WO2024104767A1 - Procédé de production d'un objet décoré, objet décoré et utilisation d'un mélange réactif pour la production d'un objet décoré - Google Patents

Procédé de production d'un objet décoré, objet décoré et utilisation d'un mélange réactif pour la production d'un objet décoré Download PDF

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Publication number
WO2024104767A1
WO2024104767A1 PCT/EP2023/080210 EP2023080210W WO2024104767A1 WO 2024104767 A1 WO2024104767 A1 WO 2024104767A1 EP 2023080210 W EP2023080210 W EP 2023080210W WO 2024104767 A1 WO2024104767 A1 WO 2024104767A1
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unit
group
layer
polymer
foamed state
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PCT/EP2023/080210
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German (de)
English (en)
Inventor
Mats Timothy Knoop
Johannes Ludwig
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Leonhard Kurz Stiftung & Co. Kg
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Publication of WO2024104767A1 publication Critical patent/WO2024104767A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes

Definitions

  • the present invention relates to a method for producing a decorated object, a decorated object and use of a reactive mixture for producing a decorated object.
  • a white color impression is achieved by incorporating titanium dioxide (TiO2) particles, which effectively scatter the incident visible light due to their high refractive index n of about 2.5.
  • TiO2 in the rutile type
  • TiO2 has a comparatively high density of approx. 4240 kg/m 3 , which can result in a disadvantageous comparatively strong settling behavior of the TiO2 particles in liquid paints and varnishes. Therefore, there is a need for an alternative to TiC that can be used as a colorant, i.e. that can be used as a white pigment to create, for example, decorated objects.
  • the present invention describes how a sponge-like, porous, polymer structure can be produced which produces a white color impression through high light scattering.
  • this structure does not have to have a refractive index on the order of TiO2.
  • the high number of interfaces results in repeated scattering of light within the structure, which is why refractive indices between 1.2 and 1.8 are sufficient for a white color impression.
  • the refractive index is determined using a method with a refractometer according to DIN EN ISO 489:2022-06 ("Plastics - Determination of refractive index (ISO 489:2022); German version EN ISO 489:2022", issue date: 2022-06).
  • This method describes a measurement of the refractive indices of molded parts, cast or extruded sheets or films using an Abbe refractometer and applies not only to isotropic transparent, translucent, colored or opaque materials, but also to anisotropic materials.
  • a polymer based on itaconic acid was developed.
  • at least one unit comprising the polymer for example in the form of a layer or in the form of particles and/or fibers
  • an object for example concrete, or by spraying it into a basic solution
  • an ionically catalyzed decarboxylation of the polyitaconic acid occurs.
  • CO2 is released from the itaconic acid molecule, for example with the formation of a lactone.
  • the decarboxylation of the polymer of the at least one unit according to the invention can be initiated thermally.
  • reaction equation (1 ) shows a possible reaction pathway for the decarboxylation of polyitaconic acid (left) and the release of CO2.
  • the possible product (right) shows a ring closure within the molecule:
  • the porous structure created by foaming is mechanically stable and, due to light refraction at a large number of interfaces, creates a white color impression of the object decorated with the polymer.
  • the object of the invention is to provide a method for producing an improved decorated object, an improved decorated object and the use of a reactive mixture for producing an improved decorated object, wherein no TiO2 particles are used to produce a white color impression.
  • step f) is a sub-step of step c) and/or is carried out after step d) and/or after step e): a) providing a reactive mixture which has a carboxylic acid-containing monomer component which comprises itaconic acid and/or itaconic acid derivatives, b) polymerizing the reactive mixture to form a polymer, c) contacting the polymer with an element, whereby at least one unit comprising the polymer is obtained, whereby the at least one unit comprising the polymer can be put into a foamed state in which the at least one unit forms a porous structure, whereby at least one unit is obtained in the foamed state, and whereby the light is refracted at the porous structure in such a way that the at least one unit has a white color impression in the foamed state, d) drying the at least one unit, e) arranging the at the at least one unit, a) providing a reactive mixture which has a carboxylic acid-containing monomer component which comprises itac
  • the object is achieved by a decorated object comprising a polymer, preferably according to claim 59, in particular produced according to a The method of claims 1 to 58, wherein the polymer comprises itaconic acid and/or itaconic acid derivatives, wherein the decorated object comprises at least one unit comprising the polymer which is placed in a foamed state, wherein the at least one unit in the foamed state has a porous structure, wherein the light is refracted at the porous structure such that the at least one unit in the foamed state has a white color impression, wherein the color impression is described as a color location in the CIELAB color space by the parameters L, a and b, and wherein the at least one unit in the foamed state has a value for the parameters of a and b selected from a range of -4 to 4.
  • a reactive mixture for producing a decorated object preferably according to claim 1, comprising at least one unit of a polymer, wherein the reactive mixture has a carboxylic acid-containing monomer component which comprises itaconic acid and/or itaconic acid derivatives, and wherein the at least one unit can be put into a foamed state, wherein at least one unit is obtained in a foamed state which has a porous structure, and wherein the porous structure has a white color impression, wherein the color impression is described as a color location in the CIELAB color space by the parameters L, a and b, and wherein the at least one unit in the foamed state has a value for the parameters a and b selected from a range from -4 to 4.
  • At least one unit comprising the polymer or a multilayer film comprising the at least one unit.
  • Color, color impression or colorfulness or individual color or individual color is understood to be a color location in a color space.
  • the color space can be the CIELAB color space in particular.
  • a different or differing color is understood to mean a color difference dE between two color locations in a color space.
  • the color space can in particular be the CIELAB color space.
  • a different color that is sufficiently perceptible to the human eye has a color difference dE in the CIELAB color space of at least 2, preferably at least 3, particularly preferably at least 5, more preferably at least 10.
  • the color location is usually determined with a color measuring device, for example with a "Datacolor 650" spectrophotometer (Datacolor AG).
  • the color location is preferably determined using the method described in EN ISO/CIE 11664-4:2020-03 ("Colorimetry - Part 4: CIE 1976 L*a*b* color space (ISO/CIE 11664-4:2019); German version EN ISO/CIE 11664-4:2019", issue date 2020-03).
  • light rays received from the illuminated sample are separated into their component wavelengths, for example via a prism.
  • the separated light is then focused on a detector, such as a CCD array, where the intensity of each wavelength (or each color if it is in the range visible to the human eye) is measured by a pixel of the array.
  • the CCD is then read out by a computer. The result is a spectrum showing the intensity of each wavelength of light.
  • a sample such as a foil, a bulk material, a cuvette or a decorated object
  • a measurement is carried out using the associated software.
  • the software then automatically calculates the resulting Lab values of the sample.
  • the brightness value L* is perpendicular to the color plane (a* b*).
  • the a coordinate indicates the color type and color intensity between green and red and the b coordinate indicates the color type and color intensity between blue and yellow.
  • L* can usually take on values between 0 and 100 and a and b can vary between -128 and +127.
  • a color is preferably perceived by a viewer as white if the values of a and b are selected from a range of -5 to 5 and preferably L is a value selected from a range of 70 to 100.
  • L is a value selected from a range of 70 to 100.
  • the viewer already perceives a slight color cast.
  • the viewer already perceives a slight color cast.
  • Colors with values for L, a and b outside the above ranges are perceived by a viewer in particular with a distinct color cast or gray cast.
  • the at least one unit in the foamed state preferably has a value for the parameters of a and b selected from a range of -4 to 4, preferably from -3 to 3, more preferably from -2 to 2 and even more preferably from -1 to 1.
  • the at least one unit in the foamed state has a value for the parameter L selected from a range from 70 to 100, preferably from 80 to 100, more preferably from 90 to 100.
  • the invention makes it possible to provide a polymer from which decorative layers can be produced which have a white color impression and do not contain any pigments, preferably white pigments such as TiC.
  • a coating according to the invention does not contain any respirable nanoparticles, which also result in disposal costs.
  • the polymer obtained can be produced from biological raw materials.
  • the amount of petroleum-based monomers can be reduced.
  • itaconic acid which is used as a monomer, can be obtained biotechnologically by fermenting molasses or synthesized from pyruvic acid. This leads to a more sustainable product. Due to the availability of the raw materials, a unit comprising the polymer can also be produced cost-effectively.
  • the decorated objects are suitable in the form of a facade panel that will retain the color impression even under climatic conditions such as moisture or mechanical stress. Further advantageous embodiments of the invention are specified in the subclaims.
  • step a) the reactive mixture is provided which has a carboxylic acid-containing monomer component, wherein this carboxylic acid-containing monomer component comprises itaconic acid and/or itaconic acid derivatives.
  • Step a) is carried out at the beginning of the process.
  • the inventors have surprisingly found that it is possible to design the reactive mixture, the polymer and/or the at least one unit in such a way that they do not have to comprise any pigments, preferably no white pigments, more preferably no TiO2, in order to have the preferred white color impression.
  • the reactive mixture comprises at least one further carboxylic acid-containing monomer selected individually or in combination from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid.
  • Preferred derivatives of itaconic acid of the carboxylic acid-containing monomer component are the anhydride of itaconic acid, the methoxy ester of itaconic acid and/or ethoxy ester of itaconic acid.
  • the itaconic acid derivative of the carboxylic acid-containing monomer component is derivatized with a maximum of one carboxylic acid and is present, for example, as an itaconic acid monoester.
  • the advantage here is that the handling of the polyitaconic acid can be improved by the at least one additional monomer of the carboxylic acid-containing component. For example, the glass transition temperature can be increased, thereby increasing the mechanical strength.
  • the foamability of the at least one unit comprising the polymer is not or only slightly affected.
  • the proportion of the carboxylic acid-containing monomer from step a) based on the total mass of the reactive mixture is selected from the range from 2.5 wt.% to 65 wt.%, preferably from 5 wt.% to 50 wt.%, more preferably from 10 wt.% to 35 wt.%.
  • “carboxylic acid-containing” is understood to mean that a molecule, for example a monomer, is present which contains at least one functional unit of the type -COOH, in particular when provided.
  • non-carboxylic acid-containing means that a molecule, for example a monomer, is present which does not contain a functional unit of the -COOH type, in particular when provided.
  • This definition therefore includes, for example, unsaturated hydrocarbons and unsaturated aromatic hydrocarbons and in particular carboxylates and carboxylic acid derivatives.
  • the reactive mixture preferably comprises at least one non-carboxylic acid-containing monomer component, which is preferably selected individually or in combination from the group consisting of esters of acrylic acid, esters of methacrylic acid, esters of itaconic acid, in particular diesters of itaconic acid, esters of maleic acid, maleic anhydride, terpenes, myrcene, styrene, isoprene, butadiene and vinyl ethers or derivatives thereof.
  • non-carboxylic acid-containing monomer component which is preferably selected individually or in combination from the group consisting of esters of acrylic acid, esters of methacrylic acid, esters of itaconic acid, in particular diesters of itaconic acid, esters of maleic acid, maleic anhydride, terpenes, myrcene, styrene, isoprene, butadiene and vinyl ethers or derivatives thereof.
