EP3046778B1 - Films de transfert thermique pour la peinture à sec de surfaces - Google Patents

Films de transfert thermique pour la peinture à sec de surfaces Download PDF

Info

Publication number
EP3046778B1
EP3046778B1 EP14766739.8A EP14766739A EP3046778B1 EP 3046778 B1 EP3046778 B1 EP 3046778B1 EP 14766739 A EP14766739 A EP 14766739A EP 3046778 B1 EP3046778 B1 EP 3046778B1
Authority
EP
European Patent Office
Prior art keywords
radiation
curable
layer
thermal transfer
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP14766739.8A
Other languages
German (de)
English (en)
Other versions
EP3046778A1 (fr
EP3046778B2 (fr
Inventor
Manfred Biehler
Dieter Litzcke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LS INDUSTRIELACKE GmbH
BASF SE
Original Assignee
LS Industrielacke GmbH
BASF SE
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=49237045&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3046778(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by LS Industrielacke GmbH, BASF SE filed Critical LS Industrielacke GmbH
Priority to NO14766739A priority Critical patent/NO3046778T3/no
Priority to SI201430640T priority patent/SI3046778T1/en
Priority to PL14766739.8T priority patent/PL3046778T5/pl
Priority to EP14766739.8A priority patent/EP3046778B2/fr
Publication of EP3046778A1 publication Critical patent/EP3046778A1/fr
Publication of EP3046778B1 publication Critical patent/EP3046778B1/fr
Application granted granted Critical
Publication of EP3046778B2 publication Critical patent/EP3046778B2/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/38242—Contact thermal transfer or sublimation processes characterised by the use of different kinds of energy to effect transfer, e.g. heat and light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/12—Transfer pictures or the like, e.g. decalcomanias
    • 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
    • B41M5/38207—Contact thermal transfer or sublimation processes characterised by aspects not provided for in groups B41M5/385 - B41M5/395
    • B41M5/38214—Structural details, e.g. multilayer systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
    • B44C1/1729—Hot stamping techniques
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/06—Printing methods or features related to printing methods; Location or type of the layers relating to melt (thermal) mass transfer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/10—Post-imaging transfer of imaged layer; transfer of the whole imaged layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/30—Thermal donors, e.g. thermal ribbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging

Definitions

  • the present invention relates to thermal transfer films and their use for the dry coating of surfaces.
  • the invention also relates to the production of such thermal transfer films and to a process for coating or coating surfaces of articles using the thermal transfer films according to the invention.
  • a liquid lacquer is applied to the surface to be coated and then dried, whereby a lacquer layer is formed on the surface.
  • the coating is usually carried out in Lackierstra- Shen, wherein for drying regularly longer dry sections are necessary, in which the paint is dried and cured with relatively high energy consumption.
  • Such methods are therefore time, energy and also staff-intensive.
  • the coating devices of the paint lines must be cleaned, resulting in service life.
  • the waste generated when cleaning the machines must be disposed of as special waste.
  • thermo transfer foils These films comprise a carrier film on which one or more polymer layers and optionally an adhesive layer are arranged.
  • the at least one polymer layer is transferred by means of pressure and / or heat from the carrier film to the surface to be coated.
  • the at least one polymer layer on the surface to be coated forms a lacquer layer without having to use organic solvents in the coating process.
  • the EP 573676 describes a method of applying a varnish with a paint on a substrate, for example on wood or plastic surfaces, in which a film is used, which applied to a support with release properties decorative layer and applied to the decorative layer partially crosslinked varnish layer having.
  • the film is applied with the lacquer layer on the surface to be coated and transferred by pressure and elevated temperature with the decorative layer on the surface, which at the same time comes to a curing of the lacquer layer.
  • paints thermally curable coatings are used. Due to the high temperatures required in the process during paint curing, the choice of substrates is severely restricted.
  • Thermal transfer films which have a decorative layer arranged on a carrier layer and a heat-activatable adhesive layer arranged on the decorative layer, wherein the carrier layer has a metallic functional layer lying directly on the decorative layer, which facilitates the detachment of the decorative layer from the carrier layer and thus an improved transfer of the To ensure decorative layer on the substrate. Due to the metallization is limited in the decorative layer.
  • thermal transfer films which are suitable for the coating of surfaces and which have a base coat layer, a colored decorative layer and an adhesive bonding layer bonded to a carrier film, are based on aqueous coating systems which contain heat-drying aqueous polymer dispersions as binders.
  • the surface hardness and abrasion resistance of the resulting coatings are often unsatisfactory. High abrasion resistant coatings can not be obtained with the thermal transfer films described there.
  • EP-A-0 210 620 describes methods for producing a textured varnish layer comprising film.
  • the EP 2078618 describes thermal transfer films comprising at least one topcoat layer disposed on a carrier film and a thermally activatable adhesive layer, wherein the topcoat layer is preferably based on an aqueous coating composition containing a UV-curable, dispersed polyurethane.
  • the thermal transfer foils described there lead to an improved surface hardness in comparison with thermal transfer foils whose lacquer layers are based on heat-drying aqueous polymer dispersions. For some applications, however, this is not satisfactory.
  • the use of aqueous coating compositions is associated with increased drying costs in the production of the thermal transfer films.
  • the coatings described therein are not always satisfactory in terms of abrasion resistance and surface properties. High abrasion resistant coatings can not be obtained with the thermal transfer films described there.
  • thermal transfer films which have at least one lacquer layer arranged on the carrier film and which are based on a non-aqueous radiation-curable, liquid composition which is at least 60% by weight, in particular at least 70% by weight, based on the total weight of the composition containing crosslinkable components selected from organic oligomers having ethylenically unsaturated double bonds and mixtures of these oligomers with monomers having at least one ethylenically unsaturated double bond and having a heat-sealable polymeric adhesive layer (4) containing at least one radiation-curable component contains, are particularly suitable for coating surfaces.
  • crosslinkable components selected from organic oligomers having ethylenically unsaturated double bonds and mixtures of these oligomers with monomers having at least one ethylenically unsaturated double bond and having a heat-sealable polymeric adhesive layer (4) containing at least one radiation-curable component contains
  • non-aqueous, radiation-curable coating compositions with a high proportion of crosslinkable components allows the targeted adaptation of the thermal transfer film for different substrates, namely for both hard as well as highly elastic substrates.
  • the temperature load of the material to be coated during transfer of the lacquer layer (s) on the surface to be coated is comparatively low, since a final curing easily by irradiating the coated surface with high-energy radiation such as UV or electron radiation can be performed and no subsequent annealing is necessary.
  • the radiation-curable, liquid compositions used for the preparation of the lacquer layer contain at least 60 wt .-%, in particular at least 70 wt .-%, z. B. 60 to 99 wt .-%, in particular 70 to 95 wt .-%, based on the total weight of the composition, curable components which have ethylenically unsaturated double bonds.
  • the constituents are preferably selected such that 1.5 to 8 mol, in particular 2.0 to 7 mol, and especially 2.5 to 6.5 mol, of ethylenically unsaturated double bonds per kg of the coating composition are present in the composition.
  • the ethylenically unsaturated double bonds of the curable constituents of the liquid, radiation-curable composition which forms the lacquer layer are preferably in the form of acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular at least 90% or 100%, based on the total amount the ethylenically unsaturated double bonds present in the composition, in the form of acrylic or methacrylic groups and especially in the form of acrylic groups.
  • the acrylic and methacrylic groups may be in the form of (meth) acrylamide or (meth) acrylate groups, the latter being preferred.
  • the curable components of the radiation-curable composition forming the lacquer layer comprise at least 90% or 100%, based on the total amount of ethylenically unsaturated double bonds present in the composition, of acrylate groups.
  • the liquid, radiation-curable compositions which are used to prepare the lacquer layer contain at least one oligomer which has ethylenically unsaturated double bonds.
  • the oligomers preferably have on average a functionality in the range from 1.5 to 10, in particular in the range from 2 to 8.5, ie the number of ethylenically unsaturated double bonds per molecule is on average in the range from 1.5 to 10 and in particular Range from 2 to 8.5.
  • Also suitable are mixtures of different oligomers with different Functionality, wherein the average functionality is preferably in the range of 1.5 to 10, in particular in the range of 2 to 8.5.
  • the oligomers typically have a linear or branched skeleton which carries on average more than one ethylenically unsaturated double bond, preferably in the form of the abovementioned acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular in the form of acrylic or methacrylic groups, wherein the ethylenically unsaturated double bonds may be linked via a linker to the skeleton or are part of the skeleton.
  • Suitable oligomers are, in particular, oligomers from the group of polyethers, polyesters, polyurethanes and epoxide-based oligomers. Preference is given to oligomers which have substantially no aromatic structural units and to mixtures of oligomers having aromatic groups and oligomers without aromatic groups.
  • the oligomers are selected from polyether (meth) acrylates, i. H. Polyethers having acrylic or methacrylic groups, polyester (meth) acrylates, d. H. Polyesters having acrylic or methacrylic groups, epoxide (meth) acrylates, d. H. Reaction products of polyepoxides with hydroxyl-functionalized acrylic or methacrylic compounds, urethane (meth) acrylates, d. H. Oligomers having a (poly) urethane backbone and acrylic or methacrylic groups, for example, reaction products of polyisocyanates with hydroxyl-functionalized acrylic or methacrylic compounds, and unsaturated polyester resins, d. H. Polyesters having a plurality of preferably present in the polymer backbone ethylenically unsaturated double bonds, for. As condensation products of maleic acid or fumaric acid with aliphatic di- or polyols, and mixtures thereof.
  • the oligomers typically have a number average molecular weight of at least 400 g / mol, especially at least 500 g / mol, e.g. B. in the range of 400 to 4000 g / mol and in particular in the range of 500 to 2000 g / mol.
  • the monomers typically have molecular weights below 400 g / mol, z. B. in the range of 100 to ⁇ 400 g / mol.
  • Suitable polyether (meth) acrylates are, above all, aliphatic polyethers, in particular poly (C 2 -C 4 ) -alkylene ethers, which on average have from 2 to 4 acrylate or methacrylate groups. Examples of these are the Laromer® grades PO33F, LR8863, GPTA, LR8967, LR8962, LR9007 from BASF SE, which in some cases are blends with monomers.
  • Suitable polyester (meth) acrylates are, in particular, aliphatic polyesters which on average have from 2 to 6 acrylate or methacrylate groups. Examples of these are the Laromer® grades PE55F, PE56F, PE46T, LR9004, PE9024, PE9045, PE44F, LR8800, LR8907, LR9032, PE9074, PE9079, PE9084 from BASF SE, which in some cases are blends with monomers.
  • Suitable polyurethane acrylates are, above all, urethane-containing compounds which have on average 2 to 10, in particular 2 to 8.5, acrylate or methacrylate groups and which are preferably obtainable by reaction of aromatic or aliphatic di- or oligoisocyanates with hydroxyalkyl acrylates or hydroxyalkyl methacrylates.
  • these are the Laromer® grades UA19T, UA9028, UA9030, LR8987, UA9029, UA9033, UA9047, UA9048, UA9050, UA9072, UA9065 and UA9073 from BASF SE, some of which are blends with monomers.
  • the radiation-curable, liquid composition forming the lacquer layer comprises at least one oligomer selected from urethane acrylates and polyester acrylates and mixtures thereof, and optionally one or more monomers.
  • the radiation-curable, liquid composition which forms the lacquer layer comprises at least one urethane acrylate and optionally one or more monomers.
  • the radiation-curable, liquid composition forming the lacquer layer comprises at least one polyester acrylate and optionally one or more monomers.
  • the radiation-curable, liquid composition forming the lacquer layer comprises at least one urethane acrylate and at least one polyester acrylate and optionally one or more monomers.
  • the radiation-curable, liquid composition forming the lacquer layer comprises at least one aliphatic urethane acrylate and at least one aromatic urethane acrylate or at least two different aliphatic urethane acrylates and optionally one or more monomers.
  • the radiation-curable, liquid composition which forms the lacquer layer comprises at least one aliphatic urethane acrylate, at least one aromatic urethane acrylate and at least one polyester acrylate and optionally one or more monomers.
  • the crosslinkable constituents of the radiation-curable, liquid composition used to prepare the lacquer layer may contain one or more monomers, which are also referred to as reactive diluents.
  • the monomers typically have molecular weights below 400 g / mol, e.g. B. in the range of 100 to ⁇ 400 g / mol.
  • Suitable monomers generally have 1 to 6, in particular 2 to 4, ethylenically unsaturated double bonds per molecule.
  • the ethylenically unsaturated double bonds are preferably in the form of the abovementioned acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular in the form of acrylic or methacrylic groups and especially as acrylate groups.
  • Preferred monomers are selected from esters of acrylic acid with monohydric to trihydric, especially dihydric to trihydric, aliphatic or cycloaliphatic alcohols which preferably have 2 to 20 C atoms, for example monoesters of acrylic acid with C 1 -C 20 - Alkanols, benzyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, (5-ethyl-1,3-dioxan-5-yl) methanol, phenoxyethanol, 1,4-butanediol or 4-tert-butylcyclohexanol; Diesters of acrylic acid with ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol or tripropylene glycol; Triesters of acrylic acid with trimethylolpropane or pent
  • Suitable monomers are, in particular, trimethylolpropane diacrylate, trimethylolpropane triacrylate, ethylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diarylate, phenoxyethyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 4-t-butylcyclohexyl acrylate, 4-hydroxybutyl acrylate and trimethylolformalmonoacrylate (acrylic acid (5-ethyl-1,3-) dioxan-5-yl) methylester).
  • the radiation-curable, liquid composition forming the lacquer layer comprises at least one oligomer, e.g. B. 1, 2 or 3 oligomers, especially at least one, z. B. 1, 2 or 3, the oligomers mentioned as preferred and at least one monomer, for. B. 1, 2 or 3 monomers, especially at least one, z. B. 1, 2 or 3, the monomers mentioned as preferred.
  • the oligomer preferably forms the major constituent of the curable components of the composition, ie, the oligomer (s) account for at least 50 wt .-%, in particular at least 60 wt .-%, based on the total amount of oligomer and monomer.
  • the weight ratio of oligomer to monomer is in particular in the range from 1: 1 to 20: 1 and especially in the range from 3: 2 to 10: 1.
  • the radiation-curable, liquid composition used to prepare the lacquer layer comprises exclusively or almost exclusively, i. H. at least 90% by weight, in particular at least 95% by weight, especially at least 99% by weight, based on the total amount of radiation-curable constituents of the composition, of one or more oligomers, eg. B. 2, 3 or 4 oligomers, in particular 2, 3 or 4 of the oligomers mentioned as preferred.
  • the proportion of monomers is at most 10% by weight, in particular not more than 5% by weight, especially not more than 1% by weight or 0% by weight, based on the total amount of radiation-curable constituents of the composition.
  • Such compositions preferably contain at least one polyester acrylate and / or polyurethane acrylate and at least one polyether acrylate.
  • the radiation-curable, liquid composition used to prepare the lacquer layer generally contains one or more further constituents, such as photoinitiators, inert fillers, abrasives, leveling agents, coloring constituents, in particular color pigments, organic solvents and the like. According to the invention, these constituents do not exceed 40% by weight, in particular not more than 30% by weight, eg. B. 1 to 40 wt .-%, in particular 5 to 30 wt .-%, based on the total weight of the radiation-curable, liquid composition.
  • the radiation-curable, liquid composition contains no or not more than 10% by weight, based on its total weight, of non-polymerizable volatiles.
  • volatile substances are understood as meaning substances which have a boiling point or an evaporation point below 250 ° C. under atmospheric pressure, for example organic solvents.
  • the radiation-curable, liquid composition used to prepare the lacquer layer preferably contains at least one photoinitiator.
