Process for producing a decorated object, a decorated object and use of a reactive mixture for producing a decorated object

Abstract

The present invention relates to a process for producing a decorated object (1), wherein the process comprises the following steps, in particular wherein step f) is a sub-step of step c) and / or is performed after step d) and / or after step e): a) providing a reactive mixture comprising a carboxylic acid-containing monomer component which comprises itaconic acid and / or itaconic acid derivatives, b) polymerizing the reactive mixture to afford a polymer, c) contacting the polymer with an element (2) to obtain at least one unit (3) comprising the polymer, wherein the at least one unit (3) comprising the polymer is convertible into a foamed state in which the at least one unit (3) forms a porous structure to obtain at least one unit in the foamed state (3') and wherein the porous structure refracts light in such a way that the at least one unit in the foamed state (3') exhibits a white color impression, d) drying the at least one unit (3), e) arranging the at least one unit (3) and / or the at least one unit in the foamed state (3') over the full area or regions of an object (1), f) converting at least one unit (3) into a foamed state to obtain the at least one unit in the foamed state (3'), g) obtaining a decorated object (1') comprising the at least one unit in the foamed state (3'), wherein the color impression is described as a color point In the CIELAB color space by the parameters L, a and b and wherein the at least one unit in the foamed state (3') has a value for the parameters of a and b selected from a range from -4 to 4, and to a decorated object and to the use of a reactive mixture in a process for producing a decorated object.

Description

[0001] LEONHARD KURZ Foundation & Co. KG, Schwabacher Str. 482, 90763 Fürth

[0002] Method for producing a decorated object, a decorated object and use of a reactive mixture for producing a decorated object

[0003] 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.

[0004] In many products, 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.

[0005] However, the production of an object that contains TiO2 and / or has TiO2 on its surface is problematic:

[0006] (i) an additional work step for incorporating the TiO2 particles, which increases costs, (ii) complicated disposal procedures due to possible environmental damage caused by TiO2 particles, (iii) suspected health problems and effects such as pneumonia caused by, for example, respirable particles, (iv) TiO2 (in the rutile type) has a comparatively high density of approximately 4240 kg / m 3 , which can result in a 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, for example, to create decorated objects.

[0007] In order to obtain a white color impression, it is therefore necessary to resort to a possibility to obtain the optical effect of a refractive index n in the order of magnitude of TiO2 (n = 2.5).

[0008] The present invention describes how to create a sponge-like, porous, polymeric structure that produces a white color impression through high light scattering. Advantageously, this structure does not need to have a refractive index on the order of TiO2. Due to the high number of interfaces, repeated light scattering occurs within the structure, which is why refractive indices between 1.2 and 1.8 are sufficient for a white color impression.

[0009] The refractive index is determined using a refractometer method as defined in 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 the 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.

[0010] For this purpose, a polymer based on itaconic acid was developed. Applying at least one unit comprising the polymer, for example in the form of a layer or in the form of particles and / or fibers, to an object, such as concrete, or spraying it into a basic solution results in an ionically catalyzed decarboxylation of the polyitaconic acid. In other words, CO2 is released from the itaconic acid molecule, for example, with the formation of a lactone. This leads to foaming of the at least one unit formed from the polymer. Alternatively or additionally, the decarboxylation of the polymer of the at least one unit according to the invention can be initiated thermally.

[0011] The following reaction equation (1) shows a possible reaction pathway for the decarboxylation of polyitaconic acid (left) resulting in the release of CO2. As a result of the reaction, the possible product (right) exhibits a ring closure within the molecule:

[0012] The porous structure created by foaming is mechanically stable and, due to light refraction at a high number of interfaces, creates a white color impression of the object decorated with the polymer.

[0013] Thus, 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.

[0014] The object is achieved by providing a method for producing an object, in particular according to claim 1, wherein the method comprises the following steps, in particular wherein 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 thatthat 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 least one unit and / or the at least one unit in the foamed state over the entire surface or in regions on an object, f) putting at least one unit into a foamed state while maintaining the at least one unit in the foamed state, g) obtaining a decorated object comprising the at least one unit in the foamed state, 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.

[0015] The object is further achieved by a decorated object comprising a polymer, preferably according to claim 59, in particular produced by a process 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 in such a way that the at least one unit in the foamed state has a white color impression, wherein the color impression is described as a color locus 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.

[0016] The object is further achieved, in particular by claim 60, by the use of 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.

[0017] Furthermore, it is possible to provide at least one unit comprising the polymer or a multilayer film comprising the at least one unit.

[0018] Color, color impression, or colorfulness, or individual color or individual color, refers to a color location within a color space. The color space can be, in particular, the CIELAB color space. The color space can also be the RGB color space (R = red; G = green; B = blue) or the CMYK color space (C = cyan; M = magenta; Y = yellow; K = black), or color spaces such as RAL, HKS, or the Pantone® color space.

[0019] A different or differing color is understood to be 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, and further preferably at least 10.

[0020] The color coordinate, especially in the CIELAB color space, is usually determined using a colorimeter, such as a Datacolor 650 spectrophotometer (Datacolor AG). The color coordinate 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).

[0021] In the device, light rays received from the illuminated sample are separated into their component wavelengths, for example via a prism.

[0022] This splits the light into a number of narrow bands or measurement channels (typically 20 to 40 bands with a width selected from a range of approximately 10 nm to 20 nm). The separated light is then focused onto 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 indicating the intensity of each wavelength of light.

[0023] To determine the color space, a sample, such as a film, a bulk sample, a cuvette, or a decorated object, is clamped in front of the device's light aperture and a measurement is taken using the associated software. The software then automatically calculates the sample's resulting Lab values.

[0024] The value of dE (or Delta E or AE) between the color coordinates (L* a*, b*) P and (L* a* b*) v is calculated as Euclidean distance:

[0025] The brightness value L* is perpendicular to the color plane (a* b*). The a coordinate indicates the chromaticity and color intensity between green and red, and the b coordinate indicates the chromaticity and color intensity between blue and yellow. The larger the positive a and b values ​​and the smaller the negative a and b values, the more intense the hue. If a = 0 and b = 0, the hue is achromatic on the brightness axis. Typically, L* can assume values ​​between 0 and 100, and a and b can vary between -128 and +127.

[0026] A viewer preferably perceives a color as white if the values ​​of a and b are selected from a range of -5 to 5 and preferably if L is a value selected from a range of 70 to 100. In the edge regions of the above values ​​of the coordinates of a and b, preferably at a value of ±0.5 for the values ​​of a and b, the viewer already perceives a slight color cast. In the edge regions of the above values ​​of the coordinates of L, preferably at a value of ±5 for the values ​​of L, 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.

[0027] The at least one unit in the foamed state 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, and even more preferably from -1 to 1. Preferably, 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.

[0028] 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.

[0029] By eliminating TiC particles, the aforementioned disadvantages of TiO2 are avoided. For example, a coating according to the invention does not contain respirable nanoparticles, which also result in disposal costs.

[0030] Another advantage is that the resulting polymer can be produced from biological raw materials. In other words, the amount of petroleum-based monomers can be reduced. For example, itaconic acid, used as a monomer, can be obtained biotechnologically through the fermentation of molasses or synthesized from pyruvic acid. This results in a more sustainable product. Furthermore, due to the availability of raw materials, a unit comprising the polymer can be produced cost-effectively.

[0031] This makes it possible to obtain decorated objects with a white color impression that exhibits good durability. For example, the decorated objects are suitable in the form of a facade panel, which will retain their color impression even under climatic conditions such as humidity or mechanical stress. Further advantageous embodiments of the invention are described in the subclaims.

[0032] In step a), the reactive mixture is prepared, which comprises 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 composition of the constituents of the reactive mixture is selected such that the sum of the constituents amounts to 100 wt. % (wt. % = weight percent) based on the total weight of the reactive mass.

[0033] 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.

[0034] It is possible that 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.

[0035] Preferred derivatives of itaconic acid in 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 itaconic acid derivative of the carboxylic acid-containing monomer component is preferably derivatized with at most one carboxylic acid and is present, for example, as an itaconic acid monoester. The advantage here is that the at least one additional monomer of the carboxylic acid-containing component can improve the handling of the polyitaconic acid. For example, the glass transition temperature can be increased, thereby increasing the mechanical strength. In addition, the foamability of the at least one unit comprising the polymer is not affected or only slightly affected.

[0036] 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.%.

[0037] Preferably, “carboxylic acid-containing” means that a molecule, for example a monomer, is present which contains at least one functional unit of the type -COOH, in particular when provided.

[0038] Preferably, "non-carboxylic acid-containing" means a molecule, for example a monomer, that does not contain a functional unit of the -COOH type, especially when provided. This definition thus includes, for example, unsaturated hydrocarbons and unsaturated aromatic hydrocarbons, and in particular carboxylates and carboxylic acid derivatives.