  • the proportion of the non-carboxylic acid-containing monomer from step a) based on the total mass of the reactive mixture is preferably selected from the range from 5 wt.% to 50 wt.%, preferably from 15 wt.% to 35 wt.%, more preferably from 20 wt.% to 30 wt.%.
  • the advantage of using a non-carboxylic acid-containing monomer component and/or polymer component in the above proportion of the total weight of the reactive mixture is that, on the one hand, this reduces the water solubility of the polymer, thereby increasing, for example, the applicability in outdoor areas.
  • the foaming ability of the at least one unit comprising the polymer is not significantly influenced by the above proportion.
  • the reactive mixture preferably comprises a solvent, preferably water and/or an organic solvent, individually or as mixtures selected from ethanol, 1-propanol, 2-propanol, acetone, 2-butanone (MEK), acetate, in particular ethyl acetate and/or lactyl acetate.
  • a solvent preferably water and/or an organic solvent, individually or as mixtures selected from ethanol, 1-propanol, 2-propanol, acetone, 2-butanone (MEK), acetate, in particular ethyl acetate and/or lactyl acetate.
  • the proportion of solvent based on the total mass of the reactive mixture is selected from the range from 15 wt.% to 95 wt.%, preferably from 30 wt.% to 85 wt.%, more preferably from 40 wt.% to 70 wt.%, even more preferably from 45 wt.% to 60 wt.%.
  • a solvent is understood to mean a medium in which the other components of the reactive mixture are diluted, the solvent being separated off after polymerization, in particular being separated off essentially completely.
  • a solvent preferably has a boiling point of at most 200 °C.
  • An organic solvent is understood to mean a solvent that has at least one carbon atom in its molecular structure.
  • the reactive mixture comprises an initiator for the
  • Polymerization preferably an initiator for radical polymerization.
  • the proportion of initiator based on the total mass of the reactive mixture is selected from the range from 0.05 wt.% to 1.5 wt.%, preferably from 0.1 wt.% to 1 wt.%, more preferably from 0.25 wt.% to 0.5 wt.%.
  • the reactive mixture may comprise at least one additive which is selected individually or in combination from the group consisting of crosslinker, flow agent, stabilizer, light stabilizer, flame retardant, defoamer, leveling additive, hydrophobizing agent, plasticizer, deactivator, antioxidant, radical chain terminator.
  • additives selected individually or in combination from the group consisting of crosslinker, flow agent, stabilizer, light stabilizer, flame retardant, defoamer, leveling additive, hydrophobizing agent, plasticizer, deactivator, antioxidant, radical chain terminator.
  • the reactive mixture comprises fillers which are selected individually or in combination from the group comprising mineral fillers, sand, diatomaceous earth, layered silicates, talc, aluminates, carbon fibers, wood flour, starch, glass fibers.
  • the processability of the reactive mixture or polymer can be improved and the stability of at least one unit obtained from the polymer can be increased.
  • a reactive mixture suitable for the process according to the invention has the following composition, wherein the details of the individual components are each based on the total mass of the reactive mixture and wherein the components are selected so that they add up to 100% by weight:
  • Carboxylic acid-containing monomer component 2.5 wt.% - 65 wt.%
  • Non-carboxylic acid-containing monomer component 5 wt.% - 50 wt.%
  • Carboxylic acid-containing monomer component 5 wt.% - 50 wt.%
  • Non-carboxylic acid-containing monomer component 15 wt.% - 35 wt.%
  • Carboxylic acid-containing monomer component 10 wt.% - 35 wt.%
  • Non-carboxylic acid-containing monomer component 20 wt.% - 30 wt.%
  • Solvent 45 wt% - 60 wt%
  • step b) a polymer is obtained from the reactive mixture provided in step a), in particular wherein the polymer obtained comprises at least itaconic acid as a monomer unit.
  • Step b) is preferably carried out after step a).
  • a polymer obtained in step b) preferably comprises the monomers of the carboxylic acid-containing monomer component provided in step a) and optionally the monomers of the non-carboxylic acid-containing monomer component.
  • step b) is carried out at a temperature of the reactive mixture selected from a range of 20 °C to 110 °C, preferably from 40 °C to 85 °C, more preferably from 50 °C to 70 °C.
  • the polymer obtained in step b) has a value for the number average molar mass selected from a range from 500 g/mol to 500,000 g/mol, preferably from 750 g/mol to 100,000 g/mol, more preferably from 1000 g/mol to 50,000 g/mol, even more preferably from 1500 g/mol to 20,000 g/mol.
  • the above molar mass offers the advantage that, on the one hand, a polymer is obtained which has a high mechanical resistance, for example to abrasion, and, on the other hand, the polymer can still be processed with reasonable effort.
  • the polymer prepared in step b) has at least one further carboxylic acid-containing monomer unit which is selected individually or in combination from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid.
  • the proportion of the carboxylic acid-containing monomer in the polymer based on the total mass of the polymer is selected from the range from 2.5 wt.% to 100 wt.%, preferably from 5 wt.% to 80 wt.%, more preferably from 10 wt.% to 50 wt.%.
  • the polymer prepared in step b) has at least one non-carboxylic acid-containing monomer component which is selected from the group, individually or in combination, consisting of esters of acrylic acid, esters of methacrylic acid, esters of itaconic acid, preferably monoesters of itaconic acid, esters of maleic acid, maleic anhydride, terpenes, myrcene, styrene, isoprene, butadiene, vinyl ethers or derivatives thereof.
  • non-carboxylic acid-containing monomer component which is selected from the group, individually or in combination, consisting of esters of acrylic acid, esters of methacrylic acid, esters of itaconic acid, preferably monoesters of itaconic acid, esters of maleic acid, maleic anhydride, terpenes, myrcene, styrene, isoprene, butadiene, vinyl ethers or derivatives thereof.
  • the proportion of the monomer of the non-carboxylic acid-containing component based on the total mass of the polymer is preferably selected from the range from 0 wt.% to 97.5 wt.%, preferably from 5 wt.% to 90 wt.%, more preferably from 15 wt.% to 85 wt.%.
  • the non-carboxylic acid-containing component comprises a monomer with at least one blocked carboxylic acid, wherein the at least one blocked carboxylic acid is deblocked in or after step b), so that in the polymer after step b) the at least one blocked carboxylic acid is present as at least one carboxylic acid.
  • the deblocking can be carried out, for example, thermally or chemically.
  • a polymer is understood to be a molecule which is formed from the chemical reaction of at least 3 monomers. Molecules which are formed from fewer than 5 monomers are preferably referred to as oligomers.
  • the polymer obtained in step b) has a polydispersity value selected from a range from 1.8 to 4, preferably from 1.9 to 3, more preferably from 2 to 2.5, even more preferably from 2.1 to 2.4.
  • Polydispersity is a measure of the width of the molar mass distribution. It is calculated from the ratio of weight average Mw, ie the molar mass based on the ratio of the weight of the polymer chains of an identical mass to the number average M n , ie the molar mass based on the ratio of the number of polymer chains of an identical length to the total number of all polymer chains.
  • the above polydispersity value has the advantage of achieving a broad dispersity of the polymer. The broad dispersity in turn enables easier processing and/or handling of the polymer, in particular due to a wider melting range.
  • step c) the polymer obtained in step b) is brought into contact with an element, whereby the at least one unit comprising the polymer is obtained.
  • Step c) is preferably carried out after step b) and before step d).
  • the element can be, for example, a volume of liquid, preferably a basic solution, or a carrier layer. It is also possible for the volume of liquid, preferably the basic solution, to be arranged on a carrier layer.
  • the at least one unit obtained can be designed as a layer, film, particle or fiber. In this case, it is possible for an emulsion paint, a varnish, a powder, a transfer film, in particular a laminating film or a transfer film with a transfer layer that can be detached from the carrier layer to be obtained.
  • the element is a basic aqueous solution comprising divalent or polyvalent cations of at least one metal, wherein the at least one metal is preferably selected from the group consisting of Mg, Ca, Sr, Ba, Al, Fe, Co or mixtures thereof.
  • step f The inventors have surprisingly found that the presence of divalent or polyvalent cations makes it particularly easy to convert at least one unit into a foamed state, i.e. step f). It is assumed that the ions catalyze the decarboxylation of the polyitaconic acid.
  • alkali metals of the 1st main group of the periodic table such as sodium or potassium
  • other monovalent ions such as ammonium
  • pH value selected from a range from 8 to 14, preferably from 10 to 14, more preferably from 12 to 14.
  • the element comprises monovalent or polyvalent anions selected from the group consisting of phosphate, phosphite, carbonate, bicarbonate, hydroxide, aluminate, sulfate, sulfite or mixtures thereof.
  • the cations and anions are selected from water-soluble salts.
  • the polymer prefferably brought into contact with the element, in particular in the form of a liquid volume, preferably a basic solution, by means of a spraying process.
  • the spraying process is preferably selected from air spraying processes, ultrasonic spraying processes, electrostatic spraying processes, wherein the at least one unit in the form of particles and/or fibers is obtained by means of the spraying process.
  • the polymer for spraying is dissolved and/or dispersed in a solvent, preferably an organic solvent, more preferably methyl ethyl ketone, acetone, ethanol and/or mixtures thereof.
  • a solvent preferably an organic solvent, more preferably methyl ethyl ketone, acetone, ethanol and/or mixtures thereof.
  • the element is a carrier layer or comprises one. It is also possible that the element is arranged on a carrier layer in regions or over the entire surface. It is possible that in step c) the contacting is carried out by arranging the at least one unit comprising the polymer on the carrier layer in regions or over the entire surface, wherein the at least one unit is obtained in the form of a layer.
  • a transfer film is obtained by contacting the at least one unit with the element, wherein the transfer film comprises a carrier layer and a transfer layer.
  • the transfer layer has the at least one unit.
  • the transfer layer is detachable from the carrier layer.
  • the carrier layer consists of a polyester, a polyolefin or a combination thereof, in particular PET.
  • the carrier layer preferably has a layer thickness selected from a range of 5.7 pm to 100 pm, preferably 19 pm to 50 pm.
  • step c) the at least one unit with an application weight selected from a range from 5 g/m 2 to 20 g/m 2 , preferably from 8 g/m 2 to 12 g/m 2 , is arranged on the carrier layer.
  • step c) the at least one unit with a layer thickness selected from a range of 5 pm to 20 pm, preferably 8 pm to 12 pm, is arranged on the carrier layer.
  • the layer thickness is measured in particular in the dried state of the layer.
  • step c) at least one of the following methods is used to arrange the at least one unit or one or more further layers on the carrier layer: gravure printing, screen printing, Inkjet printing, flexographic printing, offset printing, spraying, casting, injection molding.
  • the polymer can be dissolved, melted or dispersed in the unit, for example.