  • photoinitiators is meant substances which upon irradiation with UV radiation, ie light of wavelength below 420 nm, in particular below 400 nm, decompose to form free radicals and thus trigger a polymerization of the ethylenically unsaturated double bonds.
  • the radiation-curable, liquid composition comprises at least one photoinitiator having at least one absorption band, which has a maximum in the range of 220 to 420 nm, in particular in the range of 240 to 400 nm and which is coupled with the initiation of the decay process.
  • the nonaqueous, liquid, radiation-curable composition preferably contains at least one photoinitiator which has at least one absorption band with a maximum in the range from 220 to 420 nm, in particular a maximum in the range from 240 to 400 nm.
  • Preferred photoinitiators are selected, in particular, from the groups of the alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzoins and acylphosphine oxides.
  • the liquid, radiation-curable composition preferably comprises at least one photoinitiator which has an absorption band with a maximum ⁇ max in the range from 230 to 340 nm.
  • the non-aqueous, liquid, radiation-curable composition used to prepare the lacquer layer preferably comprises at least two photoinitiators which differ from one another and in which the maxima of the absorption bands differ, preferably by at least 40 nm and in particular by at least 60 nm.
  • such a non-aqueous, liquid, radiation-curable composition contains a mixture of at least two mutually different photoinitiators, wherein at least one photoinitiator (hereinafter photoinitiator I) has an absorption band with a maximum ⁇ max in the range of 340 to 420 nm and especially in the range of 360 has up to 420 nm and wherein at least one further photoinitiator (hereinafter photoinitiator II) has an absorption band with a maximum ⁇ max in the range of 220 to 340 and especially in the range of 230 to 320 nm.
  • the weight ratio of the total amount of photoinitiators I to the total amount of photoinitiators II is in the range of 2: 1 to 1:20.
  • Preferred photoinitiators which have an absorption band having a maximum ⁇ max in the range from 220 to 340 and especially in the range of 230 to 320 nm, the above-mentioned alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic esters, benzophenones, and benzoins.
  • Preferred photoinitiators which have an absorption band with a maximum ⁇ max in the range of 340 to 420 nm and especially in the range of 360 to 420 nm are the abovementioned acylphosphine oxides.
  • the photoinitiators comprise at least one alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone and at least one acylphosphine oxide and optionally a phenylglyoxalic acid ester and optionally a benzophenone.
  • the weight ratio of acylphosphine oxide to alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone is in the range of 2: 1 to 1:20.
  • the total amount of photoinitiators is typically in the range of 0.5 to 10% by weight, especially 1 to 5% by weight, based on the total weight of the non-aqueous, liquid, radiation-curable composition.
  • nonaqueous, liquid, radiation-curable compositions according to the invention can also be formulated without initiators, in particular when the subsequent curing is carried out by means of electron beams.
  • the non-aqueous, liquid, radiation-curable compositions may contain one or more fillers, i. H. solid, non-soluble in the oligomers and the monomers, particulate components.
  • these include, in particular aluminum oxides, for example in the form of corundum and silica, such as fumed silica and synthetic, amorphous silica, z. B. precipitated silica.
  • the average particle sizes of the fillers can vary over wide ranges and are typically in the range from 1 nm to 100 .mu.m, in particular in the range from 10 nm to 50 .mu.m, depending on the type of filler.
  • the total amount of filler will generally not exceed 40% by weight, in particular 30% by weight, based on the total weight of the composition and, if present, is typically in the range from 1 to 39.5% by weight and in particular in the range of 2 to 29 wt .-%.
  • the non-aqueous, liquid, radiation-curable compositions contain one or more abrasives.
  • Abrasives are fillers which give the lacquer layer increased surface hardness and improved abrasion resistance. These include especially corundum, quartz flour, glass powder, z. As glass flakes and nanoscale silicas.
  • non-aqueous, liquid, radiation-curable compositions may contain one or more further additives, for example leveling agents, for.
  • leveling agents for.
  • siloxane-containing polymers such as polyether siloxane copolymers
  • UV stabilizers for. B. sterically hindered amines (so-called HALS stabilizers).
  • Table A1 raw material Amount [% by weight] 1) Urethane acrylate, functionality about 2.0 to 6.0 15 - 30 Polyester acrylate, functionality 3.0 to 3.5 5 - 15 Trimethylolpropaneformalmonoacrylat 5 - 15 trimethylolpropane 10 - 20 Dipropyleneglycoldiacrylate 10 - 20 Aliphatic urethane acrylate, functionality 1.5 to 3.5 3 - 15 Alumina (corundum) 20 - 30 Pyrogenic silica 0.1 - 5 phenylglyoxylate 0,5 - 3 acylphosphine 0.2 - 1 alpha-hydroxyalkylphenone 0,5 - 3 1) based on the total weight of the composition raw material Amount [% by weight] 1) Urethane acrylate, functionality about 2.0 to 6.0 20 - 35 Alipha
  • the thermal transfer films according to the invention may comprise one or more superposed lacquer layers which, according to the invention, are based on the nonaqueous, liquid, radiation-curable compositions described above.
  • the total layer thickness of the lacquer layer, d. H. in the case of several lacquer layers, the sum of all layer thicknesses is typically in the range from 10 to 120 ⁇ m, in particular in the range from 30 to 80 ⁇ m. In the case of one layer, therefore, the layer thickness of the lacquer layer is preferably in the range from 10 to 120 ⁇ m, in particular in the range from 30 to 80 ⁇ m. In the case of several layers, the individual layer thicknesses are typically in the range from 10 to 100 ⁇ m, in particular in the range from 20 to 70 ⁇ m.
  • the thermal transfer film according to the invention comprises exactly one lacquer layer arranged on the carrier foil.
  • the thermal transfer film according to the invention comprises a coating layer arranged on the carrier film and one or more, for.
  • the lacquer layers can be arranged directly on one another.
  • a decorative layer can also be provided between two lacquer layers in order to give the article coated with the thermal transfer film a colored design.
  • Decorative layers typically have layer thicknesses in the range from 0.5 to 5 ⁇ m, in particular in the range from 0.5 to 2.5 ⁇ m and especially in the range from 1 to 1.5 ⁇ m.
  • the thermal transfer films according to the invention have at least one polymeric adhesive layer, in particular exactly one adhesive layer.
  • the adhesive layer is arranged either directly on the lacquer layer, or in the case of several lacquer layers directly on the uppermost lacquer layer, or a decorative layer can also be provided between the lacquer layer and the adhesive layer.
  • the adhesive layer is heat sealable according to the invention, ie it is not sticky at room temperature and develops its adhesive effect only when heated. It has proved to be advantageous if the adhesive layer contains at least one component which is radiation-curable, ie crosslinked upon exposure to high-energy radiation, for example when irradiated with UV light or electron radiation. This ingredient is organic oligomers or polymers that have ethylenically unsaturated double bonds.
  • the heat-sealable adhesive layer according to the invention preferably comprises at least one polymer as the main constituent. The polymer itself may be radiation-curable or blended with one or more radiation-curable oligomers or polymers having ethylenically unsaturated double bonds.
  • the polymers which form the main constituent of the heat-sealable adhesive layer are crosslinkable in a preferred embodiment, ie they crosslink upon heating and / or by the action of high-energy radiation, for example when irradiating with UV light and forming covalent bonds between the polymer chains.
  • the adhesive layer comprises both oligomeric and / or polymeric components which can be crosslinked by heating, as well as components which are crosslinkable by the action of high-energy radiation. This can be achieved, for example, by the adhesive layer comprising both polymers which crosslink on heating and oligomers or polymers which are crosslinked by the action of high-energy radiation.
  • the adhesive layer can also contain so-called dual-cure polymers, ie polymers which crosslink both when exposed to high-energy radiation and when heated.
  • the adhesive layer contains at least one water-insoluble polymer, which is usually used for the production of adhesive layers, and which is selected in particular from pure acrylate polymers, styrene acrylate polymers, polyurethanes, in particular polyesterurethanes and polyetherurethanes, and which is physically drying or self-crosslinking, and at least one radiation-curing oligomer or polymer.
  • Physically drying polymers are those polymers which, upon drying, form a solid polymer film in which the polymer chains are uncrosslinked.
  • Self-crosslinking polymers are those polymers which, upon drying, form a solid polymer film in which the polymer chains are crosslinked.
  • self- Polymers have reactive functional groups, for example hydroxyl groups, carboxyl groups, isocyanate groups, blocked isocyanate groups, ketocarbonyl groups or epoxide groups, which can react with one another or with the reactive groups of a crosslinking agent to form covalent bonds.
  • the adhesive layer contains at least one water-insoluble polymer which is selected from polyurethanes, in particular polyesterurethanes and polyetherurethanes, and which is physically drying or self-crosslinking, and at least one radiation-curing oligomer or polymer.
  • the adhesive layer contains at least one water-insoluble polymer selected from self-crosslinking pure acrylate polymers and self-crosslinking styrene-acrylate polymers, and at least one radiation-curing oligomer or polymer.
  • the adhesive layer contains at least one water-insoluble polymer selected from self-crosslinking pure acrylate polymers and self-crosslinking styrene-acrylate polymers and at least one water-insoluble polymer selected from polyurethanes, especially polyesterurethanes and polyetherurethanes, and which is physically drying or self-crosslinking and at least one radiation-curing oligomer or polymer.
  • the radiation-curable oligomers and polymers of the adhesive layer are basically those oligomers and polymers which have ethylenically unsaturated double bonds. These double bonds are preferably at least 90% or 100%, based on the total amount of ethylenically unsaturated double bonds, in the form of acrylic or methacrylic groups and especially in the form of acrylic groups.
  • the acrylic and methacrylic groups may be in the form of (meth) acrylamide or (meth) acrylate groups, the latter being preferred.
  • at least 90% or 100% of the radiation-curable constituents of the adhesive layer based on the total amount of the ethylenically unsaturated double bonds present in the adhesive layer, comprise acrylate groups.
  • the radiation-curable oligomers and polymers of the adhesive layer preferably have on average a functionality in the range of 2 to 20, in particular in the range of 2 to 10, ie the number of ethylenically unsaturated double bonds per molecule is on average in the range of 2 to 20 and in particular in the range of 2 to 10.
  • the radiation-curable oligomers and polymers of the adhesive layer are selected from polyether (meth) acrylates, polyester (meth) acrylates, epoxide (meth) acrylates, urethane (meth) acrylates, for example reaction products of polyisocyanates with hydroxyl-functionalized acrylic or methacrylic compounds, and unsaturated polyester resins.
  • the radiation-curable oligomers and polymers of the adhesive layer are selected from polyether (meth) acrylates, epoxide (meth) acrylates and urethane (meth) acrylates.
  • Suitable polyurethane acrylates are, above all, urethane-containing polymers which have on average 2 to 10, in particular 2 to 8.5, acrylate or methacrylate groups, in particular polyether urethane arylates, and which are preferably obtainable by reacting isocyanate group-containing polyether urethanes with hydroxyalkyl acrylates or hydroxyalkyl methacrylates , Examples include the Laromer® grades LR 8949, LR 8983 and LR 9005 from BASF SE.
  • the polymers, which preferably form the main constituent of the heat-sealable adhesive layer, in the uncrosslinked state have a glass transition temperature Tg, determined by means of differential scanning calorimetry (DSC) according to ASTM D3418 in the range from -60 to 90 ° C., in particular 0 to 90 ° C, and / or it is partially crystalline polymers having a melting point in the range of -60 to 90 ° C, in particular 0 to 90 ° C, determined by DSC is. If the adhesive composition contains a plurality of polymers, these may also have different glass transition temperatures in the uncrosslinked state.
  • DSC differential scanning calorimetry
  • At least a part, in particular at least 30% by weight of these polymers, based on the total amount of the polymer components of the adhesive composition, in the uncrosslinked state has a glass transition temperature Tg in the range from 0 to 90 ° C., in particular in the range from 20 to 90 ° C have.
  • Adhesive compositions for producing heat-sealable polymer layers are familiar to the person skilled in the art and can be obtained commercially or prepared by mixing commercially available adhesive raw materials according to known preparatory formulations. Preference is given to liquid adhesive compositions. In principle, solvent-based adhesives and water-based adhesives are suitable.
  • the adhesive layer (4) is preferably based on at least one aqueous polymer dispersion, ie water-based adhesives are used to produce the adhesive layer, ie adhesives which contain the polymers and optionally oligomers in the form of aqueous polymer dispersion. Preference is given to liquid, water-based adhesive compositions containing not more than 10% by weight of volatile, organic, non-polymerizable constituents, such as organic solvents. Suitable polymer dispersions are above all self-crosslinking aqueous polymer dispersions, ie aqueous polymer dispersions containing a reactive dispersed polymer and optionally a crosslinking agent which reacts with the reactive groups of the reactive polymer during drying and / or heating to form bonds.
  • self-crosslinking aqueous pure acrylate dispersions self-crosslinking aqueous styrene-acrylate dispersions and self-crosslinking aqueous polyurethane dispersions, in particular aqueous polyetherurethane dispersions and polyesterurethane dispersions.
  • Pure acrylate dispersions are understood as meaning aqueous polymer dispersions based on alkyl acrylates and alkyl methacrylates.
  • styrene acrylates is meant aqueous polymer dispersions based on styrene, alkyl acrylates and optionally alkyl methacrylates.
  • Polyurethane dispersions are understood as meaning aqueous dispersions of polyurethanes, in particular polyetherurethanes and polyesterurethanes.
  • the polymers have reactive functional groups, for example hydroxyl groups, carboxyl groups, isocyanate groups, blocked isocyanate groups, ketocarbonyl groups or epoxide groups which can react with the reactive groups of the crosslinking agent to form covalent bonds.
  • Suitable crosslinking agents are compounds having at least two reactive groups, for example hydrazide groups, amino groups, hydroxyl groups, epoxide groups, isocyanate groups.
  • self-crosslinking aqueous polymer dispersions are the products available under the trade names Luhydran® A 849, Acronal® 849 S, Joncryl® 8330, Joncryl® 8383 from BASF SE and Alberdingk® AC 2742 from Alberdingk Boley GmbH.
