/L, are suitable for use in the composition of the present invention.
Preferably, the water soluble divalent metal salt may be 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 film forming agent may be selected from the group consisting of hydrophilic polymers, 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 embedded 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 composition may further comprise a charged polymer, preferably a cationic polymer. The charged polymer may comprise a polyamine and/or polyimine.
Preferably diamine or diimine based polymers are used as cationic polymers, as they do not significantly influence the rheological properties of the surface treatment. Excellent fixation of dyes is reached by diamine based polymers. It was found that the use of a combination of cationic polymer and divalent metal salt results in a synergistic effect in enhancing transfer efficiency compared to the effect on transfer efficiency of the components not in combination with each other.
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 ink jet 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 acidic or slightly alkaline 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 providing the film forming agent and the dye-fixing agent, mixing the film forming agent and dye-fixing agent in an acidic to slightly alkaline aqueous medium. In an embodiment of the present invention the 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 one 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 .1 to 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, preferably a cationic polymer selected from the group consisting of polyamines and polyimines, and the dye-fixing agent comprises a divalent metal. The film forming layer does not comprise starch nanoparticles having an average particle size of 500 nm or less. In case the film forming layer comprises an organic polymer, not being a polyamine and/or polyimine, the concentration of the divalent metal is present at an amount of at least 2.0 mmol/m2. The concentration of the divalent metal can be less than 2.0 mmol/m2 in case the film forming layer comprises a cationic polymer selected from the group consisting of polyamines and polyimines.
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, preferably a cationic polymer, and a divalent metal, sublimable dyes are immobilised on top of the surface of the paper composition comprising the film forming layer in a fast and efficient manner, whereas any further ink material, e.g. an aqueous medium such as water, is absorbed by the substrate. Because the sublimable dyes are quickly immobilised, excessive dot gain and uncontrolled conglomeration of dyes is stopped. Consequently, phenomena like line growth, ink bleed and/or ink feathering are further reduced, resulting in excellent definition, allowing high resolution print settings 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, dye-fixing agent comprising a divalent metal, optionally in combination with a cationic polymer selected from the group consisting of polyamines and polyimines, embedded in the film forming layer acts as protective agent against ghosting as described above. The divalent metal of the paper composition according to the present invention may be a salt as stated above. Preferably, 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 film forming agent 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 film forming layer may further comprising a charged polymer, preferably a cationic polymer. The charged polymer may comprise a polyamine and/or polyimine. Preferably diamine or diimine based polymers are used as cationic polymers, as they do not significantly influence the rheological properties of the surface treatment. Excellent fixation of dyes is reached by diamine based polymers. It was found that the use of a combination of cationic polymer and divalent metal salt results in a synergistic effect in enhancing transfer efficiency compared to the effect on transfer efficiency of the components not in combination with each other.
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 interact with the dye-fixing agent 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, optionally in combination with a cationic polymer selected from the group consisting of polyamines polyimines, 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 wood free papers, synthetic paper and regenerated paper. More generally, the terms 'paper-based substrate' is meant to encompass a substrate based on cellulosic and/or lingo 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 0.025 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, 40 to 125 g/m2 paper and 45 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 0.20 to 2.00 kg/tonne internal sizing agent, preferably 0.50 to 1.70 kg/tonne, more preferably 0.70 to 1 .50 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. In an embodiment of the present invention the paper composition may have a porosity between 120 and 300 ml/min, more preferably between 130 and 280 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 at least 2.0 mmol/m2 divalent metal, preferably between 2.5 to 10 mmol/m2 divalent metal, preferably between 3.0 to 7.0 mmol/m2 and more preferably between 4.0 to 6.0 mmol/m2 divalent metal. In a particular preferred embodiment, the paper composition comprises about 5.5 mmol/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 (g/m2) ratio of divalent metal to film forming agent is between 2 : 1 to 1 : 4, preferably 3 : 2 to 1 : 3.
With regard to the composition of the present invention for surface treating a substrate, it was found that the preferred dry weight (g/m2) ratio of water soluble divalent metal salt to film forming agent is between 1 : 1 to 1 : 3, preferably about 1 : 2.
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 of the present invention. Optionally, the opposite surface of the substrate may be provided with the same or a similar film forming layer in order to further reduce the 'ghosting effect'. However, such additional layer is not necessarily required. As already stated above, the film forming layer provided on the side to be printed has sufficient binding properties to retain the sublimable dyes on the treated surface of the paper composition and to prevent migration of the sublimable dyes through the substrate.