  • step c) one or more further layers are arranged over the entire surface or in certain areas on the carrier layer.
  • the one or more layers are selected from the group consisting of release layer, primer layer, functional layer and protective layer.
  • the release layer enables non-destructive detachment of the at least one unit, the one or more further layers and/or the transfer layer from the carrier layer, wherein the release layer is arranged in contact with the carrier film and/or the transfer layer.
  • the release layer remains on the carrier layer, the transfer layer and/or on the carrier layer and the transfer layer after detachment.
  • the release layer preferably consists of a wax, preferably montan wax, silicone or combinations thereof, or comprises these.
  • the release layer preferably has a layer thickness selected from a range from 0.01 pm to 1 pm, preferably from 0.02 pm to 0.7 pm, more preferably from 0.02 pm to 0.5 pm.
  • the protective layer is preferably arranged on the side of the transfer layer facing away from the carrier layer, with the protective layer preferably forming the visible side of the decorated object.
  • the protective layer protects the underlying layers or units against mechanical or chemical stress during the process, in particular when arranging them on the object, or when using the decorated object.
  • the protective layer is designed as a self-supporting protective layer or as a non-self-supporting protective layer.
  • the protective layer has a layer thickness selected from a range from 0.5 pm to 10 pm, preferably from 0.8 pm to 5 pm.
  • the protective layer is preferably formed from or comprises at least one polymer, individually or in combination, selected from: polyester, polyolefin, polyurethane, polyacrylate, styrene resin, ketone resin.
  • the protective layer is preferably transparent. It is also possible for the protective layer to be colored and/or designed as a translucent protective layer.
  • Transparent is understood to mean a transmission of a unit, an area or a layer which has a value selected from a range of 50% to 100%, preferably from 70% to 100%, in particular for at least one wavelength of the spectrum of light perceptible to the visible eye, in particular for at least one wavelength selected from a range of 400 nm to 800 nm. If the unit, the area or the layer has a transmission value of less than 50%, preferably less than 30%, it is understood to be “opaque”.
  • the protective layer prefferably, the protective layer is peeled off or at least partially dissolved.
  • the primer layer increases the adhesion of the transfer layer to the object through chemical and/or physical interactions.
  • the primer layer in the decorated object is firmly bonded to the object.
  • materially bonded preferably means that two objects, elements, layers and/or units cannot be separated without causing damage.
  • the primer layer may comprise at least one polymer, which preferably has at least one dissociable functional group.
  • the dissociable functional group offers the advantage that, particularly when decorating mineral or mineral-containing objects, such as concrete, ionic bonds, covalent bonds and/or hydrogen bonds can be formed between the object and the primer layer. Furthermore, mechanical interlocking can be formed, particularly through the formation of crystalline structures that grow into the primer layer.
  • dissociable functional group is preferably understood to mean a functional group covalently bound to the at least one polymer, which reacts on contact with an acidic aqueous, neutral aqueous or alkaline aqueous medium in such a way that anionic and/or cationic charges can be generated at least in equilibrium.
  • dissociable functional group means that partial structures of the dissociable functional group can react in equilibrium into at least two or more molecules and/or positively and/or negatively charged ions on contact with an acidic aqueous, neutral aqueous or alkaline aqueous medium.
  • a suitable dissociable functional group can, for example, release at least one proton, thereby forming an anionic functional group, or absorb a proton, forming a cationic functional group.
  • the at least one primer layer has a layer thickness selected from a range from 50 nm to 100 pm, preferably from 100 nm to 50 pm, particularly preferably from 250 nm to 20 pm.
  • the at least one dissociable functional group of the primer layer has an amino group and/or a hydroxy group and/or a free acid group, which is preferably selected from the group consisting of carboxy group, sulfonic acid group, sulfuric acid monoester group, phosphonic acid group, phosphoric acid monoester group and combinations thereof, preferably carboxy group, sulfonic acid group and combinations thereof, more preferably carboxy group, and/or a capped acid group, which is preferably selected from the group consisting of carboxylic acid ester group, carboxylic acid anhydride group, carboxylic acid halide group, sulfonic acid ester group, sulfonic acid anhydride groups, sulfonic acid halide group, phosphonic acid ester group and combinations thereof, more preferably carboxylic acid ester group, carboxylic acid anhydride group, sulfonic acid ester group and combinations thereof, more preferably carboxylic acid ester group, carboxylic acid anhydride group, sulf
  • At least one dissociable functional group of the primer layer is a free acid group, which is preferably selected from the group consisting of carboxy group, sulfonic acid group, phosphonic acid group and combinations thereof, and/or that at least one dissociable functional group is a capped acid group.
  • the primer layer comprises a polymer which comprises at least one free, anionic, functional group, which is preferably selected from the group consisting of anionically functionalized epoxy polymers and copolymers, anionically functionalized acrylic polymers and copolymers, anionically functionalized methacrylic polymers and copolymers, anionically functionalized polyurethane polymers and copolymers and mixtures thereof, preferably anionically functionalized acrylic polymers, anionically functionalized methacrylic polymers, anionically functionalized polyurethane polymers, copolymers thereof and mixtures thereof.
  • anionically functionalized epoxy polymers and copolymers anionically functionalized acrylic polymers and copolymers, anionically functionalized methacrylic polymers and copolymers, anionically functionalized polyurethane polymers and copolymers and mixtures thereof, preferably anionically functionalized acrylic polymers, anionically functionalized methacrylic polymers, anionically functionalized polyurethane polymers, copolymers thereof and mixtures thereof
  • the primer layer prefferably be made of or comprise physically setting adhesives or chemically hardening adhesives. This offers the advantage of improved adhesion when decorating objects made of plastic, stone or organic materials such as paper, cardboard and/or wood.
  • the at least one unit is arranged in regions or over the entire surface of a surface that consists of or comprises concrete, in particular fresh concrete or hardened concrete.
  • the at least one unit comprising the polymer itself can act as a primer layer.
  • the carboxyl groups of the at least one unit can also form ionic bonds, covalent bonds and/or hydrogen bonds between the Object and the at least one unit.
  • mechanical interlocking can be formed, in particular by the formation of crystalline structures during the hardening of the concrete, which grow into the at least one unit.
  • the functional layer is preferably in contact with the release layer, the protective layer and/or the at least one unit.
  • the functional layer is preferably selected from the group consisting of transparent and/or colored lacquer layers, in particular comprising one or more dyes and/or pigments, replication layers with a molded optically active surface structure, reflection layers, in particular opaque reflection layers, transparent reflection layers, metallic reflection layers or dielectric reflection layers, optically variable layers, optically active layers, interference multilayer systems, volume hologram layers, liquid crystal layers, in particular cholesteric liquid crystal layers, electrically conductive layers, antenna layers, electrode layers, magnetic layers, magnetic storage layers, adhesion promoter layers, barrier layers and combinations thereof.
  • the at least one functional layer can preferably be opaque and/or transparent at least in regions.
  • the at least one functional layer can preferably be designed as a pattern, decoration, grid, geometric figure, motif, alphanumeric character, logo, or combinations thereof.
  • the method further comprises at least the following step, which is preferably carried out after step c) or is a sub-step of step c): h) separating the at least one unit from the element, wherein the at least one unit after step h) is in the form of particles and/or fibers.
  • the separation of the element which is particularly designed as a layer, can be carried out by one of the following methods: grinding, brushing, blasting, scratching.
  • the method further comprise at least one of the following steps, which are preferably carried out after step c) and/or h): i) comminuting and/or fractionating the particles and/or fibers, j) dispersing the particles and/or fibers in a medium.
  • the particles and/or fibers are comminuted using a stirred ball mill, impact mill, roller mill, grinder, and/or dissolver.
  • Dispersing is preferably carried out using processes including agitator ball mill, impact mill, roller mill, extruder and dissolver. Binders, varnishes and/or solvents can be used as a medium for dispersion.
  • Pigment preparation obtained in particular comprising the at least one unit in the form of particles and/or fibers.
  • step d) of the process the at least one unit is dried.
  • step d) is carried out after step c) and/or before step e). It is possible that in step d) at least one of the following methods is used for drying: vacuum drying, centrifugation, exposure to IR radiation, continuous passage of gas.
  • the gas can be air and/or nitrogen, wherein the gas has a higher temperature compared to the unit.
  • step d the at least one unit is washed with a further organic solvent which has a lower boiling point than the solvent comprised by the reactive mixture.
  • the washing described enables drying to be carried out at a lower temperature. This can further ensure that the polyitaconic acid does not decarboxylate during drying.
  • water when using water as the solvent for the reactive mixture, it can be ensured that the water is completely removed.
  • the at least one unit comprising the polymer has, based on the total mass of the at least one unit, a proportion of components having a boiling point of lower than 110 °C, selected from a range from 0 wt.% to 10 wt.%, preferably from 0 wt.% to 8 wt.%, more preferably from 0 wt.% to 5 wt.%.
  • Step d) is preferably carried out until the mass of at least one unit is constant.
  • a unit comprising the polymer obtained in step c) which is dried before further processing has a more uniform foaming behavior. This gives units in the foamed state which have a uniform surface to the human eye. Without prior drying When foamed, the unit has a surface with bubbles and cavities that are visible to the human eye.
  • step d) is carried out at an ambient pressure selected from a range of 500 mbar to 1000 mbar.
  • the ambient temperature in particular the temperature of the surrounding gas, is selected from a range of 50 °C to 120 °C, preferably from 60 °C to 110 °C, more preferably from 80 °C to 100 °C.
  • an acceleration acts on the at least one unit which is selected from a range of 9.81 m/s 2 to 100,000 m/s 2 , preferably from 20 m/s 2 to 20,000 m/s 2 , more preferably from 100 m/s 2 to 5,000 m/s 2 .
  • step e) of the method the at least one unit and/or the at least one unit in the foamed state is arranged over the entire surface or in regions on an object.
  • step e) is carried out after step d) or after step f). It is possible that step e) is carried out before step f) and/or preferably before step g).
  • the at least one unit comprising the polymer and/or the at least one unit in the foamed state is arranged on the object by at least one of the following methods: spraying method, printing method, spreading method, sprinkling, doctoring, laminating method, transfer method, embossing method, adhesive method.
  • the object has at least one surface on which at least the at least one unit is arranged in regions or over the entire surface.
  • This at least one surface preferably consists of a material that is selected from the group consisting of concrete, in particular fresh concrete or hardened concrete, artificial stone, natural stone, wood, polymer, ceramic, Consists of or comprises paper, metal, composite material, or combinations thereof.
