Method for producing decorated object, decorated object and use of reactive mixture for producing decorated object

Abstract

The invention relates to a method for producing a decorated object (1), said method comprising the following steps, in particular wherein step f) is a sub-step of step c) and / or after step d) and / or after step e): a) providing a reactive mixture comprising a monomer component comprising a carboxylic acid, said monomer component comprising itaconic acid and / or itaconic acid derivatives, the invention relates to a method for producing a polymer, comprising the steps of: a) forming a reactive mixture, b) polymerizing the reactive mixture to form a polymer, c) contacting the polymer with an element (2), in which at least one unit (3) comprising the polymer is obtained, in which the at least one unit (3) comprising the polymer can be converted into a foamed state, in which the at least one unit (3) forms a porous structure, wherein at least one unit (3 ') in the foamed state is obtained, and wherein the porous structure refracts light such that the at least one unit (3') in the foamed state 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 (3 ') in the foamed state over the entire area or a partial region of the object (1), f) converting the at least one unit (3) into the foamed state in order to obtain the at least one unit (3') in the foamed state, g) obtaining a decorative object (1 ') comprising the at least one unit (3') in the foamed state, wherein the color impression is described by parameters L, a and b as color coordinates in the CIELAB color space, and wherein the at least one unit (3 ') in the foamed state has values of parameters a and b selected from the range of-4 to 4, to a decorative object and to the use of the reactive mixture in a method for producing a decorative object.

Description

Technical Field

[0001] The present invention relates to a method for producing a decorative object, a decorative object, and the use of a reactive mixture for producing a decorative object. Background Art

[0002] In many products, a white color impression is achieved by introducing titanium dioxide (TiO₂) particles, which effectively scatter incident visible light due to their high refractive index n of approximately 2.5.

[0003] However, the production of objects with TiO₂ and / or having TiO₂ arranged on their surface has the following problems:

[0004] (i) Additional operating steps for introducing TiO₂ particles, which increases costs, (ii) a complex disposal process due to possible environmental damage caused by TiO₂ particles, (iii) suspected health problems and effects, such as pneumonia caused by particles that can be inhaled into the lungs, (iv) TiO₂ (rutile type) has a relatively high density of approximately 4240 kg / m 3 which can particularly lead to an unfavorable and relatively significant sedimentation behavior of TiO₂ particles in liquid paints and varnishes.

[0005] Therefore, there is a need for an alternative to TiO₂ that can be used as a colorant, i.e., it can be used as a white pigment to manufacture, for example, decorative objects.

[0006] Therefore, in order to obtain a white color impression, it is necessary to resort to the possibility of obtaining an optical effect with a refractive index n of the same order of magnitude as TiO₂ (n = 2.5). Summary of the Invention

[0007] The present invention describes how a spongy porous polymer structure that produces a white color impression by strong light scattering can be produced. Advantageously, this structure does not necessarily have a refractive index of the same order of magnitude as TiO₂. Due to the large number of boundary surfaces, light is scattered repeatedly within the structure, and thus a refractive index even between 1.2 and 1.8 is sufficient to produce a white color impression.

[0008] The refractive index is determined according to the method of using a refractometer in accordance with DIN EN ISO 489:2022-06 ("Plastics - Determination of refractive index (ISO 489:2022); German version EN ISO 489:2022", release date: 2022-06). The method describes measuring the refractive index of molded parts, cast or extruded sheets or films with an Abbe refractometer, and is applicable not only to isotropic transparent, translucent, colored, or opaque materials, but also to anisotropic materials.

[0009] For this purpose, it has been developed based on polymers of itaconic acid. By applying at least one unit containing 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 an alkaline solution, ionic-catalyzed decarboxylation of polyitaconic acid occurs. In other words, CO2 is released from the molecules of itaconic acid, for example, to form lactones. This results in the foaming of the at least one unit formed by the polymer. Alternatively or additionally, decarboxylation of the polymer of the at least one unit according to the invention can be thermally initiated.

[0010] In the following reaction equation (1), one possible reaction path (left side) of polyitaconic acid decarboxylation leads to the release of CO2. Through this reaction, the possible product (right side) has a closed loop within the molecule:

[0011]

[0012] The porous structure produced by foaming is mechanically stable and gives a white color impression of the object decorated with the polymer due to light refraction on its large number of side surfaces.

[0013] Therefore, the object of the present 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, in which TiO2 particles are not used to create a white color impression.

[0014] The object is achieved by providing a method for producing an object, in particular the method according to claim 1, wherein the method comprises the following steps, in particular where step f) is a sub-step of step c), and / or is carried out after step d) and / or after step e):

[0015] a) Providing a reactive mixture containing a carboxylic acid-containing monomer component, the monomer component containing itaconic acid and / or itaconic acid derivatives,

[0016] b) Polymerizing the reactive mixture to form a polymer,

[0017] c) Contacting the polymer with an element, where at least one unit containing the polymer is obtained,

[0018] where the at least one unit containing the polymer can be converted into a foamed state, in which the at least one unit forms a porous structure, where at least one unit in the foamed state is obtained, and where the porous structure refracts light so that the at least one unit in the foamed state exhibits a white color impression,

[0019] d) Drying the at least one unit,

[0020] e) arranging the at least one unit and / or the at least one unit in the foamed state on the entire area or a partial area of the object,

[0021] f) converting at least one unit into the foamed state to obtain the at least one unit in the foamed state,

[0022] g) obtaining a decorative object comprising the at least one unit in the foamed state,

[0023] wherein the color impression is described by the parameters L, a, and b as color coordinates in the CIELAB color space,

[0024] and wherein the at least one unit in the foamed state has values of the parameters a and b selected from the range of -4 to 4.

[0025] Furthermore, the object is achieved by a decorative object comprising a polymer, preferably produced by the method according to claim 59, in particular according to claims 1 to 58, wherein the polymer comprises itaconic acid and / or itaconic acid derivatives, wherein the decorative object comprises at least one unit comprising the polymer, which has been converted into the foamed state, wherein the at least one unit in the foamed state has a porous structure, wherein the porous structure refracts light such that the at least one unit in the foamed state exhibits a white color impression, wherein the color impression is described by the parameters L, a, and b as color coordinates in the CIELAB color space, and wherein the at least one unit in the foamed state has values of the parameters a and b selected from the range of -4 to 4.

[0026] Furthermore, the object is achieved in particular by claim 60, by the use of a reactive mixture for producing a decorative object preferably according to claim 1, the decorative object comprising at least one unit of a polymer, wherein the reactive mixture comprises a carboxylic acid-containing monomer component, the monomer component comprising itaconic acid and / or itaconic acid derivatives, and wherein the at least one unit is convertible into the foamed state, wherein at least one unit in the foamed state is obtained, which has a porous structure, and wherein the porous structure exhibits a white color impression, wherein the color impression is described by the parameters L, a, and b as color coordinates in the CIELAB color space, and wherein the at least one unit in the foamed state has values of the parameters a and b selected from the range of -4 to 4.

[0027] It is also possible to provide at least one unit comprising the polymer, or a multilayer film comprising the at least one unit.

[0028] A color, color impression or hue, or a single color or a single hue, is understood to mean the color coordinates in a color space. The color space can in particular be 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 a color space such as RAL, HKS or a color space of this kind.

[0029] Different colors or distinguishable colors are understood to mean the color distance dE between two color coordinates in a color space. The color space can in particular be the CIELAB color space. Different colors that can be perceived easily enough by the human eye have a color distance dE in the CIELAB color space of at least 2, preferably at least 3, particularly preferably at least 5, and more preferably at least 10.

[0030] The color coordinates in the CIELAB color space in particular are usually determined using a colorimeter, for example using a "Datacolor 650" spectrophotometer (Datacolor AG). The color coordinates are preferably determined by 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", release date 2020-03).

[0031] In this instrument, the light beam received by the illuminated sample is separated into its component wavelengths, for example by means of a prism. The light is thus decomposed into a number of narrow bands or measurement channels (usually 20 to 40 bands, the width of which is selected from the range of approximately 10 nm to 20 nm). The separated light is then focused onto a detector, for example a CCD array, where the intensity of each wavelength (or each color, if it is in the visible range of the human eye) is measured by a pixel of the array. The CCD is then read by a computer. The result is a spectrum indicating the intensity of each wavelength of the light.

[0032] To determine the color space, a sample (for example a film, a packed bed, a cuvette or a decorative object) is clamped in front of the light aperture of the instrument and the measurement is carried out with the aid of the relevant software. The software then automatically calculates the resulting Lab values of the sample.

[0033] The color coordinates (L*, a*, b*) p and (L*, a*, b*) v The value of dE (or also called Delta E or ΔE) between them is calculated as the Euclidean distance:

[0034]

[0035] Here, the luminance value L* is perpendicular to the color plane (a*, b*). The a coordinate represents the chromaticity and color intensity between green and red, and the b coordinate represents the chromaticity and color intensity between blue and yellow. The higher the positive a and b values and the lower the negative a and b values, the more positive the hue. If a = 0 and b = 0, there is an achromatic hue on the luminance axis. Generally, L* can take values between 0 and 100, and a and b can vary between -128 and +127.

[0036] Preferably, if the values of a and b are selected from the range of -5 to 5 and preferably L has a value selected from the range of 70 to 100, the observer perceives the color as white. Within the boundary ranges of the above values of the a and b coordinates, preferably at values of ±0.5 of the values of a and b, the observer is aware of a slight color deviation. Within the boundary ranges of the above values of the L coordinate, preferably at values of ±5 of the value of L, the observer is aware of a slight color deviation. Colors with values of L, a, and b outside the above ranges are particularly perceived by the observer as having a distinct color deviation or gray deviation.

[0037] The at least one unit in the foamed state preferably has values of parameters a and b selected from the range of -4 to 4, preferably -3 to 3, more preferably -2 to 2, and even more preferably -1 to 1. The at least one unit in the foamed state preferably has a value of parameter L selected from the range of 70 to 100, preferably 80 to 100, more preferably 90 to 100.

[0038] By the present invention, it is possible to provide a polymer that can be used to manufacture a decorative layer that exhibits a white color impression and does not have pigments, preferably white pigments such as TiO2.

[0039] By omitting TiO2 particles, the above disadvantages of TiO2 are avoided. For example, the coating according to the present invention does not have nanoparticles that can be inhaled into the lungs, which also brings disposal costs.

[0040] A further advantage is that the resulting polymer can be made based on biological raw materials. In other words, the amount of petroleum-based monomers can be reduced. For example, itaconic acid, which is considered as a monomer, can be obtained biotechnologically by fermenting molasses or synthesized from pyruvic acid. This results in a more sustainable product. Due to the availability of raw materials, units containing the polymer can also be produced economically.

[0041] Therefore, it is possible to obtain a decorative object that exhibits a white color impression and has good durability. The decorative object is thus suitable, for example, in the form of a panel, which can maintain the color impression even under climatic conditions such as humidity or mechanical load.

[0042] Further advantageous design options of the present invention are indicated in the dependent claims.

[0043] In step a), a reactive mixture is provided which has a monomer component containing carboxylic acid, wherein the monomer component containing carboxylic acid comprises itaconic acid and / or itaconic acid derivatives. Step a) is carried out at the start of the method. The composition of the components of the reactive mixture is selected such that the sum of the components constitutes 100% by weight (wt% = weight percentage) relative to the total weight of the reactive mass.

[0044] The inventors have surprisingly found that it is possible to design the reactive mixture, the polymer, and / or the at least one unit such that they do not have to contain a pigment, preferably do not have to contain a white pigment, and more preferably do not have to contain TiO2, in order to exhibit a preferred white color impression.

[0045] The reactive mixture can have at least one other monomer containing carboxylic acid, which is selected individually or in combination from acrylic acid, methacrylic acid, fumaric acid, and maleic acid.

[0046] Preferred itaconic acid derivatives of the monomer component containing carboxylic acid are the acid anhydride of itaconic acid, the methoxy ester of itaconic acid, and / or the ethoxy ester of itaconic acid. The itaconic acid derivatives of the monomer component containing carboxylic acid are preferably derivatized on at most one carboxylic acid and are present, for example, as itaconic acid monoesters.

[0047] It is advantageous here that the processability of the polyitaconic acid can be improved by means of the at least one other monomer of the component containing carboxylic acid. For example, the glass transition temperature can be increased, thereby increasing the mechanical tolerance. Additionally, the foamability of the at least one unit containing the polymer is not affected or is hardly affected.

[0048] The proportion of the monomer containing carboxylic acid from step a) is selected in the range from 2.5% to 65% by weight, preferably from 5% to 50% by weight, and more preferably from 10% to 35% by weight, relative to the total mass of the reactive mixture.

[0049] The term "containing carboxylic acid" is preferably understood to mean the presence of molecules containing at least one functional unit of the -COOH type, such as monomers, especially when provided.

[0050] The term "not containing carboxylic acid" is preferably understood to mean the presence of molecules that do not contain a functional unit of the -COOH type, such as monomers, especially when provided. This definition thus encompasses, for example, unsaturated hydrocarbons and unsaturated aromatic hydrocarbons, especially carboxylic acid esters and carboxylic acid derivatives.

[0051] The reactive mixture preferably has at least one monomer component not containing carboxylic acid, which is preferably selected individually or in combination from esters of acrylic acid, esters of methacrylic acid, esters of itaconic acid, especially diesters of itaconic acid, esters of maleic acid, maleic anhydride, terpenes, myrcene, styrene, isoprene, butadiene, and vinyl ethers or their derivatives.

[0052] The proportion of the carboxylic acid-free monomers from step a) is preferably selected from the range of 5% to 50% by weight, preferably 15% to 35% by weight, more preferably 20% to 30% by weight, based on the total mass of the reactive mixture.

[0053] The advantage of using the carboxylic acid-free monomer component and / or polymer component in the above-mentioned proportion based on the total weight of the reactive mixture is that this firstly reduces the water solubility of the polymer, thereby improving, for example, its outdoor applicability. Secondly, the above-mentioned proportion does not significantly affect the foaming ability of the at least one unit containing the polymer.