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 dye 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 polyester or materials coated with 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 polyester or material coated with polyester. Also, the transfer of the sublimable ink to the surface of the support material in step vi) is preferably performed by using thermal dye
sublimation.
The invention will now be further illustrated with reference to the following examples.
Examples
Paper compositions (A-E) without internal sizing agent and paper composition (F- M) with internal sizing agent were printed with dye sublimation ink, transferred onto a fabric comprising polyester and the transfer print was evaluated for transfer efficiency (in descending order or importance of L* value green, a* value red and L* value blue), print uniformity (visual appearance of mottle) and print quality (visual appearance of print definition and feathering).
To evaluate transfer efficiency the green, red and blue secondary (mix colours) on the polyester fabric were measured using an X-RITE®939 Spectro-densitometer.
The Roughness Bendtsen and Porosity Bendtsen of the paper compositions was measured using, respectively, ISO 8791 -2:2013 and ISO 5636-3:2013 methods.
The results of the measured values and visual inspection of the different compositions are shown in tables 1 and 2. For the visual inspection, the following scoring system was used:
= 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%.
Table 1 . Measured and visually inspected transfer efficiency, print quality and uniformity of surface treated and surface untreated paper compositions without internal sizing agent.
Figure imgf000014_0001
Table 2. Measured and visually inspected transfer efficiency, print quality and uniformity of surface treated and surface untreated paper compositions with internal sizing agent.
Figure imgf000015_0001
Given the results provided in table 1 , it can be concluded that efficient transfer paper (composition B) is obtained using a coating comprising 0.23 g/m2 divalent salt, which corresponds to 2.07 mmol/m2 divalent salt/divalent metal. Composition C, comprising 0.17 g/m2 divalent salt (corresponds to 1 .50 mmol/m2 divalent salt/divalent metal) and a cationic polymer also showed good results on transfer efficiency, whereas a similar composition (not included in table 1 ) comprising 0.18 g/m2 divalent metal salt (corresponds to 1.62 mmol/m2 divalent salt/divalent metal) with a coating not comprising a cationic polymer, showed bad results on transfer efficiency.
Depending on the composition of the paper used, i.e. a paper composition with or without internal sizing agent, the amount of divalent metal may be varied to result in a transfer paper having at least 65% of transfer efficiency. The presence of an internal sizing agent (see: table 2) did result in an increase of transfer efficiency providing paper compositions with a transfer efficiency of at least 90%
(Compositions L and M).

Claims

Claims
1. Composition for surface treating a substrate, comprising:
a film forming agent; and
- a dye-fixing agent,
wherein:
the film forming agent comprises a cationic polymer; and
the dye-fixing agent comprises a water soluble divalent metal salt,
characterised in that the cationic polymer is selected from the group of
polyamines and polyimines.
2. Composition for surface treating a substrate, comprising:
a film forming agent; and
a dye-fixing agent,
wherein:
the film forming agent comprises an organic polymer; and
the dye-fixing agent comprises a water soluble divalent metal salt,
characterised in that the concentration of the water soluble divalent metal salt in the composition is chosen such that after treating the substrate the divalent metal is present at an amount of at least 2.0 mmol/m2,
with the proviso that the film forming agent does not comprise starch nanoparticies having an average particle size of 500 nm or less.
3. Composition according to claim 1 or 2, characterised in that the water soluble divalent metal salt is selected from the group consisting of calcium chloride, magnesium chloride, calcium bromide, magnesium bromide, calcium nitrate, magnesium nitrate, calcium acetate and magnesium acetate, preferably selected from the group consisting of calcium chloride and magnesium chloride. 4. Composition according to any of the preceding claims, characterised in that the film forming agent comprises a hydrophilic polymer.
5. Composition according to claim 4, characterised in that the hydrophilic polymer is 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.
6. Composition according to any of claims 2-5, characterised in that the composition further comprises a cationic polymer.
7. Composition according to any of the preceding claims, characterised in that the composition comprises a surface sizing agent. 8. Composition according to any of the preceding claims, characterised in that the composition comprises an aqueous solution.
9. Composition according to any of the preceding claims, characterised in that the 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.
10. Composition according to any of the preceding claims, characterised in that the composition has a viscosity of 5 to 900 mPa-s, preferably 10 to 90 mPa-s. 1 1. Method for preparing the composition as claimed in any of the preceding claims, comprising the steps of:
providing the film forming agent and dye-fixing agent; and
mixing the resulting mixture in an aqueous medium. 12. Method according to claim 11 , characterised in that the 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.