  • step e) comprises the following sub-steps: e1) providing at least one mold element, preferably formwork, with at least one outer surface and at least one inner surface, e2) applying a flowable or plastically deformable mineral building material mixture comprising water and at least one mineral binder to the at least one inner surface of the mold element, preferably formwork, e3) at least partially solidifying the mineral building material mixture to obtain a dimensionally stable mineral green body, and e4) at least partially hardening the mineral building material mixture, wherein I) the transfer film is arranged before step e1) with the side of the carrier layer facing away from the transfer layer on the at least one inner surface of the mold element provided, preferably formwork, and in step e1) the transfer layer is at least partially brought into contact with the flowable or plastically deformable mineral building material mixture, wherein in step e3) a decorated, mineral green body is obtained, and/or wherein II) the transfer film in and/or after step e3) is arranged with the following sub-steps: e1) providing
  • the at least one mineral binder is a hydraulic binder, a non-hydraulic binder or a Mixture thereof.
  • the at least one mineral binder is selected from the group consisting of calcium silicate hydrates, cement, lime, clay, gypsum, loam, magnesia binder and combinations thereof.
  • the mineral building material mixture can comprise or consist of concrete, mortar, sand-lime brick, silicate ceramic or a combination thereof.
  • step f) the at least one unit is placed in a foamed state, wherein the at least one unit has a porous structure after step f). In the foamed state, the at least one unit has a white color impression at least in some areas.
  • Step f) is preferably carried out after step d) and/or after step e) and before step g). It is also possible for step f) to be carried out after or during step c). It is also possible for the timing of step f) to at least partially overlap with the timing of step c), step d) and/or step e).
  • the at least one unit is subjected to a temperature selected from a range from 60 °C to 300 °C, preferably from 75 °C to 250 °C, more preferably from 100 °C to 180 °C.
  • the at least one unit has this temperature, in particular on one of its outer surfaces.
  • step d) and the bringing of the at least one unit into a foamed state are carried out inline directly one after the other, in particular for the steps d) and f) to overlap in time. It is thus possible for steps d) and f) to be carried out in the same device.
  • step f) is carried out at a higher average temperature than step d).
  • step f) the at least one unit is placed in a foamed state over its entire surface.
  • step f) the at least one unit is partially put into a foamed state, so that the at least one unit has foamed and unfoamed regions next to each other.
  • step f) it is also possible for step f) to be carried out several times, whereby at least when step f) is carried out for the first time, the at least one unit is put into a foamed state in some areas, so that foamed and unfoamed areas are present next to one another in the at least one unit.
  • step f) when step f) is carried out at least once further, the at least one unit can be put into a foamed state over its entire surface.
  • the foamed or unfoamed areas can be in the form of a pattern, a decoration, a grid, a geometric figure, a motif, alphanumeric characters, a logo, or combinations thereof.
  • the formation of the foamed or unfoamed areas can, together with other layers, in particular with the functional layer and/or with the object, form a pattern, a decoration, a grid, a geometric figure, a motif, an alphanumeric character, a logo, or combinations thereof.
  • the foamed or unfoamed areas are arranged in register or in register accuracy with areas of other layers, in particular the functional layer and/or the object.
  • Accurate registration means the positioning accuracy of two or more layers, elements, areas, units and/or layers relative to one another. The registration accuracy should be within a specified tolerance and as low as possible. At the same time, the registration accuracy of several layers, elements, areas, units and/or layers relative to one another is an important feature in order to increase process reliability and/or product quality, but also security against counterfeiting. Accurate positioning can be achieved in particular using sensory, preferably optically detectable register marks. These register marks can either represent special separate layers, elements, units, areas and/or layers or can themselves be part of the layers, elements, units, areas and/or layers to be positioned.
  • the at least one unit as one or more layers or partial layers on the carrier layer, for example by means of printing processes such as gravure printing, screen printing, inkjet printing, flexographic printing, it is possible to produce a transparency gradient or transparency progression over the printed surface by applying the unit and/or the one or more layers or partial layers thereof, for example by means of a gravure anilox roller with a correspondingly varying cell depth or by means of a correspondingly varying droplet size of an inkjet print head or by means of correspondingly varying screen openings of a screen printing screen, a correspondingly varying application weight for the unit, so that the locally different layer thicknesses result in a unit of different thickness in the foamed state with a correspondingly different opacity even after the unit has dried and foamed.
  • printing processes such as gravure printing, screen printing, inkjet printing, flexographic printing
  • area refers in particular to a defined area of a layer or unit which, when viewed perpendicular to a plane defined by the unit, or transfer layer. In other words, the defined area can extend through layers arranged one above the other.
  • the at least one unit only has the defined white color impression after it has been put into the foamed state. If the at least one unit is designed as a layer, it is preferably transparent in the unfoamed state. In the foamed state, the at least one unit is preferably opaque.
  • step f) and/or the formation of the porous structure is initiated by contacting the at least one unit with the object, i.e. at the beginning or during step e).
  • the object comprises a catalyst that catalyzes the formation of the porous structure.
  • the object preferably has divalent or polyvalent cations of at least one metal, wherein the at least one metal is preferably selected from the group consisting of Mg, Ca, Sr, Ba, Al, Fe, Co, or mixtures thereof.
  • the object also has monovalent or polyvalent anions selected from the group consisting of phosphate, phosphite, carbonate, hydrogen carbonate, hydroxide, aluminate, sulfate, sulfite or mixtures thereof.
  • the object preferably has compounds, in particular salts, which are formed from at least one of the possible combinations of the above anions and cations.
  • the object can be contacted, preferably sprayed and/or poured over, with a layer and/or a volume of liquid comprising the above anions and/or cations.
  • the presence of divalent or polyvalent cations is particularly advantageous for rendering the at least one unit into a foamed state in step f). It is believed that the ions catalyze the decarboxylation of the polyitaconic acid.
  • an open-pore and/or closed-pore structure is formed in the at least one unit in the foamed state in step f).
  • the at least one unit has a value for a refractive index selected from the range from 1.2 to 1.8, preferably from 1.3 to 1.7.
  • the at least one unit in the foamed state has a very high number of refractive planes, so that an observer perceives a white color impression even with a value for the refractive index selected from the range of 1.2 to 1.8.
  • a lower refractive index is therefore necessary to form a white color impression.
  • the porous structure has pores having a pore diameter selected from a range from 0.03 pm to 10 pm, preferably from 0.4 pm to 3 pm, more preferably from 0.5 pm to 1.8 pm.
  • the porous structure has pores whose
  • Pore walls have a thickness selected from a range of 0.1 pm to 1 pm, preferably 0.1 pm to 0.75 pm and more preferably from 0.15 pm to 0.4 pm.
  • the above thickness of the pore walls is advantageous because, on the one hand, it ensures that the pore walls have sufficient permeability for the incident light so that it can be refracted at as many interfaces as possible and, on the other hand, it ensures that the porous structure has sufficient mechanical strength.
  • the pore diameters and/or the pore wall thickness are preferably determined by using a scanning electron microscope (SEM), a transmission electron microscope (TEM) or an atomic force microscope (AFM). Methods known in the prior art can be used for this purpose.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • AFM atomic force microscope
  • the degree of foaming i.e. the extent of decarboxylation of the itaconic acid compared to the itaconic acid of an unfoamed sample, can be determined by methods known in the art. For example, infrared spectroscopy (IR) and nuclear magnetic resonance spectroscopy (NMR), preferably 1 H-NMR, can be used, whereby the characteristic bands for itaconic acid and its degradation products after decarboxylation are known from the prior art.
  • IR infrared spectroscopy
  • NMR nuclear magnetic resonance spectroscopy
  • ATR-FTIR ATR-FTIR infrared spectroscopy
  • ATR Attenuated Total Reflectance
  • FTIR Fourier Transform Infra-Red
  • the method further comprises the following step, which is preferably carried out after step f) and/or before step g): k) stabilising the porous structure, in particular by providing a protective layer.
  • step k) can be carried out by a method selected from the group comprising spraying methods, preferably air spraying methods, ultrasonic spraying methods and/or electrostatic spraying methods, dipping methods and/or printing methods, preferably gravure printing, screen printing, inkjet printing and/or flexographic printing, and/or combinations thereof.
  • the protective layer applied in step k) at least partially fills the porous structure.
  • the protective layer applied in step k) can have the preferred properties of a protective layer described in step c).
  • step g) a decorated object is obtained, wherein the decorated object has the at least one unit in the foamed state.
  • the object is integrally connected to the at least one unit.
  • the resulting decorated object can be used in a variety of areas.
  • the resulting decorated object is a facade element, a wallpaper, a casing element, a brickwork, a door, a floor covering, a tile, a packaging box, a piece of furniture, or a combination thereof, and/or can be used as such.
  • process steps are carried out once or several times. In particular, process steps can be repeated.
  • a preferred process has at least the following steps a), b), c), d), e), f) and g), wherein further steps can be inserted in particular between these steps.
  • the steps are preferably carried out in the sequence a), b), c), d), e), f) and g), or a), b), c), d), f), e) and g). It is also possible that steps or sub-steps of the method overlap in time, ie that a step or sub-step is not yet fully completed before a further step or sub-step is started.
  • the above-mentioned material characteristics can also be applied equivalently in a process or the above-mentioned process characteristics can be applied in the product.
  • Fig. 1a and 1b show schematic representations of the sequence of process steps.
  • Fig. 2 shows a schematic representation of a transfer film.
  • FIG. 3 shows another schematic representation of a
  • Fig. 4a and 4b show objects decorated with transfer layers.
  • Fig. 5a and 5b each show a SEM image of a unit which is designed as a transfer layer and is either in the unfoamed state or has been converted into the foamed state.
  • Fig. 6 shows a SEM image of a layered unit that has been put into the foamed state, in plan view.
  • Fig. 7 shows a SEM image of a decorated object.
  • Fig. 1a and 1b show a flow diagram of a method for producing a decorated object T.
  • Each of the methods according to Fig. 1a and 1b comprises at least the method steps a) to g): a) providing a reactive mixture which has a carboxylic acid-containing monomer component which comprises itaconic acid and/or itaconic acid derivatives, b) polymerizing the reactive mixture to form a polymer, c) contacting the polymer with an element 2, whereby at least one unit 3 comprising the polymer is obtained, whereby the at least one unit 3 comprising the polymer can be put into a foamed state in which the at least one unit 3 forms a porous structure, whereby at least one unit is obtained in the foamed state 3', and whereby the light is refracted at the porous structure in such a way that the at least one unit in the foamed state 3' has a white color impression, d) drying the at least one unit 3, e) arranging the at least one unit 3 and
  • step a) the reactive mixture is provided which has a carboxylic acid-containing monomer component, wherein the carboxylic acid-containing monomer component comprises itaconic acid and/or itaconic acid derivatives.
  • Step a) is carried out as shown in Figs. 1 a and 1 b, in each case at the beginning of the process.
  • composition of the components of the reactive mixture is selected such that the sum of the components amounts to 100% by weight based on the total weight of the reactive mass.
  • the reactive mixture, the polymer and/or the at least one unit 3 comprises no pigments, preferably no white pigments, more preferably no TiO2.
  • the reactive mixture comprises at least one further carboxylic acid-containing monomer selected individually or in combination from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid.