[0054] The reactive mixture preferably contains a solvent, preferably water and / or an organic solvent, which is / are selected, individually or in a mixture, from ethanol, 1-propanol, 2-propanol, acetone, 2-butanone (MEK), acetates, in particular ethyl acetate and / or lactyl acetate.

[0055] The proportion of the solvent is preferably selected from the range of 15% to 95% by weight, preferably 30% to 85% by weight, more preferably 40% to 70% by weight, even more preferably 45% to 60% by weight, based on the total mass of the reactive mixture.

[0056] The solvent is understood to mean the medium in which the other components of the reactive mixture are diluted, and the solvent is separated out, especially substantially completely separated out, after the polymerization process. The solvent preferably has a boiling point of at most 200 °C. An organic solvent is understood to mean a solvent having at least one carbon atom in its molecular structure.

[0057] The reactive mixture preferably contains a polymerization initiator, preferably a free-radical polymerization initiator.

[0058] It is also possible that the proportion of the initiator is selected from the range of 0.05% to 1.5% by weight, preferably 0.1% to 1% by weight, more preferably 0.25% to 0.5% by weight, based on the total mass of the reactive mixture.

[0059] It is also possible that the reactive mixture contains at least one additive, which is / are selected, individually or in combination, from crosslinking agents, plasticizers (flow agents), stabilizers, light stabilizers, flame retardants, defoaming agents, leveling additives, hydrophobizing agents, softeners (plasticizers), deactivators, antioxidants, free-radical chain breakers.

[0060] In addition, it is also possible that the reactive mixture contains fillers, which are / are selected, individually or in combination, from mineral fillers, sand, diatomaceous earth, phyllosilicates, talc, aluminates, carbon fibers, wood flour, starch, glass fibers.

[0061] By using additives and fillers, the processability of the reactive mixture or polymer can be improved, and the durability of the at least one unit obtained from the polymer can be increased.

[0062] The reactive mixture suitable for the process according to the invention preferably has the following composition, where the data given for each component are each relative to the total mass of the reactive mixture, and where the components are so selected that they together constitute 100% by weight:

[0063] Carboxylic acid-containing monomer component: 2.5% to 65% by weight,

[0064] Carboxylic acid-free monomer component: 5% to 50% by weight,

[0065] Solvent: 15% to 95% by weight,

[0066] Initiator: 0.05% to 1.5% by weight,

[0067] Additive: 0% to 3% by weight,

[0068] Filler: 0% to 10% by weight.

[0069] More preferably:

[0070] Carboxylic acid-containing monomer component: 5% to 50% by weight,

[0071] Carboxylic acid-free monomer component: 15% to 35% by weight,

[0072] Solvent: 30% to 85% by weight,

[0073] Initiator: 0.1% to 1% by weight,

[0074] Additive: 0% to 2% by weight,

[0075] Filler: 0% to 7% by weight.

[0076] Even more preferably:

[0077] Carboxylic acid-containing monomer component: 10% to 35% by weight,

[0078] Carboxylic acid-free monomer component: 20% to 30% by weight,

[0079] Solvent: 45% to 60% by weight,

[0080] Initiator: 0.25% to 0.5% by weight,

[0081] Additive: 0% to 1% by weight,

[0082] Filler: 0 wt% - 5 wt%.

[0083] 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). The polymer obtained in step b) preferably has monomers of the carboxylic acid-containing monomer component provided in step a) and optionally monomers of the carboxylic acid-free monomer component.

[0084] Preferably, step b) is carried out at a temperature of the reactive mixture in the range selected from 20 °C to 110 °C, preferably 40 °C and 85 °C, more preferably 50 °C to 70 °C.

[0085] Preferably, the polymer obtained in step b) has a value of the number-average molar mass in the range selected from 500 g / mol to 500,000 g / mol, preferably 750 g / mol to 100,000 g / mol, more preferably 1,000 g / mol to 50,000 g / mol, even more preferably 1,500 g / mol to 20,000 g / mol.

[0086] The advantages provided by the above molar mass are that, on the one hand, a polymer is obtained that exhibits high mechanical tolerance, such as high mechanical tolerance to wear, and on the other hand, the polymer can still be processed at reasonable cost.

[0087] It is possible that the polymer made in step b) has at least one other carboxylic acid-containing monomer unit, which is individually or combinatorially selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid.

[0088] The proportion of the carboxylic acid-containing monomer in the polymer, relative to the total mass of the polymer, is selected from the range of 2.5 wt% to 100 wt%, preferably 5 wt% to 80 wt%, more preferably 10 wt% to 50 wt%.

[0089] Preferably, the polymer made in step b) has at least one carboxylic acid-free monomer component, which is individually or combinatorially selected from 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.

[0090] The proportion of the monomers of the carboxylic acid-free component, relative to the total mass of the polymer, is preferably selected from the range of 0 wt% to 97.5 wt%, preferably 5 wt% to 90 wt%, more preferably 15 wt% to 85 wt%.

[0091] It is also possible that, in step a), the carboxylic acid-free component comprises monomers having at least one blocked carboxylic acid, wherein the at least one blocked carboxylic acid is deblocked in or after step b) such that the at least one blocked carboxylic acid is present as at least one carboxylic acid in the polymer after step b). The deblocking can be carried out, for example, thermally or chemically.

[0092] A polymer is preferably understood to mean a molecule formed by the chemical reaction of at least 3 monomers. A molecule formed from fewer than 5 monomers is preferably called an oligomer.

[0093] The polymer obtained in step b) preferably has a polydispersity value in the range selected from 1.8 to 4, preferably 1.9 to 3, more preferably 2 to 2.5, and even more preferably 2.1 to 2.4.

[0094] Polydispersity is a measure of the distribution width of the molar mass. It is calculated from the ratio of the weight-average M w (i.e., the molar mass based on the weight ratio of polymer chains of the same mass) to the number-average M n (i.e., the molar mass based on the ratio of the number of polymer chains of the same length to the total number of all polymer chains). The greater the polydispersity, the broader the distribution of the molar mass.

[0095] The advantage achieved by the above values of polydispersity is that a broad dispersity of the polymer is achieved. The broad dispersity in turn makes the polymer easier to process and / or handle, especially due to the broader melting range.

[0096] In step c), the polymer obtained in step b) is brought into contact with an element, wherein 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 liquid volume (Flüssigkeitsvolumen), preferably the liquid volume of an alkaline solution, or a carrier layer. It is also possible that the liquid volume, preferably the liquid volume of an alkaline solution, is arranged on the carrier layer. The at least one unit obtained can be in the form of a layer, a film, particles or fibers. It is possible here to obtain a dispersion paint, varnish, powder, transfer film, especially a laminated film or a transfer film having a transfer layer sheet that can be peeled off from the carrier layer.

[0097] The element can be an alkaline aqueous solution containing divalent or more-valent cations of at least one metal, wherein the at least one metal is preferably selected from Mg, Ca, Sr, Ba, Al, Fe, Co or a mixture thereof.

[0098] The inventors have surprisingly found that, due to the presence of divalent or more-valent cations, the conversion of the at least one unit into a foamed state, i.e., step f), can be carried out particularly effectively. It is presumed that the ions catalyze the decarboxylation of polyitaconic acid.

[0099] Alkali metals from Group 1 of the periodic table, such as sodium or potassium, and other monovalent ions, such as ammonium, for example in an alkaline solution, have no promoting effect on the conversion of said at least one unit into a foamed state.

[0100] The term "alkaline" is preferably understood to mean that an element, object and / or solution has a pH value in the range selected from 8 to 14, preferably 10 to 14, more preferably 12 to 14.

[0101] The element preferably contains a monovalent or polyvalent anion selected from phosphate, phosphite, carbonate, bicarbonate, hydroxide, aluminate, sulfate, sulfite or a mixture thereof.

[0102] The cation and anion are preferably selected from water-soluble salts.

[0103] It is possible to achieve the contact of the polymer with the element (especially in the form of a liquid volume, preferably the liquid volume of an alkaline solution) by means of a spraying method. The spraying method is preferably selected from air spraying, ultrasonic spraying, electrostatic spraying, wherein the at least one unit is obtained in the form of particles and / or fibers by the spraying method.

[0104] For spraying, the polymer is preferably dissolved and / or dispersed in a solvent, preferably an organic solvent, more preferably methyl ethyl ketone, acetone, ethanol and / or a mixture thereof.

[0105] It is also possible that in step c), the element is or comprises a carrier layer. It is also possible that the element is arranged on a partial area or the entire area of the carrier layer.

[0106] It is possible that in step c), the contact is achieved by arranging the at least one unit containing the polymer on a partial area or the entire area of the carrier layer, wherein the at least one unit is obtained in the form of a layer.

[0107] Preferably, a transfer film is obtained by contacting the at least one unit with the element, wherein the transfer film comprises a carrier layer and a transfer laminate. The transfer laminate has the at least one unit. The transfer laminate is preferably peelable from the carrier layer. Or it is also possible that the transfer laminate is not peelable from the carrier layer, whereby the transfer film is preferably usable as a laminated film.

[0108] The carrier layer preferably consists of polyester, polyolefin or a combination thereof, especially of PET.

[0109] In addition, the carrier layer preferably has a layer thickness in the range selected from 5.7 μm to 100 μm, preferably 19 μm to 50 μm.

[0110] Preferably, in step c), the at least one unit is in an amount selected from 5 g / m 2 to 20 g / m2 , preferably 8 g / m 2 to 12 g / m 2 of the applied weight is arranged on the carrier layer.

[0111] It is also possible that in step c), the at least one unit is arranged on the carrier layer with a layer thickness in the range selected from 5 μm to 20 μm, preferably 8 μm to 12 μm. The layer thickness is measured here in particular in the dry state of the layer.

[0112] Preferably, in step c), in order to arrange the at least one unit or one or more additional layers on the carrier layer, at least one of the following methods is used in each case: gravure printing, screen printing, inkjet printing, flexographic printing, offset printing, spraying, casting, injection molding. During the arrangement process, the polymer can be present in the unit, for example, in dissolved, molten or dispersed form.

[0113] It is possible that in step c), one or more additional layers are arranged on the entire area or a partial area of the carrier layer. In particular, the one or more layers are selected from a release layer, a primer layer, a functional layer, a protective layer.

[0114] The release layer enables the at least one unit, the one or more additional layers and / or the transfer layer sheet to be peeled off from the carrier layer without damage, wherein the release layer is arranged in contact with the carrier film and / or the transfer layer sheet. After the peeling process, the release layer preferably remains on the carrier layer, remains on the transfer layer sheet and / or remains on the carrier layer and the transfer layer sheet.

[0115] The release layer preferably consists of wax, preferably montan wax, silicone or a combination thereof, or contains wax, preferably montan wax, silicone or a combination thereof. The release layer preferably has a layer thickness in the range selected from 0.01 μm to 1 μm, preferably 0.02 μm to 0.7 μm, more preferably 0.02 μm to 0.5 μm.

[0116] The protective layer is preferably arranged on the side of the transfer layer sheet facing away from the carrier layer, wherein the protective layer preferably constitutes the visible side of the decorative object. The protective layer protects the underlying layers or units from mechanical loads or chemical exposure during the process of the method, in particular during the arrangement on the object or also during the use of the decorative object.

[0117] The protective layer is preferably configured as a self-supporting protective layer or a non-self-supporting protective layer.

[0118] The protective layer preferably has a layer thickness in the range selected from 0.5 μm to 10 μm, preferably 0.8 μm to 5 μm.

[0119] Preferably, the protective layer is formed of or comprises at least one polymer, individually or in combination, selected from: polyesters, polyolefins, polyurethanes, polyacrylates, styrene resins, ketone resins.

[0120] The protective layer is preferably transparent. It is also possible that the protective layer is configured to be colored and / or configured to be a protective layer with transparent pigments (lasierend).

[0121] The term "transparent" is understood to mean that the transmittance value of the unit, region or layer is selected from the range of 50% to 100%, preferably 70% to 100%, especially for at least one wavelength in the spectrum perceptible to the naked eye, especially for at least one wavelength selected from the range of 400 nm to 800 nm. If the unit, region or layer has a transmittance value of less than 50%, preferably less than 30%, it is understood to be "opaque".

[0122] It is also possible that the protective layer is removed again after step e) or step g). Preferably, here, the protective layer is peeled off or at least partially dissolved.

[0123] The primer layer improves the adhesion of the transfer laminate to the object by chemical and / or physical interactions. In a decorated object, the primer layer is preferably integrally bonded to the object.

[0124] The term "integrally bonded" is preferably understood to mean that two objects, elements, layers and / or units cannot be separated without damage.

[0125] The primer layer may comprise at least one polymer which preferably has at least one dissociable functional group.

[0126] The dissociable functional group provides the following advantages, especially when decorating mineral or mineral-containing objects such as concrete, ionic bonds, covalent bonds and / or hydrogen bridge bonds can be formed between the object and the primer layer. Mechanical interlocking can also be formed, especially by forming a crystal structure that grows into the primer layer.

[0127] The term "dissociable functional group" is preferably understood to mean a functional group that is covalently bonded to the at least one polymer and reacts when contacted with an acidic aqueous medium, a neutral aqueous medium or a basic aqueous medium so that at least in equilibrium anionic and / or cationic charges can be generated. For example, the term "dissociable functional group" means that a partial structure of the dissociable functional group can react when contacted with an acidic aqueous medium, a neutral aqueous medium or a basic aqueous medium to form at least two or more molecules and / or positively charged and / or negatively charged ions in equilibrium. Suitable dissociable functional groups can, for example, give at least one proton, forming an anionic functional group here, or receive a proton, forming a cationic functional group here.

[0128] Furthermore, the at least one primer layer has a layer thickness in the range selected from 50 nm to 100 μm, preferably 100 nm to 50 μm, particularly preferably 250 nm to 20 μm.