  • Suitable aqueous polymer dispersions are, above all, UV-crosslinkable polymer dispersions, ie polymer dispersions which comprise a dispersed polymer which has polymerizable ethylenically unsaturated double bonds which are preferably in the form of the abovementioned acrylic groups, methacrylic groups, allyl groups, fumaric acid groups, maleic acid groups and / or maleic anhydride groups, in particular Form of acrylic or methacrylic groups are present, wherein the ethylenic unsaturated double bonds can be linked via a linker to the skeleton or are part of the skeleton.
  • UV-crosslinkable aqueous polymer dispersions are aqueous dispersions of polyester acrylates, urethane acrylates and epoxy acrylates, such as those sold by BASF under the trade names Laromer® PE22WN, PE55WN, LR8949, LR8983, LR9005, UA9060, UA9095 and UA9064.
  • the aqueous adhesive composition contains, in addition to the polymer of a physically drying or self-crosslinking polymer dispersion, at least one radiation-curable component which is generally selected from the aforementioned polymers and oligomers which have ethylenically unsaturated double bonds and which is preferably also present in dispersed form.
  • the radiation-curable oligomers and polymers of the aqueous adhesive composition are, in particular, those oligomers and polymers whose double bonds are at least 90% or 100%, based on the total amount of ethylenically unsaturated double bonds, in the form of acrylic or methacrylic groups and especially in the form of acrylic groups available.
  • the acrylic and methacrylic groups may be in the form of (meth) acrylamide or (meth) acrylate groups, the latter being preferred.
  • the radiation-curable oligomers and polymers of the aqueous adhesive composition preferably have on average a functionality in the range of 2 to 20, in particular in the range of 2 to 10, d. H. the number of ethylenically unsaturated double bonds per molecule is on average in the range from 2 to 20 and in particular in the range from 2 to 10. Also suitable are mixtures of different oligomers or polymers with different functionality, the average functionality preferably in the range from 2 to 20, especially in the range of 2 to 10.
  • the radiation-curable oligomers and polymers of the aqueous adhesive composition are selected from polyether (meth) acrylates, polyester (meth) acrylates, epoxide (meth) acrylates, urethane (meth) acrylates, and unsaturated polyester resins.
  • the radiation-curable oligomers and polymers of the aqueous adhesive composition are selected from polyether (meth) acrylates, epoxide (meth) acrylates and polyurethane (meth) acrylates.
  • Suitable polyurethane acrylates are, above all, urethane-containing polymers which have on average 2 to 10, in particular 2 to 8.5, acrylate or methacrylate groups and which are preferably obtainable by reacting isocyanate-group-containing polyurethanes with hydroxyalkyl acrylates or hydroxyalkyl methacrylates.
  • Examples include the Laromer® grades LR 8949, LR 8983 and LR9005 from BASF SE.
  • the adhesive compositions used for the preparation of the polymeric adhesive layer may contain the additives customary for this purpose, for example waxes, tackifier resins, defoamers, leveling agents, surfactants, pH adjusting agents, one or more of the aforementioned fillers and UV stabilizers, eg. B. sterically hindered amines (so-called HALS stabilizers).
  • additives customary for this purpose for example waxes, tackifier resins, defoamers, leveling agents, surfactants, pH adjusting agents, one or more of the aforementioned fillers and UV stabilizers, eg. B. sterically hindered amines (so-called HALS stabilizers).
  • the adhesive composition used to make the polymeric adhesive layer contains a UV-curable polymer, it usually also contains at least one photoinitiator, typically among the aforementioned alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzene derivatives, acylphosphine oxides , Oxime esters, alpha-aminoalkylphenones and benzoins.
  • at least one photoinitiator typically among the aforementioned alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzene derivatives, acylphosphine oxides , Oxime esters, alpha-aminoalkylphenones and benzoins.
  • Preferred photoinitiators are selected, in particular, from the groups of the alpha-hydroxyalkylphenones, alpha-dialkoxyacetophenones, phenylglyoxalic acid esters, benzophenones, benzoins and acylphosphine oxides.
  • the adhesive composition used to make the polymeric adhesive layer contains a UV-curable polymer
  • it preferably contains at least one photoinitiator having an absorption band with a maximum ⁇ max in the range of 230 to 340 nm.
  • it contains at least two mutually different photoinitiators in which the maxima of the absorption bands differ, preferably by at least 40 nm and in particular at least 60 nm.
  • the photoinitiators comprise at least one alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone and at least one acylphosphine oxide and optionally a phenylglyoxalic acid ester and optionally a benzophenone.
  • the weight ratio is of acylphosphine oxide to alpha-hydroxyalkylphenone or alpha-dialkoxyacetophenone in the range from 2: 1 to 1:20.
  • the total amount of photoinitiators is typically in the range from 0.5 to 10% by weight, in particular from 1 to 5% by weight, based on the total weight of the adhesive composition used to make the polymeric adhesive layer.
  • Adhesive composition 1 UV-curable, unpigmented
  • Adhesive composition 1 30 -70 parts a self-crosslinking aqueous acrylate dispersion (50% strength by weight) 10-50 parts a radiation-curable polyurethane acrylate dispersion (40-50% strength by weight), 5-10 Parts of a hydrophobized fumed silica 5-10 Parts of a nonionic wax dispersion 1,5-3 Parts of a blend of an alpha-hydroxyalkylphenone and benzophenone 0.5-1 Parts of an acylphosphine oxide and optionally the following ingredients 0-20 Parts of water 0.8-1.5 parts a mineral-containing defoamer 0.4-1.2 parts a polyethersiloxane copolymer 0.5-1.0 parts a fluorosurfactant-containing leveling agent 2-4 parts Butyl glycol as a film-forming aid 0.3-0.5 Parts of
  • carnauba wax polyethylene wax, a combination of carnauba wax and polyethylene wax or a combination of several polyethylene waxes 1-3 parts a blend of an alpha-hydroxyalkylphenone and benzophenone 0.5-1 parts an acylphosphine oxide and optionally the following ingredients 0.2-1.0 parts a polyethersiloxane copolymer 1-10 parts Hydroxystyrolacrylat copolymer 0.1-5 parts Plasticizer, z. B. triethyl citrate 0,5-5 parts water 0,5-5 parts Butyl glycol as a film-forming aid 0.01-1 parts Base, e.g.
  • Hydroxystyrolacrylat copolymer 1-3 parts a blend of an alpha-hydroxyalkylphenone and benzophenone 0.5-1 parts an acylphosphine oxide and optionally the following ingredients 0.1-5 parts Plasticizer, z. B. triethyl citrate 0.2-1.0 parts a polyethersiloxane copolymer 0.2-1.0 parts a defoamer, z. B. a silicone defoamer or a siloxane-free defoamer; 0.3-0.5 parts a flow aid, z. B.
  • a fluorosurfactant-containing leveling agent 0,5-5 parts water 0,5-5 parts
  • Butyl glycol as a film-forming aid 0.01-1 parts
  • Base e.g. As an organic amine 30 -70 parts a polyester urethane dispersion (40% strength by weight) 10-50 parts a radiation-curable aqueous polyether urethane acrylate dispersion (40-50% strength by weight) 1.5-3 parts a blend of an alpha-hydroxyalkylphenone and benzophenone 0.5-1 parts an acylphosphine oxide and optionally the following ingredients 0-20 parts water 0.8-1.5 parts a polysiloxane defoamer 0.4-1.2 parts a polyethersiloxane copolymer 0.5-1.0 parts a fluorosurfactant-containing leveling agent 0.01-0.5 Parts of a polyurethane thickener 15 -60 parts a polyester urethane dispersion (40% strength by weight) 15 -60 parts a self-crosslinking
  • lacquer layer (s) and / or the adhesive layer (s) are colored.
  • lacquer layer (s) and / or the adhesive layer (s) may contain one or more coloring constituents such as organic and / or inorganic pigments or dyes.
  • these pigments are titanium dioxide as a white pigment, furthermore iron oxide pigments such as iron oxide yellow, iron oxide red, iron oxide black, black pigments such as carbon black, phthalocyanine pigments such as heliogen blue or heliogen green, bismuth pigments such as bismuth vanadate yellow and diketopyrrolopyrrole red.
  • Metallization effects may also include metal pigments such as iron pigments, pearlescent pigments and aluminum pigments.
  • Preferred pigments typically have particle sizes in the range from 0.1 to 100 .mu.m, in particular in the range from 1 to 50 .mu.m.
  • Adhesive layers typically have layer thicknesses in the range of 5 to 25 ⁇ m.
  • the thermal transfer films according to the invention naturally have at least one carrier foil on which the at least one lacquer layer is arranged.
  • the carrier films are usually plastic films made of thermoplastic flexible polymers. In particular, these are polyester films, polyamide films, polypropylene films, films of polyvinyl alcohol or polyesteramide films. Also suitable are so-called coextrudate films, d. H. multilayered films, wherein the plastic material in the individual layers may be different.
  • the plastic material which forms the carrier film is predominantly amorphous. Waxed or siliconized papers are also suitable.
  • the carrier film (2) has a thickness in the range of 3 to 200 .mu.m, in particular 10 to 100 .mu.m and especially from 20 to 50 microns. Also suitable are thin carrier films with film thicknesses in the range of 3 to 30 microns.
  • the surface structure of the carrier film on which the lacquer layer is arranged naturally determines the degree of gloss of the lacquer layer which is obtained in the coating method according to the invention. Smooth surfaces result in shiny or glossy surfaces, whereas rough surfaces can achieve matt effects. It is possible to create coarser structures in the paint surface by a strong structuring of the surface.
  • the surface of the carrier film on which the lacquer layer is arranged may have a conventional release layer, which facilitates the detachment of the lacquer layer from the carrier film in the coating method according to the invention.
  • thermal transfer films can be carried out in analogy to conventional film coating technologies, as described in the cited prior art, with the difference that in the preparation of the paint layer no heat-drying step is carried out, but by applying the non-aqueous radiation-curable, liquid Composition obtained on the carrier film liquid lacquer layer is at least partially cured by treatment with high-energy radiation such as electron beam or UV radiation.
  • the application of the non-aqueous, radiation-curable, liquid composition to the carrier film in step i) of the process according to the invention can be carried out in a manner known per se, for example by knife coating, rolling, casting or spraying. In this way, one obtains a coating of the carrier film with the radiation-curable composition, which can then be cured by treatment with high-energy radiation.
  • the order quantity is usually chosen such that a layer thickness results in the above-mentioned ranges.
  • the order quantity is in the range of 10 to 120 g / m 2 , in particular in the range of 30 to 80 g / m 2 and in the case of several layers, preferably in the range of 10 to 100 g / m 2 and in particular 20 to 70 g / m 2 .
  • step ii) of the method according to the invention the coating obtained in step i) is then at least partially cured by means of high-energy radiation.
  • a decorative layer can be applied to the not yet cured or partially cured coating prior to complete curing.
  • the adhesive layer may also be applied prior to curing.
  • step ii) of the process according to the invention the coating obtained in step i) is only partially cured.
  • the layer obtained in step i) is at least partially cured.
  • the coating obtained in step i) is irradiated with high-energy radiation.
  • the irradiation can be carried out by the carrier foil or by direct irradiation of the coating. Preference is given to direct irradiation.
  • the irradiation can be effected by means of electron radiation or with UV light, for example with UV lamps or UV-emitting light-emitting diodes.
  • UV radiation is used for curing in step ii).
  • UV radiation is used in the wavelength range from 200 to 400 nm.
  • medium-pressure mercury lamps or high-pressure mercury lamps for this purpose.
  • gallium or iron-doped high-pressure mercury lamps are used.
  • the irradiation in step ii) is preferably carried out in such a way that only partial polymerization of the ethylenically unsaturated double bonds contained in the nonaqueous, radiation-curable, liquid composition takes place.
  • the radiation density required for this purpose can be determined by the expert by means of routine experiments.
  • the irradiation in step ii) takes place at a radiation density in the range from 80 to 2000 J / m 2 , in particular in the range from 110 to 400 J / m 2 .
  • the curing in step ii) can be carried out under air atmosphere or under an oxygen-poor atmosphere at residual oxygen concentrations below 2000 ppm, eg. B. at residual oxygen concentrations in the range of 50 to 1000 ppm, take place.
  • the curing preferably takes place under air.
  • the thermal transfer film according to the invention comprises a plurality of lacquer layers
  • the first lacquer layer is at least partially cured by high-energy radiation before the application of the further lacquer layer (s).
  • a decorative layer is applied to the lacquer layer prior to the application of the adhesive layer or, in the case of multiple lacquer layers, to the first lacquer layer.
  • This decorative layer can be applied in a manner known per se by suitable printing methods, for example by flat, gravure, inkjet or digital printing.
  • the lacquer layer is partially cured before applying the decorative layer, wherein the partial curing is preferably carried out only to the extent that just applying the decorative layer is possible.
  • the printing inks used to produce the decorative layer can be conventional printing inks or UV-curing printing inks.
  • the application of the heat-sealable adhesive layer in step iv) of the method according to the invention can be carried out in a manner known per se.
  • a liquid adhesive composition in particular an aqueous adhesive composition in the usual manner, for example, by knife coating, rolling, pouring or spraying on the paint layer or on the decorative layer is usually applied.
  • the adhesive layer is dried, for example by heat.
  • the application amount of the liquid adhesive composition is usually selected so that, after drying, a layer thickness results in the above ranges.
  • the application rate is in the range of 5 to 50 g solids per m 2 , in particular in the range of 5 to 15 g solids per m 2 .
  • the following film constructions 1 to 12 can be produced by using the steps given there.
  • the film structures 7 to 12 correspond to the film structures 1 to 6 with the difference that a pigment-containing adhesive composition is used.
  • the resulting thermal transfer films can then be made up in the usual way, for. B. are wound into rolls.
  • the thermal transfer films according to the invention are particularly suitable for the dry coating of surfaces of objects.
  • the lacquer layer or the lacquer layers on the surface to be coated of the article hereinafter also referred to as a substrate transferred
  • the adhesive layer after irradiation a good bond between the or the paint layers and the substrate causes.
  • the use of the thermal transfer films according to the invention is not limited to certain substrates, but they can be very versatile applied to both hard and elastic substrates.