[0039] 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. 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.%.

[0040] 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, its outdoor applicability. On the other hand, the above proportion does not significantly affect the foamability of the at least one unit comprising the polymer.

[0041] 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.

[0042] Preferably, the proportion of the 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.%.

[0043] 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. Preferably, a solvent 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 preferably comprises an initiator for the

[0044] Polymerization, preferably an initiator for radical polymerization.

[0045] Furthermore, it is possible that 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.%.

[0046] It is also possible for the reactive mixture to comprise at least one additive 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.

[0047] Furthermore, it is also possible for the reactive mixture to comprise fillers selected individually or in combination from the group comprising mineral fillers, sand, diatomaceous earth, phyllosilicates, talc, aluminates, carbon fibers, wood flour, starch, glass fibers.

[0048] By using additives and fillers, the processability of the reactive mixture or polymer can be improved and the stability of the at least one unit obtained from the polymer can be increased.

[0049] Preferably, 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:

[0050] Carboxylic acid-containing monomer component: 2.5 wt% - 65 wt%, Non-carboxylic acid-containing monomer component: 5 wt% - 50 wt%,

[0051] Solvent: 15 wt% - 95 wt%,

[0052] Initiator: 0.05 wt% - 1.5 wt%,

[0053] Additive: 0 wt% - 3 wt%,

[0054] Filler: 0 wt% - 10 wt%.

[0055] Further preferred:

[0056] Carboxylic acid-containing monomer component: 5 wt% - 50 wt%,

[0057] Non-carboxylic acid-containing monomer component: 15 wt% - 35 wt%,

[0058] Solvent: 30 wt% - 85 wt%,

[0059] Initiator: 0.1 wt% - 1 wt%,

[0060] Additive: 0 wt% - 2 wt%,

[0061] Filler: 0 wt% - 7 wt%.

[0062] Even more preferred:

[0063] Carboxylic acid-containing monomer component: 10 wt% - 35 wt%,

[0064] Non-carboxylic acid-containing monomer component: 20 wt% - 30 wt%,

[0065] Solvent: 45 wt% - 60 wt%,

[0066] Initiator: 0.25 wt% - 0.5 wt%,

[0067] Additive: 0 wt% - 1 wt%,

[0068] Filler: 0 wt% - 5 wt%.

[0069] In step b), a polymer is obtained from the reactive mixture provided in step a), in particular wherein the resulting polymer 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) preferably takes place at a temperature of the reactive mixture selected from a range from 20°C to 110°C, preferably from 40°C to 85°C, more preferably from 50°C to 70°C.

[0070] Preferably, 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 1,000 g / mol to 50,000 g / mol, even more preferably from 1,500 g / mol to 20,000 g / mol.

[0071] 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.

[0072] It is possible that the polymer prepared in step b) comprises at least one further carboxylic acid-containing monomer unit selected individually or in combination from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid.

[0073] 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%.

[0074] The polymer prepared in step b) preferably comprises at least one non-carboxylic acid-containing monomer component selected individually or in combination from the group 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.%.

[0075] Furthermore, it is possible for the non-carboxylic acid-containing component in step a) to comprise 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 the at least one blocked carboxylic acid is present as at least one carboxylic acid in the polymer after step b). Deblocking can be carried out, for example, thermally or chemically.

[0076] A polymer is preferably understood to be a molecule formed from the chemical reaction of at least three monomers. Molecules formed from fewer than five monomers are preferably referred to as oligomers.

[0077] Preferably, the polymer obtained in step b) has a polydispersity value selected from a range of 1.8 to 4, preferably 1.9 to 3, more preferably 2 to 2.5, even more preferably 2.1 to 2.4.

[0078] Polydispersity is a measure of the width of the molar mass distribution. It is calculated from the ratio of weight average Mw, i.e. the molar mass based on the ratio of the weight of the polymer chains of an identical mass to the number average M n , i.e., the molar mass based on the ratio of the number of polymer chains of identical length to the total number of all polymer chains. The greater the polydispersity, the broader the molar mass distribution. The above polydispersity value has the advantage of achieving a broad polymer dispersity. The broad dispersity, in turn, enables easier processing and / or handling of the polymer, particularly due to a wider melting range.

[0079] In step c), the polymer obtained in step b) is contacted 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. Furthermore, it is 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, particles 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.

[0080] It is possible that 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.

[0081] The inventors have surprisingly discovered that the presence of divalent or polyvalent cations allows for the conversion of at least one unit into a foamed state, i.e., step f), to be carried out particularly well. It is assumed that the ions catalyze the decarboxylation of the polyitaconic acid.

[0082] The presence of alkali metals of the 1st main group of the periodic table, such as sodium or potassium, as well as other monovalent ions, such as ammonium, for example in a basic solution, has no beneficial effect on the transformation of at least one unit into a foamed state.

[0083] By “basic” it is preferably understood that an element, an object and / or a solution has a pH value selected from a range of 8 to 14, preferably from 10 to 14, more preferably from 12 to 14.

[0084] Preferably, the element comprises monovalent or polyvalent anions selected from the group consisting of phosphate, phosphite, carbonate, bicarbonate, hydroxide, aluminate, sulfate, sulfite or mixtures thereof.

[0085] Preferably, the cations and anions are selected from water-soluble salts.

[0086] It is possible for the polymer to be brought into contact with the element, particularly in the form of a liquid volume, preferably a basic solution, by a spraying process. The spraying process is preferably selected from air spraying, ultrasonic spraying, and electrostatic spraying, with the at least one unit being obtained in the form of particles and / or fibers by the spraying process.

[0087] Preferably, 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.

[0088] Furthermore, it is possible for the element in step c) to be a carrier layer or to comprise one. It is also possible for the element to be arranged on a carrier layer in regions or over the entire surface. It is possible for the contacting in step c) to be effected 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.

[0089] Preferably, by contacting the at least one unit with the element, a transfer film is obtained, wherein the transfer film comprises a carrier layer and a transfer layer. The transfer layer comprises the at least one unit. Preferably, the transfer layer is detachable from the carrier layer. Alternatively, it is also possible for the transfer layer not to be detachable from the carrier layer, whereby the transfer film is preferably used as a laminating film.

[0090] The carrier layer preferably consists of a polyester, a polyolefin or a combination thereof, in particular of PET.

[0091] Furthermore, 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.

[0092] Preferably, in step c) the at least one unit with an application weight is selected from a range of 5 g / m 2 up to 20 g / m 2 , preferably 8 g / m 2 up to 12 g / m 2 , arranged on the carrier layer.

[0093] It is further possible that in step c), the at least one unit is arranged on the carrier layer 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.

[0094] Preferably, in 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, or injection molding. During the arrangement, the polymer can be present in the unit, for example, in dissolved, melted, or dispersed form.

[0095] It is possible that in step c) one or more additional layers are applied to the entire surface or in certain regions of the carrier layer. In particular, the one or more layers are selected from the group consisting of release layer, primer layer, functional layer, and protective layer.

[0096] The release layer enables non-destructive detachment of the at least one unit, the one or more additional 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. Preferably, the release layer remains on the carrier layer, the transfer layer, and / or on the carrier layer and the transfer layer after detachment.

[0097] The release layer preferably consists of or comprises a wax, preferably montan wax, silicone, or combinations thereof. The release layer preferably has a layer thickness selected from a range of 0.01 μm to 1 μm, preferably from 0.02 μm to 0.7 μm, more preferably from 0.02 μm to 0.5 μm.

[0098] 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 from mechanical or chemical stress during the process, in particular during placement on the object, or during use of the decorated object. The protective layer is preferably designed as a self-supporting protective layer or as a non-self-supporting protective layer.

[0099] Preferably, the protective layer has a layer thickness selected from a range of 0.5 pm to 10 pm, preferably from 0.8 pm to 5 pm.

[0100] 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.

[0101] 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.

[0102] “Transparent” is understood to mean a transmission of a unit, a region 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 light spectrum perceivable by the visible eye, in particular for at least one wavelength selected from a range of 400 nm to 800 nm. If the unit, the region or the layer has a transmission value of less than 50%, preferably less than 30%, it is understood to be “opaque”.

[0103] It is also possible for the protective layer to be removed again after step e) or step g). Preferably, the protective layer is peeled off or at least partially dissolved.

[0104] The primer layer increases the adhesion of the transfer layer to the object through chemical and / or physical interactions. Preferably, the primer layer is bonded to the object in the decorated object.

[0105] The term “materially bonded” preferably means that two objects, elements, layers and / or units cannot be separated without destruction.

[0106] The primer layer may comprise at least one polymer which preferably has at least one dissociable functional group.

[0107] 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.