[0129] Preferably, the at least one dissociable functional group of the primer layer has an amino group and / or a hydroxyl group and / or a free acid group, which is preferably selected from a carboxyl group, a sulfonic acid group, a sulfuric acid monoester group, a phosphonic acid group, a phosphoric acid monoester group, and combinations thereof, preferably a carboxyl group, a sulfonic acid group, and combinations thereof, more preferably a carboxyl group, and / or a blocked acid group, which is preferably selected from a carboxylic acid ester group, a carboxylic acid anhydride group, a carboxyl halide group, a sulfonic acid ester group, a sulfonic acid anhydride group, a sulfonyl halide group, a phosphonic acid ester group, and combinations thereof, more preferably a carboxylic acid ester group, a carboxylic acid anhydride group, a sulfonic acid ester group, and combinations thereof, more preferably a carboxylic acid ester group, a carboxylic acid anhydride group, and combinations thereof, more 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.

[0130] It is possible that at least one dissociable functional group of the primer layer is a free acid group, which is preferably selected from a carboxyl group, a sulfonic acid group, a phosphonic acid group, and combinations thereof, and / or at least one dissociable functional group comprises a blocked acid group or consists of a blocked acid group, which is preferably selected from a carboxylic acid ester group, a carboxylic acid anhydride group, a sulfonic acid ester group, a sulfonic acid anhydride group, and combinations thereof.

[0131] It is possible that the primer layer has a polymer comprising at least one free anionic functional group, wherein the functional group is preferably selected from anionic-functionalized epoxy polymers and copolymers, anionic-functionalized acrylic polymers and copolymers, anionic-functionalized methacrylic polymers and copolymers, anionic-functionalized polyurethane polymers and copolymers, and mixtures thereof, preferably anionic-functionalized acrylic polymers, anionic-functionalized methacrylic polymers, anionic-functionalized polyurethane polymers, their copolymers, and mixtures thereof.

[0132] In addition, it is also possible that the primer layer is formed of a physically setting adhesive or a chemically curing adhesive, or comprises these adhesives. This provides the advantage of improved adhesion when decorating objects made of, in particular, plastics, stone, or organic materials such as, for example, paper, cardboard, and / or wood.

[0133] Alternatively, it is possible that no primer layer is present. This is particularly advantageous if the at least one unit is arranged on a local area or the entire area of a surface composed of or containing concrete, in particular fresh concrete or hardened concrete.

[0134] This is because the at least one unit containing the polymer itself can act as a primer layer. As described above, it is also possible that carboxyl groups of the at least one unit form ionic bonds, covalent bonds, and / or hydrogen bridge bonds between the object and the at least one unit. A mechanical interlock can also be formed, in particular by forming a crystal structure during the curing of the concrete, which structure grows into the at least one unit.

[0135] The functional layer preferably contacts the release layer, the protective layer, and / or the at least one unit.

[0136] The functional layer is preferably selected from transparent and / or colored paint layers (which particularly contain one or more dyes and / or pigments), replication layers having a molded optically active surface structure, reflective layers (in particular opaque reflective layers, transparent reflective layers, metal reflective layers, or dielectric reflective layers), optically variable layers, optically active layers, multi-layer interference systems, volume holographic layers, liquid crystal layers (in particular cholesteric liquid crystal layers), conductive layers, antenna layers, electrode layers, magnetic layers, magnetic storage layers, adhesion promoter layers, barrier layers, and combinations thereof.

[0137] The at least one functional layer can preferably be opaque and / or transparent at least in a local region.

[0138] The at least one functional layer can preferably be configured as a pattern, decoration, grille, geometric figure, pattern, alphanumeric character, logo, or a combination thereof.

[0139] In addition, it is also possible that the method further has at least the following steps, which are preferably carried out after step c) or are sub-steps of step c):

[0140] h) Separating the at least one unit from the element, wherein the at least one unit exists in the form of particles and / or fibers after step h).

[0141] The separation from the element, which is particularly in the form of a layer, can be carried out by one of the following methods: grinding, brushing, sandblasting, scraping.

[0142] In addition, it is possible that the method further has at least one of the following steps, which are preferably carried out after step c) and / or h):

[0143] i) Crushing and / or classifying the particles and / or fibers,

[0144] j) Dispersing the particles and / or fibers in a medium.

[0145] The particles and / or fibers are preferably crushed by means of a stirred ball mill, impact mill, roller mill, grinder, and / or dissolver.

[0146] Dispersion is preferably carried out by means of a method comprising a stirred ball mill, an impact mill, a roller mill, an extruder and a dissolver. As the dispersion medium, for example, a binder, a varnish and / or a solvent can be used.

[0147] Advantageously, after step j), a dispersion-type paint and / or varnish and / or printing ink and / or paste and / or pigment preparation is obtained, which particularly comprises the at least one unit in the form of particles and / or fibres.

[0148] In step d) of the method, the at least one unit is dried. Step d) is preferably carried out after step c) and / or before step e).

[0149] It is possible to use at least one of the following methods in step d) for drying: vacuum drying, centrifugation, application of infrared radiation, continuous gas enveloping flow For example, the gas can be air and / or nitrogen, wherein the temperature of the gas is higher than that of the unit.

[0150] It is additionally possible that at the start of step d) or during step d), the at least one unit is washed with another organic solvent having a boiling point lower than the solvent comprised in the reactive mixture. The washing enables on the one hand that the drying can be carried out at a lower temperature. It is thus also possible to ensure that itaconic acid does not decarboxylate during drying. On the other hand, if water is used as the solvent in the reactive mixture, it is ensured that the water is completely removed.

[0151] Preferably, after step d), the at least one unit comprising the polymer has, relative to the total mass of the at least one unit, a proportion of components having a boiling point lower than 110 °C in the range selected from 0 wt% to 10 wt%, preferably 0 wt% to 8 wt%, more preferably 0 wt% to 5 wt%.

[0152] Step d) is preferably carried out until a constant mass of the at least one unit is achieved.

[0153] The inventors have surprisingly found that units comprising the polymer obtained in step c) and dried before further processing exhibit a more uniform foaming behavior. In this way, units in the foamed state with a surface that is uniform to the human eye are obtained. Without prior drying, the units in the foamed state have a surface with bubbles and shrinkage cavities visible to the human eye.

[0154] Step d) is preferably carried out at an ambient pressure selected from the range of 500 mbar to 1000 mbar. Alternatively or additionally, the ambient temperature, in particular the temperature of the surrounding gas, is selected from the range of 50 °C to 120 °C, preferably 60 °C to 110 °C, more preferably 80 °C to 100 °C. It is also possible that in step d), an acceleration selected from the range of 9.81 m / s 2 to 100,000 m / s 2 , preferably 20 m / s 2 to 20,000 m / s 2 , more preferably 100 m / s 2 to 5000 m / s 2 is applied to the at least one unit.

[0155] In step e) of the method, the at least one unit and / or the at least one unit in the foamed state are arranged on the entire area or a partial area of the object. Step e) is preferably carried out after step d) or after step f). It is possible that step e) is carried out before step f) and / or preferably before step g).

[0156] Preferably, in step e), the at least one unit containing the polymer and / or the at least one unit in the foamed state is arranged on the object by means of at least one of the following methods: spraying method, printing method, brushing method, spreading method, scraping method, lamination method, transfer method, embossing method, adhesive bonding method.

[0157] The at least one unit is arranged on at least a partial area or the entire area of at least one surface of the object. The at least one surface preferably consists of a material selected from: concrete, in particular fresh or hardened concrete, artificial stone, natural stone, wood, polymer, ceramic, paper, metal, composite material or a combination thereof, or contains the material.

[0158] In a preferred embodiment, it is possible that step e) comprises the following sub-steps:

[0159] e1) providing at least one mold element, preferably a template, having at least one outer surface and at least one inner surface,

[0160] e2) applying a flowable or plastically deformable mineral building material mixture containing water and at least one mineral binder to the at least one inner surface of the mold element, preferably the template,

[0161] e3) at least partially solidifying the mineral building material mixture to obtain a dimensionally stable mineral green body, and

[0162] e4) at least partially hardening the mineral building material mixture,

[0163] wherein I) before step e1), the transfer film is arranged on at least one inner surface of the provided mold element, preferably a template, on the side of the carrier layer facing away from the transfer layer sheet, and in step e1), the transfer layer sheet is brought at least partially into contact with the flowable or plastically deformable mineral building material mixture, wherein a decorated mineral green body is obtained in step e3),

[0164] and / or

[0165] wherein II) in and / or after step e3), the transfer film is arranged on the dimensionally stable mineral green body with at least part of the transfer layer sheet, wherein a decorated dimensionally stable mineral green body is obtained,

[0166] and wherein in alternative I) and II), a decorated mineral molded body is obtained as a decorative object in step g).

[0167] It is possible here that the at least one mineral binder comprises a hydraulic binder, a non-hydraulic binder or a mixture thereof. The at least one mineral binder is preferably selected from calcium silicate hydrate, cement, lime, clay, gypsum, loam (Lehm), magnesia binder and combinations thereof. Furthermore, the mineral building material mixture can comprise concrete, mortar, lime sandstone, silicate ceramics or combinations or consist thereof.

[0168] In step f), the at least one unit is converted into a foamed state, wherein the at least one unit has a porous structure after step f). The at least one unit exhibits a white color impression at least in local regions in the foamed state. Step f) is preferably carried out after step d) and / or after step e) and before step g). It is also possible that step f) is carried out after or during step c). It is also possible that the chronological implementation of step f) at least partially overlaps with the chronological implementation of step c), step d) and / or step e).

[0169] Preferably, in step f), the at least one unit is exposed to a temperature in the range selected from 60 °C to 300 °C, preferably 75 °C to 250 °C, more preferably 100 °C to 180 °C. The at least one unit preferably has this temperature, especially at one of its outer surfaces.

[0170] It is possible that the drying in step d) and the conversion of the at least one unit into a foamed state are carried out directly successively in-line, especially the implementation of steps d) and f) overlaps in time. It is thus possible that steps d) and f) are carried out in the same device. Step f) is preferably carried out at a higher average temperature than step d).

[0171] Preferably, in step f), the at least one unit is converted into a foamed state over its entire area.

[0172] Alternatively, it is also possible that in step f), the at least one unit is converted into a foamed state in a partial area, so that the at least one unit has foamed areas and non-foamed areas adjacent to each other.

[0173] It is also possible that step f) is carried out multiple times, wherein at least during the first execution of step f), the at least one unit is converted into a foamed state in a partial area, so that foamed areas and non-foamed areas exist adjacent to each other in the at least one unit. In particular, during at least one further execution of step f), the at least one unit can be converted into a foamed state over its entire area.

[0174] The foamed areas or non-foamed areas can be formed in the form of a pattern, decoration, grille, geometric figure, pattern, alphanumeric character, logo or a combination thereof.

[0175] The formation of the foamed areas or non-foamed areas can form a pattern, decoration, grille, geometric figure, pattern, alphanumeric character, logo or a combination thereof with other layers, in particular with functional layers and / or with the object.

[0176] In particular, it can be designed that the foamed areas or non-foamed areas are arranged in registration (im Register bzw.registergenau) with other layers, in particular with areas of the functional layer and / or with areas of the object.

[0177] The term "registration" is understood to mean the positional accuracy of two or more laminae, elements, areas, units and / or layers relative to each other. Here, the registration accuracy should vary within a predetermined tolerance and should be as small as possible. At the same time, the registration accuracy of multiple laminae, elements, areas, units and / or layers relative to each other is an important feature for improving process reliability and / or product quality as well as anti-counterfeiting protection. Here, positionally accurate positioning can be achieved in particular by means of registration marks that can be detected by sensors, preferably optically. These registration marks can here be special individual laminae, elements, units, areas and / or layers, or can themselves be part of the laminae, elements, units, areas and / or layers to be positioned.

[0178] In order to arrange the at least one unit as one or more layers or sub-layers on a carrier layer (for example, respectively by means of printing methods such as gravure printing, screen printing, inkjet printing, flexographic printing), in order to produce a transparency gradient or transparency distribution on the printing surface, it is possible, for example, by means of cavities with corresponding variations A gravure printing anilox roll of a certain depth produces the unit and / or one or more of its layers or sub-layers, or a corresponding varying application weight of the unit is established by a corresponding varying droplet size of an inkjet print head or by a corresponding varying mesh opening of a screen printing mesh, so that, by means of locally different layer thicknesses, even after drying and foaming of the unit, a unit in a foamed state with different thicknesses and correspondingly different covering powers is produced.

[0179] The region is here particularly understood as the defined surface of the layer or unit that is occupied when viewed perpendicular to the plane formed by the unit or the transfer laminate. In other words, the defined region can extend through layers arranged one above the other in an overlapping manner.

[0180] The at least one unit preferably exhibits a defined white color impression only after it has been converted into a foamed state. If the at least one unit is configured as a layer, it is preferably transparent in the non-foamed state. In the foamed state, the at least one unit is preferably opaque.

[0181] In particular, it is possible to trigger step f) and / or the formation of a porous structure by contact of the at least one unit with an object, i.e., at the start of step e) or during step e). In particular, the object contains a catalyst that catalyzes the formation of the porous structure.

[0182] The object preferably has divalent or higher-valent cations of at least one metal, where the at least one metal is preferably selected from Mg, Ca, Sr, Ba, Al, Fe, Co or a mixture thereof. The object also has a monovalent or polyvalent anion selected from phosphate, phosphite, carbonate, bicarbonate, hydroxide, aluminate, sulfate, sulfite or a mixture thereof. The object preferably has a compound, in particular a salt, formed by at least one possible combination of the above anions and cations.

[0183] Alternatively or additionally, the object can be in contact with a layer and / or a liquid volume containing the above anions and / or cations, preferably sprayed and / or poured with it.

[0184] The presence of divalent or higher-valent cations particularly favors the conversion of the at least one unit into a foamed state in step f). It is presumed that the ions catalyze the decarboxylation of polyitaconic acid.

[0185] In step f), an open-cell and / or closed-cell structure is preferably formed in the at least one unit in the foamed state.

[0186] When the at least one unit is in the foamed state, it has a refractive index value in a range selected from 1.2 to 1.8, preferably 1.3 to 1.7, particularly due to the porous structure.

[0187] The at least one cell in the foamed state advantageously has a very large number of refractive planes, such that the observer already perceives a white color impression even in the case where the refractive index value is selected from the range of 1.2 to 1.8. Thus, a lower refractive index is required to form a white color impression as compared to white pigments such as TiO2.