  • Preferred derivatives of itaconic acid of the carboxylic acid-containing monomer component are the anhydride of itaconic acid, the methoxy ester of itaconic acid and/or the ethoxy ester of itaconic acid.
  • the proportion of the carboxylic acid-containing monomer from step a) based on the total mass of the reactive mixture is selected from the range from 2.5 wt.% to 65 wt.%, preferably from 5 wt.% to 50 wt.%, more preferably from 10 wt.% to 35 wt.%.
  • the reactive mixture comprises at least one non-carboxylic acid-containing monomer component, which component or its derivatives is selected individually or in combination from the group consisting of esters of acrylic acid, esters of methacrylic acid, esters of itaconic acid, preferably dieesters of itaconic acid, esters of maleic acid, maleic anhydride, terpenes, myrcene, styrene, isoprene, butadiene and vinyl ethers.
  • non-carboxylic acid-containing monomer component which component or its derivatives is selected individually or in combination from the group consisting of esters of acrylic acid, esters of methacrylic acid, esters of itaconic acid, preferably dieesters of itaconic acid, esters of maleic acid, maleic anhydride, terpenes, myrcene, styrene, isoprene, butadiene and vinyl ethers.
  • the proportion of the non-carboxylic acid-containing monomer from step a) based on the total mass of the reactive mixture is preferably selected from the range from 5 wt.% to 50 wt.%, preferably from 15 wt.% to 35 wt.%, more preferably from 20 wt.% to 30 wt.%.
  • the reactive mixture preferably comprises a solvent, preferably water and/or an organic solvent, individually or as mixtures selected from ethanol, 1-propanol, 2-propanol, acetone, 2-butanone (MEK), acetate, in particular ethyl acetate and/or lactyl acetate.
  • a solvent preferably water and/or an organic solvent, individually or as mixtures selected from ethanol, 1-propanol, 2-propanol, acetone, 2-butanone (MEK), acetate, in particular ethyl acetate and/or lactyl acetate.
  • the proportion of solvent based on the total mass of the reactive mixture is selected from the range from 15 wt.% to 95 wt.%, preferably from 30 wt.% to 85 wt.%, more preferably from 40 wt.% to 70 wt.%, even more preferably from 45 wt.% to 60 wt.%.
  • the reactive mixture after step a) comprises an initiator for the polymerization, preferably an initiator for a radical polymerization.
  • the proportion of initiator based on the total mass of the reactive mixture is selected from the range from 0.05 wt.% to 1.5 wt.%, preferably from 0.1 wt.% to 1 wt.%, more preferably from 0.25 wt.% to 0.5 wt.%.
  • the reactive mixture after step a) comprises at least one additive which is selected individually or in combination from the group consisting of crosslinker, flow agent, stabilizer, light stabilizer, flame retardant, defoamer, leveling additive, hydrophobizing agent, plasticizer, deactivator, antioxidant or radical chain terminator.
  • the reactive mixture according to step a) comprises fillers which, individually or in combination, are selected from the group comprising mineral fillers, sand, diatomaceous earth, layered silicates, talc, aluminates, carbon fibers, wood flour, starch and glass fibers.
  • a reactive mixture suitable for the process according to the invention according to Fig. 1a and 1b has the following composition, wherein the details of the individual components are each based on the total mass of the reactive mixture and the components are selected so that they add up to 100% by weight:
  • Carboxylic acid-containing monomer component 2.5 wt.% - 65 wt.%
  • Non-carboxylic acid-containing monomer component 5 wt.% - 50 wt.%
  • Solvent 15 wt.% - 95 wt.%
  • Carboxylic acid-containing monomer component 5 wt.% - 50 wt.%
  • Non-carboxylic acid-containing monomer component 15 wt.% - 35 wt.%
  • Carboxylic acid-containing monomer component 10 wt.% - 35 wt.%
  • Non-carboxylic acid-containing monomer component 20 wt.% - 30 wt.%
  • Solvent 45 wt% - 60 wt%
  • step b) a polymer is obtained from the reactive mixture provided in step a).
  • step b) is preferably carried out after step a).
  • step b) is carried out at a temperature of the reactive mixture selected from a range of 20 °C to 110 °C, preferably from 40 °C to 85 °C, more preferably from 50 °C to 70 °C.
  • the polymer obtained in step b) has a value for the number average molar mass selected from a range from 500 g/mol to 500,000 g/mol, preferably from 750 g/mol to 100,000 g/mol, more preferably from 1000 g/mol to 50,000 g/mol, even more preferably from 1500 g/mol to 20,000 g/mol.
  • the polymer prepared in step b) has at least one further carboxylic acid-containing monomer unit selected from the group selected individually or in combination from acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride.
  • the proportion of the carboxylic acid-containing monomer in the polymer based on the total mass of the polymer is selected from the range from 2.5 wt.% to 100 wt.%, preferably from 5 wt.% to 80 wt.%, more preferably from 10 wt.% to 50 wt.%.
  • the polymer prepared in step b) has at least one non-carboxylic acid-containing monomer component which is selected from the group of components individually or in combination consisting of esters of acrylic acid, esters of methacrylic acid, esters of itaconic acid, esters of maleic acid, terpenes, myrcene, styrene, isoprene, butadiene, vinyl ethers and derivatives thereof.
  • non-carboxylic acid-containing monomer component which is selected from the group of components individually or in combination consisting of esters of acrylic acid, esters of methacrylic acid, esters of itaconic acid, esters of maleic acid, terpenes, myrcene, styrene, isoprene, butadiene, vinyl ethers and derivatives thereof.
  • the proportion of the monomer of the non-carboxylic acid-containing component based on the total mass of the polymer is preferably selected from the range from 0 wt.% to 97.5 wt.%, preferably from 5 wt.% to 90 wt.%, more preferably from 15 wt.% to 85 wt.%.
  • the polymer obtained in step b) has a polydispersity value selected from a range from 1.8 to 4, preferably from 1.9 to 3, more preferably from 2 to 2.5, even more preferably from 2.1 to 2.4.
  • step c) the polymer obtained in step b) is contacted with an element 2, whereby the at least one unit 3 comprising the polymer is obtained.
  • step c) is preferably carried out after step b) and before step d).
  • the element 2 can be, for example, a liquid volume, preferably a basic solution, or a carrier layer 5. It is also possible that the liquid volume, preferably the basic solution, is arranged on a carrier layer 5.
  • the at least one unit 3 obtained can be designed as a layer, film, particle and/or fiber. In this case, it is possible to obtain an emulsion paint, a varnish, a powder, a transfer film, in particular a laminating film or a transfer film 4 with a transfer layer 6 that can be detached from the carrier layer 5.
  • the element 2 is a basic aqueous solution comprising divalent or polyvalent cations of at least one metal, wherein the at least one metal is preferably selected from the group consisting of Mg, Ca, Sr, Ba, Al, Fe, Co or mixtures thereof.
  • the element 2 has a pH value selected from a range of 8 to 14, preferably 10 to 14, more preferably 12 to 14.
  • the element 2 comprises monovalent or polyvalent anions selected from the group consisting of phosphate, phosphite, carbonate, bicarbonate, hydroxide, aluminate, sulfate, sulfite or mixtures thereof.
  • the cations and anions are selected from water-soluble salts.
  • a spraying process preferably selected from air spraying processes, ultrasonic spraying processes, electrostatic spraying processes, wherein the at least one unit 3 in the form of particles and/or fibers is obtained by the spraying process.
  • the polymer for spraying is dissolved and/or dispersed in a solvent, preferably an organic solvent, more preferably methyl ethyl ketone, acetone, ethanol and/or mixtures thereof.
  • the particles are preferably irregular or regular, preferably spherical, platelet-shaped or rod-shaped.
  • the particles have a value for an average volume-related particle diameter that is selected from a range of 0.5 pm to 1000 pm, preferably 1 pm to 750 pm, more preferably 3 pm to 300 pm.
  • the fibers have a length to width shape factor selected from a range of 3:1 to 1000:1, preferably 10:1 to 500:1.
  • step c) the element 2 is a carrier layer 5 or comprises it.
  • step c) the contacting is carried out by arranging the at least one unit 3 comprising the polymer on the carrier layer 5 in a region-wise or full-surface manner, wherein the at least one unit 3 is obtained in the form of a layer.
  • a transfer film 4 is obtained by contacting the at least one unit 3 with the element 2.
  • Fig. 2 shows a schematic structure of a transfer film 4 obtained after step c), wherein the transfer film 4 has a carrier layer 5 and a transfer layer 6 comprising the at least one unit 3.
  • the transfer layer 6 is detachable from the carrier layer 5.
  • the transfer film 4 shown in Fig. 2 can have a unit 3 that has not yet been put into the foamed state 3' or a unit 3' that has already been put into the foamed state.
  • the transfer layer 6 cannot be removed from the carrier layer 5, wherein the transfer film 4 can preferably be used as a laminating film.
  • the carrier layer 5 consists of a polyester, a polyolefin or a combination thereof, in particular of PET.
  • the carrier layer 5 preferably has a layer thickness selected from a range of 5.7 pm to 100 pm, preferably 19 pm to 50 pm.
  • the polymer is arranged on the carrier layer 5 with an application weight selected from a range from 5 g/m 2 to 20 g/m 2 , preferably from 8 g/m 2 to 12 g/m 2 .
  • step c) the polymer is arranged on the carrier layer 5 with a layer thickness selected from a range of 5 pm to 20 pm, preferably 8 pm to 12 pm.
  • the layer thickness is measured in particular in the dried state of the layer.
  • step c) at least one of the following methods is used to arrange the at least one unit 3 or one or more further layers on the carrier layer 5: gravure printing, screen printing, inkjet printing, flexographic printing, offset printing, spraying, casting, injection molding.
  • step c) one or more further layers are arranged over the entire surface or in regions on the carrier layer 5.
  • the one or more layers are selected from the group consisting of release layer 7, primer layer 8, functional layer, protective layer 9.
  • Fig. 3 shows a transfer film 4 which has a carrier layer 5 and a transfer layer 6 like the transfer film 4 shown in Fig. 2.
  • the transfer film 4 according to Fig. 3 has a release layer 7, a primer layer 8 and a protective layer 9.
  • a transfer film 4 can also have a functional layer which is not shown in Fig. 3. This functional layer can be arranged as desired between, on and/or under other layers, depending on the function.
  • the release layer 7 is arranged in the transfer film 4 according to Fig. 3 in contact with the carrier layer 5.
  • a protective layer 9 is also arranged on the release layer 7, which after the carrier layer 5 has been detached represents the visible side of the transfer layer 6.
  • the unit 3 according to the invention is applied as a layer on the protective layer 9, on which in turn a primer layer 8 is arranged.
  • the release layer 7 remains on the carrier layer 5, the transfer layer 6 and/or on the carrier layer 5 and the transfer layer 6 after detachment.
  • the release layer 7 consists of or comprises a wax, preferably montan wax, or silicone, or combinations thereof.