[0108] The term “dissociable functional group” is preferably understood to mean a functional group covalently bonded to the at least one polymer, which reacts upon 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. For example, a dissociable functional group means that partial structures of the dissociable functional group can react in equilibrium upon contact with an acidic aqueous, neutral aqueous, or alkaline aqueous medium into at least two or more molecules and / or positively and / or negatively charged ions. A suitable dissociable functional group can, for example, donate at least one proton, forming an anionic functional group, or accept a proton, forming a cationic functional group.

[0109] Furthermore, the at least one primer layer has a layer thickness selected from a range of 50 nm to 100 pm, preferably from 100 nm to 50 pm, particularly preferably from 250 nm to 20 pm.

[0110] Preferably, the at least one dissociable functional group of the primer layer comprises an amino group and / or a hydroxyl 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 and combinations thereof, more preferably carboxylic acid ester group, sulfonic acid ester group and combinations thereof, more preferably carboxylic acid ester group, and / or a combination thereof.

[0111] It is possible that at least one dissociable functional group of the primer layer 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.

[0112] It is possible for the primer layer to comprise a polymer that 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.

[0113] Furthermore, it is also possible for the primer layer to be formed from or comprise physically setting adhesives or chemically curing 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.

[0114] Alternatively, it is possible for no primer layer to be present. This is particularly advantageous if the at least one unit is arranged partially or over its entire surface on a surface consisting of or comprising concrete, in particular fresh concrete or hardened concrete.

[0115] This is because the at least one unit comprising the polymer itself can act as a primer layer. As already explained above, 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. Furthermore, mechanical interlocking can be formed, particularly through the formation of crystalline structures during the curing of the concrete, which grow into the at least one unit.

[0116] The functional layer is preferably in contact with the release layer, the protective layer and / or the at least one unit.

[0117] 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.

[0118] The at least one functional layer can preferably be opaque and / or transparent at least in some areas.

[0119] The at least one functional layer can preferably be designed as a pattern, decoration, grid, geometric figure, motif, alphanumeric character, logo, or combinations thereof.

[0120] Furthermore, it is also possible for the method to further comprise 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 is in the form of particles and / or fibers after step h).

[0121] 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.

[0122] Furthermore, it is possible for the method to 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.

[0123] Preferably, the particles and / or fibers are comminuted using a stirred ball mill, impact mill, roller mill, grinder, and / or dissolver.

[0124] Dispersing is preferably carried out using processes including stirred ball mills, impact mills, roller mills, extruders, and dissolvers. Binders, coatings, and / or solvents can be used as dispersion media, for example.

[0125] Advantageously, after step j), an emulsion paint and / or a varnish and / or a printing ink and / or a paste and / or a

[0126] Pigment preparation obtained, in particular comprising the at least one unit in the form of particles and / or fibers.

[0127] In step d) of the process, the at least one unit is dried.

[0128] Preferably, step d) is performed after step c) and / or before step e). It is possible that at least one of the following drying methods is used in step d): vacuum drying, centrifugation, exposure to IR radiation, or continuous gas flow. For example, the gas can be air and / or nitrogen, with the gas having a higher temperature than the unit.

[0129] Additionally, it is possible that at the beginning of or during step d), the at least one unit is washed with another organic solvent that has a lower boiling point than the solvent comprised by the reactive mixture. The described washing allows, on the one hand, drying to be carried out at a lower temperature. This further ensures that the polyitaconic acid does not decarboxylate during drying. On the other hand, using water as the solvent for the reactive mixture ensures that the water is completely removed.

[0130] Preferably, after step d), 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 of 0 wt.% to 10 wt.%, preferably from 0 wt.% to 8 wt.%, more preferably from 0 wt.% to 5 wt.%.

[0131] Step d) is preferably carried out until the mass of at least one unit is constant.

[0132] The inventors have surprisingly discovered that a unit comprising the polymer obtained in step c) that is dried prior to further processing exhibits more uniform foaming behavior. This results in units in the foamed state that have a uniform surface to the human eye. Without prior drying, the unit in the foamed state has a surface with bubbles and cavities visible to the human eye.

[0133] Preferably, step d) is carried out at an ambient pressure selected from a range of 500 mbar to 1000 mbar. Alternatively or additionally, 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. Furthermore, it is possible that in step d) an acceleration acting on the at least one unit is selected from a range of 9.81 m / s. 2 up to 100,000 m / s 2 , preferably 20 m / s 2 up to 20,000 m / s 2 , more preferably 100 m / s 2 up to 5,000 m / s 2 , is carried out.

[0134] In 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 certain regions on an object. Preferably, step e) is performed after step d) or after step f). It is possible for step e) to be performed before step f) and / or preferably before step g).

[0135] Preferably, in step e), 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, doctor blade coating, laminating method, transfer method, embossing method, adhesive method.

[0136] The object has at least one surface on which at least one unit is arranged in regions or over its entire surface. This at least one surface is preferably made of a material 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.

[0137] In a preferred embodiment, it is possible that step e) comprises the following sub-steps: e1) providing at least one shaped 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 shaped 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 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 provided shaped element, preferably formwork,is arranged 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 transfer layer 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 shaped body is obtained as the decorated object.

[0138] It is possible for the at least one mineral binder to comprise a hydraulic binder, a non-hydraulic binder, or a mixture thereof. Preferably, 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. Furthermore, the mineral building material mixture can comprise or consist of concrete, mortar, sand-lime brick, silicate ceramic, or a combination thereof.

[0139] In step f), the at least one unit is brought into 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 regions. Step f) is preferably carried out after step d) and / or after step e) and before step g). Furthermore, it is possible for step f) to be carried out after or during step c). Furthermore, it is possible for the temporal implementation of step f) to at least partially overlap with the temporal implementation of step c), step d) and / or step e).

[0140] Preferably, in step f), the at least one unit is subjected to a temperature selected from a range of 60°C to 300°C, preferably from 75°C to 250°C, more preferably from 100°C to 180°C. Preferably, the at least one unit has this temperature, in particular on one of its outer surfaces.

[0141] It is possible for the drying of step d) and the transfer of the at least one unit to a foamed state to be carried out inline directly one after the other, in particular for the execution of steps d) and f) to overlap in time. Thus, it is possible for steps d) and f) to be carried out in the same device. Preferably, step f) is carried out at a higher average temperature than step d). Preferably, in step f), the at least one unit is transferred to a foamed state over its entire surface.

[0142] Alternatively, it is also possible that in step f) the at least one unit is brought into a foamed state in regions, so that the at least one unit has foamed and unfoamed regions next to each other.

[0143] Furthermore, it is possible for step f) to be performed multiple times, wherein at least during the first execution of step f), the at least one unit is partially foamed, so that foamed and unfoamed regions exist side by side in the at least one unit. In particular, during at least one further execution of step f), the at least one unit can be foamed over its entire surface.

[0144] 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.

[0145] 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.

[0146] In particular, it can be provided that the foamed or unfoamed areas are arranged in register or with precise register to areas of other layers, in particular the functional layer and / or the object. Precise register is understood to mean the positional accuracy of two or more layers, elements, areas, units and / or layers relative to one another. The register accuracy should be within a specified tolerance and be as small as possible. At the same time, the register accuracy of several layers, elements, areas, units and / or layers with one another is an important feature in order to increase process reliability and / or product quality, but also security against counterfeiting. Precise positioning can be achieved in particular by means of 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.

[0147] In order to arrange 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 correspondingly different opacity even after the unit has been dried and foamed.

[0148] In this context, a region is understood to mean, in particular, a defined area of ​​a layer or unit that, when viewed perpendicular to a plane formed by the unit or transfer layer, is occupied. In other words, the defined region can extend through layers arranged one above the other.

[0149] Preferably, the at least one unit exhibits the defined white color impression only after it has been brought into the foamed state. If the at least one unit is configured as a layer, it is preferably transparent in the unfoamed state. In the foamed state, the at least one unit is preferably opaque.

[0150] In particular, it is possible for step f) and / or the formation of the porous structure to be initiated by contacting the at least one unit with the object, i.e., at the beginning of or during step e). In particular, the object comprises a catalyst that catalyzes the formation of the porous structure.

[0151] The object preferably comprises 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. Furthermore, the object comprises monovalent or polyvalent anions selected from the group consisting of phosphate, phosphite, carbonate, bicarbonate, hydroxide, aluminate, sulfate, sulfite, or mixtures thereof. The object preferably comprises compounds, in particular salts, formed from at least one of the possible combinations of the above anions and cations.

[0152] Alternatively or additionally, the object can be contacted, preferably sprayed and / or poured over, with a layer and / or a volume of liquid containing the above-mentioned anions and / or cations. The presence of divalent or polyvalent cations is particularly advantageous for converting 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.

[0153] Preferably, an open-pore and / or closed-pore structure is formed in the at least one unit in the foamed state in step f).

[0154] In the foamed state, the at least one unit has, in particular due to the porous structure, a value for a refractive index selected from the range of 1.2 to 1.8, preferably from 1.3 to 1.7.