[0188] The porous structure preferably has pores with a pore diameter selected from the range of 0.03 μm to 10 μm, preferably 0.4 μm to 3 μm, more preferably 0.5 μm to 1.8 μm.

[0189] What is achieved thereby is that, firstly, there are a sufficient number of refractive planes to form a white color impression. Secondly, a uniform surface with sufficient mechanical tolerance is obtained.

[0190] It is also possible that the porous structure has pores with a pore wall thickness selected from the range of 0.1 μm to 1 μm, preferably 0.1 μm to 0.75 μm, more preferably 0.15 μm to 0.4 μm.

[0191] The above-mentioned thickness of the pore wall is advantageous because it firstly means that the pore wall exhibits sufficient transmittance to incident light so that the light can be refracted on as many boundary surfaces as possible, and secondly, sufficient mechanical tolerance of the porous structure is obtained.

[0192] The pore diameter and / or the pore wall thickness are preferably determined by using a scanning electron microscope (REM), a transmission electron microscope (TEM) or a scanning force microscope (AFM). For this purpose, methods known in the prior art can be used.

[0193] The degree of foaming, i.e., the degree of decarboxylation of itaconic acid compared to the itaconic acid of the non-foamed sample, can be determined by methods known in the prior art. For example, infrared spectroscopy (IR) and nuclear magnetic resonance spectroscopy (NMR) can be used, preferably 1 1H-NMR, where the characteristic spectral bands of itaconic acid and its decomposition products after decarboxylation are known in the prior art.

[0194] For example, for analysis, the sample can be measured non-destructively using ATR-FTIR (ATR-FTIR infrared spectroscopy, ATR = attenuated total reflection, FTIR = Fourier transform infrared), or approximately 30 mg of a small amount of the sample can be dissolved in approximately 0.6 ml of deuterated water and measured using NMR.

[0195] It is also possible that the method further has the following step, which is preferably carried out after step f) and / or before step g):

[0196] k) Stabilize the porous structure, in particular by arranging a protective layer.

[0197] This enables better protection of the porous structure of the at least one cell in the foamed state against mechanical loads and chemical exposure. For example, step k) can be carried out by means of a method selected from spraying methods, preferably air spraying, ultrasonic spraying and / or electrostatic spraying, impregnation methods and / or printing methods, preferably gravure printing, screen printing, inkjet printing and / or flexographic printing, and / or combinations thereof.

[0198] Preferably, the protective layer applied in step k) at least partially fills the porous structure.

[0199] The protective layer applied in step k) can have the preferred properties of the protective layer described for step c).

[0200] In step g), a decorated object is obtained, wherein the decorated object has the at least one cell in the foamed state. The object is preferably integrally bonded to the at least one cell.

[0201] The resulting decorated object can be used in many fields. For example, the resulting decorated object is a facade element, wallpaper, housing element, masonry structure, door, floor covering, tile, packaging cardboard, furniture or a combination thereof, and / or can be used as such.

[0202] It is also possible that these method steps are carried out one or more times. In particular, the method steps can be repeated. Preferred methods have at least the following steps a), b), c), d), e), f) and g), wherein additional steps can in particular be inserted between these steps. These steps are preferably carried out in the order a), b), c), d), e), f) and g), or a), b), c), d), f), e) and g). It is also possible that the steps or sub-steps of the method overlap in time, that is to say, one step or sub-step has not been completely finished before another step or sub-step begins.

[0203] The product features mentioned above can of course also be used equivalently for the method, or the method features already mentioned can be used for the product.

[0204] The invention is illustrated below by means of a plurality of embodiments and with reference to the drawings. The embodiments shown should not therefore be understood as restrictive. Description of the Drawings

[0205] Figure 1a and 1b Schematic diagram showing the sequence of method steps.

[0206] Figure 2 Schematic diagram showing a transfer film.

[0207] Figure 3 Further schematic diagram showing a transfer film.

[0208] Figure 4a and 4b display an object decorated with a transfer layer sheet.

[0209] Figure 5a and 5b each display a REM image of units that are formed as a transfer layer sheet and are either in an unfoamed state or have been converted into a foamed state.

[0210] Figure 6 Display a REM image of units that are formed as a layer and have been converted into a foamed state in a top view.

[0211] Figure 7 Display a REM image of the decorated object.

[0212] Figure 1a and 1b Display a flow chart of a method for producing a decorated object 1'. Figure 1a and 1b The methods in each include at least method steps a) to g):

[0213] a) Provide a reactive mixture containing a monomer component containing carboxylic acid, the monomer component containing itaconic acid and / or itaconic acid derivatives,

[0214] b) Polymerize the reactive mixture to form a polymer,

[0215] c) Bring the polymer into contact with element 2, where at least one unit 3 containing the polymer is obtained,

[0216] where the at least one unit 3 containing the polymer can be converted into a foamed state, in which the at least one unit 3 forms a porous structure, where at least one unit 3' in the foamed state is obtained, and where the porous structure refracts light so that the at least one unit 3' in the foamed state exhibits a white color impression,

[0217] d) Dry the at least one unit 3,

[0218] e) Arrange the at least one unit 3 and / or the at least one unit 3' in the foamed state on the entire area or a partial area of the object 1,

[0219] f) Convert at least one unit 3 into a foamed state to obtain the at least one unit 3' in the foamed state,

[0220] g) Obtain a decorated object 1' containing the at least one unit 3' in the foamed state,

[0221] where the color impression is described by the parameters L, a and b as color coordinates in the CIELAB color space,

[0222] and wherein said at least one cell 3' in the foamed state has values of parameters a and b selected from the range of -4 to 4.

[0223] The method step sequence shown below Figure 1a and 1b will be elaborated on the steps.

[0224] In step a), a reactive mixture having a monomer component containing carboxylic acid is provided, wherein the monomer component containing carboxylic acid comprises itaconic acid and / or itaconic acid derivatives. As Figure 1a and 1b shown, step a) is carried out at the beginning of the method in each case.

[0225] The composition of the components of the reactive mixture is selected such that the sum of the components constitutes 100% by weight relative to the total weight of the reactive material.

[0226] Preferably, the reactive mixture, the polymer and / or said at least one cell 3 do not contain pigments, preferably do not contain white pigments, and more preferably do not contain TiO2.

[0227] It is possible that the reactive mixture has at least one other monomer containing carboxylic acid, which is individually or combinatorially selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid.

[0228] Preferred itaconic acid derivatives of the monomer component containing carboxylic acid are the acid anhydride of itaconic acid, the methoxy ester of itaconic acid and / or the ethoxy ester of itaconic acid.

[0229] Relative to the total mass of the reactive mixture, the proportion of the monomer containing carboxylic acid from step a) is selected from the range of 2.5% to 65% by weight, preferably 5% to 50% by weight, and more preferably 10% to 35% by weight.

[0230] The reactive mixture preferably has at least one monomer component not containing carboxylic acid, and the component or its derivatives are individually or combinatorially selected from esters of acrylic acid, esters of methacrylic acid, esters of itaconic acid, preferably diesters of itaconic acid, esters of maleic acid, maleic anhydride, terpenes, myrcene, styrene, isoprene, butadiene and vinyl ethers.

[0231] Relative to the total mass of the reactive mixture, the proportion of the monomer not containing carboxylic acid from step a) is preferably selected from the range of 5% to 50% by weight, preferably 15% to 35% by weight, and more preferably 20% to 30% by weight.

[0232] The reactive mixture preferably contains a solvent, preferably water and / or an organic solvent, which is / are selected, individually or as a mixture, from ethanol, 1-propanol, 2-propanol, acetone, 2-butanone (MEK), acetates, in particular ethyl acetate and / or lactoyl acetate.

[0233] Relative to the total mass of the reactive mixture, the proportion of the solvent is preferably selected from the range of 15% by weight to 95% by weight, preferably 30% by weight to 85% by weight, more preferably 40% by weight to 70% by weight, even more preferably 45% by weight to 60% by weight.

[0234] After step a), the reactive mixture preferably contains a polymerization initiator, preferably a free-radical polymerization initiator.

[0235] It is also possible that, relative to the total mass of the reactive mixture, the proportion of the initiator is selected from the range of 0.05% by weight to 1.5% by weight, preferably 0.1% by weight to 1% by weight, more preferably 0.25% by weight to 0.5% by weight.

[0236] It is also possible that, after step a), the reactive mixture contains at least one additive, which is / are selected, individually or in combination, from crosslinking agents, plasticizers, stabilizers, light stabilizers, flame retardants, defoaming agents, leveling additives, hydrophobizing agents, softeners, deactivators, antioxidants or free-radical chain breakers.

[0237] It is also possible that, after step a), the reactive mixture contains a filler, which is / are selected, individually or in combination, from mineral fillers, sand, diatomaceous earth, phyllosilicates, talc, aluminates, carbon fibers, wood flour, starch, glass fibers.

[0238] Suitable for according to Figure 1a and 1b The reactive mixture for the process according to the invention preferably has the following composition, where the data given for each component are each relative to the total mass of the reactive mixture and the components are thus selected such that they together make up 100% by weight:

[0239] Carboxylic acid-containing monomer component: 2.5% by weight - 65% by weight,

[0240] Carboxylic acid-free monomer component: 5% by weight - 50% by weight,

[0241] Solvent: 15% by weight - 95% by weight,

[0242] Initiator: 0.05% by weight - 1.5% by weight,

[0243] Additive: 0% by weight - 3% by weight,

[0244] Filler: 0% by weight - 10% by weight.

[0245] More preferably:

[0246] Carboxylic acid-containing monomer component: 5 wt% - 50 wt%,

[0247] Carboxylic acid-free monomer component: 15 wt% - 35 wt%,

[0248] Solvent: 30 wt% - 85 wt%,

[0249] Initiator: 0.1 wt% - 1 wt%,

[0250] Additive: 0 wt% - 2 wt%,

[0251] Filler: 0 wt% - 7 wt%.

[0252] Even more preferably:

[0253] Carboxylic acid-containing monomer component: 10 wt% - 35 wt%,

[0254] Carboxylic acid-free monomer component: 20 wt% - 30 wt%,

[0255] Solvent: 45 wt% - 60 wt%,

[0256] Initiator: 0.25 wt% - 0.5 wt%,

[0257] Additive: 0 wt% - 1 wt%,

[0258] Filler: 0 wt% - 5 wt%.

[0259] In step b), a polymer is obtained from the reactive mixture provided in step a). According to Figure 1a and 1b , step b) is preferably carried out after step a).

[0260] Preferably, step b) is carried out at a temperature of the reactive mixture in the range selected from 20 °C to 110 °C, preferably 40 °C and 85 °C, more preferably 50 °C to 70 °C.

[0261] Preferably, the polymer obtained in step b) has a number average molar mass value in the range selected from 500 g / mol to 500,000 g / mol, preferably 750 g / mol to 100,000 g / mol, more preferably 1000 g / mol to 50,000 g / mol, even more preferably 1500 g / mol to 20,000 g / mol.

[0262] It is possible that the polymer made in step b) has at least one other carboxylic acid-containing monomer unit, which is individually or combinatorially selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride.

[0263] Based on the total mass of the polymer, the proportion of the carboxylic acid-containing monomer in the polymer is selected from the range of 2.5% by weight to 100% by weight, preferably 5% by weight to 80% by weight, more preferably 10% by weight to 50% by weight.

[0264] Preferably, the polymer prepared in step b) has at least one monomer component that does not contain carboxylic acid, which is individually or combinatorially selected from the group 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 their derivatives.

[0265] Based on the total mass of the polymer, the proportion of the monomer of the component that does not contain carboxylic acid is preferably selected from the range of 0% by weight to 97.5% by weight, preferably 5% by weight to 90% by weight, more preferably 15% by weight to 85% by weight.

[0266] The polymer obtained in step b) preferably has a polydispersity value selected from the 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.

[0267] In step c), the polymer obtained in step b) is contacted with element 2, wherein at least one unit 3 containing the polymer is obtained. According to Figure 1a and 1b , step c) is preferably carried out after step b) and before step d). Element 2 can be, for example, a liquid volume, preferably the liquid volume of an alkaline solution, or a carrier layer 5. It is also possible that the liquid volume, preferably the liquid volume of an alkaline solution, is arranged on the carrier layer 5. The obtained at least one unit 3 can be in the form of a layer, a film, particles and / or fibers. It is possible here to obtain a dispersion paint, a varnish, a powder, a transfer film, especially a laminated film or a transfer film 4 having a transfer layer sheet 6 that can be peeled off from the carrier layer 5.

[0268] It is possible that element 2 is an alkaline aqueous solution containing at least one divalent or higher-valent cation of a metal, wherein the at least one metal is preferably selected from Mg, Ca, Sr, Ba, Al, Fe, Co or a mixture thereof.

[0269] Element 2 preferably has a pH value selected from the range of 8 to 14, preferably 10 to 14, more preferably 12 to 14.

[0270] Element 2 preferably contains a monovalent or polyvalent anion selected from phosphate, phosphite, carbonate, bicarbonate, hydroxide, aluminate, sulfate, sulfite or a mixture thereof.

[0271] The cation and anion are preferably selected from water-soluble salts.

[0272] It is possible to achieve the contact of the polymer with element 2 (especially in the form of a liquid volume, preferably the liquid volume of an alkaline solution) by means of a spraying method preferably selected from air spraying method, ultrasonic spraying method, and electrostatic spraying method, wherein the at least one unit 3 is obtained in the form of particles and / or fibers by the spraying method.

[0273] For spraying, the polymer is preferably dissolved and / or dispersed in a solvent, preferably an organic solvent, more preferably methyl ethyl ketone, acetone, ethanol, and / or a mixture thereof.

[0274] The particles are preferably irregular or regular, preferably in the form of spheres, flakes, or rods. In particular, the particles have a value of the volume-based average particle diameter in the range selected from 0.5 μm to 1000 μm, preferably 1 μm to 750 μm, more preferably 3 μm to 300 μm.

[0275] The fibers preferably have an aspect ratio shape factor in the range selected from 3:1 to 1000:1, preferably 10:1 to 500:1.

[0276] It is also possible that in step c), element 2 is or comprises a carrier layer 5.