  • the release layer 7 of a transfer film 4 according to Fig. 3 preferably has a layer thickness selected from a range from 0.01 pm to 1 pm, preferably from 0.02 pm to 0.7 pm, more preferably from 0.02 pm to 0.5 pm.
  • the transfer film 4 according to Fig. 3 can have a self-supporting protective layer 9 or a non-self-supporting protective layer 9.
  • the protective layer 9 has a layer thickness selected from a range of 0.5 pm to 10 pm, preferably from 0.8 pm to 5 pm.
  • the protective layer 9 is preferably formed from or comprises at least one polymer, individually or in combination, selected from: polyester, polyolefin, polyurethane, polyacrylate, styrene resin, ketone resin.
  • the protective layer 9 is preferably transparent. It is also possible for the protective layer 9 to be colored and/or to be designed as a translucent protective layer 9.
  • the protective layer 9 is also possible for the protective layer 9 to be removed again after step e) or step g) of a method according to Fig. 1a and 1b.
  • the protective layer 9 is preferably peeled off or at least partially dissolved.
  • the primer layer 8 of the transfer film 4 according to Fig. 3 is preferably materially bonded to the object 1 in the decorated object T after step e) of a method according to Figs. 1a and 1b.
  • the primer layer 8 comprises at least one polymer which preferably has at least one dissociable functional group.
  • the at least one primer layer 8 has a layer thickness selected from a range from 50 nm to 100 pm, preferably from 100 nm to 50 pm, more preferably from 250 nm to 20 pm.
  • the at least one dissociable functional group of the primer layer 8 has an amino group and/or a hydroxy group and/or a free acid group, which is preferably selected from the group consisting of carboxy group, sulfonic acid group, sulfuric acid monoester group, phosphonic acid group, phosphoric acid monoester group and combinations thereof, preferably carboxy group, Sulfonic acid group and combinations thereof, more preferably carboxy group, and/or a capped acid group which is preferably selected from the group consisting of carboxylic acid ester group, carboxylic acid anhydride group, carboxylic acid halide group, sulfonic acid ester group, sulfonic acid anhydride groups, sulfonic acid halide group, phosphonic acid ester group and combinations thereof, more preferably carboxylic acid ester group, carboxylic acid anhydride group, sulfonic acid ester group and combinations thereof, more preferably carboxylic acid ester group, carboxylic acid anhydride group, sulfonic
  • At least one dissociable functional group of the primer layer 8 comprises or consists of a free acid group, which is preferably selected from the group consisting of carboxy group, sulfonic acid group, phosphonic acid group and combinations thereof, and/or that at least one dissociable functional group comprises or consists of a capped acid group, which is preferably selected from the group consisting of carboxylic acid ester group, carboxylic acid anhydride group, sulfonic acid ester group, sulfonic acid anhydride group and combinations thereof.
  • the primer layer 8 comprises a polymer that comprises at least one free, anionic, functional group, which preferably consists of the group consisting of anionically functionalized epoxy polymers and copolymers, anionically functionalized acrylic polymers and copolymers, anionically functionalized methacrylic polymers and copolymers, anionically functionalized polyurethane polymers and copolymers and mixtures thereof, preferably anionically functionalized acrylic polymers, anionically functionalized methacrylic Polymers, anionically functionalized polyurethane polymers, copolymers thereof, and mixtures thereof.
  • anionically functionalized epoxy polymers and copolymers preferably consists of the group consisting of anionically functionalized epoxy polymers and copolymers, anionically functionalized acrylic polymers and copolymers, anionically functionalized methacrylic polymers and copolymers, anionically functionalized polyurethane polymers and copolymers and mixtures thereof, preferably anionically functionalized acrylic polymers, anionically functionalized meth
  • the primer layer 8 of the transfer film 4 according to Fig. 3 is formed from or comprises physically setting adhesives or chemically curing adhesives.
  • the functional layer of a transfer film 4 according to Fig. 3 is preferably selected from the group consisting of transparent and/or colored lacquer layers, in particular comprising one or more dyes and/or pigments, replication layers with a molded optically active surface structure, reflection layers, in particular opaque reflection layers, transparent reflection layers, metallic reflection layers or dielectric reflection layers, optically variable layers, optically active layers, interference multilayer systems, volume hologram layers, liquid crystal layers, in particular cholesteric liquid crystal layers, electrically conductive layers, antenna layers, electrode layers, magnetic layers, magnetic storage layers, adhesion promoter layers, barrier layers and combinations thereof.
  • the at least one functional layer can preferably be opaque and/or transparent at least in regions.
  • the at least one functional layer can preferably be designed as a pattern, decoration, grid, geometric figure, motif, alphanumeric character, logo, or combinations thereof.
  • a transfer film 4 which comprises at least one carrier layer 5 and a transfer layer 6, as shown for example in Fig. 2, it is also possible that the method, in addition to the sequence of steps shown in Fig. 1a and 1b, further comprises at least the following step h).
  • Step h) is preferably carried out after step c) or is a sub-step of step c).
  • h) separating the at least one unit 3 from the element 2, wherein the at least one unit 3 is in the form of particles and/or fibers after step h).
  • the transfer layer 6 is separated again, whereby the particles and/or fibers obtained can be further processed.
  • the separation can be carried out by one of the following methods: grinding, brushing, blasting, scratching.
  • Further processing of the particles and/or fibers obtained can be carried out, for example, by further optional steps in the process. It is thus possible for the process to further comprise at least one of the following steps, which are preferably carried out after step c) and/or h): i) comminution and/or fractionation of the particles and/or fibers, j) dispersing the particles and/or fibers in a medium.
  • the particles and/or fibers are comminuted using a stirred ball mill, impact mill, roller mill, grinder, and/or dissolver.
  • Dispersing is preferably carried out using processes including agitator ball mill, impact mill, roller mill, extruder and dissolver. Binders, varnishes and/or solvents can be used as a medium for dispersion.
  • step j) an emulsion paint and/or a varnish and/or a printing ink and/or a pigment preparation is obtained, in particular comprising the at least one unit 3 in the form of particles and/or fibers.
  • step d) of the method the at least one unit 3 is dried.
  • step d) is carried out after step c) and/or before step e).
  • step d) at least one of the following methods is used for drying: vacuum drying, centrifugation, exposure to IR radiation, continuous passage of gas.
  • the gas can be air and/or nitrogen, in particular where the gas has a higher temperature compared to the unit.
  • step d) the at least one unit 3 is washed with a further organic solvent which has a lower boiling point than the solvent comprised by the reactive mixture.
  • the at least one unit 3 comprising the polymer has, based on the total mass of the at least one unit 3 after step d), a proportion of components which have a boiling point of lower than 110 °C, selected from a range from 0 wt.% to 10 wt.%, preferably from 0 wt.% to 8 wt.%, more preferably from 0 wt.% to 5 wt.%.
  • Step d) is preferably carried out until the mass of at least one unit 3 is constant.
  • step d) is carried out at an ambient pressure selected from a range of 500 mbar to 1000 mbar.
  • the ambient temperature is selected from a range of 50 °C to 120 °C, preferably from 60 °C to 110 °C, more preferably from 80 °C to 100 °C.
  • an acceleration acts on the at least one unit 3 which is selected from a range of 9.81 m/s 2 to 100,000 m/s 2 , preferably from 20 m/s 2 to 20,000 m/s 2 , more preferably from 100 m/s 2 to 5,000 m/s 2 .
  • step e) of a method according to Fig. 1 a and Fig. 1 b the at least one unit 3 and/or the at least one unit in the foamed state 3' is arranged over the entire surface or in regions on an object 1.
  • step e) is carried out after step d) or after step f). It is possible that step e) is carried out before step f) and/or preferably before step g).
  • the at least one unit 3 comprising the polymer and/or the at least one unit in the foamed state 3' is arranged on the object 1 by at least one of the following methods: spraying method, printing method, spreading method, sprinkling, doctoring, laminating method, transfer method, embossing method, adhesive method.
  • the object 1 has at least one surface on which at least the at least one unit 3 is arranged in regions or over the entire surface.
  • This at least one surface preferably consists of a material that is selected from the group consisting of or comprising concrete, in particular fresh concrete or hardened concrete, artificial stone, natural stone, wood, polymer, ceramic, paper, metal, composite material, or combinations thereof.
  • step e) comprises the following sub-steps: e1) providing at least one mold element, preferably formwork, with at least one outer surface and at least one inner surface, e2) applying a flowable or plastically deformable mineral building material mixture, which comprises water and at least one mineral binder, to the at least one inner surface of the mold element, preferably formwork, e3) at least partially solidifying the mineral building material mixture to obtain a dimensionally stable, mineral green body, and e4) at least partially hardening the mineral building material mixture, wherein I) the transfer film 4 is coated with the
  • Transfer layer 6 is arranged on the at least one inner surface of the provided molded element, preferably formwork, and in step e1) the transfer layer 6 is at least partially brought into contact with the flowable or plastically deformable mineral building material mixture, wherein in step e3) a decorated mineral green body is obtained, and/or wherein II) the transfer film 4 is arranged in and/or after step e3) with the transfer layer 6 at least partially on the dimensionally stable mineral green body, wherein a decorated, dimensionally stable mineral green body is obtained, and wherein in alternatives I) and II) in step g) a decorated mineral molded body is obtained as the decorated object T.
  • the at least one mineral binder may comprise a hydraulic binder, a non-hydraulic binder or a mixture thereof.
  • the at least one mineral binder is selected from the group consisting of calcium silicate hydrates, cement, lime, clay, gypsum, loam, magnesia binder and combinations thereof.
  • the mineral building material mixture can comprise or consist of concrete, mortar, sand-lime brick, silicate ceramic or a combination thereof.
  • step f) the at least one unit is placed in a foamed state 3', wherein the at least one unit 3' has a porous structure after step f).
  • step f) is preferably carried out after step d) and/or after step e) and before step g). Furthermore, it is possible that step f) is carried out after or during step c). It is also possible that the timing of step f) overlaps at least partially with the timing of step c), step d) and/or step e).
  • the at least one unit 3' has a white color impression at least in some areas.
  • the at least one unit in the foamed state 3' preferably has a value for the parameters a and b selected from a range from -4 to 4, preferably from -3 to 3, more preferably from -2 to 2, even more preferably from -1 to 1.
  • the at least one unit in the foamed state 3' has a value for the parameter L selected from a range from 70 to 100, preferably from 80 to 100, more preferably from 90 to 100.
  • the at least one unit 3 is subjected to a temperature selected from a range from 60 °C to 300 °C, preferably from 75 °C to 250 °C, more preferably from 100 °C to 180 °C.
  • the at least one unit 3 has this temperature, in particular on one of its outer surfaces.
  • step d) and the bringing of the at least one unit into a foamed state 3' to be carried out inline directly one after the other, in particular for the steps d) and f) to overlap in time. It is thus possible for steps d) and f) to be carried out in the same device.