[0155] Advantageously, 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 at a refractive index value selected from the range of 1.2 to 1.8. Compared to white pigments such as TiC, a lower refractive index is therefore required to create a white color impression.

[0156] Preferably, the porous structure has pores having a pore diameter selected from a range of 0.03 pm to 10 pm, preferably from 0.4 pm to 3 pm, more preferably from 0.5 pm to 1.8 pm.

[0157] This ensures, on the one hand, a sufficient number of refraction planes to create a white color impression. On the other hand, a uniform surface with sufficient mechanical strength is obtained.

[0158] Furthermore, it is possible that the porous structure has pores whose

[0159] 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 0.15 pm to 0.4 pm.

[0160] The above thickness of the pore walls is advantageous because, on the one hand, 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, a sufficient mechanical strength of the porous structure is maintained.

[0161] The pore diameters and / or pore wall thickness are preferably determined using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or an atomic force microscope (AFM). For this purpose, methods known in the prior art can be used.

[0162] The degree of foaming, i.e. the extent of decarboxylation of 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, where the characteristic bands for itaconic acid and its degradation products after decarboxylation are known from the state of the art.

[0163] For example, a sample can be analyzed non-destructively using ATR-FTIR (ATR-FTIR infrared spectroscopy, ATR = Attenuated Total Reflectance, FTIR = Fourier Transform Infra-Red) or a small amount of a sample of approximately 30 mg can be dissolved in approximately 0.6 ml of deuterated water and measured using NMR.

[0164] Furthermore, it is possible for the method to further comprise 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.

[0165] This makes it possible to even better protect the porous structure of the at least one unit in the foamed state from mechanical and chemical stress. For example, step k) can be carried out by a process selected from the group consisting of spraying processes, preferably air spraying processes, ultrasonic spraying processes and / or electrostatic spraying processes, dipping processes and / or printing processes, preferably gravure printing, screen printing, inkjet printing and / or flexographic printing, and / or combinations thereof.

[0166] Preferably, the protective layer applied in step k) at least partially fills the porous structure.

[0167] The protective layer applied in step k) may have the preferred properties of a protective layer described in step c).

[0168] In step g), a decorated object is obtained, wherein the decorated object comprises the at least one unit in the foamed state. Preferably, the object is integrally bonded to the at least one unit.

[0169] The resulting decorated object can be used in a variety of areas. For example, the resulting decorated object is a facade element, wallpaper, a casing element, a masonry element, 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.

[0170] It is also possible for the method steps to be carried out once or more than once. In particular, method steps can be repeated. A preferred method has at least the following steps a), b), c), d), e), f) and g), wherein in particular further steps can be inserted 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). Furthermore, it is possible for steps or sub-steps of the method to overlap in time, i.e. that a step or sub-step is not yet fully completed before a further step or sub-step is started.

[0171] Of course, 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.

[0172] The invention is explained below using several exemplary embodiments with the aid of the accompanying drawings. The exemplary embodiments shown are therefore not to be understood as limiting.

[0173] Fig. 1a and 1b show schematic representations of the sequence of process steps.

[0174] Fig. 2 shows a schematic representation of a transfer film.

[0175] Fig. 3 shows a further schematic representation of a

[0176] Transfer film.

[0177] Fig. 4a and 4b show objects decorated with transfer layers.

[0178] Fig. 5a and 5b each show an SEM image of a unit formed as a transfer layer, either in the unfoamed state or in the foamed state. Fig. 6 shows a SEM image of a unit formed as a layer, which has been foamed, in a top view.

[0179] Fig. 7 shows an SEM image of a decorated object.

[0180] Fig. 1a and 1b show a flow diagram of a process for producing a decorated object T. Each of the processes according to Fig. 1a and 1b comprises at least the process steps a) to g): a) Providing a reactive mixture comprising a carboxylic acid-containing monomer component comprising 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 3' is obtained in the foamed state, and whereby the light is refracted at the porous structure such that the at least one unit 3' has a white color impression in the foamed state, d) Drying the at least one unit 3,e) Arranging the at least one unit 3 and / or the at least one unit in the foamed state 3' over the entire surface or in regions on an object 1, f) Putting at least one unit 3 into a foamed state while obtaining the at least one unit in the foamed state 3', g) Obtaining a decorated object 1' comprising the at least one unit in the foamed state 3', 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 3' has a value for the parameters a and b selected from a range from -4 to 4.

[0181] In the following, the steps of the sequence of process steps shown in Fig. 1 a and 1 b will be explained.

[0182] In step a), the reactive mixture is prepared, which comprises 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 at the beginning of the process, as shown in Figures 1a and 1b.

[0183] The 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.

[0184] Preferably, the reactive mixture, the polymer and / or the at least one unit 3 does not comprise any pigments, preferably no white pigments, more preferably no TiO2.

[0185] It is possible that 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.

[0186] Preferred derivatives of itaconic acid in 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 of 2.5 wt.% to 65 wt.%, preferably from 5 wt.% to 50 wt.%, more preferably from 10 wt.% to 35 wt.%.

[0187] Preferably, the reactive mixture comprises at least one non-carboxylic acid-containing monomer component, which component or derivatives thereof are 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.

[0188] 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.%.

[0189] 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.

[0190] Preferably, the proportion of the 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.%.

[0191] The reactive mixture according to step a) preferably comprises an initiator for the polymerization, preferably an initiator for a free-radical polymerization. Furthermore, the proportion of initiator, based on the total mass of the reactive mixture, can be 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.%.

[0192] It is also possible for the reactive mixture after step a) to comprise at least one additive 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.

[0193] Furthermore, it is possible that 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, phyllosilicates, talc, aluminates, carbon fibers, wood flour, starch and glass fibers.

[0194] Preferably, 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 wt.%:

[0195] 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%,

[0196] Initiator: 0.05 wt% - 1.5 wt%,

[0197] Additive: 0 wt% - 3 wt%,

[0198] Filler: 0 wt% - 10 wt%.

[0199] Further preferred:

[0200] Carboxylic acid-containing monomer component: 5 wt% - 50 wt%, Non-carboxylic acid-containing monomer component: 15 wt% - 35 wt%,

[0201] Solvent: 30 wt% - 85 wt%,

[0202] Initiator: 0.1 wt% - 1 wt%,

[0203] Additive: 0 wt% - 2 wt%,

[0204] Filler: 0 wt% - 7 wt%.

[0205] Even more preferred:

[0206] Carboxylic acid-containing monomer component: 10 wt% - 35 wt%,

[0207] Non-carboxylic acid-containing monomer component: 20 wt% - 30 wt%,

[0208] Solvent: 45 wt% - 60 wt%,

[0209] Initiator: 0.25 wt% - 0.5 wt%,

[0210] Additive: 0 wt% - 1 wt%,

[0211] Filler: 0 wt% - 5 wt%.

[0212] In step b), a polymer is obtained from the reactive mixture prepared in step a). According to Figs. 1a and 1b, step b) is preferably carried out after step a).

[0213] Preferably, 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.

[0214] Preferably, 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 1,000 g / mol to 50,000 g / mol, even more preferably from 1,500 g / mol to 20,000 g / mol.

[0215] It is possible that the polymer prepared in step b) comprises at least one further carboxylic acid-containing monomer unit selected individually or in combination from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride.

[0216] 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%.

[0217] Preferably, the polymer prepared in step b) comprises 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.

[0218] 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.%.

[0219] Preferably, the polymer obtained in step b) has a polydispersity value selected from a range of 1.8 to 4, preferably 1.9 to 3, more preferably 2 to 2.5, even more preferably 2.1 to 2.4.

[0220] In 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. According to Fig. 1a and 1b, step c) is preferably carried out after step b) and before step d). The element 2 can, for example, be a liquid volume, preferably a basic solution, or a carrier layer 5. It is further possible for the liquid volume, preferably the basic solution, to be 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 for 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 to be obtained.

[0221] It is possible that 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.

[0222] Preferably, the element 2 has a pH value selected from a range of 8 to 14, preferably from 10 to 14, more preferably from 12 to 14.

[0223] Preferably, the element comprises 2 monovalent or polyvalent anions selected from the group consisting of phosphate, phosphite, carbonate, bicarbonate, hydroxide, aluminate, sulfate, sulfite or mixtures thereof.

[0224] Preferably, the cations and anions are selected from water-soluble salts.

[0225] It is possible for the polymer to be brought into contact with the element 2, in particular in the form of a liquid volume, preferably a basic solution, by a spraying process, preferably selected from air spraying processes, ultrasonic spraying processes, and electrostatic spraying processes, wherein the at least one unit 3 is obtained in the form of particles and / or fibers by the spraying process. The polymer is preferably dissolved and / or dispersed in a solvent, preferably an organic solvent, more preferably methyl ethyl ketone, acetone, ethanol, and / or mixtures thereof, for spraying.