  • the substrates can be, for example, articles made of plastic, for example ABS, polycarbonate, melamine, polyester, including glass fiber reinforced Polyester, hard PVC, soft PVC, rubber, wood including exotic natural woods, wood materials, eg. As veneer, MDF, HDF, Feinspan- or multiplex plates, mineral fibers, z. As mineral fiber boards, paper, textile including synthetic leather, metal or plastic-coated materials act.
  • the thermal transfer films according to the invention are preferably suitable for smooth, preferably plane or slightly curved surfaces. In principle, however, even more complex structures can be coated in this way.
  • the substrates to be coated may be undecorated or already have decorative surfaces.
  • thermal transfer films according to the invention it is particularly advantageous to coat exotic natural woods, which often present problems in wet painting, since the contents bleed or adhesion problems are caused.
  • the coated using the thermal transfer films of the invention objects, for.
  • wood fiber boards, MDF boards or natural wood panels that have been primed using the thermal transfer films of the invention can be readily coated with a conventional UV coating, with no intermediate sanding is required.
  • such a primed article can also be dry-coated with a thermal transfer film according to the invention.
  • the thermal transfer films according to the invention allow a virtually waste-free coating of articles.
  • a change from colorless to color, from dull to glossy can take place very rapidly, without a cleaning step being required between these changes. Drying times are eliminated, and after the coating can be continued directly, z. B. applied a conventional paint job or the coated article to be packaged.
  • the carrier film can be peeled off or initially remain as a protective film on the coated surface.
  • the use of the thermal transfer films according to the invention permits a dust-free coating.
  • the space requirements and personnel costs compared to conventional painting process is much lower.
  • the thermal transfer films of the invention provide compared to the known from the prior art thermal transfer films surfaces with particularly high valence, especially high scratch and abrasion resistance.
  • surfaces of quality classes AC3 to AC4 can be achieved.
  • the surfaces obtained using the thermal transfer films according to the invention regularly show values above 20 N when tested with the Hamberger planer. The surfaces thus obtained regularly meet the requirements of the highest stress group of the furniture standard DIN 68861.
  • thermal transfer films according to the invention for coating surfaces of articles is typically carried out in a process which comprises the abovementioned steps a) to d), which are described in more detail below and which are analogous to those described in EP 2078618 A2 described procedure can be performed. On the relevant content of EP 2078618 A2 is hereby incorporated by reference.
  • the thermal transfer film of the invention is first applied to the surface of the substrate to be coated and then heat sealed.
  • the heat sealing is typically carried out using pressure in suitable presses, wherein the temperature of the press is typically in the range of 100 to 250 ° C, preferably in the range of 160 to 220 ° C.
  • the thus coated substrate with high-energy radiation, d. H. irradiated with UV or electron radiation the coating layer cures completely.
  • the irradiation may be performed prior to removal of the carrier sheet or subsequently.
  • the irradiation can by means of electron radiation, z. B. using gallium radiators or with UV light, for example, with UV lamps or UV-emitting LEDs, done.
  • UV radiation is used for curing in step ii).
  • UV radiation is used in the wavelength range from 200 to 400 nm.
  • medium-pressure mercury lamps or high-pressure mercury lamps for this purpose.
  • gallium or iron-doped high-pressure mercury lamps are used.
  • the irradiation in step ii) takes place at a radiation density in the range from 40 to 2000 J / m 2 , in particular in the range from 100 to 400 J / m 2 .
  • a system for carrying out the method according to the invention comprises at least one commonly used thermal transfer device, which preferably has a cutting device and / or a winding device for the carrier film.
  • the equipment may include a first thermal transfer device with which the article is primed and a second thermal transfer device, with which the article is finished, have.
  • a conventional thermal transfer device can be constructed as follows: From a film unwinding the wound as a roll thermal transfer film is fed to a heated roller press having at least one driven, heated, optionally rubberized roller, which is optionally adjustable in height.
  • the roller press usually has one of the heated roller opposite counter-pressure roller, which may be rubberized. This causes the necessary pressing pressure, whereby the lacquer layer is transferred by means of the adhesive layer to the surface of an object which is guided between the two rollers.
  • the counter-pressure roller can be designed so that it causes the separation of the carrier film from the paint layer.
  • the separated carrier film can be removed with a cutter or fed to a Folienaufwickelinnate.
  • a plate press can be used, which is opened after a predetermined time.
  • the coated article with the coated side past a source of high energy radiation, such as an electron gun or UV emitter, exposing the coated side of the article to high energy radiation and achieving final cure.
  • a source of high energy radiation such as an electron gun or UV emitter
  • the article thus coated is subsequently fed to a collecting device, for example a stacking device.
  • the carrier film can be removed with a cutter or fed to a film take-up device.
  • the object coated in the thermal transfer device can also be supplied to a further thermal transfer device after removal of the carrier film before or after curing by means of high-energy radiation, in which a further lacquer layer is applied to the coated surface of the article by means of a further thermal transfer film according to the invention.
  • a further lacquer layer is applied to the coated surface of the article by means of a further thermal transfer film according to the invention.
  • curing with high-energy radiation is carried out as described above.
  • a first embodiment of a device for the continuous implementation of the method according to the invention with solid substrates comprises a lay-on conveyor belt, an unwinding station for the wound as a roll thermal transfer film, a thermal transfer device with roller press, as described above, a winding device for the carrier film, a drying channel with UV emitter, a discharge belt and a stacking device.
  • the substrates to be coated are placed on the conveyor belt and guided at the desired feed rate through the thermal transfer device.
  • the lacquer layer is transferred to the substrate and the carrier foil separated and taken up by the take-up device.
  • the lacquer layer is cured in the drying channel.
  • the winding station can also be arranged after the drying channel, so that the carrier film initially remains on the substrate and acts there as a protective film.
  • a second embodiment of an apparatus for continuously carrying out the method according to the invention with elastic substrates comprises a unwinding station for the substrate, a unwinding station for the wound as a roll thermal transfer film, a thermal transfer device with roller press, as described above, a drying channel with UV lamps and a winding device for the coated substrate.
  • the substrate to be coated is guided through the thermal transfer device at the desired feed rate together with the thermal transfer film.
  • the thermal transfer film is bonded to the substrate.
  • the thus coated substrate is passed through the drying channel, whereby the lacquer layer cures and received by the winding station. After cutting, the carrier film can be removed.
  • a third embodiment of a device for continuously carrying out the method according to the invention with solid substrates comprises a conveyor belt, an unwinding station for the wound as a roll thermal transfer film, a thermal transfer device with heated platen press and optionally a take-up device for the carrier film or a cutting device.
  • the substrates to be coated are placed on the conveyor belt and fed together with the thermal transfer film in the plate press.
  • the press is closed and pressurized with the desired pressure.
  • the lacquer layer is transferred to the substrate.
  • the substrate is driven out of the press and passed through the drying channel, whereby the lacquer layer cures.
  • the carrier film can remain on the substrate and serve as a protective film.
  • the carrier film before or after the drying channel be cut with a cutting device.
  • a further embodiment of a device for the discontinuous implementation of the method according to the invention with solid substrates comprises a conveyor belt, an unwinding station for wound as a roll thermal transfer film, a cutting device, thermal transfer device with heated platen press and a drying channel with UV lamp.
  • the substrate to be coated is placed on the conveyor belt.
  • the thermal transfer film is unwound to the desired length, placed with the adhesive layer on the substrate to be coated and cut.
  • Substrate and foil are fed into the plate press.
  • the press is closed and pressurized with the desired pressure.
  • the lacquer layer is transferred to the substrate.
  • the coated substrate is driven out of the press and passed through the drying channel, whereby the lacquer layer cures.
  • the carrier film can remain on the substrate and serve as a protective film. Alternatively, it is possible to separate the film from the UV channel.
  • the adhesive composition 1 was prepared by mixing the ingredients indicated in the following table.
  • Adhesive formulation 1 raw material Amount [% by weight] 1) Self-crosslinking aqueous polyacrylate dispersion 1 39.0 Aqueous polyether urethane acrylate dispersion 1 16.4 Polyether emulsion 0.44 Polymeric fluorosurfactant 0.35 carnauba wax dispersion 1.20 Modified polyethylene wax 7.3 Pyrogenic silica 1.5 Synthetic silicic acid 1.3 Micronized polyethylene wax 1.7 polyurethane dispersion 13.0 dimethylpolysiloxane 0.4 Aliphatic epoxy acrylate 6.1 Styrene-acrylate dispersion (50%) 4.4 triethylcitrate 1.75 alpha-hydroxyalkylphenone 1.0 acylphosphine 0.7 benzophenone 0.85 butylglycol 1.0 water 1.0 aminoalcohol 0.17 1) based on the total weight of the composition
  • the adhesive formulation 2 was prepared by mixing the constituents indicated in the following table.
  • the adhesive formulation 3 was prepared by mixing the constituents indicated in the following table.
  • the adhesive formulation 4 was prepared by mixing the constituents indicated in the following table.
  • a device was used for the irradiation, in which the coated or printed film with a defined feed rate of a Ga-doped mercury lamps with the power of 120 W / cm was passed.
  • Example 1 Film for use as a color lacquer in the furniture sector
  • the paint formulation 4 was applied with a layer thickness of 40 g / m 2 .
  • the thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
  • the UV-curable gravure ink was applied to the gelled lacquer layer.
  • the so-printed film was again passed to the Ga-doped mercury lamp for curing at a feed rate of 30 m / min.
  • the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
  • Example 2 Film for use as a color lacquer in the furniture sector
  • the lacquer formulation 5 having a layer thickness of 70 g / m 2 was applied to an undyed polyethylene terephthalate support film having a layer thickness of 23 ⁇ m.
  • the thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
  • the UV-curable gravure ink was applied to the gelled lacquer layer.
  • the so-printed film was again passed to the Ga-doped mercury lamp for curing at a feed rate of 30 m / min.
  • the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
  • Example 3 Film for use as a clearcoat in the furniture sector
  • the paint formulation 6 was applied with a layer thickness of 40 g / m 2 .
  • the thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
  • the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
  • Example 4 Film for use as exterior color paint
  • the paint formulation 7 was applied with a layer thickness of 45 g / m 2 .
  • the thus-coated film was passed past the Ga-doped mercury radiator at a feed rate of 30 m / min to gel the lacquer layer.
  • the UV-curable gravure ink was applied to the gelled lacquer layer.
  • the so-printed film was again passed to the Ga-doped mercury lamp for curing at a feed rate of 30 m / min.
  • the adhesive formulation 3 with a layer thickness of 15 g / m 2 was applied to the printed lacquer layer and thermally dried.
  • Example 3 The film of Example 3 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) on a beech wood panel. Subsequently, the thus laminated film was irradiated by Verbeiin the laminated side at a feed rate of 20 m / min to two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film.
  • the sample thus obtained was analyzed by ATR-FTIR spectroscopy using an FT-IR spectrometer from Nicolet (Nicolet 380) and a Golden Gate® probe head. Compared to a non-irradiated sample, a significant decrease in the absorption bands characteristic of acrylate groups was observed at 810 cm-1 (> 40%) and 1410 cm-1 (> 30%).
  • the film from Example 1 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at a constant contact pressure on an MDF board. Subsequently, the thus laminated plate was irradiated by passing the laminated side at a feed rate of 20 m / min on two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film. Subsequently, the carrier film was removed.
  • Example 1 For comparison purposes, the film of Example 1 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at the same contact pressure on an MDF board, but no subsequent irradiation was made.
  • the preparation was carried out in analogy to the preparation of Sample 1, using instead of the film of Example 1, the film of Example 2.
  • the preparation was carried out in analogy to the preparation of the comparative sample V1, using instead of the film of Example 1, the film of Example 2.
  • the film from Example 3 was laminated by means of a heated roller (180 ° C, object temperature maximum 50 ° C) at a constant contact pressure on a beech wood panel. Subsequently, the thus laminated plate was irradiated by passing the laminated side at a feed rate of 20 m / min on two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film. Subsequently, the carrier film was removed.
  • Example 3 For comparison purposes, the film of Example 3 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at the same contact pressure on a beech wood panel, but no subsequent irradiation was made.
  • the film from Example 43 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at a constant contact pressure on a PVC plate. Subsequently, the thus laminated plate was irradiated by passing the laminated side at a feed rate of 15 m / min at two UV lamps (mercury radiator and Ga-doped mercury radiator), each with a power of 120 W / cm through the film. Subsequently, the carrier film was removed.
  • Example 4 For comparison purposes, the film of Example 4 was laminated by means of a heated roller (180 ° C, object temperature 50 ° C maximum) at the same contact pressure on a PVC plate, but no subsequent irradiation was made.
  • Table P Results of tests P1 - P8 sample UV curing P1 P2 P3 P4 [N] P5 [N] P6 P7 [Umin -1 ] P8 [Umin -1 ] 1 Yes 5 5 5 20 1.2 GT0 nb nb 2 Yes 5 5 5 19 1.0 GT0 620 1600 3 Yes 5 5 5 18 1.1 GT0 nb nb 4 Yes 5 5 5 19 1.3 GT1 nb nb V1 No 4-5 5 5 13 0.7 GT5 nb nb V2 No 4-5 4-5 5 14 0.6 GT4 630 1550 V3 No 4 4 5 13 0.7 GT4 nb nb V4 No 5 5 13 0.7 GT3 nb nb