  • step f) is carried out at a higher average temperature than step d).
  • the at least one unit 3 is placed into a foamed state over its entire surface.
  • the at least one unit 3 is partially put into a foamed state, so that the at least one unit has foamed areas and unfoamed areas next to each other.
  • step f) it is also possible for step f) to be carried out several times, whereby at least when step f) is carried out for the first time, the at least one unit 3 is put into a foamed state in some areas, so that foamed and unfoamed areas are present next to one another in the at least one unit.
  • step f) when step f) is carried out at least once further, the at least one unit 3 can be put into a foamed state over its entire surface.
  • the foamed or unfoamed areas can be in the form of a pattern, a decoration, a grid, a geometric figure, a motif, alphanumeric characters, logos, or combinations thereof.
  • the formation of the foamed or unfoamed areas can, together with other layers, in particular with the functional layer and/or with the object, form a pattern, a decoration, a grid, a geometric figure, a motif, an alphanumeric character, a logo, or combinations thereof.
  • the foamed areas or unfoamed areas are arranged in register or in register accuracy with areas of further layers, in particular the functional layer and/or the object.
  • the at least one unit 3 only has the defined white color impression when it has been put into the foamed state. If the at least one unit 3 is designed as a layer, it is preferably transparent in the unfoamed state.
  • the at least one unit in the foamed state 3' is preferably opaque.
  • step f) is initiated at the beginning or during step e).
  • the object 1 comprises a catalyst which catalyzes the formation of the porous structure.
  • the object 1 preferably has divalent or polyvalent cations of at least one metal, wherein the at least one metal is preferably selected from the group consisting of Mg, Ca, Sr, Ba, Al, Fe, Co or mixtures thereof.
  • the object 1 also has monovalent or polyvalent anions selected from the group consisting of phosphate, phosphite, carbonate, hydrogen carbonate, hydroxide, aluminate, sulfate, sulfite or mixtures thereof.
  • the object 1 preferably has compounds, in particular salts, which are formed from at least one of the possible combinations of the above preferred anions and cations.
  • the object 1 can be contacted with, preferably sprayed or poured over, a layer and/or a volume of liquid comprising the above anions and/or cations.
  • an open-pore and/or closed-pore structure is formed in the at least one unit in the foamed state 3' in step f).
  • the at least one unit in the foamed state 3' has, in particular due to the porous structure, a value for a refractive index between 1.2 and 1.8, preferably between 1.3 and 1.7.
  • the porous structure has pores having a pore diameter selected from a range of 0.03 pm and 10 pm, preferably from 0.4 pm to 3 pm, more preferably from 0.5 pm to 1.8 pm.
  • the porous structure can have pores whose pore walls have a thickness selected from a range from 0.1 pm to 1 pm, preferably 0.1 pm to 0.75 pm and more preferably from 0.15 pm to 0.4 pm.
  • the method in addition to the steps listed in Fig. 1a and 1b, further comprises the following step, which is preferably carried out after step f) and/or before step g): k) stabilizing the porous structure, in particular by arranging a protective layer,
  • step k) can be carried out by a method selected from the group comprising spraying methods, preferably air spraying methods, ultrasonic spraying methods and/or electrostatic spraying methods, dipping methods and/or printing methods, preferably gravure printing, screen printing, inkjet printing and/or flexographic printing, and/or combinations thereof.
  • spraying methods preferably air spraying methods, ultrasonic spraying methods and/or electrostatic spraying methods, dipping methods and/or printing methods, preferably gravure printing, screen printing, inkjet printing and/or flexographic printing, and/or combinations thereof.
  • the protective layer applied in step k) at least partially fills the porous structure.
  • the protective layer applied in step k) can have the preferred properties of a protective layer described in step c).
  • a method according to the invention has step g) as the last method step.
  • step g) a decorated
  • Object T wherein the decorated object T is the at least one unit in the foamed state 3.
  • the object 1 is integrally connected to the at least one unit 3.
  • Fig. 4a and Fig. 4b show a schematic structure of a decorated object T.
  • the decorated object T according to Fig. 4a has a unit in the foamed state 3' arranged on the object 1.
  • the unit 3 was arranged on the object 1, for example, by means of a transfer film 4 according to Fig. 2.
  • the unit 3 can also be a layer which has particles, wherein these particles were dispersed in a medium according to steps i) and j) and then arranged on the object 1.
  • Fig. 4b shows a decorated object T on which, for example, the transfer layer 6 of the transfer film 4 according to Fig. 3 has been arranged.
  • the decorated object T has a primer layer 8 which is in contact with the object T.
  • the primer layer 8 contacts a unit in the foamed state 3', which in turn is in contact with a protective layer 9.
  • the protective layer 9 forms the visible side of the decorated object T.
  • the transfer layer 6 does not comprise a protective layer 9 and that the protective layer 9 was arranged by step k) after the transfer layer 6 was arranged on the object 1.
  • the obtained decorated object T for example according to Fig. 4a or Fig. 4b, can be used in a variety of areas.
  • the obtained decorated object T is a facade element, a wallpaper, a housing element, a masonry, a door, a floor covering, a tile, a packaging box, a piece of furniture, or a combination thereof, and/or can be used as such.
  • step c) the polymer was applied to an element 2 in the form of a carrier layer 5.
  • the unit 3 was Layer and formed the transfer layer 6 of the transfer film 4, wherein the transfer layer 6 was detachable from a carrier layer 5.
  • the decorated object 1' was to be a decorated concrete part as shown in Fig. 4a.
  • a batch polymer was first synthesized by means of a free radical polymerization of myrcene and itaconic acid in ethanol according to steps a) and b), whereby the solvent was not limited to ethanol.
  • composition of the reactive mixture corresponded to 24.4 g of myrcene (24.4 wt. %) and 15.6 g of itaconic acid (15.6 wt. %) in 60 g of ethanol (60 wt. %).
  • the initiator used was 0.37 g of the azo initiator V-65 (0.37 wt. %) at a polymerization temperature of 65 °C.
  • a PET carrier layer 5 (thickness of the PET carrier layer 5 from 5 pm to 150 pm, preferably from 7 pm to 100 pm) was then used and coated with a release layer 7 made of montan ester wax that was at least 50 nm thick.
  • the coated PET carrier layer 5 was then coated with a doctor blade on the side of the release layer 7 with polymer dissolved in ethanol as described in step c).
  • the application weight of the dried layer of the polymer in various tests with different layer thicknesses was 1.6 g/m 2 , 4 g/m 2 , 8 g/m 2 , 10 g/m 2 , 12 g/m 2 , 18.5 g/m 2 . This corresponds to a layer thickness in the dried state of approx. 1.6 pm, 4 pm, 8 pm, 10 pm, 12 pm or 18.5 pm.
  • step d) the coating was dried to constant weight at approx. 150 °C using a hot air stream (hair dryer) for approx. 10 seconds and formed a closed transfer layer 6 of the transfer film 4.
  • the concrete was mixed by combining 1935 g of gravel (fraction: 2 mm to 8 mm), 2565 g of sand (fraction: 0 mm to 2 mm) and 900 g of CEM ll/A-LL 42.5 N (Portland limestone cement) and stirring this mixture with 450 g of water to form a homogeneous concrete mixture.
  • Each transfer film 4 was arranged with the transfer layer 6 on a plate made of ABS material with a thickness of 1 mm and 300 g of the prepared concrete was applied in contact with the transfer layer 6 to each transfer film 4 within a formwork (see step e)).
  • step g After complete hardening of the concrete at room temperature, a mineral composite body was formed according to step g), which was coated on one side with the transfer film 4 used in each case.
  • the concrete bodies were freed from the formwork and left to dry completely under atmospheric conditions. After 24 hours of drying, the PET carriers were removed from the concrete, with the transfer layers 6 remaining attached to the concrete and forming a smooth coating on the composite body. The white color of the paint layer had also already fully developed during this period.
  • the resulting aqueous dispersion was added to ethanol to remove impurities, as the impurities dissolve in the ethanol in particular.
  • the solvents were removed by filtration (pore 4) and the remaining polymeric solid was dried at 40 °C in a vacuum drying cabinet (air pressure approx. 20 mbar) for approx. 10 hours.
  • the resulting powder was ground manually in a mortar and heated to approx. 170 °C in a round-bottom flask while swirling.
  • the particle size of the pigment particles was determined by means of dynamic light scattering. Particle size is preferably understood to mean the volume-related particle diameter.
  • the resulting prepared powder was dispersed in a solvent, e.g. ethanol, using dispersing additives (in the example: Solsperse 35000) and a dispersion with a solids content of 18.5 wt.% (consisting of dispersing additive and pigment) was obtained.
  • the dispersion (100 wt.%) consisted of 7.5 wt.% dispersing additives, 81.5 wt.% ethanol and 11 wt.% pigment.
  • This dispersion was then added to a binder solution (in the example: 36% solution of Degacryl HS 4240D in ethanol) so that the total solids content of the paint made up of pigment and binder was approximately 23% by weight.
  • a binder solution in the example: 36% solution of Degacryl HS 4240D in ethanol
  • This paint was spread onto a carrier film using a doctor blade and the resulting paint film was heated using a hot air stream (hair dryer) for approximately 30 seconds. dried.
  • the application weight of the dry layer was about 8 g/m 2 , which corresponds to a layer thickness of about 8 pm of the dried layer.
  • a PET carrier layer 5 (thickness of the PET carrier layer 5 from 5 pm to 150 pm, preferably from 7 pm to 100 pm) was used as the carrier film.
  • the carrier layer 5 can optionally be coated with a release layer 7 made of montan ester wax that is at least 50 nm thick before the paint is applied by knife coating.
  • One or more adhesion-promoting layers, primer layers or adhesive layers can optionally be applied to the knife-coated and dried paint. This makes it possible to produce transfer films for use as cold stamping films and/or hot stamping films.
  • the doctored lacquer can also be present in only one layer on the carrier layer 5 and, due to the thermoplastic properties of the binder, can be used, for example, as a hot stamping foil, in which the lacquer layer detaches from the carrier layer 5 under the influence of mechanical pressure and heat and adheres to a substrate.
  • At least one unit 3 comprising the polymer is obtained as particles.
  • the particles can be dispersed in a medium in a further step, in particular the medium comprising the particles can be applied to an object 1, for example as an emulsion paint.
  • This example has the step sequence according to Fig. 1 a, and additionally comprises steps i) and j).
  • the polymer for example the batch of Example 2, was dried in a vessel or applied to a carrier in a drying cabinet under vacuum at 40 °C until the mass was constant.
  • the layer of dried polymer was then crushed using a mortar and a homogeneously ground powder was obtained.
  • the particles were heated in a temperature-resistant vessel such as a round-bottomed flask with gentle circular shaking over a burner flame or a hot air dryer. This continued until the first spherical particles were obtained from the powder. These particles had a white color appearance.