[0226] The particles are preferably irregular or regular, preferably spherical, platelet-shaped, or rod-shaped. In particular, the particles have a value for an average volume-related particle diameter selected from a range of 0.5 pm to 1000 pm, preferably 1 pm to 750 pm, more preferably 3 pm to 300 pm.

[0227] Preferably, the fibers have a length to width ratio selected from a range of 3:1 to 1000:1, preferably 10:1 to 500:1.

[0228] Furthermore, it is possible that in step c) the element 2 is or comprises a carrier layer 5.

[0229] It is possible that in 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.

[0230] Preferably, 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. In particular, 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. Alternatively, it is also possible for the transfer layer 6 not to be detachable from the carrier layer 5, wherein the transfer film 4 can preferably be used as a laminating film.

[0231] Preferably, the carrier layer 5 consists of a polyester, a polyolefin or a combination thereof, in particular of PET.

[0232] Furthermore, 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.

[0233] Preferably, in step c) the polymer is selected with an application weight from a range of 5 g / m 2 up to 20 g / m 2 , preferably 8 g / m 2 up to 12 g / m 2 , arranged on the carrier layer 5.

[0234] It is further possible that in 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.

[0235] Preferably, in 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.

[0236] It is possible that in step c) one or more further layers are arranged over the entire surface or in certain regions on the carrier layer 5. In particular, the one or more layers are selected from the group consisting of release layer 7, primer layer 8, functional layer, and 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. In addition, 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 further 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 its function.

[0237] 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 further 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 to the protective layer 9, on which a primer layer 8 is arranged.

[0238] Preferably, 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 the release.

[0239] Preferably, the release layer 7 consists of or comprises a wax, preferably montan wax, or silicone, or combinations thereof.

[0240] The release layer 7 of a transfer film 4 according to Fig. 3 preferably has a layer thickness selected from a range of 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.

[0241] The transfer film 4 according to Fig. 3 can have a self-supporting protective layer 9 or a non-self-supporting protective layer 9.

[0242] The protective layer 9 preferably has a layer thickness selected from a range of 0.5 μm to 10 μm, preferably from 0.8 μm to 5 μm. 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.

[0243] The protective layer 9 is preferably transparent. Furthermore, it is possible for the protective layer 9 to be colored and / or designed as a translucent protective layer 9.

[0244] It is also possible for the protective layer 9 to be removed again after step e) or step g) of a method according to Figs. 1a and 1b. Preferably, the protective layer 9 is peeled off or at least partially dissolved.

[0245] The primer layer 8 of the transfer film 4 according to Fig. 3 is preferably integrally bonded to the object 1 in the decorated object T after step e) of a method according to Figs. 1a and 1b.

[0246] The primer layer 8 comprises at least one polymer which preferably has at least one dissociable functional group.

[0247] Furthermore, the at least one primer layer 8 has a layer thickness selected from a range of 50 nm to 100 pm, preferably from 100 nm to 50 pm, more preferably from 250 nm to 20 pm.

[0248] Preferably, 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 and combinations thereof, more preferably carboxylic acid ester group, sulfonic acid ester group and combinations thereof, more preferably carboxylic acid ester group, and / or a combination thereof.

[0249] It is possible that 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.

[0250] It is possible for the primer layer 8 to comprise a polymer that 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.

[0251] Furthermore, it is also possible that 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.

[0252] 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.

[0253] The at least one functional layer can preferably be opaque and / or transparent at least in some areas.

[0254] The at least one functional layer can preferably be designed as a pattern, decoration, grid, geometric figure, motif, alphanumeric character, logo, or combinations thereof.

[0255] If, for example, a transfer film 4 is present which comprises at least one carrier layer 5 and a transfer layer 6, as shown, for example, in Fig. 2, it is also possible for the method to further comprise at least the following step h) in addition to the sequence of steps shown in Figs. 1a and 1b. 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).

[0256] The transfer layer 6 is then separated again, allowing the resulting particles and / or fibers to be further processed. Separation can be achieved by one of the following methods: grinding, brushing, blasting, or scratching.

[0257] Further processing of the resulting particles and / or fibers can be carried out, for example, by additional optional steps in the process. Thus, it is 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) comminuting and / or fractionating the particles and / or fibers; j) dispersing the particles and / or fibers in a medium.

[0258] Preferably, the particles and / or fibers are comminuted using a stirred ball mill, impact mill, roller mill, grinder, and / or dissolver.

[0259] Dispersing is preferably carried out using processes including stirred ball mills, impact mills, roller mills, extruders, and dissolvers. Binders, coatings, and / or solvents can be used as dispersion media, for example.

[0260] Advantageously, after 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. In step d) of the process, the at least one unit 3 is dried. Figures 1a and 1b show that step d) is carried out after step c) and / or before step e).

[0261] It is possible that at least one of the following drying methods is used in step d): vacuum drying, centrifugation, exposure to IR radiation, or continuous gas flow. For example, the gas can be air and / or nitrogen, particularly where the gas has a higher temperature than the unit.

[0262] In addition, it is possible that at the beginning or during step d) the at least one unit 3 is washed with another organic solvent which has a lower boiling point than the solvent comprised by the reactive mixture.

[0263] Preferably, 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 of 0 wt.% to 10 wt.%, preferably from 0 wt.% to 8 wt.%, more preferably from 0 wt.% to 5 wt.%.

[0264] Step d) is preferably carried out until the mass of at least one unit 3 is constant.

[0265] Preferably, step d) is carried out at an ambient pressure selected from a range of 500 mbar to 1000 mbar. Alternatively or additionally, 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. Furthermore, it is possible that in step d) an acceleration acting on the at least one unit 3 is selected from a range of 9.81 m / s. 2 up to 100,000 m / s2 , preferably 20 m / s 2 up to 20,000 m / s 2 , more preferably 100 m / s 2 up to 5,000 m / s 2 , is carried out.

[0266] In step e) of a method according to Fig. 1a and Fig. 1b, 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. Preferably, step e) is carried out after step d) or after step f). It is possible for step e) to be carried out before step f) and / or preferably before step g).

[0267] Preferably, in step e), 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, scattering, doctor blade coating, laminating method, transfer method, embossing method, adhesive method.

[0268] The object 1 has at least one surface on which at least one unit 3 is arranged in regions or over its entire surface. This at least one surface preferably consists of a material 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.

[0269] In a preferred embodiment of a method according to Fig. 1 a and Fig. 1 b, it is possible that 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 before step e1) is provided with the

[0270] Transfer layer 6 is arranged on the side of the carrier layer 5 facing away from the transfer layer 6 on the at least one inner surface of the provided shaped 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 in and / or after step e3) is arranged 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 shaped body is obtained as the decorated object T.

[0271] It is possible for the at least one mineral binder to comprise a hydraulic binder, a non-hydraulic binder, or a mixture thereof. Preferably, 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. Furthermore, the mineral building material mixture can comprise or consist of concrete, mortar, sand-lime brick, silicate ceramic, or a combination thereof.

[0272] In 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). As shown in Figs. 1a and 1b, step f) is preferably carried out after step d) and / or after step e) and before step g). Furthermore, it is possible for step f) to be carried out after or during step c). Furthermore, it is possible for the temporal implementation of step f) to at least partially overlap with the implementation of step c), step d) and / or step e).

[0273] The at least one unit 3' has a white color impression at least in some areas in the foamed state.

[0274] 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. Preferably, 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.

[0275] Preferably, in step f), the at least one unit 3 is subjected to a temperature selected from a range of 60°C to 300°C, preferably from 75°C to 250°C, more preferably from 100°C to 180°C. Preferably, the at least one unit 3 has this temperature, in particular on one of its outer surfaces.

[0276] It is possible for the drying of step d) and the conversion 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 execution of steps d) and f) to overlap in time. Thus, it is possible for steps d) and f) to be carried out in the same device. Preferably, step f) is carried out at a higher average temperature than step d).

[0277] Preferably, in step f), the at least one unit 3 is placed in a foamed state over its entire surface. Alternatively, it is also possible for the at least one unit 3 to be placed in a foamed state in certain regions in step f), so that the at least one unit has foamed regions and unfoamed regions adjacent to one another.

[0278] Furthermore, it is possible for step f) to be performed multiple times, wherein at least during the first execution of step f), the at least one unit 3 is partially foamed, so that foamed and unfoamed regions are present side by side in the at least one unit. In particular, during at least one further execution of step f), the at least one unit 3 can be foamed over its entire surface.

[0279] 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.

[0280] 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.

[0281] In particular, it can be provided that the foamed areas or unfoamed areas are arranged in register or precisely in register with areas of further layers, in particular the functional layer and / or the object. Preferably, the at least one unit 3 only exhibits the defined white color impression once it has been placed in the foamed state. If the at least one unit 3 is configured as a layer, it is preferably transparent in the unfoamed state. The at least one unit in the foamed state 3' is preferably opaque.