[0277] It is possible that in step c), the contact is achieved by arranging the at least one unit 3 containing the polymer on a local area or the entire area of the carrier layer 5, wherein the at least one unit 3 is obtained in the form of a layer.

[0278] Preferably, a transfer film 4 is obtained by contacting the at least one unit 3 with element 2. Figure 2 Shows a schematic structure of the transfer film 4 obtained after step c), wherein the transfer film 4 has a carrier layer 5 and a transfer layer sheet 6 containing the at least one unit 3. In particular, the transfer layer sheet 6 can be peeled off from the carrier layer 5. Figure 2 The transfer film 4 shown in may have units 3 that have not been converted into a foamed state 3', or units 3' that have been converted into a foamed state.

[0279] Alternatively, it is also possible that the transfer layer sheet 6 cannot be peeled off from the carrier layer 5, wherein the transfer film 4 is preferably usable as a laminated film.

[0280] The carrier layer 5 preferably consists of polyester, polyolefin, or a combination thereof, especially consisting of PET.

[0281] In addition, the carrier layer 5 preferably has a layer thickness in the range selected from 5.7 μm to 100 μm, preferably 19 μm to 50 μm.

[0282] Preferably, in step c), the polymer is in an amount selected from 5 g / m 2 to 20 g / m 2 , preferably 8 g / m2 in the range from 1 g / m to 12 g / m 2 The applied weights in the range are arranged on the carrier layer 5.

[0283] It is also possible that, in step c), the polymer is arranged on the carrier layer 5 with a layer thickness in the range selected from 5 μm to 20 μm, preferably 8 μm to 12 μm. Here, the layer thickness is measured particularly in the dry state of the layer.

[0284] Preferably, in step c), in order to arrange the at least one unit 3 or one or more additional layers on the carrier layer 5, at least one of the following methods is used in each case: gravure printing, screen printing, inkjet printing, flexographic printing, offset printing, spraying, casting, injection molding.

[0285] It is possible that, in step c), one or more additional layers are arranged on the entire area or a partial area of the carrier layer 5. In particular, the one or more layers are selected from a release layer 7, a primer layer 8, a functional layer, and a protective layer 9.

[0286] Thus, similar to Figure 2 the transfer film 4 shown in Figure 3 a transfer film 4 is shown having a carrier layer 5 and a transfer layer sheet 6. According to Figure 3 the transfer film 4 further has a release layer 7, a primer layer 8, and a protective layer 9. The transfer film 4 may additionally have a functional layer not shown in Figure 3 The functional layer may be arranged at any position between, above, and / or below other layers depending on the function.

[0287] In the transfer film 4 according to Figure 3 the release layer 7 is arranged in contact with the carrier layer 5. A protective layer 9 is also arranged on the release layer 7, which forms the visible side of the transfer layer sheet 6 after the carrier layer 5 is peeled off. The unit 3 according to the invention is applied as a layer to the protective layer 9, and then the primer layer 8 is arranged on the unit.

[0288] After the peeling process, the release layer 7 preferably remains on the carrier layer 5, remains on the transfer layer sheet 6, and / or remains on both the carrier layer 5 and the transfer layer sheet 6.

[0289] The release layer 7 preferably consists of wax, preferably lignite wax, or silicone or a combination thereof, or contains wax, preferably lignite wax, or silicone or a combination thereof.

[0290] According to Figure 3 the release layer 7 of the transfer film 4 preferably has a layer thickness in the range selected from 0.01 μm to 1 μm, preferably 0.02 μm to 0.7 μm, more preferably 0.02 μm to 0.5 μm.

[0291] According to Figure 3The transfer film 4 may have a self-supporting protective layer 9 or a non-self-supporting protective layer 9.

[0292] The protective layer 9 preferably has a layer thickness in the range selected from 0.5 μm to 10 μm, preferably 0.8 μm to 5 μm.

[0293] Preferably, the protective layer 9 is formed of or contains at least one polymer selected individually or in combination from: polyester, polyolefin, polyurethane, polyacrylate, styrene resin, ketone resin.

[0294] The protective layer 9 is preferably transparent. It is also possible that the protective layer 9 is colored and / or is a protective layer 9 configured with a transparent pigment.

[0295] It is also possible that the protective layer 9 is removed again after step e) or step g) of the method according to Figure 1a and 1b Preferably, here, the protective layer 9 is peeled off or at least partially dissolved.

[0296] Preferably, in the decoration of the object 1' after step e) of the method according to Figure 1a and 1b , the primer layer 8 of the transfer film 4 according to Figure 3 is integrally bonded to the object 1.

[0297] The primer layer 8 contains at least one polymer which preferably has at least one dissociable functional group.

[0298] In addition, the at least one primer layer 8 has a layer thickness in the range selected from 50 nm to 100 μm, preferably 100 nm to 50 μm, more preferably 250 nm to 20 μm.

[0299] Preferably, the at least one dissociable functional group of the primer layer 8 has an amino group and / or a hydroxyl group and / or a free acid group, which is preferably selected from a carboxyl group, a sulfonic acid group, a sulfuric acid monoester group, a phosphonic acid group, a phosphoric acid monoester group and combinations thereof, preferably a carboxyl group, a sulfonic acid group and combinations thereof, more preferably a carboxyl group, and / or a blocked acid group, which is preferably selected from a carboxylic acid ester group, a carboxylic anhydride group, a carboxyl halide group, a sulfonic acid ester group, a sulfonic anhydride group, a sulfonyl halide group, a phosphonic acid ester group and combinations thereof, more preferably a carboxylic acid ester group, a carboxylic anhydride group, a sulfonic acid ester group and combinations thereof, more preferably a carboxylic acid ester group, a carboxylic anhydride group and combinations thereof, more 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.

[0300] It is possible that the at least one dissociable functional group of the primer layer 8 is a free acid group, which is preferably selected from carboxyl groups, sulfonic acid groups, phosphonic acid groups, and combinations thereof, and / or at least one dissociable functional group comprises a blocked acid group or consists of a blocked acid group, which is preferably selected from carboxylic acid ester groups, carboxylic anhydride groups, sulfonic acid ester groups, sulfonic anhydride groups, and combinations thereof.

[0301] It is possible that the primer layer 8 has a polymer comprising at least one free anionic functional group, where the functional group is preferably selected from anionic-functionalized epoxy polymers and copolymers, anionic-functionalized acrylic polymers and copolymers, anionic-functionalized methacrylic polymers and copolymers, anionic-functionalized polyurethane polymers and copolymers, and mixtures thereof, preferably anionic-functionalized acrylic polymers, anionic-functionalized methacrylic polymers, anionic-functionalized polyurethane polymers, their copolymers, and mixtures thereof.

[0302] In addition, it is also possible that, according to Figure 3 the primer layer 8 of the transfer film 4 is formed of a physically setting adhesive or a chemically curing adhesive, or contains these adhesives.

[0303] According to Figure 3 the functional layer of the transfer film 4 is preferably selected from transparent and / or colored paint layers (which particularly contain one or more dyes and / or pigments), replication layers having a molded optically active surface structure, reflective layers (especially opaque reflective layers, transparent reflective layers, metal reflective layers, or dielectric reflective layers), optically variable layers, optically active layers, multilayer interference systems, volume holographic layers, liquid crystal layers (especially cholesteric liquid crystal layers), conductive layers, antenna layers, electrode layers, magnetic layers, magnetic storage layers, adhesion promoter layers, barrier layers, and combinations thereof.

[0304] The at least one functional layer can preferably be opaque and / or transparent at least in a local region.

[0305] The at least one functional layer can preferably be configured as a pattern, decoration, grille, geometric figure, pattern, alphanumeric character, logo, or a combination thereof.

[0306] If, for example, the transfer film 4 is a transfer film comprising at least a carrier layer 5 and a transfer layer sheet 6 as shown in, for example, Figure 2 it is also possible that the method not only comprises Figure 1a and 1b the step sequences shown in, but also comprises at least the following step h). Step h) is preferably carried out after step c) or is a sub-step of step c).

[0307] h) Separating the at least one unit 3 from the element 2, where the at least one unit 3 exists in the form of particles and / or fibers after step h).

[0308] Here, the transfer laminate 6 is separated off again, where the resulting particles and / or fibres can be further processed. This separation can be carried out by means of one of the following methods: grinding, brushing, sandblasting, scraping.

[0309] The further processing of the resulting particles and / or fibres can be carried out, for example, by means of further optional steps in the method. It is thus possible that the method also has at least one of the following steps, which are preferably carried out after step c) and / or h):

[0310] i) comminuting and / or classifying the particles and / or fibres,

[0311] j) dispersing the particles and / or fibres in a medium.

[0312] The particles and / or fibres are preferably comminuted by means of a stirred ball mill, impact mill, roller mill, grinder and / or dissolver.

[0313] The dispersion is preferably carried out by means of a method comprising a stirred ball mill, impact mill, roller mill, extruder and dissolver. As the dispersion medium, it is possible to use, for example, a binder, varnish and / or solvent.

[0314] Advantageously, after step j), a dispersion paint and / or varnish and / or printing ink and / or pigment preparation is obtained, which particularly comprises the at least one unit 3 in the form of particles and / or fibres.

[0315] In step d) of the method, the at least one unit 3 is dried. Figure 1a and 1b It is shown that step d) is carried out after step c) and / or before step e).

[0316] It is possible to use at least one of the following methods in step d) to carry out the drying: vacuum drying, centrifugation, application of infrared radiation, continuous gas envelope flow. For example, the gas can be air and / or nitrogen, in particular where the temperature of the gas is higher than that of the unit.

[0317] It is additionally possible to wash the at least one unit 3 with another organic solvent having a boiling point lower than the solvent comprised in the reactive mixture at the start of step d) or during the course of step d).

[0318] Preferably, after step d), the at least one unit 3 comprising the polymer has a proportion of components having a boiling point below 110 °C in the range from 0 wt% to 10 wt%, preferably from 0 wt% to 8 wt%, more preferably from 0 wt% to 5 wt%, based on the total mass of the at least one unit 3.

[0319] Step d) is preferably carried out until the quality of the at least one unit 3 is constant.

[0320] Step d) is preferably carried out at an ambient pressure in the range selected from 500 mbar to 1000 mbar. Alternatively or additionally, the ambient temperature is selected from the range of 50 °C to 120 °C, preferably 60 °C to 110 °C, more preferably 80 °C to 100 °C. It is also possible that in step d), an acceleration in the range selected from 9.81 m / s 2 to 100,000 m / s 2 is applied to the at least one unit 3, preferably 20 m / s 2 to 20,000 m / s 2 and more preferably 100 m / s 2 to 5000 m / s 2 is applied.

[0321] In step e) of the method according to Figure 1a and Figure 1b the at least one unit 3 and / or the at least one unit 3' in the foamed state are arranged on the entire area or a partial area of the object 1. Step e) is preferably 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).

[0322] Preferably, in step e), the at least one unit 3 containing the polymer and / or the at least one unit 3' in the foamed state are arranged on the object 1 by means of at least one of the following methods: spraying method, printing method, brushing method, spreading method, scraping method, lamination method, transfer method, embossing method, adhesive bonding method.

[0323] The at least one unit 3 is arranged at least on a partial area or the entire area of at least one surface of the object 1. The at least one surface preferably consists of a material selected from the group consisting of or containing the following: concrete, in particular freshly made or set concrete, artificial stone, natural stone, wood, polymer, ceramic, paper, metal, composite material or a combination thereof.

[0324] In a preferred embodiment of the method according to Figure 1a and Figure 1b step e) may include the following sub-steps:

[0325] e1) providing at least one mold element, preferably a template, which has at least one outer surface and at least one inner surface,

[0326] e2) applying a flowable or plastically deformable mineral building material mixture containing water and at least one mineral binder to the at least one inner surface of the mold element, preferably the template

[0327] e3) At least partially solidify the mineral building material mixture to obtain a dimensionally stable green mineral body, and

[0328] e4) At least partially harden the mineral building material mixture,

[0329] wherein I) before step e1), the transfer film 4 is arranged on at least one inner surface of the provided mold element, preferably a template, on the side of the carrier layer 5 facing away from the transfer layer sheet 6, and in step e1), the transfer layer sheet 6 is brought into at least partial contact with the flowable or plastically deformable mineral building material mixture, wherein a decorated green mineral body is obtained in step e3),

[0330] and / or

[0331] wherein II) in and / or after step e3), the transfer film 4 is arranged on the dimensionally stable green mineral body with at least part of the transfer layer sheet 6, wherein a decorated dimensionally stable green mineral body is obtained,

[0332] and wherein in alternative I) and II), a decorated mineral molded body is obtained as the decorative object 1' in step g).

[0333] It is possible here that the at least one mineral binder comprises a hydraulic binder, a non-hydraulic binder or a mixture thereof. The at least one mineral binder is preferably selected from calcium silicate hydrate, cement, lime, clay, gypsum, loam, magnesia binder and combinations thereof. In addition, the mineral building material mixture may comprise concrete, mortar, lime sandstone, silicate ceramic or a combination thereof or consist of them.

[0334] In step f), the at least one unit is converted into a foamed state 3', wherein the at least one unit 3' has a porous structure after step f). As Figure 1a and 1b shown, step f) is preferably carried out after step d) and / or after step e) and before step g). It is also possible that step f) is carried out after or during step c). It is also possible that the temporal implementation of step f) at least partially overlaps in time with the implementation of step c), step d) and / or step e).

[0335] The at least one unit 3' exhibits a white color impression at least in local regions in the foamed state.

[0336] The at least one unit 3' in the foamed state preferably has values of the parameters a and b selected from the range of -4 to 4, preferably -3 to 3, more preferably -2 to 2, and even more preferably -1 to 1. The at least one unit 3' in the foamed state preferably has a value of the parameter L selected from the range of 70 to 100, preferably 80 to 100, more preferably 90 to 100.

[0337] Preferably, in step f), the at least one unit 3 is exposed to a temperature selected from the range of 60 °C to 300 °C, preferably 75 °C to 250 °C, more preferably 100 °C to 180 °C. The at least one unit 3 preferably has this temperature, especially at one of its outer surfaces.