13. Method according to claim 11 or 12, characterised in that the method further comprises mixing a surface sizing agent.
14. Method for surface treating a substrate, comprising the steps of:
a) providing a composition according to any of claims 1 -10;
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). 15. Method according to claim 14, characterised in that in step c) the composition is applied to the substrate by using a roller coater, roller knife coater, blade coater, kiss roll coater, size press or film press.
16. Method according to claim 14 or 15, characterised in that the dry weight of the composition provided in step a) is 0.50 to 2.3 g/m2, preferably 0.70 to 2.0 g/m2, more preferably 0.90 to 1 .8 g/m2.
17. Paper composition for transfer printing obtainable by the method according to any of claims 14-16, characterised in that the transfer efficiency is at least 65%.
18. 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 a cationic polymer and the dye-fixing agent comprises a divalent metal,
characterised in that the cationic polymer is selected from the group of
polyamines and polyimines. 19. 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 the dye-fixing agent comprises a divalent metal,
characterised in that the divalent metal is present at an amount of at least 2.0 mmol/m2,
with the proviso that the film forming agent does not comprise starch nanoparticles having an average particle size of 500 nm or less.
20. Paper composition according to claims 18 or 19, characterised in that the divalent metal is 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 selected from the group consisting of calcium chloride and magnesium chloride.
21. Paper composition according to any of claims 18-20, characterised in that the film forming agent comprises a hydrophilic polymer. 22. Paper composition according to claim 21 , characterised in that the hydrophilic polymer is selected from the group consisting of polyvinyl alcohol, polydiallyldimethylammonium chloride, polyethylenimine, starch and ceilulosic polymers including cellulose nitrate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose and carboxymethylcellulose.
23. Paper composition according to any of claims 19-22, characterised in that the film forming layer comprises a charged polymer, preferably a cationic polymer.
24. Paper composition according to any of claims 18-23, characterised in that the composition comprises a sizing agent.
25. Paper composition according to any of claims 17-24, characterised in that the substrate comprises a paper-based substrate. 26. Paper composition according to any of claims 17-25, characterised in that the substrate comprises at least 25 g/m2 paper, at least 35 g/m2, at least 45 g/m2 or at least 55 g/m2.
27. Paper composition according to any of claims 17-26, characterised in that the substrate comprises an internal sizing agent.
28. Paper composition according to claim 27, characterised in that the internal sizing agent is selected from the group consisting of alkyl ethene dimer and alkyl succinic anhydride.
29. Paper composition according to claim 27 or 28, characterised in that the substrate comprises 0.20 to 2.00 kg/tonne internal sizing agent, preferably 0.50 to 1.70 kg/tonne, more preferably 0.70 to 1 .50 kg/tonne. 30. Paper composition according to any of claims 17-29, characterised in that the paper composition has a porosity of at least 100 ml/min, preferably at least 150 ml/min, more preferably at least 200 ml/min.
3 . Paper composition according to any of claims 17-30, characterised in that the paper composition comprises 2.5 to 10 mmol/m2 divalent metal, preferably 3.0 to 7.0 mmol/m2, more preferably 4.0 to 6.0 mmol/m2, most preferred about 5.5 mmol/m2.
32. Paper composition according to any of claims 17-31 , characterised in that the dry weight ratio of divalent metal to film forming agent is 2 : 1 to 1 : 4, preferably
3 : 2 to 1 : 3.
33. Paper composition according to any of claims 17-32, characterised in that the surface of the substrate on the side to be printed is provided with the film forming layer.
34. Use of the paper composition according to any of claims 17-33 for application as a transfer paper in a method for printing a surface of a support material other than paper, by means of transfer printing.
35. Use according to claim 34, characterised in that the method comprises thermal dye sublimation.
36. Use according to claim 34 or 35, characterised in that the support material comprises polyester or materials coated with polyester.
37. Method for printing the paper composition according to any of claims 17-33, comprising the steps of:
i. providing a paper composition according to any of claims 17-33;
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.
38. Method according to claim 37, characterised in that step iii is performed by using an inkjet printer.
39. 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 according the method of claim 37 or 38;
v. providing a support material other than paper; and
vi. transferring the sublimable ink to the surface of the support material.
40. Method according to claim 39, characterised in that the support material comprises polyester or material coated with polyester.
41. Method according to claim 39 or 40, characterised in that step vi comprises thermal sublimation.
PCT/NL2018/050054 2017-01-27 2018-01-25 Paper composition for transfer printing WO2018139925A1 (en)

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