[0282] In particular, it is possible for step f) to be initiated at the beginning of or during step e). In particular, object 1 comprises a catalyst that catalyzes the formation of the porous structure.

[0283] The object 1 preferably comprises 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. Furthermore, the object 1 comprises monovalent or polyvalent anions selected from the group consisting of phosphate, phosphite, carbonate, bicarbonate, hydroxide, aluminate, sulfate, sulfite, or mixtures thereof. The object 1 preferably comprises compounds, in particular salts, formed from at least one of the possible combinations of the above-mentioned preferred anions and cations.

[0284] Alternatively or additionally, the object 1 can be contacted, preferably sprayed or poured over, with a layer and / or a volume of liquid comprising the above anions and / or cations.

[0285] Preferably, an open-pore and / or closed-pore structure is formed in the at least one unit in the foamed state 3' in step f).

[0286] The at least one unit in the foamed state 3' has, in particular due to the porous structure, a refractive index value between 1.2 and 1.8, preferably between 1.3 and 1.7. Preferably, the porous structure has pores with a pore diameter selected from a range of 0.03 pm to 10 pm, preferably from 0.4 pm to 3 pm, more preferably from 0.5 pm to 1.8 pm.

[0287] Furthermore, it is possible for the porous structure to have 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 0.15 pm to 0.4 pm.

[0288] Furthermore, it is possible that 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,

[0289] For example, step k) can be carried out by a process selected from the group comprising spraying processes, preferably air spraying processes, ultrasonic spraying processes and / or electrostatic spraying processes, dipping processes and / or printing processes, preferably gravure printing, screen printing, inkjet printing and / or flexographic printing, and / or combinations thereof.

[0290] Preferably, the protective layer applied in step k) at least partially fills the porous structure.

[0291] The protective layer applied in step k) may have the preferred properties of a protective layer described in step c).

[0292] As can be seen from Fig. 1a and 1b, a method according to the invention comprises step g) as the last method step. In step g), a decorated

[0293] Object T is obtained, wherein the decorated object T comprises the at least one unit in the foamed state 3. Preferably, 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.

[0294] The decorated object T according to Fig. 4a comprises 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. Alternatively, the unit 3 can also be a layer comprising particles, wherein these particles were dispersed in a medium according to steps i) and j) and then arranged on the object 1.

[0295] 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. However, it is also possible that the transfer layer 6 does not comprise a protective layer 9 and that the protective layer 9 was arranged by step k) after the arrangement of the transfer layer 6 on the object 1.

[0296] The resulting decorated object T, for example, according to Fig. 4a or Fig. 4b, can be used in a variety of areas. Preferably, the resulting decorated object T is a facade element, a wallpaper, a casing element, a masonry element, 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.

[0297] Example 1:

[0298] According to the process shown in Fig. 1a, in step c), the polymer was applied to an element 2 in the form of a carrier layer 5. The unit 3 was present as a layer and formed the transfer layer 6 of the transfer film 4, with the transfer layer 6 being removable from a carrier layer 5. The decorated object 1' was to be a decorated concrete part as shown in Fig. 4a.

[0299] For this purpose, 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.

[0300] The 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.

[0301] Subsequently, a PET carrier layer 5 (thickness of the PET carrier layer 5 from 5 μm to 150 μm, preferably from 7 μm to 100 μm) was used and coated with a release layer 7 of montan ester wax at least 50 nm thick. Subsequently, the coated PET carrier layer 5 was 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 polymer layer 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 approximately 1.6 pm, 4 pm, 8 pm, 10 pm, 12 pm and 18.5 pm respectively.

[0302] Optionally, it is possible to arrange further layers, in particular protective layers 9 and / or functional layers, on the carrier layer 5 or the release layer 7 before applying the dissolved polymer by doctor blade, so that a transfer film 4 comparable to the transfer film 4 shown in Fig. 3 is obtained. According to step d), the coating was dried to constant weight at approximately 150 °C using a hot air stream (hair dryer) for approximately 10 seconds, forming a closed transfer layer 6 of the transfer film 4.

[0303] The concrete was mixed by blending 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 mix.

[0304] In each case, a 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)).

[0305] After complete curing of the concrete at room temperature, a mineral composite body was formed according to step g), which was coated on one side with the respective transfer film 4 used.

[0306] After three days, the concrete bodies were removed from the formwork and allowed to dry completely under atmospheric conditions. After 24 hours of drying, the PET carriers were removed from the concrete, leaving the transfer layer 6 adhering to the concrete and forming a smooth coating on the composite body. The white color of the paint layer had also fully developed during this time.

[0307] Example 2:

[0308] A polymer was produced from a reactive mixture consisting of 50 wt% water, 9.5 wt% semi-neutralized itaconic acid semi-neutralized with potassium hydroxide, i.e., with the addition of wt% KOH based on itaconic acid (e.g., 4 g KOH to 9.3 g itaconic acid), 40.5 wt% methyl methacrylate, and 1 wt% V-50 (water-soluble azo initiator). A polymer was produced at 60 °C for 12 hours under vigorous mechanical stirring.

[0309] The resulting aqueous dispersion was added to ethanol to remove impurities, as the impurities dissolve in the ethanol. The solvents were removed by filtration (pore 4), and the remaining polymeric solid was dried at 40 °C in a vacuum drying oven (air pressure approx. 20 mbar) for approximately 10 hours. The resulting powder was ground manually in a mortar and heated to approximately 170 °C in a round-bottom flask while swirling.

[0310] The particle size Dso of the pigment particles obtained by milling was Dso = 10 pm (equivalent to the average particle size); Dw = 3.5 pm; D90 = 39.5 pm. In other words, 80% of the pigment particles were between 3.5 pm and 39.5 pm in size. The particle size of the pigment particles was determined using dynamic light scattering. Particle size is preferably understood as the volume-related particle diameter.

[0311] The resulting prepared powder was dispersed in a solvent, e.g., ethanol, with the aid of dispersing additives (in the example: Solsperse 35000), resulting in a dispersion with a solids content of 18.5 wt.% (consisting of dispersing additive and pigment). The dispersion (100 wt.%) consisted of 7.5 wt.% dispersing additives, 81.5 wt.% ethanol, and 11 wt.% pigment.

[0312] This dispersion was then added to a binder solution (in the example: a 36% solution of Degacryl HS 4240D in ethanol) so that the total solids content of the coating, consisting of pigment and binder, was approximately 23% by weight. This coating was applied to a carrier film using a doctor blade, and the resulting coating film was dried using a hot air stream (hair dryer) for approximately 30 seconds. The application weight of the dry layer was approximately 8 g / m². 2 , which corresponds to approximately 8 pm layer thickness of the dried layer.

[0313] A PET carrier layer 5 (thickness of the PET carrier layer 5 from 5 μm to 150 μm, preferably from 7 μm to 100 μm) was used as the carrier film. The carrier layer 5 can optionally be coated with a release layer 7 of montan ester wax, at least 50 nm thick, before the coating is applied. One or more adhesion-promoting layers, primer layers, or adhesive layers can optionally be applied to the coated and dried coating. This allows for the creation of transfer films for use as cold stamping films and / or hot stamping films.

[0314] Without a release layer, adhesion-promoting layers, primer layers or adhesive layers, the doctor-applied 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.

[0315] Example 3:

[0316] Furthermore, it is possible for at least one unit 3 comprising the polymer to be 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 shown in Fig. 1a, additionally comprising steps i) and j).

[0317] For this purpose, the polymer, for example, from the batch of Example 2, was dried in a vessel or applied to a support in a drying cabinet under vacuum at 40 °C until constant mass was reached. Optionally, it is possible to wash the polymer with ethanol, especially if a water-containing solvent was used for the synthesis, to achieve absolute freedom from water. This promotes the conformity of the particles obtained by the heating carried out later in the process.

[0318] The layer of dried polymer was then crushed using a mortar and a homogeneously ground powder was obtained.

[0319] The particles were heated in a temperature-resistant container, such as a round-bottomed flask, with gentle circular shaking over a burner flame or a hot air gun. This continued until the first spherical particles appeared from the powder. These particles appeared white.

[0320] 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 application of the particles dispersed in a medium and the further processing can be carried out, for example, analogously to Example 1.

[0321] Table 1: Example formulations of a varnish with the polymer shown in Example 2

[0322] A polymeric binder, particularly a styrene-acrylate-based binder, can be used, for example, Synexil SAB 05. A calcium carbonate filler, for example, can be used, for example, Omyacarb 5-GU. An associative thickener, for example, can be used, for example, Optiflo H 600. A defoamer, for example, can be used, for example, Surfynol DF110 D. An Aerosil filler, for example, can be used, for example, Aerosil TT 600. An opacifying emulsion, for example, can be used, for example, Ropaque Ultra EF. An optical brightener, for example, can be used, for example, Tinopal OB.