Claims (16)

  1. Film de transfert thermique (1), comprenant:
    a) un film support (2),
    b) au moins une couche de vernis (3) agencée sur le film support (2),
    c) au moins une couche adhésive polymère thermoscellable (4),
    la couche de vernis étant à base d'une composition liquide non aqueuse durcissable par rayonnement qui contient au moins 60 % en poids, par rapport au poids total de la composition, de constituants durcissables qui sont choisis parmi les oligomères organiques qui comprennent des doubles liaisons éthyléniquement insaturées et les mélanges de ces oligomères avec des monomères qui comprennent au moins une double liaison éthyléniquement insaturée,
    et la couche adhésive polymère thermoscellable (4) contenant au moins un constituant durcissable par rayonnement qui est choisi parmi les oligomères et les polymères qui comprennent des doubles liaisons éthyléniquement insaturées.
  2. Film de transfert thermique selon la revendication 1, caractérisé en ce que la composition durcissable par rayonnement qui forme la couche de vernis contient 1,5 à 8 moles de doubles liaisons éthyléniquement insaturées par kg de la composition.
  3. Film de transfert thermique selon l'une quelconque des revendications précédentes, caractérisé en ce que les oligomères dans la composition durcissable par rayonnement qui forme la couche de vernis comprennent en moyenne 1,5 à 10, notamment 2 à 8, doubles liaisons éthyléniquement insaturées par molécule.
  4. Film de transfert thermique selon l'une quelconque des revendications précédentes, caractérisé en ce que les doubles liaisons éthyléniquement insaturées dans les oligomères et les monomères de la composition durcissable par rayonnement qui forme la couche de vernis se présentent sous la forme de groupes acryle ou méthacryle.
  5. Film de transfert thermique selon l'une quelconque des revendications précédentes, caractérisé en ce que les oligomères de la composition durcissable par rayonnement qui forme la couche de vernis sont choisis parmi les polyéther-(méth)acrylates, les polyester-(méth)acrylates, les époxyde-(méth)acrylates, les uréthane-(méth)acrylates, les résines de polyester insaturées et leurs mélanges.
  6. Film de transfert thermique selon l'une quelconque des revendications précédentes, caractérisé en ce que la composition liquide durcissable par rayonnement contient au moins un photoinitiateur qui présente une bande d'absorption ayant un maximum λmax dans la plage allant de 220 à 420 nm.
  7. Film de transfert thermique selon l'une quelconque des revendications précédentes, caractérisé en ce que la couche de vernis (3) présente une épaisseur de couche de 10 à 120 µm.
  8. Film de transfert thermique selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend une couche décorative entre la couche de vernis (3) et la couche adhésive (4).
  9. Film de transfert thermique selon l'une quelconque des revendications précédentes, caractérisé en ce que la couche adhésive (4) est à base d'au moins une dispersion aqueuse de polymère qui contient un oligomère ou un polymère durcissable par rayonnement UV sous forme dispersée.
  10. Film de transfert thermique selon la revendication 9, dans lequel le polymère durcissable par rayonnement UV est un polyuréthane-acrylate, notamment un polyéther-uréthane-acrylate.
  11. Film de transfert thermique selon l'une quelconque des revendications précédentes, caractérisé en ce que la couche adhésive (14) est à base d'au moins deux dispersions aqueuses de polymère, au moins une dispersion de polymère contenant un polymère durcissable par rayonnement UV sous forme dispersée et au moins une autre dispersion de polymère contenant un polymère auto-réticulant sous forme dispersée.
  12. Procédé de fabrication d'un film de transfert thermique selon l'une quelconque des revendications précédentes, comprenant:
    i. l'application de la composition liquide non aqueuse durcissable par rayonnement, un revêtement durcissable par un rayonnement riche en énergie étant obtenu;
    ii. l'exposition du revêtement durcissable obtenu à l'étape i. à un rayonnement riche en énergie, la couche de vernis (3) étant obtenue;
    iii. éventuellement l'application d'une couche décorative sur le revêtement durcissable ou sur la couche de vernis (3); et
    iv. l'application de la couche adhésive polymère thermoscellable (4).
  13. Procédé selon la revendication 12, dans lequel l'exposition du revêtement durcissable par un rayonnement riche en énergie a lieu avant l'application de la couche adhésive et avant l'application éventuelle de la couche décorative.
  14. Procédé selon la revendication 12 ou 13, dans lequel l'exposition du revêtement durcissable par un rayonnement riche en énergie a lieu de sorte que seule une polymérisation partielle des doubles liaisons éthyléniquement insaturées contenues dans la composition liquide non aqueuse durcissable par rayonnement ait lieu.
  15. Procédé de revêtement de surfaces d'objets, comprenant les étapes suivantes :
    a) l'application du film de transfert thermique (1) selon l'une quelconque des revendications 1 à 11 avec la couche adhésive sur la surface à revêtir ;
    b) le thermoscellage du film de transfert, une surface revêtue avec le film de transfert étant obtenue;
    c) l'exposition de la surface revêtue avec le film de transfert à un rayonnent UV ou à un faisceau d'électrons;
    d) éventuellement le décollement du film support (2).
  16. Utilisation de films de transfert thermique selon l'une quelconque des revendications 1 à 11 pour le vernissage à sec d'objets.
EP14766739.8A 2013-09-18 2014-09-18 Films de transfert thermique pour la peinture à sec de surfaces Active EP3046778B2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
NO14766739A NO3046778T3 (fr) 2013-09-18 2014-09-18
SI201430640T SI3046778T1 (en) 2013-09-18 2014-09-18 Termotransfer foil for dry surface painting
PL14766739.8T PL3046778T5 (pl) 2013-09-18 2014-09-18 Folie termotransferowe do suchego lakierowania powierzchni
EP14766739.8A EP3046778B2 (fr) 2013-09-18 2014-09-18 Films de transfert thermique pour la peinture à sec de surfaces