[0338] It is possible that the drying in step d) and the conversion of the at least one unit into the foamed state 3' are carried out directly successively online, especially with an overlap in the times of carrying out steps d) and f). It is thus possible that steps d) and f) are carried out in the same device. Step f) is preferably carried out at a higher average temperature than step d).

[0339] Preferably, in step f), the at least one unit 3 is converted into the foamed state over its entire area.

[0340] Alternatively, it is also possible that, in step f), the at least one unit 3 is converted into the foamed state in a local area such that the at least one unit has foamed areas and non-foamed areas adjacent to each other.

[0341] It is also possible that step f) is carried out multiple times, where at least during the first carrying out of step f), the at least one unit 3 is converted into the foamed state in a local area so that foamed areas and non-foamed areas exist adjacent to each other in the at least one unit. In particular, during at least one further carrying out of step f), the at least one unit 3 can be converted into the foamed state over its entire area.

[0342] The foamed areas or non-foamed areas can be formed in the form of a pattern, decoration, grille, geometric figure, pattern, alphanumeric character, logo, or a combination thereof.

[0343] The formation of the foamed areas or non-foamed areas can form a pattern, decoration, grille, geometric figure, pattern, alphanumeric character, logo, or a combination thereof with other layers, especially with functional layers and / or with the object.

[0344] In particular, it can be designed that the foamed areas or non-foamed areas are arranged in registration with other layers, especially with areas of functional layers and / or with areas of the object.

[0345] Preferably, the at least one unit 3 exhibits a defined white color impression only when it has been converted into a foamed state. If the at least one unit 3 is configured as a layer, it is preferably transparent in the non-foamed state. The at least one unit 3' in the foamed state is preferably opaque.

[0346] In particular, it is possible to initiate step f) at the start of step e) or during step e). In particular, the object 1 contains a catalyst that catalyzes the formation of a porous structure.

[0347] The object 1 preferably has divalent or higher-valent cations of at least one metal, where the at least one metal is preferably selected from Mg, Ca, Sr, Ba, Al, Fe, Co or a mixture thereof. The object 1 also has a monovalent or polyvalent anion selected from phosphate, phosphite, carbonate, bicarbonate, hydroxide, aluminate, sulfate, sulfite or a mixture thereof. The object 1 preferably has a compound, in particular a salt, formed by at least one possible combination of the above-mentioned preferred anions and cations.

[0348] Alternatively or additionally, the object 1 can be in contact with a layer and / or a liquid volume containing the above-mentioned anions and / or cations, preferably sprayed or poured with it.

[0349] In step f), an open-cell and / or closed-cell structure is preferably formed in the at least one unit 3' in the foamed state.

[0350] The at least one unit 3' in the foamed state has a refractive index value between 1.2 and 1.8, preferably between 1.3 and 1.7, especially due to the porous structure.

[0351] The porous structure preferably has pores with a pore diameter selected from the range of 0.03 μm and 10 μm, preferably 0.4 μm to 3 μm, more preferably 0.5 μm to 1.8 μm.

[0352] It is also possible that the porous structure has pores with a pore wall thickness selected from the range of 0.1 μm to 1 μm, preferably 0.1 μm to 0.75 μm, more preferably 0.15 μm to 0.4 μm.

[0353] It is also possible that the method not only has Figure 1a and 1b the steps listed therein, but also has the following steps, which are preferably carried out after step f) and / or before step g):

[0354] k) Stabilize the porous structure, in particular by arranging a protective layer.

[0355] For example, step k) can be carried out by means of a method selected from spraying methods, preferably air spraying, ultrasonic spraying and / or electrostatic spraying, dipping methods and / or printing methods, preferably gravure printing, screen printing, inkjet printing and / or flexographic printing, and / or combinations thereof.

[0356] Preferably, the protective layer applied in step k) at least partially fills the porous structure.

[0357] The protective layer applied in step k) can have the preferred properties of the protective layer described for step c).

[0358] As Figure 1a and 1b can be seen, the method according to the invention has step g) as the last method step. In step g), a decorated object 1' is obtained, wherein the decorated object 1' has the at least one unit 3 in a foamed state. The object 1 is preferably integrally bonded to the at least one unit 3. Figure 4a and Figure 4b shows a schematic construction of the decorated object 1'.

[0359] The decorated object 1' according to Figure 4a has a unit 3' in a foamed state arranged on the object 1. The unit 3 has been arranged on the object 1, for example, by means of a transfer film 4 according to Figure 2 Alternatively, the unit 3 can also be a layer with particles, wherein the particles have been dispersed in a medium according to steps i) and j) and subsequently arranged on the object 1.

[0360] Figure 4b shows a decorated object 1' with a transfer film 4 arranged thereon, for example, according to Figure 3 The decorated object 1' has a primer layer 8 in contact with the object 1'. The primer layer 8 contacts the unit 3' in a foamed state, which in turn contacts the protective layer 9. Here, the protective layer 9 forms the visible side of the decorated object 1'. However, it is also possible that the transfer film 6 does not contain the protective layer 9, and the protective layer 9 is arranged in step k) after the transfer film 6 is arranged on the object 1.

[0361] For example, according to Figure 4a or Figure 4b the resulting decorated object 1' can be used in many fields. The resulting decorated object 1' is preferably a facade element, wallpaper, housing element, masonry structure, door, floor covering, tile, packaging cardboard, furniture or a combination thereof, and / or can be used as such. Detailed Description

[0362] Example 1:

[0363] According to Figure 1aIn the method, in step c), the polymer is applied to the element 2 in the form of the carrier layer 5. The unit 3 exists as a layer and forms the transfer layer sheet 6 of the transfer film 4, where the transfer layer sheet 6 can be peeled off from the carrier layer 5. It is intended to obtain a concrete component decorated as the decorative object 1' as shown in Figure 4a the decorated concrete component shown in

[0364] For this purpose, first, a batch polymer is synthesized by radical polymerization of myrcene and itaconic acid in ethanol, for example, according to steps a) and b), where the solvent is not limited to ethanol.

[0365] Here, the composition of the reactive mixture corresponds to 24.4 g of myrcene (24.4% by weight) and 15.6 g of itaconic acid (15.6% by weight) in 60 g of ethanol (60% by weight). As the initiator, 0.37 g of azo initiator V-65 (0.37% by weight) is used at a polymerization temperature of 65 °C.

[0366] Subsequently, a PET carrier layer 5 (the thickness of the PET carrier layer 5 is 5 μm to 150 μm, preferably 7 μm to 100 μm) is introduced and coated with a release layer 7 having a thickness of at least 50 nm and composed of lignite ester wax. Subsequently, as described with respect to step c), the coated PET carrier layer 5 is coated with the polymer dissolved in ethanol on one side of the release layer 7 using a doctor blade. In each test with different layer thicknesses, the applied weight of the dried layer of the polymer is 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 layer thicknesses in the dry state of approximately 1.6 μm, 4 μm, 8 μm, 10 μm, 12 μm, and 18.5 μm, respectively.

[0367] Optionally, it is possible to arrange additional layers, in particular a protective layer 9 and / or a functional layer, on the carrier layer 5 or the release layer 7 before applying the dissolved polymer by doctor blade coating, in order to obtain a transfer film 4 equivalent to the transfer film 4 shown in Figure 3 .

[0368] According to step d), the coating is dried at approximately 150 °C for approximately 10 seconds using a hot air stream (hair dryer) until a constant weight is achieved, and a closed transfer layer sheet 6 of the transfer film 4 is formed.

[0369] Concrete is mixed by mixing 1935 g of gravel (fraction: 2 mm to 8 mm), 2565 g of sand (fraction: 0 mm to 2 mm) and 900 g of CEMII / A-LL 42.5N (Portland limestone cement) together and stirring the mixture with 450 g of water to form a homogeneous concrete mixture.

[0370] In each case, the transfer film 4 is arranged as a transfer laminate 6 on a plate made of ABS material and having a thickness of 1 mm, and in each case 300 g of the formulated concrete is applied in contact with the transfer laminate 6 onto each transfer film 4 inside the form (see step e)).

[0371] After the concrete has completely hardened at room temperature, a mineral composite is formed according to step g), which mineral composite is coated on one side with the transfer film 4 used in each case.

[0372] After three days, the concrete shaped body is removed from the form and allowed to dry completely under atmospheric conditions. After drying for 24 hours, the PET carrier is peeled off from the concrete, where the transfer laminate 6 remains adhered to the concrete and forms a smooth coating on the composite. During this time, the white coloring of the paint layer has also been completely formed.

[0373] Example 2:

[0374] Starting from the following reactive mixture: The reactive mixture consists of 50 wt.% water, 9.5 wt.% itaconic acid semi-neutralized with potassium hydroxide (i.e., adding wt.% of KOH relative to itaconic acid (e.g., 4 g KOH / 9.3 g itaconic acid)), 40.5 wt.% methyl methacrylate and 1 wt.% V-50 (water-soluble azo initiator). At 60 °C, under vigorous mechanical stirring, the polymer is produced over 12 hours.

[0375] The resulting aqueous dispersion is added to ethanol to remove impurities by the impurities dissolving particularly in ethanol. The solvent is removed by filtration (pore 4), and the remaining polymer solid is dried in a vacuum drying oven (air pressure approximately 20 mbar) at 40 °C for approximately 10 hours. The resulting powder is manually ground in a mortar and heated to approximately 170 °C while swirling in a round-bottom flask.

[0376] The particle size D of the pigment particles obtained by grinding 50 is D 50 = 10 μm (equivalent to the median particle size); D 10 = 3.5 μm; D 90= 39.5 μm. In other words, the size of 80% of the pigment particles is between 3.5 μm and 39.5 μm. The particle size of the pigment particles is measured by dynamic light scattering. The particle size is preferably understood to refer to the volume-based particle diameter.

[0377] The obtained prepared powder is dispersed in a solvent such as ethanol with the aid of a dispersion additive (in this example: Solsperse 35000), and a dispersion (composed of the dispersion additive and the pigment) with a solids content of 18.5% by weight is obtained. This dispersion (100% by weight) consists of 7.5% by weight of the dispersion additive, 81.5% by weight of ethanol, and 11% by weight of the pigment.

[0378] Subsequently, this dispersion is added to a binder solution (in this example: a 36% solution of Degacryl HS 4240D in ethanol) so that the total solids content of the paint composed of the pigment and the binder is approximately 23% by weight. The paint is applied to the carrier film using a doctor blade, and the resulting paint film is dried for approximately 30 seconds with the aid of a hot air stream (hair dryer). The application weight of the dried layer is approximately 8 g / m 2 , which roughly corresponds to a layer thickness of 8 μm for the dried layer.

[0379] A PET carrier layer 5 (the thickness of the PET carrier layer 5 is 5 μm to 150 μm, preferably 7 μm to 100 μm) is introduced as the carrier film. Before applying the paint by doctor blade coating, the carrier layer 5 may optionally have been coated with a release layer 7 at least 50 nm thick and composed of montan wax ester. One or more adhesion promoter layers, primer layers, or adhesive layers can be optionally applied to the paint that has been applied by doctor blade coating and dried. Thus, a transfer film used as a cold embossing film and / or a hot embossing film can be achieved.

[0380] In the absence of a release layer, an adhesion promoter layer, a primer layer, or an adhesive layer, the paint applied by doctor blade coating may also be provided as a single layer on the carrier layer 5, and due to the thermoplastic nature of the binder, it can be used as a hot embossing film, for example. In this case, the paint layer peels off from the carrier layer 5 under the influence of mechanical pressure and heat and adheres to the substrate.

[0381] Example 3:

[0382] It is also possible that at least one unit 3 containing the polymer is obtained in particle form. These particles can be dispersed in a medium in a further step. In particular, the medium containing these particles can be applied to the object 1 as a dispersion-type paint, for example. This example has a Figure 1a step sequence according to, and here it additionally includes steps i) and j).

[0383] To this end, the polymer from a batch such as from Example 2 (in a container or already applied to a carrier) is dried in a drying oven under vacuum and at 40 °C until a constant mass is achieved. Optionally, it may be possible, especially if an aqueous solvent was used for the synthesis, to wash the polymer with ethanol to achieve absolute anhydrousness. This is advantageous for the consistency of the particles obtained by heating in subsequent steps of the method.

[0384] Subsequently, the layer consisting of the dried polymer is comminuted using a mortar, and a homogeneously ground powder is obtained.

[0385] While gently rotating and shaking, the particles are heated in a heat-resistant container such as a round-bottom flask above a burner flame or a hot air blower. This is carried out until the first spherical particles are obtained from the powder. The particles exhibit a white color impression.

[0386] Subsequently, the particles can be classified and dispersed in a medium, in particular the medium containing the particles can be applied to the object 1, for example, as a dispersion paint or varnish. The application and further processing of the particles dispersed in the medium can be carried out, for example, analogously to Example 1.

[0387] Table 1: Exemplary formulation of a paint with the polymer made from Example 2

[0388] Component Paint 1 Paint 2 Water 28.00g 28.00g Polymer binder 26.00g 26.00g Made polymer 28.00g 28.00g Calcium carbonate filler 15.00g 18.00g Associative thickener 0.90g 1.20g Defoamer 0.10g 0.10g Aerosil filler 1.00g 2.00g Emulsifying emulsion --- 5.00g Fluorescent brightener 0.25g 0.25g

[0389] As a polymer binder, especially a styrene-acrylate-based binder, Synexil SAB 05 can be used, for example. As a calcium carbonate filler, Omyacarb 5-GU can be used, for example. As an associative thickener, Optiflo H 600 can be used, for example. As an antifoaming agent, Surfynol DF110 D can be used, for example. As an Aerosil filler, Aerosil TT 600 can be used, for example. As an opacifying emulsion, Ropaque Ultra EF can be used, for example. As a fluorescent brightening agent, Tinopal OB can be used, for example.

[0390] Example 4:

[0391] It is also possible to obtain the at least one unit 3 containing the polymer in the form of particles or fibers by spraying the dissolved polymer into an alkaline solution. The particles and / or fibers can be dried, comminuted, classified, and dispersed in a medium in further steps as described for steps i) and j), in particular the medium containing the particles can be applied to the object 1, for example, as a dispersion paint.