  • the particles can then be fractionated and dispersed in a medium, in particular wherein the medium comprising the particles, for example as emulsion paint or varnish, can be applied to an object 1.
  • the medium comprising the particles for example as emulsion paint or varnish
  • the application of the particles dispersed in a medium and the further processing can be carried out, for example, analogously to Example 1.
  • Example formulations of a varnish with the polymer shown in Example 2 are listed in Table 1: Example formulations of a varnish with the polymer shown in Example 2
  • Synexil SAB 05 can be used as a polymeric binder, in particular a binder based on styrene acrylate.
  • Omyacarb 5-GU can be used as a calcium carbonate filler.
  • Optiflo H 600 can be used as an associative thickener.
  • Surfynol DF110 D can be used as a defoamer.
  • Aerosil TT 600 can be used as an Aerosil filler.
  • Ropaque Ultra EF can be used as an opacifying emulsion. Tinopal OB can be used as an optical brightener.
  • At least one unit 3 comprising the polymer can be obtained as particles or fibers by spraying a dissolved polymer into a basic solution.
  • the particles and/or fibers can be dried, comminuted, fractionated and dispersed in a medium in a further step, as described for steps i) and j), in particular wherein the medium comprising the particles can be applied to an object 1, for example as an emulsion paint.
  • a solution containing 20% by weight of the polymer for example the batch from Example 1, was used.
  • a basic solution was then prepared by dissolving Ca(OH)2 in 250 g of water until saturated.
  • the polymer solution was then sprayed into the basic solution using a commercially available spray gun (for example TIMBERTECH ABPST01 airbrush set) at a working pressure of 1 bar.
  • the polymer precipitated on the surface of the basic solution in the form of particles and/or fibers.
  • the layer of dried polymer was then crushed using a mortar and a homogeneously ground powder was obtained.
  • the particles of the powder had a white color appearance.
  • the particles can then be fractionated and dispersed in a medium, in particular wherein the medium comprising the particles can be applied to an object 1, for example as an emulsion paint.
  • the application of the particles dispersed in a medium and the further processing can be carried out, for example, analogously to Example 1.
  • Example 1 To compare the color impression of an object T decorated according to the invention with an object 1 that was coated with a TiO2-containing lacquer layer, a concrete was prepared as described in Example 1 and cured in the form of several test specimens.
  • TiO2-containing dispersions were created, the TiO2 content of which was adjusted to between 10 wt.% and 52 wt.% based on the solids of the dried layer.
  • Transfer films according to Example 1 were produced from these dispersions.
  • a corresponding layer of a TiO2-containing dispersion was now printed onto the release layer using gravure printing, with each transfer film containing different layers of the TiO2- containing dispersion with different TiC contents based on the solids of the dried layer.
  • test specimens were each coated with a TiC-containing dispersion through the transfer film.
  • the application weight of the TiC-containing layer was 10 g/m 2 in each case. This corresponded to a layer thickness in the dry state of approx. 10 pm.
  • the TiC-containing layer formed a continuous layer on the test specimen.
  • Example 1 For a direct comparison of the color impression of the samples obtained according to Example 1 and Comparative Example 1, their color location in the CIELAB color space was determined.
  • the color location in the CIELAB color space was determined using a color measuring device, for example a "Datacolor 650" spectrophotometer, with one sample being clamped in front of the measuring opening.
  • Tables 2 and 3 show the results of the brightness values L and the a and b coordinates in the CIELAB color space.
  • Table 4 shows which layer thickness in the dry state was required for the samples produced according to the invention according to Example 1 in order to achieve a comparable white color impression and/or opacity to the samples of Comparative Example 1 produced according to the prior art.
  • Table 2 Values for the color coordinates in the CIELAB color space (L, a, b) of the samples prepared according to Comparative Example 1. The samples are designated according to their solid content of TiO2.
  • Table 3 Values for the color coordinates in the CIELAB color space (L, a, b) of the samples prepared according to Example 1.
  • Table 4 Allocation of the layer thickness in the dry state of a coating according to the invention to a TiO2-containing layer (layer thickness in the dry state approx. 10 pm) with comparable opacity.
  • the values in Tables 2 and 3 show that comparable color locations could be achieved by decorating the concrete according to the invention. This means that the hiding power of the decoration according to the invention can be very close to that of the prior art.
  • the sample according to the invention shows a positive b-value at high application weights, which results in a slight shift of the color impression towards yellow.
  • a coating according to comparative example 1 achieves a comparable color impression with a layer thickness of 10 pm in the dry state and a TiO2 content of 30 wt.%. This shows that 30 wt.% TiO2 can be saved when using a decoration according to the invention.
  • SEM images were taken of parts of the transfer film 4 described in Example 1, the unit 3 comprising the polymer being designed in the form of a layer or the transfer layer 6.
  • One image shows a unit in the unfoamed state and one image shows a unit in the foamed state 3'.
  • SEM images were taken of the decorated object T obtained in Example 1. The SEM images are shown in Fig. 5a and 5b, Fig. 6 and Fig. 7.
  • sample bodies were cut out of the films to be examined or the coated object and coated with gold by sputtering.
  • the sample bodies had dimensions of approximately 20 mm x 10 mm x 4 mm (20 mm x 10 mm base area, thickness 4 mm).
  • the cut surfaces of transfoils comprising a carrier layer 5 made of PET and a unit 3 in the form of a transfer layer 6 were examined in the unfoamed state (Fig. 5a) and foamed state 3' (Fig. 5b).
  • the image in Fig. 5a was created at a magnitude of x950, a working distance of 10 mm, a spot size of 60 and an acceleration voltage of 5 kV.
  • the measuring bar is 20 pm.
  • the image in Fig. 5b was created at a magnitude of x120, a working distance of 13 mm, a spot size of 60 and an acceleration voltage of 15 kV.
  • the measuring bar is 100 pm.
  • the transfer layer 6 has a compact structure in the unfoamed state, whereas a porous structure was formed in the foamed state. Furthermore, the formation of the porous structure of the transfer layer 6 led to an increase in the layer thickness by a factor of between 8 and 10.
  • the SEM images of Fig. 6 show a top view of a unit in the foamed state 3', for example the transfer layer 6 of the transfer film 4 according to Example 1.
  • the image of Fig. 6 was created at a magnitude of x1500, a working distance of 15 mm, a spot size of 60 and an acceleration voltage of 15 kV.
  • the measuring bar is 10 pm.
  • Fig. 6 illustrates the porous structure of the transfer layer 6, which creates the white color impression through refraction at the multitude of interfaces formed.
  • the SEM image of Fig. 7 shows a cut edge of an object 1 made of concrete, whereby the object 1 was coated with a unit 3 according to the invention.
  • the unit 3 was in the foamed state 3'
  • the image in Fig. 7 was taken at a magnitude of x250, a working distance of 17 mm, a spot size of 60 and an acceleration voltage of 10 kV.
  • the measuring bar is 100 pm.
  • Fig. 7 shows that the transfer layer 6 has a strong adhesion to the concrete, which can be explained by a mechanical and chemical “anchoring" of the transfer layer to the concrete. Furthermore, it is particularly evident that the transfer layer formed a closed and smooth surface that seals the concrete.

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Abstract

La présente invention concerne un procédé de production d'un objet décoré (1), le procédé comprenant les étapes suivantes, en particulier dans lesquelles l'étape f) est une sous-étape de l'étape c) et/ou est exécutée après l'étape d) et/ou après l'étape e) : a) fourniture d'un mélange réactif comprenant un composant monomère contenant de l'acide carboxylique qui comprend de l'acide itaconique et/ou des dérivés d'acide itaconique, b) polymérisation du mélange réactif pour obtenir un polymère, c) mise en contact du polymère avec un élément (2) afin d'obtenir au moins une unité (3) comprenant le polymère, l'au moins une unité (3) qui comprend le polymère étant convertible en un état expansé dans lequel l'au moins une unité (3) forme une structure poreuse afin d'obtenir au moins une unité dans l'état expansé (3') et la structure poreuse réfractant la lumière de sorte que l'au moins une unité dans l'état expansé (3') présente une impression de couleur blanche, d) séchage de l'au moins une unité (3), e) arrangement de l'au moins une unité (3) et/ou de l'au moins une unité dans l'état expansé (3') sur toute la zone ou les régions d'un objet (1), f) conversion d'au moins une unité (3) en un état expansé afin d'obtenir ladite unité dans l'état expansé (3'), g) obtention d'un objet décoré (1') comprenant ladite unité dans l'état expansé (3'), l'impression de couleur étant décrite en tant que point de couleur dans l'espace colorimétrique CIELAB par les paramètres L, a et b et l'au moins une unité dans l'état expansé (3') ayant une valeur pour les paramètres a et b choisie dans une plage de -4 à 4. L'invention se rapporte également à un objet décoré et à l'utilisation d'un mélange réactif dans un procédé de production d'un objet décoré.
PCT/EP2023/080210 2022-11-14 2023-10-30 Procédé de production d'un objet décoré, objet décoré et utilisation d'un mélange réactif pour la production d'un objet décoré WO2024104767A1 (fr)

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DE102022130058.7A DE102022130058A1 (de) 2022-11-14 2022-11-14 Verfahren zur Herstellung eines dekorierten Objektes, ein dekoriertes Objekt und Verwendung einer reaktiven Mischung zur Herstellung eines dekorierten Objektes
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Citations (4)

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CA2007314A1 (fr) * 1989-02-10 1990-08-10 Patricia L. Marlette Element autocollant, a trois dimensions
EP0392847A2 (fr) * 1989-04-12 1990-10-17 Minnesota Mining And Manufacturing Company Article moulé prévu pour adhérer à un substrat et méthode de production
US20050137341A1 (en) * 2003-12-11 2005-06-23 Hawrylko Roman B. Foamable polyvinyl chloride compound tolerant of high heat conditions
JP2015212494A (ja) * 2014-05-07 2015-11-26 株式会社ユポ・コーポレーション 建築装飾シート

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US3804700A (en) 1972-05-10 1974-04-16 Rohm & Haas Decorative laminate
DE2617243A1 (de) 1975-05-30 1977-11-03 Rohm & Haas Polymermasse
GB1594587A (en) 1976-10-15 1981-07-30 Rohm & Haas Waterproof textile laminates
JPS56109781A (en) 1980-02-01 1981-08-31 Taisei Corp Production of ornamental board

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2007314A1 (fr) * 1989-02-10 1990-08-10 Patricia L. Marlette Element autocollant, a trois dimensions
EP0392847A2 (fr) * 1989-04-12 1990-10-17 Minnesota Mining And Manufacturing Company Article moulé prévu pour adhérer à un substrat et méthode de production
US20050137341A1 (en) * 2003-12-11 2005-06-23 Hawrylko Roman B. Foamable polyvinyl chloride compound tolerant of high heat conditions
JP2015212494A (ja) * 2014-05-07 2015-11-26 株式会社ユポ・コーポレーション 建築装飾シート

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