[0323] Example 4:

[0324] Furthermore, it is possible for at least one unit 3 comprising the polymer to 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.

[0325] For this purpose, a solution containing 20 wt.% 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. After the precipitate was washed with water and separated by filtration, it was dried to constant weight under standard conditions (air temperature of 23 °C and a relative humidity of 50%) according to DIN EN ISO 291:2008-08 (“Plastics - Standard conditions for conditioning and testing (ISO 291:2008) - German version EN ISO 291:2008”, issue date: 2008-08).

[0326] The layer of dried polymer was then crushed using a mortar and pestle, resulting in a homogeneously ground powder. The powder particles appeared white.

[0327] 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.

[0328] Comparison example 1:

[0329] To compare the color impression of an object T decorated according to the invention with an object 1 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.

[0330] Furthermore, several TiO2-containing dispersions were prepared, the TiO2 content of which was adjusted between 10 wt.% and 52 wt.%, based on the solids content of the dried layer. Transfer films were produced from these dispersions according to Example 1. In contrast to Example 1, instead of applying the polymer dissolved in ethanol to the PET carrier layer 5 with the release layer, a corresponding layer of a TiO2-containing dispersion was gravure printed onto the release layer, with each transfer film comprising different layers of the TiO2-containing dispersion with different TiC contents, based on the solids content of the dried layer.

[0331] Subsequently, each sample was coated with a TiC-containing dispersion through the transfer film. The application weight of the TiC-containing layer was 10 g / m 2This corresponded to a dry layer thickness of approximately 10 pm. The TiC-containing layer formed a continuous layer on the specimen.

[0332] For a direct comparison of the color impression of the samples obtained according to Example 1 and Comparative Example 1, their color coordinates in the CIELAB color space were determined. The color coordinates in the CIELAB color space were determined using a colorimeter, for example, a Datacolor 650 spectrophotometer, with one sample clamped in front of the measuring aperture.

[0333] Tables 2 and 3 show the results of the brightness values ​​L and the a and b coordinates in the CIELAB color space.

[0334] Table 4 shows which layer thickness in the dry state was required for the samples produced according to the invention in 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.

[0335] 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.

[0336] Table 3: Values ​​for the color coordinate in the CIELAB color space (L, a, b) of the samples produced according to Example 1. Table 4: Assignment 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 coordinates could be achieved with the inventive concrete decoration. Thus, a good approximation of the hiding power of the inventive decoration compared to the state of the art is possible.

[0337] In contrast to the sample containing TiC, 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.

[0338] Furthermore, it can be demonstrated that complete coverage, i.e., a homogeneous color impression in which the object 1' to be decorated is no longer visible, is possible with a layer thickness of approximately 10 μm in the dry state of the coating according to the invention. A coating according to Comparative Example 1 achieves a comparable color impression with a layer thickness of 10 μm 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.

[0339] Furthermore, SEM images were taken of parts of the transfer film 4 described in Example 1, wherein the unit 3 comprising the polymer was configured in the form of a layer or transfer layer 6. One image shows a unit in the unfoamed state and one image shows a unit in the foamed state 3'. Furthermore, SEM images were taken of the decorated object T obtained in Example 1. The SEM images are shown in Figs. 5a and 5b, Figs. 6, and Fig. 7.

[0340] For the SEM images, sample specimens were cut out of the films to be examined or the coated object and coated with gold by sputtering. The sample specimens had dimensions of approximately 20 mm x 10 mm x 4 mm (20 mm x 10 mm base area, thickness 4 mm). In the SEM images of Fig. 5a and 5b, the cut surfaces of trans films 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 the 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 acquired at a magnitude of x120, a working distance of 13 mm, a spot size of 60, and an accelerating voltage of 15 kV. The beamwidth is 100 pm.

[0341] As can be clearly seen in Figs. 5a and 5b, the transfer layer 6 has a compact structure in the unfoamed state, while 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.

[0342] The SEM images in 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 in Fig. 6 was taken 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 beam is 10 pm.

[0343] Fig. 6 illustrates the formed porous structure of the transfer layer 6, which creates the white color impression through refraction at the multitude of formed interfaces.

[0344] The SEM image of Fig. 7 shows a cut edge of a concrete object 1, wherein the object 1 was coated with a unit 3 according to the invention. The unit 3 was placed in the foamed state 3'. The image of Fig. 7 was created 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 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.

[0345] Of course, the listed versions can be combined with each other as desired and do not represent any limitations.

[0346] List of reference symbols

[0347] 1 object

[0348] 1 ' decorated object 2 element

[0349] 3 Unit

[0350] 3' unit in foamed state

[0351] 4 Transfer film 5 Carrier layer

[0352] 6 Transfer position

[0353] 7 Release layer

[0354] 8 Primer layer 9 Protective layer

Claims

Patent claims Method for producing a decorated object (1'), characterized in that the method comprises the following steps, in particular wherein 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 (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 thatthat 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 / or the at least one unit in the foamed state (3') over the entire surface or in regions on an object (1), f) placing at least one unit (3) into a foamed state while maintaining the at least one unit in the foamed state (3'), g) maintaining a decorated object (1') comprising the at least one unit in the foamed state (3'), 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 (3') has a value for the parameters a and b selected from a range of -4 to 4. Method according to one of the preceding claims, characterized in that the reactive mixture, the polymer and / or the at least one unit (3) comprising the polymer does not comprise any pigments, preferably no white pigments, more preferably no TiO2. Method according to one of the preceding claims, characterized in that the reactive mixture comprises at least one further carboxylic acid-containing monomer which is selected individually or in combination from the group consisting of acrylic acid, methacrylic acid, fumaric acid and maleic acid.Process according to one of the preceding claims, characterized in that the reactive mixture comprises at least one non-carboxylic acid-containing monomer component, which component or derivatives thereof are selected from the group, individually or in combination, consisting of esters of acrylic acid, esters of methacrylic acid, esters of itaconic acid, esters of maleic acid, maleic anhydride. Terpenes, preferably myrcene, styrene, isoprene, butadiene, vinyl ether. The process according to any one of the preceding claims, characterized in that the reactive mixture comprises at least one additive selected individually or in combination from the group consisting of crosslinker, flow agent, stabilizer, light stabilizer, flame retardant, defoamer, flow control additive, hydrophobizing agent, plasticizer, deactivator, antioxidant, and / or radical chain terminator, or fillers selected individually or in combination from the group consisting of mineral fillers, sand, diatomaceous earth, phyllosilicates, talc, aluminates, carbon fibers, wood flour, starch, and glass fibers.Process according to one of the preceding claims, characterized in that the reactive mixture comprises a solvent, preferably 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, and / or an initiator, preferably an initiator for a radical polymerization. Process according to one of the preceding claims, characterized in that the proportion of the 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.%. preferably from 40 wt.% to 70 wt.%, even more preferably from 45 wt.% to 60 wt.%. Process according to one of the preceding claims, characterized in that the proportion of the monomer of the non-carboxylic acid-containing component, based on the total mass of the reactive mixture, is 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.%. Process according to one of the preceding claims, characterized in that the proportion of the carboxylic acid-containing monomer, 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.%. Process according to one of the preceding claims, characterized in that 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.%. Process according to one of the preceding claims, characterized in that the initiator is selected from the group consisting of azo compounds, peroxides, or mixtures thereof. Process according to one of the preceding claims. characterized in that 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. Process according to one of the preceding claims, characterized in that 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 1,000 g / mol to 50,000 g / mol, even more preferably from 1,500 g / mol to 20,000 g / mol. Process according to one of the preceding claims, characterized in that 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. Process according to one of the preceding claims, characterized in that the polymer obtained in step b) has a value for the glass transition temperature selected from a range from -20 °C to 110 °C, preferably from -20 °C to 50 °C, more preferably from -10 °C to 25 °C. Method according to one of the preceding claims, characterized in that that 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. Method according to one of the preceding claims, characterized in that 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. Method according to one of the preceding claims, characterized in that the element (2) has a pH selected from a range from 8 to 14, preferably from 10 to 1, more preferably from 12 to 14.Method according to one of the preceding claims, characterized in that the method further comprises at least the following step, which is preferably carried out after step c): h) separating the at least one unit (3) from element (2), wherein the at least one unit (3) is in the form of particles and / or fibers after step h). Method according to one of the preceding claims, characterized in that. that the method further comprises 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. Method according to one of the preceding claims, characterized in that the contacting of the polymer with the element (2) takes place by 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.Method according to one of the preceding claims, characterized in that the particles are irregularly or regularly formed, preferably spherically, platelet-shaped or rod-shaped, in particular with a value for an average volume-related particle diameter which 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. Method according to one of the preceding claims, characterized in that the fibers have a shape factor of length to width selected from a range of 3:1 to 1000:1, preferably from 10:1 to 500:

1. Method according to one of the preceding claims. characterized in that in step c) the element (2) is a carrier layer (5) or comprises such a carrier layer or in that the element (2) is arranged on a carrier layer (5) in some areas or over the entire surface. Method according to one of the preceding claims, characterized in that in step c) the contacting takes place by arranging the at least one unit (3) comprising the polymer on the carrier layer (5) in some areas or over the entire surface, wherein the at least one unit (3) is obtained in the form of a layer. Method according to one of the preceding claims, characterized in that by contacting the at least one unit (3) with the element (2), a transfer film (4) is obtained, wherein the transfer film (4) has a carrier layer (5) and a transfer layer (6) comprising the at least one unit (3), in particular wherein the transfer layer (6) is detachable from the carrier layer (5).Method according to one of the preceding claims, characterized in that the carrier layer (5) consists of a polyester, a polyolefin or a combination thereof, in particular of PET, and / or that the carrier layer (5) has a layer thickness selected from a range of 5.7 pm to 100 pm, preferably 19 pm to 50 pm. Method according to one of the preceding claims, characterized in that. that in step c) the polymer is applied with a coating weight selected from a range of 5 g / m 2 up to 20 g / m 2 , preferably 8 g / m 2 up to 12 g / m 2, is arranged on the carrier layer (5), and / or that in 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 from 8 pm to 12 pm. Method according to one of the preceding claims, characterized in that in step c) one or more further layers are arranged over the entire area or in regions on the carrier layer (5), in particular wherein the further layers are selected from the group consisting of the release layer (7), primer layer (8), functional layer and / or protective layer (9).Method according to one of the preceding claims, characterized in that the release layer (7) consists of a wax or comprises this and / or that the release layer (7) has a layer thickness selected from a range of 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 and / or that the release layer (11) is arranged in contact with the carrier layer (6) and / or the transfer layer (6). Method according to one of the preceding claims, characterized in that the protective layer (9) is arranged on the side of the transfer layer (6) facing away from the carrier layer (6) and / or that 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 and / or that the protective layer (9) is made of a polyester. a polyolefin, a polyurethane, or a combination thereof. Method according to one of the preceding claims, characterized in that the primer layer (8) comprises at least one polymer having at least one dissociable functional group and / or that the at least one primer layer (8) has a layer thickness selected from a range of 50 nm to 100 μm, preferably from 100 nm to 50 μm, particularly preferably from 250 nm to 20 μm. Method according to one of the preceding claims, characterized in that the at least one dissociable functional group of the primer layer (8) is 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 and combinations thereof, further, preferably a carboxylic acid ester group, a sulfonic acid ester group, and combinations thereof, more preferably a carboxylic acid ester group, and / or is a combination thereof. Method according to one of the preceding claims, characterized in that the at least one dissociable functional group of the primer layer (8) is a free acid group, which is preferably selected from the group consisting of a carboxy group, a sulfonic acid group, a 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 a carboxylic acid ester group, a carboxylic acid anhydride group, a sulfonic acid ester group, a sulfonic acid anhydride group, and combinations thereof.Method according to one of the preceding claims, characterized in that the functional layer is 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. Method according to one of the preceding claims, characterized in that in step c) for arranging the at least one unit (3) or one or more further layers on the carrier layer (5) at least one of the following methods is used: gravure printing, screen printing, inkjet printing, flexographic printing, offset printing, spraying, casting, injection molding. Method according to one of the preceding claims, characterized in that in step d) for drying at least one of the following methods is used: vacuum drying, centrifugation, exposure to IR radiation, continuous passage of gas, preferably air and / or nitrogen.Method according to one of the preceding claims, characterized in that after step d), the at least one unit (3), based on the total mass of the at least one unit (3), has a proportion of components which have a boiling point of lower than 110 °C, selected from a range of 0 wt.% to 10 wt.%, preferably from 0 wt.% to 8 wt.%, more preferably from 0 wt.% to 5 wt.%. Method according to one of the preceding claims, characterized in that step d) is carried out at an ambient pressure selected from a range of 500 mbar to 1000 mbar and / or at a. Ambient temperature 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, and / or at an acceleration acting on the at least one unit (3) selected from a range of 9.81 m / s 2 up to 100,000 m / s 2 , preferably 20 m / s 2 up to 20,000 m / s 2, more preferably 100 m / s 2 up to 5,000 m / s 2, is carried out. Method according to one of the preceding claims, characterized in that in step e) 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, spreading method, sprinkling, doctor blade coating, lamination method, transfer method, embossing method, adhesive method. Method according to one of the preceding claims, characterized in that the object (1) has at least one surface which consists of a material that consists of or comprises a material selected from the group consisting of concrete, in particular fresh concrete or hardened concrete, artificial stone, natural stone, wood, polymer, ceramic, paper, metal, composite material, or mixtures thereof.Method according to one of the preceding claims, characterized in that the decorated object (T) obtained in step g) 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. Method according to one of the preceding claims, characterized in that step e) comprises the following sub-steps: e1) providing at least one shaped 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 shaped 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) before step e1) with the side of the carrier layer (5) facing away from the transfer layer (6) on the at least one inner surface of the provided shaped element, preferably formwork,is arranged 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) in and / or after step e3) with the transfer layer (6) is at least partially arranged on the dimensionally stable, mineral green body, wherein a decorated, dimensionally stable, mineral green body is obtained, and wherein, in alternatives I) and II), a decorated, mineral shaped body is obtained as the decorated object (T) in step g). Method according to one of the preceding claims, characterized in that the at least one mineral binder comprises a hydraulic binder, a non-hydraulic binder, or a mixture thereof. Method according to one of the preceding claims, characterized in that 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. Method according to one of the preceding claims, characterized in that the mineral building material mixture comprises or consists of concrete, mortar, sand-lime brick, silicate ceramic, or a combination thereof.Method according to one of the preceding claims, characterized in that at least the primer layer (8), the at least one unit (3), or the at least one unit in the foamed state (3') is chemically bonded to the object (1) by forming ionic bonds, covalent bonds and / or hydrogen bonds and / or by mechanical interlocking. Method according to one of the preceding claims,. characterized in that in step f) the at least one unit (3) is placed in a foamed state over its entire surface, or in that in step f) the at least one unit (3) is placed in a foamed state in some regions, so that foamed and unfoamed regions are present next to one another in the at least one unit (3). Method according to one of the preceding claims, characterized in that step f) is carried out several times, wherein at least during the first implementation of step f) the at least one unit (3) is placed in a foamed state in some regions, so that foamed and unfoamed regions are present next to one another in the at least one unit (3), and in particular wherein during at least one further implementation of step f) the at least one unit (3) is placed in a foamed state over its entire surface.Method according to one of the preceding claims, characterized in that the at least one unit in the foamed state (3') 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, and wherein preferably 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. Method according to one of the preceding claims,. that the formation of the porous structure is initiated by contacting the at least one unit (3) with the object (1), in particular that the object (1) comprises a catalyst which catalyzes the formation of the porous structure. Method according to one of the preceding claims, characterized in that the porous structure is formed by decarboxylation of the polymer, in particular wherein the decarboxylation is catalyzed ionically, in particular basic. Method according to one of the preceding claims, characterized in that an open-pore and / or closed-pore structure is formed in the at least one unit in the foamed state (3'). Method according to one of the preceding claims, characterized in that the at least one unit in the foamed state (3'), in particular due to the porous structure, has a value for a refractive index between 1.2 and 1.8, preferably between 1.3 and 1.7.Method according to one of the preceding claims, characterized in that the porous structure has pores which have 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. Method according to one of the preceding claims, characterized in that 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, more preferably 0.15 pm to 0.4 pm. Method according to one of the preceding claims, characterized in that in step f) the at least one unit (3) is subjected to or has a temperature selected from a range of 60°C to 300°C, preferably 75°C to 250°C, more preferably 100°C to 180°C.Method according to one of the preceding claims, characterized in that the method further comprises the following step, which is preferably carried out after step f): k) stabilizing the porous structure, in particular by arranging a protective layer, Decorated object (T) comprising a polymer, in particular produced according to a method of claims 1 to 58, characterized in that the polymer comprises itaconic acid and / or itaconic acid derivatives, wherein the decorated object (T) comprises at least one unit (3') comprising the polymer, which is placed in a foamed state, wherein the at least one unit in the foamed state (3') has a porous structure. and wherein 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, 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 (3') has a value for the parameters of a and b selected from a range of -4 to 4.Use of a reactive mixture for producing a decorated object (1'), preferably according to claim 1, comprising at least one unit (3) of a polymer, characterized in that 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 (3) can be put into a foamed state, wherein at least one unit in a foamed state (3') is obtained which has a porous structure and wherein the porous structure has a white color impression, wherein the color impression is described as a color locus in the CIELAB color space by the parameters L, a and b, and wherein the at least one unit in the foamed state (3') has a value for the parameters a and b selected from a range from -4 to 4.

Images