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13185007 2013-09-18
PCT/EP2014/069895 WO2015040113A1 (fr) 2013-09-18 2014-09-18 Films à transfert thermique pour la peinture à sec de surfaces
EP14766739.8A EP3046778B2 (fr) 2013-09-18 2014-09-18 Films de transfert thermique pour la peinture à sec de surfaces

Publications (3)

Publication Number Publication Date
EP3046778A1 EP3046778A1 (fr) 2016-07-27
EP3046778B1 true EP3046778B1 (fr) 2017-12-20
EP3046778B2 EP3046778B2 (fr) 2022-08-17

Family

ID=49237045

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14766739.8A Active EP3046778B2 (fr) 2013-09-18 2014-09-18 Films de transfert thermique pour la peinture à sec de surfaces

Country Status (12)

Country Link
US (2) US20160297226A1 (fr)
EP (1) EP3046778B2 (fr)
JP (1) JP6581589B2 (fr)
CN (1) CN105555545B (fr)
DK (1) DK3046778T4 (fr)
ES (1) ES2663451T5 (fr)
NO (1) NO3046778T3 (fr)
PL (1) PL3046778T5 (fr)
PT (1) PT3046778T (fr)
RU (1) RU2674190C2 (fr)
SI (1) SI3046778T1 (fr)
WO (1) WO2015040113A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10106643B2 (en) * 2015-03-31 2018-10-23 3M Innovative Properties Company Dual-cure nanostructure transfer film
US20170057268A1 (en) * 2015-09-01 2017-03-02 Jerry Surber Process for Producing Printed Wooden Plaques and Trophies
DE102015117261A1 (de) * 2015-10-09 2017-04-13 Weilburger Graphics GmbH Kleber, Verwendung bestimmter Druckwerke und Verfahren ausschließlich für die Kaltfolienveredelung
PT3500535T (pt) * 2016-08-19 2020-09-01 Xylo Tech Ag Painel revestido e processo de fabrico do painel revestido
CN114521167B (zh) * 2019-09-25 2024-04-16 巴斯夫涂料有限公司 将压纹结构转印到涂层表面的方法以及可以用作压纹模具的复合物
WO2022040513A1 (fr) * 2020-08-20 2022-02-24 Wayne State University Compositions et procédés de revêtement
DE102020128927A1 (de) 2020-11-03 2022-05-05 Aluminium Féron GmbH & Co. KG Transferfolie für Möbel
DE102021000890A1 (de) * 2021-02-19 2022-08-25 Giesecke+Devrient Currency Technology Gmbh Sicherheitselement und Verfahren zu seiner Herstellung
CN115449326B (zh) * 2022-10-11 2023-05-19 东莞市德聚胶接技术有限公司 一种抗冲击uv固化围堰胶及其制备方法

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0210620A2 (fr) 1985-07-31 1987-02-04 Leonhard Kurz Gmbh & Co. Procédé de fabrication de feuilles avec une couche de vernis texturé
EP1304235A1 (fr) 2001-10-19 2003-04-23 MZE Engineering GmbH Procédé de production d'une couche de vernis structurée à l'aide d'un film transfert
WO2005035460A1 (fr) 2003-10-06 2005-04-21 Basf Aktiengesellschaft Agent de revetement durcissable par rayonnement, contenant un (meth)acrylate d'urethane aliphatique
EP1527825A1 (fr) 2003-11-03 2005-05-04 E.I. Du Pont De Nemours And Company Procédé pour la production de revêtements sur des substrats
WO2006005434A1 (fr) 2004-07-14 2006-01-19 Giesecke & Devrient Gmbh Element de securite et procede pour le realiser
JP2006181791A (ja) 2004-12-27 2006-07-13 Kuraray Co Ltd 転写材および積層体
WO2008061930A1 (fr) 2006-11-21 2008-05-29 Ciba Holding Inc. Appareil et procédé pour fabriquer un produit de sécurité
US20100215875A1 (en) 2009-02-26 2010-08-26 Ching-Chang Yang Thermal transfer-printing film and method utilizing the same
WO2011012520A2 (fr) 2009-07-28 2011-02-03 Sicpa Holding Sa Feuille de transfert comprenant un pigment magnétique optiquement variable, procédé de fabrication, utilisation d’une feuille de transfert, et article ou document la comprenant
US20110189477A1 (en) 2010-02-03 2011-08-04 Multi-Color Corporation Heat Transfer Label Having a UV Layer
WO2011098514A1 (fr) 2010-02-11 2011-08-18 Dsm Ip Assets B.V. Composition liquide durcissable par rayonnement pour revêtements à faible brillance
JP2012011677A (ja) 2010-06-30 2012-01-19 Dainippon Printing Co Ltd 熱転写フィルム及びこれを用いたハードコート体
DE102010034039A1 (de) 2010-08-11 2012-02-16 Bundesdruckerei Gmbh Verfahren zur Herstellung einer Folie für ein Sicherheits- und/oder Wertdokument
US20120070595A1 (en) 2010-09-22 2012-03-22 Sloat Jeffrey T Extensible Heat Transfer Labels Formed from Energy Curable Compositions
WO2013019821A1 (fr) 2011-08-01 2013-02-07 Sun Chemical Corporation Encres hautement étirables durcissables par apport d'énergie et procédé pour leur utilisation dans des applications d'étiquettes pour transfert à chaud

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3131766A1 (de) * 1981-08-11 1983-02-24 Basf Ag, 6700 Ludwigshafen Photopolymerisierbares aufzeichnungsmaterial und verfahren zur herstellung von reliefformen mittels dieses aufzeichnungsmaterials
DE3527412A1 (de) * 1985-07-31 1987-02-12 Kurz Leonhard Fa Mehrlagige folie, insbesondere heisspraegefolie und verfahren zu deren herstellung
US4902364A (en) * 1988-08-02 1990-02-20 Dennison Manufacturing Company Heat transfer decorations with patterned metallization
ES2118766T3 (es) 1992-05-19 1998-10-01 Mzi M Zaher Inst Fur Oberflach Utilizacion de un soporte con propiedades de despegado para la aplicacion de esmalte y color sobre un substrato.
JPH08108695A (ja) * 1994-10-11 1996-04-30 Dainippon Printing Co Ltd 転写シート
US6194044B1 (en) * 1996-02-02 2001-02-27 Stahls' Inc. Emblem for embroidery stitching to a substrate and method
CN1119251C (zh) * 1997-03-18 2003-08-27 雷恩哈德库兹有限公司 装饰三维基体表面的装饰箔
US6042931A (en) † 1998-06-08 2000-03-28 Avery Dennison Corporation Heat-transfer label including improved acrylic adhesive layer
GB2357061B (en) * 1999-12-08 2003-09-17 Merck Patent Gmbh Hot stamping foils
US6372074B1 (en) * 2000-06-14 2002-04-16 Avery Dennison Corporation Method of forming a protective coating for color filters
DE20209576U1 (de) * 2002-06-20 2002-08-29 Kurz Leonhard Fa Dekorationselement mit erhöhtem UV- und Abriebschutz
JP2004339415A (ja) * 2003-05-16 2004-12-02 Teikoku Printing Inks Mfg Co Ltd 感熱接着剤、その関連組成物及び感熱接着製品
DE102005013101A1 (de) * 2005-03-18 2006-09-21 Bauschlinnemann Gmbh & Co. Kg Thermotransferfolie zum Aufbringen eines Dekors, insbesondere auf Möbelteile aus Holzwerkstoffen oder dergleichen
DE102007010460A1 (de) 2007-03-01 2008-09-04 Decor Druck Leipzig Gmbh Heißtransferfolie zur Dekoration von Substratoberflächen und Verfahren zu deren Herstellung
DE102008003629A1 (de) 2008-01-09 2009-07-23 Ls Industrielacke Gmbh Thermische Transferfolie und Verfahren zur lösungsmittelfreien Lackierung
KR20110028448A (ko) * 2008-06-11 2011-03-18 바스프 에스이 가시광 광여기하에서 자유 라디칼 중합가능한 수지의 점착성-제거된 표면의 광경화 방법
JP5945927B2 (ja) * 2012-03-30 2016-07-05 大日本印刷株式会社 保護層転写シートの製造方法
JP6195146B2 (ja) * 2012-05-17 2017-09-13 大日本印刷株式会社 保護層転写シートおよびその製造方法
JP6427911B2 (ja) * 2014-03-26 2018-11-28 大日本印刷株式会社 三次元成形用シート