[0392] For this purpose, a solution with 20% by weight of said polymer is used, for example from the batch in Example 1. Additionally, an alkaline solution is provided by dissolving Ca(OH)2 in 250 g of water until saturation. Subsequently, the polymer solution is sprayed into the alkaline solution at an operating pressure of 1 bar using a commercially available spray gun (e.g., TIMBERTECH ABPST01 spray gun set). On the surface of the alkaline solution, the polymer precipitates in the form of particles and / or fibers.

[0393] After the precipitate is washed with water and separated by filtration, it is dried under standard climate (air temperature of 23 °C and relative air humidity of 50%) according to DIN EN ISO 291:2008-08 ("Plastics - Standard atmospheres for conditioning and testing (ISO 291:2008) - German version EN ISO 291:2008", release date: 2008-08) until a constant weight is achieved.

[0394] Subsequently, the layer composed of the dried polymer is ground using a mortar, and a uniformly ground powder is obtained. The particles of this powder exhibit a white color impression.

[0395] Subsequently, the particles can be classified and dispersed in a medium. In particular, the medium containing these particles can be applied to object 1, for example, as a dispersion paint. The application and further processing of the particles dispersed in the medium can be carried out, for example, similar to Example 1.

[0396] Comparative Example 1:

[0397] To compare the color impression of the decorative object 1' according to the present invention with that of object 1 coated with a TiO2-containing paint layer, concrete is formulated as described in Example 1 and cured in the form of multiple specimens.

[0398] In addition, a variety of TiO2-containing dispersions are prepared, and their TiO2 content is adjusted to be between 10% and 52% by weight based on the solids of the dried layer. Transfer films are prepared from these dispersions according to Example 1. Different from Example 1, instead of applying the polymer dissolved in ethanol to the PET carrier layer 5 with a release layer by knife coating, in this case, the corresponding layer of the TiO2-containing dispersion is printed onto the release layer by gravure printing, where each transfer film has a layer of a different TiO2-containing dispersion with a different TiO2 content based on the solids of the dried layer.

[0399] Subsequently, the specimens are coated with the respective TiO2-containing dispersion using the transfer film. The application weight of the TiO2-containing layer is 10 g / m 2 . This corresponds to a layer thickness of approximately 10 μm in the dry state. The TiO2-containing layer forms a closed layer on the specimen.

[0400] To directly compare the color impressions of the samples obtained according to Example 1 and Comparative Example 1, the color coordinates thereof in the CIELAB color space were determined. Using a colorimeter, for example, using a "Datacolor650" spectrophotometer, the color coordinates in the CIELAB color space were determined, where in each case the sample was tensioned in front of the measuring port.

[0401] Tables 2 and 3 show the results of the luminance value L and the a and b coordinates in the CIELAB color space.

[0402] Table 4 shows how much layer thickness in the dry state is required for the sample according to Example 1 made according to the present invention to achieve a white color impression and / or hiding power comparable to that of the sample of Comparative Example 1 made according to the prior art.

[0403] Table 2: Values of the color coordinates of the samples made according to Comparative Example 1 in the CIELAB color space (L, a, b). The samples are named according to their TiO2 solid content.

[0404] Name <![CDATA[TiO2 content / wt%]]> L a b Reference (concrete) 0 wt% 72.63 0.16 3.84 <![CDATA[TiO2 - 10%]]> 10 wt% 79.54 -0.16 1.62 <![CDATA[TiO2 - 20%]]> 20 wt% 85.57 -0.48 -0.17 <![CDATA[TiO2 - 30%]]> 30 wt% 87.66 -0.72 -1.27 <![CDATA[TiO2 - 40%]]> 40 wt% 87.82 -0.68 -1.62 <![CDATA[TiO2 - 50%]]> 50 wt% 88.24 -0.69 -1.61 <![CDATA[TiO2 - 52%]]> 52 wt% 90.63 -1.15 -1.36

[0405] Table 3: Values of the color coordinates of the samples made according to Example 1 in the CIELAB color space (L, a, b).

[0406] Sample (according to the present invention) Layer thickness L a b Reference (concrete) No coating 72.63 0.16 3.84 Sample 1 1.6 μm 70.85 -0.23 1.97 Sample 2 4 μm 80.42 -0.87 -0.66 Sample 3 8 μm 81.73 -0.89 -0.10 Sample 4 10 μm 85.87 -1.00 -0.21 Sample 5 12 μm 91.80 -1.03 1.69 Sample 6 18.5 μm 92.15 -1.18 1.67

[0407] Table 4: Matching relationship between the layer thickness of the coating according to the present invention in the dry state and the TiO2-containing layer having comparable hiding power (layer thickness in the dry state is about 10 μm).

[0408] <![CDATA[TiO2 content of the layer / wt%]]> Layer thickness of the coating according to the present invention / μm 10 4 20 8 30 10 52 18

[0409] The numerical values in Tables 2 and 3 show that comparable color coordinates can be achieved by means of the concrete decoration according to the present invention. Therefore, the hiding power of the decoration according to the present invention is very close compared to the prior art.

[0410] Different from the samples containing TiO2, the samples according to the present invention show a positive b value under high applied weights, which results in a slight shift of the color impression towards yellow.

[0411] It can also be shown that in the case of a layer thickness of about 10 μm in the dry state of the coating according to the present invention, it is possible to achieve complete hiding, i.e., a uniform color impression, where the decorated object 1' is no longer visible. The coating according to Comparative Example 1 achieves a comparable color impression at a layer thickness of 10 μm in the dry state with a TiO2 content of 30% by weight. This shows that by using the decoration according to the present invention, 30% by weight of TiO2 can be saved.

[0412] Furthermore, REM images of portions of the transfer film 4 described in Example 1 are obtained, in which the units 3 containing the polymer are configured in the form of a layer or a transfer laminate 6. One image shows the units in the unfoamed state and one image shows the units 3' in the foamed state. Additionally, REM images of the decorated object 1' obtained in Example 1 are obtained. The REM images are shown in Figure 5a and 5b , Figure 6 and Figure 7 .

[0413] For the REM images, in each case a specimen piece is cut out from the film to be examined or from the object to be coated and is sputter-coated with gold. The specimen piece has dimensions of approximately 20 mm × 10 mm × 4 mm (20 mm × 10 mm base; thickness 4 mm).

[0414] In the Figure 5a and 5b REM images, the cut surfaces of the transfer films each containing the units 3 in the form of a carrier layer 5 composed of PET and a transfer laminate 6 are examined in the unfoamed state ( Figure 5a ) and in the foamed state 3' ( Figure 5b ), respectively. Figure 5a The images in Figure 5b are made at a magnification of x950, a working distance of 10 mm, a spot size of 60, and an acceleration voltage of 5 kV. The measuring scale is 20 μm.

[0415] As can be clearly seen in Figure 5a and 5b , the transfer laminate 6 has a dense structure in the unfoamed state and forms a porous structure in the foamed state. Furthermore, the formation of the porous structure of the transfer laminate 6 results in an 8 - to 10-fold increase in layer thickness.

[0416] Figure 6 The REM images in Figure 6 show a top view of the units 3' in the foamed state, for example, of the transfer laminate 6 of the transfer film 4 according to Example 1.

[0417] Figure 6 show the porous structure formed by the transfer laminate 6, which produces a white color impression due to refraction at the numerous formed boundary surfaces.

[0418] Figure 7The REM image in [the figure] shows the cut edge of the object 1 made of concrete, where the object 1 has been coated with the unit 3 according to the present invention. The unit 3 has been transformed into the foamed state 3'. Figure 7 The image was made at a magnification of x250, a working distance of 17 mm, a spot size of 60, and an acceleration voltage of 10 kV. The measurement scale is 100 μm.

[0419] Figure 7 It shows that the transfer laminate 6 exhibits a strong adhesion to the concrete, which can be explained by the mechanical and chemical "anchoring effect" of the transfer laminate to the concrete. In addition, it is particularly shown that the transfer laminate forms a closed and smooth surface that seals the concrete.

[0420] It goes without saying that the given implementation variants can be combined with each other arbitrarily and do not constitute any limitation.

[0421] List of reference numerals

[0422] 1 Object

[0423] 1' Decorative object

[0424] 2 Element

[0425] 3 Unit

[0426] 3' Unit in the foamed state

[0427] 4 Transfer film

[0428] 5 Carrier layer

[0429] 6 Transfer laminate

[0430] 7 Release layer

[0431] 8 Primer layer

[0432] 9 Protective layer

Claims

1. A method for producing a decorative object (1‘), characterized in that, The method comprises the following steps, in particular where 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 comprising a monomer component containing carboxylic acid, said monomer component comprising itaconic acid and / or itaconic acid derivatives, b) Polymerizing said reactive mixture to form a polymer, c) Contacting said polymer with element (2), wherein at least one unit (3) comprising said polymer is obtained, wherein said at least one unit (3) comprising said polymer is convertible into a foamed state, in which said at least one unit (3) forms a porous structure, wherein at least one unit (3') in the foamed state is obtained, and wherein said porous structure refracts light such that said at least one unit (3') in the foamed state exhibits a white color impression, d) Drying said at least one unit (3), e) Arranging said at least one unit (3) and / or said at least one unit (3') in the foamed state on the entire area or a partial area of an object (1), f) Converting at least one unit (3) into a foamed state to obtain said at least one unit (3') in the foamed state, g) Obtaining a decorated object (1') comprising said at least one unit (3') in the foamed state, wherein said color impression is described by the parameters L, a, and b as color coordinates in the CIELAB color space, and wherein said at least one unit (3') in the foamed state has values of the parameters a and b in the range selected from -4 to 4.

2. The method according to the preceding claim, characterized in that Said reactive mixture, said polymer, and / or said at least one unit (3) comprising said polymer do not contain pigments, preferably do not contain white pigments, and more preferably do not contain TiO2.

3. The method according to any one of the preceding claims, Characterized in that, wherein said reactive mixture has at least one other carboxylic acid-containing monomer, which is selected individually or in combination from acrylic acid, methacrylic acid, fumaric acid, and maleic acid.

4. The method according to any one of the preceding claims, It is characterized in that wherein said reactive mixture has at least one monomer component that does not contain carboxylic acid, and said component or its derivatives are selected individually or in combination from 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 ethers.

5. The method according to any one of the preceding claims, It is characterized in that wherein said reactive mixture comprises at least one additive, which is selected individually or in combination from crosslinking agents, plasticizers, stabilizers, light stabilizers, flame retardants, defoaming agents, leveling additives, hydrophobizing agents, softening agents, deactivators, antioxidants, and / or free-radical chain breakers, or comprises fillers, which are selected individually or in combination from mineral fillers, sand, diatomaceous earth, phyllosilicates, talc, aluminates, carbon fibers, wood flour, starch, and glass fibers.

6. The method according to any one of the preceding claims, It is characterized in that The reactive mixture contains a solvent, preferably an organic solvent, which is selected, individually or as a mixture, from ethanol, 1-propanol, 2-propanol, acetone, 2-butanone (MEK), acetates, in particular ethyl acetate and / or lactoyl acetate, and / or an initiator, preferably a free radical polymerization initiator.

7. The method according to any one of the preceding claims, It is characterized in that, The proportion of the solvent, based on the total mass of the reactive mixture, is selected from the range of 15% to 95% by weight, preferably 30% to 85% by weight, more preferably 40% to 70% by weight, still more preferably 45% to 60% by weight.

8. The method according to any one of the preceding claims, It is characterized in that The proportion of the monomers of the component without carboxylic acid, based on the total mass of the reactive mixture, is selected from the range of 5% to 50% by weight, preferably 15% to 35% by weight, more preferably 20% to 30% by weight.

9. The method according to any one of the preceding claims, It is characterized in that The proportion of the monomers with carboxylic acid, based on the total mass of the reactive mixture, is selected from the range of 2.5% to 65% by weight, preferably 5% to 50% by weight, more preferably 10% to 35% by weight.

10. The method according to any one of the preceding claims, It is characterized in that The proportion of the initiator, based on the total mass of the reactive mixture, is selected from the range of 0.05% to 1.5% by weight, preferably 0.1% to 1% by weight, more preferably 0.25% to 0.5% by weight.

11. The method according to any one of the preceding claims, It is characterized in that The initiator is selected from azo compounds, peroxides or mixtures thereof.

12. The method according to any one of the preceding claims, It is characterized in that Step b) is carried out at a temperature of the reactive mixture selected from the range of 20°C to 110°C, preferably 40°C and 85°C, more preferably 50°C to 70°C.

13. The method according to any one of the preceding claims, It is characterized in that The polymer obtained in step b) has a number average molar mass value selected from the range of 500 g / mol to 500,000 g / mol, preferably 750 g / mol to 100,000 g / mol, more preferably 1,000 g / mol to 50,000 g / mol, still more preferably 1,500 g / mol to 20,000 g / mol.

14. The method according to any one of the preceding claims, It is characterized in that The polymer obtained in step b) has a polydispersity value selected from the range of 1.8 to 4, preferably 1.9 to 3, more preferably 2 to 2.5, still more preferably 2.1 to 2.

4.

15. The method according to any one of the preceding claims, It is characterized in that The polymer obtained in step b) has a glass transition temperature value selected from the range of -20°C to 110°C, preferably -20°C to 50°C, more preferably -10°C to 25°C.

16. The method according to any one of the preceding claims, Characterized in that, The element (2) is an alkaline aqueous solution containing divalent or higher-valent cations of at least one metal, where the at least one metal is preferably selected from Mg, Ca, Sr, Ba, Al, Fe, Co or a mixture thereof.

17. The method according to any one of the preceding claims, It is characterized in that The element (2) contains monovalent or polyvalent anions selected from phosphate, phosphite, carbonate, bicarbonate, hydroxide, aluminate, sulfate, sulfite or a mixture thereof.

18. The method according to any one of the preceding claims, It is characterized in that The element (2) has a pH value in the range selected from 8 to 14, preferably 10 to 14, more preferably 12 to 14.