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0210620A2 (fr) 1985-07-31 1987-02-04 Leonhard Kurz Gmbh & Co. Procédé de fabrication de feuilles avec une couche de vernis texturé
EP1304235A1 (fr) 2001-10-19 2003-04-23 MZE Engineering GmbH Procédé de production d'une couche de vernis structurée à l'aide d'un film transfert
WO2005035460A1 (fr) 2003-10-06 2005-04-21 Basf Aktiengesellschaft Agent de revetement durcissable par rayonnement, contenant un (meth)acrylate d'urethane aliphatique
EP1527825A1 (fr) 2003-11-03 2005-05-04 E.I. Du Pont De Nemours And Company Procédé pour la production de revêtements sur des substrats
WO2006005434A1 (fr) 2004-07-14 2006-01-19 Giesecke & Devrient Gmbh Element de securite et procede pour le realiser
JP2006181791A (ja) 2004-12-27 2006-07-13 Kuraray Co Ltd 転写材および積層体
WO2008061930A1 (fr) 2006-11-21 2008-05-29 Ciba Holding Inc. Appareil et procédé pour fabriquer un produit de sécurité
US20100215875A1 (en) 2009-02-26 2010-08-26 Ching-Chang Yang Thermal transfer-printing film and method utilizing the same
WO2011012520A2 (fr) 2009-07-28 2011-02-03 Sicpa Holding Sa Feuille de transfert comprenant un pigment magnétique optiquement variable, procédé de fabrication, utilisation d’une feuille de transfert, et article ou document la comprenant
US20110189477A1 (en) 2010-02-03 2011-08-04 Multi-Color Corporation Heat Transfer Label Having a UV Layer
WO2011098514A1 (fr) 2010-02-11 2011-08-18 Dsm Ip Assets B.V. Composition liquide durcissable par rayonnement pour revêtements à faible brillance
JP2012011677A (ja) 2010-06-30 2012-01-19 Dainippon Printing Co Ltd 熱転写フィルム及びこれを用いたハードコート体
DE102010034039A1 (de) 2010-08-11 2012-02-16 Bundesdruckerei Gmbh Verfahren zur Herstellung einer Folie für ein Sicherheits- und/oder Wertdokument
US20120070595A1 (en) 2010-09-22 2012-03-22 Sloat Jeffrey T Extensible Heat Transfer Labels Formed from Energy Curable Compositions
WO2013019821A1 (fr) 2011-08-01 2013-02-07 Sun Chemical Corporation Encres hautement étirables durcissables par apport d'énergie et procédé pour leur utilisation dans des applications d'étiquettes pour transfert à chaud

Also Published As

Publication number Publication date
ES2663451T5 (es) 2022-12-07
PL3046778T5 (pl) 2023-01-09
US20190315144A1 (en) 2019-10-17
PL3046778T3 (pl) 2018-08-31
US10710388B2 (en) 2020-07-14
CN105555545B (zh) 2020-03-03
SI3046778T1 (en) 2018-04-30
NO3046778T3 (fr) 2018-05-19
RU2674190C2 (ru) 2018-12-05
US20160297226A1 (en) 2016-10-13
WO2015040113A1 (fr) 2015-03-26
PT3046778T (pt) 2018-03-22
RU2016114693A (ru) 2017-10-20
DK3046778T4 (da) 2022-11-14
EP3046778A1 (fr) 2016-07-27
CN105555545A (zh) 2016-05-04
JP6581589B2 (ja) 2019-09-25
RU2016114693A3 (fr) 2018-05-31
EP3046778B2 (fr) 2022-08-17
DK3046778T3 (en) 2018-04-09
ES2663451T3 (es) 2018-04-12
JP2016538165A (ja) 2016-12-08

Similar Documents

Publication Publication Date Title
EP3046778B1 (fr) Films de transfert thermique pour la peinture à sec de surfaces
EP1815915A2 (fr) Procédé de fabrication de produits en plastique à utilisation polyvalente dotés d'une surface de préférence résistant à l'abrasion
DE102016212106A1 (de) Selbstheilende Oberflächenschutzfolie mit acrylatfunktionellem Top-Coat
EP2527408B1 (fr) Procédé de fabrication d'une feuille dotée d'une surface matifiée
JP2016538165A5 (fr)
JPH04117466A (ja) 塗料組成物およびこれを用いた化粧材
EP1218461B1 (fr) Procede de realisation de revetements antirayures insensibles aux conditions atmospheriques
EP0862503A1 (fr) Film de peinture adhesif
EP1829677A1 (fr) Feuille de liaison
DE60314097T2 (de) Heissschmelzbeschichtungszusammensetzung für folienübertragung und giessprozess
EP3720674B1 (fr) Procédé de transfert d'une structure gaufrée vers la surface d'un revêtement et composite comprenant ledit revêtement
EP1218462A1 (fr) Procede de realisation de revetements antirayures
DE2947597B1 (de) Verfahren zum Herstellen von Filmen oder UEberzuegen
EP0338221B1 (fr) Bande de feuille
EP2703092A1 (fr) Procédé de réglage de différents degrés de brillance pour laques durcies par radiation et leur utilisation
DE102020007628B4 (de) Verfahren zur Herstellung einer Werkstoffplatte sowie eines Kaschierfilms und Verwendung einer solchen Werkstoffplatte
EP0587591B1 (fr) Procede d'obtention de surfaces vernies mates
EP4189022B1 (fr) Encres durcissables par faisceau d'électrons à faible migration ayant un contenu bio-renouvelable
EP2290017B1 (fr) Couches de laque agglomérantes et mises en réseau par rayonnement
WO2023247775A1 (fr) Composition aqueuse de finition pour films de finition décorative
WO2003101631A1 (fr) Substrats recouverts d'un revetement antirayures et procedes de production de ces substrats
WO2022128023A1 (fr) Procédé de réalisation d'un panneau de matériau et d'un film de contre-collage
EP4279656A1 (fr) Procédé de fabrication d'un matériau composite en forme de bande présentant une surface structurée, matériau composite et son utilisation
EP2899218A1 (fr) Compositions de laque

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20160418

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: BIEHLER, MANFRED

Inventor name: LITZCKE, DIETER

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LITZCKE, DIETER

Inventor name: BIEHLER, MANFRED

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

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20170710

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 956017

Country of ref document: AT

Kind code of ref document: T

Effective date: 20180115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502014006681

Country of ref document: DE

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Ref document number: 3046778

Country of ref document: PT

Date of ref document: 20180322

Kind code of ref document: T

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20180315

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20180405

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2663451

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20180412

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

Ref country code: LT

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

Effective date: 20171220

GRAT Correction requested after decision to grant or after decision to maintain patent in amended form

Free format text: ORIGINAL CODE: EPIDOSNCDEC

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

Ref country code: GR

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

Effective date: 20180321

Ref country code: LV

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

Effective date: 20171220

Ref country code: RS

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

Effective date: 20171220

Ref country code: HR

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

Effective date: 20171220

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20171220

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: BASF SE

Owner name: LS INDUSTRIELACKE GMBH

RIN2 Information on inventor provided after grant (corrected)

Inventor name: BIEHLER, MANFRED

Inventor name: LITZCKE, DIETER

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCOW

Free format text: NEW ADDRESS: CARL-BOSCH-STRASSE 38, 67056 LUDWIGSHAFEN AM RHEIN (DE) $ LS INDUSTRIELACKE GMBH, IM WINKEL 8, 58285 GEVELSBERG (DE)

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

Ref country code: CY

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

Effective date: 20171220

Ref country code: EE

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

Effective date: 20171220

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

Ref country code: SM

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

Effective date: 20171220

Ref country code: IS

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

Effective date: 20180420

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 502014006681

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

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

Ref country code: MT

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

Effective date: 20171220

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: LEONHARD KURZ STIFTUNG & CO. KG

Effective date: 20180920

REG Reference to a national code

Ref country code: SK

Ref legal event code: T3

Ref document number: E 28147

Country of ref document: SK

PLAF Information modified related to communication of a notice of opposition and request to file observations + time limit

Free format text: ORIGINAL CODE: EPIDOSCOBS2

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

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

Ref country code: MC

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

Effective date: 20171220

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: LU

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

Effective date: 20180918

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

Ref country code: IE

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

Effective date: 20180918

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

Ref country code: HU

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

Effective date: 20140918

Ref country code: MK

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

Effective date: 20171220

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

Ref country code: AL

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

Effective date: 20171220

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

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

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20220817

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 502014006681

Country of ref document: DE

REG Reference to a national code

Ref country code: NO

Ref legal event code: TB2

Ref country code: DK

Ref legal event code: T4

Effective date: 20221110

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: SK

Ref legal event code: T5

Ref document number: E 28147

Country of ref document: SK

REG Reference to a national code

Ref country code: SE

Ref legal event code: RPEO

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Ref document number: 2663451

Country of ref document: ES

Kind code of ref document: T5

Effective date: 20221207

REG Reference to a national code

Ref country code: SI

Ref legal event code: SP73

Owner name: BASF SE; DE

Effective date: 20230119

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230301

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

Ref country code: TR

Payment date: 20230828

Year of fee payment: 10

Ref country code: RO

Payment date: 20230829

Year of fee payment: 10

Ref country code: NO

Payment date: 20230920

Year of fee payment: 10

Ref country code: NL

Payment date: 20230926

Year of fee payment: 10

Ref country code: IT

Payment date: 20230920

Year of fee payment: 10

Ref country code: GB

Payment date: 20230926

Year of fee payment: 10

Ref country code: FI

Payment date: 20230926

Year of fee payment: 10

Ref country code: CZ

Payment date: 20230918

Year of fee payment: 10

Ref country code: BG

Payment date: 20230925

Year of fee payment: 10

Ref country code: AT

Payment date: 20230919

Year of fee payment: 10

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

Ref country code: SK

Payment date: 20230830

Year of fee payment: 10

Ref country code: SI

Payment date: 20230828

Year of fee payment: 10

Ref country code: SE

Payment date: 20230926

Year of fee payment: 10

Ref country code: PT

Payment date: 20230828

Year of fee payment: 10

Ref country code: PL

Payment date: 20230822

Year of fee payment: 10

Ref country code: FR

Payment date: 20230926

Year of fee payment: 10

Ref country code: DK

Payment date: 20230927

Year of fee payment: 10

Ref country code: DE

Payment date: 20230928

Year of fee payment: 10

Ref country code: BE

Payment date: 20230926

Year of fee payment: 10

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

Ref country code: ES

Payment date: 20231018

Year of fee payment: 10

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

Ref country code: CH

Payment date: 20231001

Year of fee payment: 10