19. The method according to any one of the preceding claims, Characterized in that, The method further has at least the following steps, which are preferably carried out after step c): h) Separating the at least one unit (3) from the element (2), where the at least one unit (3) exists in the form of particles and / or fibers after step h).

20. The method according to any one of the preceding claims, It is characterized in that The method additionally has at least one of the following steps, which are preferably carried out after step c) and / or h): i) Crushing and / or classifying the particles and / or fibers, j) Dispersing the particles and / or fibers in a medium.

21. The method according to any one of the preceding claims, It is characterized in that Contact between the polymer and the element (2) is achieved by a spraying method preferably selected from air spraying method, ultrasonic spraying method, electrostatic spraying method, where the at least one unit (3) is obtained in the form of particles and / or fibers by the spraying method.

22. The method according to any one of the preceding claims, It is characterized in that The particles are in irregular or regular forms, preferably in spherical, flaky and / or rod-like forms, and particularly have a volume-based average particle diameter value in the range selected from 0.5 μm to 1000 μm, preferably 1 μm to 750 μm, more preferably 3 μm to 300 μm.

23. The method according to any one of the preceding claims, It is characterized in that The fibers have an aspect ratio shape factor in the range selected from 3:1 to 1000:1, preferably 10:1 to 500:

1.

24. The method according to any one of the preceding claims, Characterized in that, In step c), the element (2) is or contains a carrier layer (5), or the element (2) is arranged on a partial area or the entire area of the carrier layer (5).

25. The method according to any one of the preceding claims, It is characterized in that, In step c), the contact is achieved by arranging the at least one unit (3) containing the polymer on a partial area or the entire area of the carrier layer (5), where the at least one unit (3) is obtained in the form of a layer.

26. The method according to any one of the preceding claims, It is characterized in that A transfer film (4) is obtained by contacting the at least one unit (3) with the element (2), where the transfer film (4) has a carrier layer (5) and a transfer layer sheet (6) containing the at least one unit (3), especially where the transfer layer sheet (6) can be peeled off from the carrier layer (5).

27. The method according to any one of the preceding claims, It is characterized in that wherein the carrier layer (5) consists of polyester, polyolefin or a combination thereof, in particular of PET, and / or the carrier layer (5) has a layer thickness in the range selected from 5.7 μm to 100 μm, preferably 19 μm to 50 μm.

28. The method according to any one of the preceding claims, Characterized in that, in step c), the polymer is arranged on the carrier layer (5) with an application weight in the range selected from 5 g / m2 to 20 g / m2, preferably 8 g / m2 to 12 g / m2, and / or in step c), the polymer is arranged on the carrier layer (5) with a layer thickness in the range selected from 5 μm to 20 μm, preferably 8 μm to 12 μm.

29. The method according to any one of the preceding claims, Characterized in that, in step c), one or more additional layers are arranged on the entire area or a partial area of the carrier layer (5), in particular wherein the additional layer is selected from a release layer (7), a primer layer (8), a functional layer and / or a protective layer (9).

30. The method according to any one of the preceding claims, It is characterized in that the release layer (7) consists of wax or contains wax, and / or the release layer (7) has a layer thickness in the range selected from 0.01 μm to 1 μm, preferably 0.02 μm to 0.7 μm, more preferably 0.02 μm to 0.5 μm, and / or the release layer (11) is arranged in contact with the carrier layer (6) and / or the transfer layer sheet (6).

31. The method according to any one of the preceding claims, It is characterized in that the protective layer (9) is arranged on the side of the transfer layer sheet (6) facing away from the carrier layer (6), and / or the protective layer (9) has a layer thickness in the range selected from 0.5 μm to 10 μm, preferably 0.8 μm to 5 μm, and / or the protective layer (9) is formed of polyester, polyolefin, polyurethane or a combination thereof, or contains polyester, polyolefin, polyurethane or a combination thereof.

32. The method according to any one of the preceding claims, It is characterized in that the primer layer (8) contains at least one polymer having at least one dissociable functional group, and / or the at least one primer layer (8) has a layer thickness in the range selected from 50 nm to 100 μm, preferably 100 nm to 50 μm, particularly preferably 250 nm to 20 μm.

33. The method according to any one of the preceding claims, It is characterized in that the at least one dissociable functional group of the primer layer (8) is an amino group and / or a hydroxyl group and / or a free acid group, which is preferably selected from a carboxyl group, a sulfonic acid group, a sulfuric acid monoester group, a phosphonic acid group, a phosphoric acid monoester group and combinations thereof, preferably a carboxyl group, a sulfonic acid group and combinations thereof, more preferably a carboxyl group, and / or a blocked acid group, which is preferably selected from a carboxylic acid ester group, a carboxylic anhydride group, a carboxyl halide group, a sulfonic acid ester group, a sulfonic anhydride group, a sulfonyl halide group, a phosphonic acid ester group and combinations thereof, more preferably a carboxylic acid ester group, a carboxylic anhydride group, a sulfonic acid ester group and combinations thereof, more preferably a carboxylic acid ester group, a carboxylic anhydride group and combinations thereof, more 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.

34. The method according to any one of the preceding claims, It is characterized in that wherein the at least one dissociable functional group of the primer layer (8) is a free acid group, which is preferably selected from carboxyl groups, sulfonic acid groups, phosphonic acid groups, and combinations thereof, and / or at least one dissociable functional group comprises or consists of a blocked acid group, and the blocked acid group is preferably selected from carboxylic acid ester groups, carboxylic anhydride groups, sulfonic acid ester groups, sulfonic anhydride groups, and combinations thereof.

35. The method according to any one of the preceding claims, It is characterized in that wherein the functional layer is selected from transparent and / or colored paint layers that particularly contain one or more dyes and / or pigments, replication layers having a molded optically active surface structure, reflective layers, in particular opaque reflective layers, transparent reflective layers, metal reflective layers, or dielectric reflective layers, optically variable layers, optically active layers, multi-layer interference systems, volume holographic layers, liquid crystal layers, in particular cholesteric liquid crystal layers, conductive layers, antenna layers, electrode layers, magnetic layers, magnetic storage layers, adhesion promoter layers, barrier layers, and combinations thereof.

36. The method according to any one of the preceding claims, It is characterized in that in step c), in order to arrange the at least one unit (3) or one or more additional layers on the carrier layer (5), at least one of the following methods is used in each case: gravure printing, screen printing, inkjet printing, flexographic printing, offset printing, spraying, casting, injection molding.

37. The method according to any one of the preceding claims, It is characterized in that in step d), at least one of the following methods is used for drying: vacuum drying, centrifugation, application of infrared radiation, continuous gas coating flow, and the gas is preferably air and / or nitrogen.

38. The method according to any one of the preceding claims, It is characterized in that, after step d), the at least one unit (3) has a proportion of components having a boiling point below 110 °C in the range of 0 wt% to 10 wt%, preferably 0 wt% to 8 wt%, more preferably 0 wt% to 5 wt%, based on the total mass of the at least one unit (3).

39. The method according to any one of the preceding claims, It is characterized in that Step d) is carried out at an ambient pressure in the range selected from 500 mbar to 1000 mbar and / or at an ambient temperature in the range selected from 50 °C to 120 °C, preferably 60 °C to 110 °C, more preferably 80 °C to 100 °C, and / or at an acceleration in the range acting on the at least one unit (3) selected from 9.81 m / s 2 to 100 000 m / s 2 , preferably 20 m / s 2 to 20 000 m / s 2 , more preferably 100 m / s 2 to 5000 m / s 2 of the acceleration range.

40. The method according to any one of the preceding claims, It is characterized in that in step e), the at least one unit (3) containing the polymer and / or the at least one unit (3') in the foamed state is arranged on the object (1) by means of at least one of the following methods: spraying, brushing, spreading, scraping, lamination, transfer, imprinting, adhesive bonding.

41. The method according to any one of the preceding claims, It is characterized in that at least one surface of the object (1) is composed of a material selected from the group consisting of or containing the following: concrete, in particular freshly made concrete or solidified concrete, artificial stone, natural stone, wood, polymer, ceramic, paper, metal, composite material, or a mixture thereof.

42. The method according to any one of the preceding claims, It is characterized in that the decorative object (1') obtained in step g) is a facade element, wallpaper, housing element, masonry structure, door, floor covering, tile, packaging cardboard, furniture, or a combination thereof.

43. The method according to any one of the preceding claims, It is characterized in that step e) comprises the following sub-steps: e1) providing at least one mould element, preferably a formwork, having at least one outer surface and at least one inner surface, e2) applying a flowable or plastically deformable mineral building material mixture comprising water and at least one mineral binder to the at least one inner surface of the mould element, preferably the formwork, e3) at least partially solidifying the mineral building material mixture to obtain a dimensionally stable green mineral body, and e4) at least partially hardening the mineral building material mixture, wherein I) before step e1), the transfer film (4) is arranged on the at least one inner surface of the provided mould element, preferably the formwork, on the side of the carrier layer (5) facing away from the transfer laminate (6), and in step e1), the transfer laminate (6) is brought into at least partial contact with the flowable or plastically deformable mineral building material mixture, whereby a decorated green mineral body is obtained in step e3), and / or wherein II) during and / or after step e3), the transfer film (4) is arranged with the transfer laminate (6) at least partially on the dimensionally stable green mineral body, whereby a decorated dimensionally stable green mineral body is obtained, and wherein in alternative I) and II), a decorated mineral moulded body is obtained as the decorative object (1') in step g).

44. The method according to any one of the preceding claims, It is characterized in that the at least one mineral binder comprises a hydraulic binder, a non-hydraulic binder or a mixture thereof.

45. The method according to any one of the preceding claims, It is characterized in that the at least one mineral binder is selected from calcium silicate hydrate, cement, lime, clay, gypsum, loam, magnesia binder and combinations thereof.

46. The method according to any one of the preceding claims, It is characterized in that the mineral building material mixture comprises or consists of: concrete, mortar, lime sandstone, silicate ceramics or combinations thereof.

47. The method according to any one of the preceding claims, It is characterized in that at least the primer layer (8), the at least one unit (3) or the at least one unit (3') in the foamed state is integrally bonded to the object (1) chemically by forming ionic bonds, covalent bonds and / or hydrogen bridge bonds and / or by mechanical interlocking.

48. The method according to any one of the preceding claims, It is characterized in that in step f), the at least one unit (3) is converted into a foamed state over its entire area, or in step f), the at least one unit (3) is converted into a foamed state in a local area such that foamed regions and non-foamed regions exist adjacent to each other in the at least one unit (3).

49. The method according to any one of the preceding claims, Characterized in that, Step f) is carried out several times, wherein at least during the first execution of step f), the at least one unit (3) is converted into a foamed state in a local area such that a foamed region and a non-foamed region exist adjacent to each other in the at least one unit (3), and in particular wherein during at least one further execution of step f), the at least one unit (3) is converted into a foamed state over its entire area.

50. The method according to any one of the preceding claims, It is characterized in that, the at least one unit (3') in the foamed state has values of parameters a and b in a range selected from -4 to 4, preferably -3 to 3, more preferably -2 to 2, even more preferably -1 to 1, and wherein the at least one unit (3') in the foamed state preferably has a value of parameter L in a range selected from 70 to 100, preferably 80 to 100, more preferably 90 to 100.

51. The method according to any one of the preceding claims, It is characterized in that the formation of the porous structure is initiated by contact of the at least one unit (3) with the object (1), in particular, the object (1) contains a catalyst that catalyzes the formation of the porous structure.

52. The method according to any one of the preceding claims, It is characterized in that the porous structure is formed by decarboxylation of the polymer, in particular wherein the decarboxylation is catalyzed by ionic catalysis, in particular by basic catalysis.

53. The method according to any one of the preceding claims, It is characterized in that an open-cell and / or closed-cell structure is formed in the at least one unit (3') in the foamed state.

54. The method according to any one of the preceding claims, It is characterized in that the at least one unit (3') in the foamed state has a refractive index value between 1.2 and 1.8, preferably between 1.3 and 1.7, particularly due to the porous structure.

55. The method according to any one of the preceding claims, It is characterized in that the porous structure has pores with a pore diameter in a range selected from 0.03 μm and 10 μm, preferably 0.4 μm to 3 μm, more preferably 0.5 μm to 1.8 μm.

56. The method according to any one of the preceding claims, It is characterized in that the porous structure has pores with a pore wall thickness in a range selected from 0.1 μm to 1 μm, preferably 0.1 μm to 0.75 μm, more preferably 0.15 μm to 0.4 μm.

57. The method according to any one of the preceding claims, It is characterized in that in step f), the at least one unit (3) is exposed to or has a temperature in a range selected from 60 °C to 300 °C, preferably 75 °C to 250 °C, more preferably 100 °C to 180 °C.

58. The method according to any one of the preceding claims, Characterized in that, the method further has the following step, which is preferably carried out after step f): k) stabilizing the porous structure, in particular by arranging a protective layer.

59. A decorative object (1') comprising a polymer, produced in particular according to the method of claims 1 to 58, Characterized in that, the polymer comprises itaconic acid and / or itaconic acid derivatives, wherein the decorative object (1') comprises at least one unit (3') comprising the polymer, and the unit has been converted into a foamed state, wherein the at least one unit (3') in the foamed state has a porous structure, and wherein the porous structure refracts light so that the at least one unit (3') in the foamed state exhibits a white color impression, wherein the color impression is described by parameters L, a, and b as color coordinates in the CIELAB color space, and wherein the at least one unit (3') in the foamed state has values of parameters a and b selected from the range of -4 to 4.

60. Use of a reactive mixture for producing a decorative object (1'), preferably for producing a decorative object (1') according to claim 1, the decorative object comprising at least one unit (3) of a polymer, Characterized in that, wherein the reactive mixture comprises a monomer component containing carboxylic acid, and the monomer component comprises itaconic acid and / or an itaconic acid derivative, and wherein the at least one unit (3) can be converted into a foamed state, wherein at least one unit (3') in the foamed state is obtained, which has a porous structure, and wherein the porous structure exhibits a white color impression, wherein the color impression is described by parameters L, a, and b as color coordinates in the CIELAB color space, and wherein the at least one unit (3') in the foamed state has values of parameters a and b selected from the range of -4 to 4.

Images