Method for producing a hybrid material

Abstract

The invention relates to a method for producing a hybrid material, a hybrid material, and a use of a hybrid material.

Description

[0001] Ashes GbR - Arabella Romen and Nadine Sahm

[0002] Our reference number: 241059WO

[0003] Method for producing a hybrid material

[0004] SUBJECT OF THE INVENTION

[0005] The invention relates to a method for producing a hybrid material, a hybrid material and a use of a hybrid material.

[0006] BACKGROUND OF THE INVENTION

[0007] Decorative elements such as pearls and sequins have always been used in fashion for embellishments on clothing and accessories. Their structure, which refracts light, creates a unique aesthetic and lends garments and other textiles a particularly high-quality appearance with its luster. Traditionally, these decorative effects are achieved by using crystals, beads, or sequins made of glass or plastic, which are sewn or glued onto fabrics. Crystals, in particular, create a high degree of light refraction due to their ordered structure, making them sparkle brilliantly and enabling a very elegant design.

[0008] The most commonly used crystals in the high-end textile industry are glass crystals. These are often individually attached to the garment or accessory with a thread through a hole in the crystal. Plastic or resin crystals are less expensive alternatives to glass crystals, which also require a complex application process to the textile material. These materials share the characteristic of being highly visually appealing, but they are problematic from an ecological perspective and significantly increase the manufacturing effort of the hybrid material. Plastic crystals, in particular, are associated with negative environmental consequences, as these materials are difficult to recycle and can lead to microplastic pollution. While glass beads and glass crystals are durable, their production is energy-intensive, which increases their ecological footprint.Recycling these embellishments is complex because it requires a time-consuming process of separating the crystals, beads, or sequins from the textile material before the actual recycling. Furthermore, many conventional methods for attaching these decorations to textiles are resource-intensive and can reduce the textile's lifespan, as seams or adhesives can weaken the textile structure or detach over time.

[0009] With increasing awareness of sustainability and environmental protection, there is an urgent need for alternative approaches, particularly for textile decorations, that are both aesthetically pleasing and environmentally friendly. There is particular interest in new hybrid materials and manufacturing processes that are more sustainable, allow for easy recycling, require less manufacturing effort, offer high material flexibility, conserve resources, and / or improve product longevity.

[0010] TASK

[0011] The object of the present invention is to provide a method for producing a hybrid material which at least partially, preferably completely, solves the above problems, in particular allowing a less complex and therefore more cost-effective and time-saving production of such a material and / or which is more sustainable and resource-efficient than the methods known from the prior art and / or which enables the production of a hybrid material which is easy to recycle and / or durable and / or which offers high-quality aesthetics.

[0012] DESCRIPTION OF THE INVENTION

[0013] This problem is solved in particular by a method for producing a hybrid material comprising a support material on the surface of which at least one crystal is arranged, wherein the support material is selected from:

[0014] (i) a fibrous, preferably textile, carrier material, and / or

[0015] (ii) an inorganic and / or keratin-based carrier material,

[0016] the procedure comprises the following steps:

[0017] a) Providing a crystallizable, preferably aqueous, solution comprising a solvent and a solute;

[0018] b) Provision of the carrier material;

[0019] c) Bringing at least a part of the support material from step b) into contact with the crystallizable solution from step a) at a temperature of the crystallizable solution of > 20 °C, preferably > 30 °C; more preferably > 40 °C; d) Crystallizing at least a part, preferably all of the solute from the crystallizable solution to form at least one crystal on the surface of the support material brought into contact with the crystallizable solution in order to obtain the hybrid material.

[0020] A "hybrid material" (also called a composite material) is a material composed of two or more different materials. These materials can belong to different material classes. Hybrid materials are often characterized by improved mechanical, chemical, or physical properties, which can also include aesthetic properties that would not be achievable with a single material, or not in the same way. In the case of the invention, the hybrid material comprises at least one crystal and a preferably textile substrate, but may also include other materials.

[0021] A "crystallizable solution" (also called "solution" here) comprises a solvent and a solute. Under suitable conditions (e.g., by cooling, evaporation of the solvent, or addition of a nucleation site), crystal formation can be observed, and the solute precipitates in the form of crystals.

[0022] A "support material" within the meaning of this application is a solid or flexible substrate that serves as a physical base for receiving, supporting, or fixing other materials or substances. It provides a suitable surface or structure on which certain processes or chemical reactions, in this case the crystallization of the substance contained in the crystallizable solution, can take place. In principle, materials exhibiting high porosity, surface roughness, or capillary water absorption for the formation of crystallization nuclei are particularly suitable for this purpose within the scope of the invention.

[0023] Suitable carrier materials preferably have at least one of the following properties:

[0024] (a) Open porosity: an open porosity of at least 5%, preferably at least 10%, particularly preferably at least 20%, determined according to DIN EN 1936 or by mercury porosimetry;

[0025] (b) Surface roughness: a mean roughness Ra of at least 1 pm, preferably at least 5 pm, particularly preferably at least 10 pm, determined according to DIN EN ISO 4287;

[0026] (c) Capillary water absorption: a water absorption coefficient w of at least 0.1

[0027]

[0028] > preferably at least 0.5 kg / (m²) 2 ->, determined according to DIN EN ISO 15148; or a water absorption of at least 5 wt.%, preferably at least 10 wt.%, after 24 hours of water storage.

[0029] The carrier material is selected according to the invention from:

[0030] (i) a fibrous, preferably textile, carrier material; and / or

[0031] (ii) an inorganic and / or keratin-based carrier material.

[0032] Combinations of the carrier materials according to (i) and (ii) are conceivable and preferred.

[0033] Preferably, the carrier material comprises or consists of bio-based and / or compostable materials. This also applies to the hybrid material as a whole.

[0034] A “fiber material” or “fiber-containing material” refers to a material that has fine, elongated, and / or filament-like structural elements, which are hereinafter generally referred to as “fibers.” The fibers can be of natural or synthetic origin. The fiber content is preferably > 50 wt.%, more preferably > 75 wt.%. The fiber material preferably comprises or consists of long and / or continuous fibers. In alternative embodiments, however, the fiber material can also have short fibers, branched fiber structures, and / or fiber networks.

[0035] The term "fibers" as used in this application includes:

[0036] ■ Fibers in the narrower sense, i.e. natural or synthetic textile fibers;

[0037] ■ Collagen fibers, especially as found in leather and hides; as well as

[0038] ■ Cellulose-based fibers, especially wood fibers.

[0039] The substrate material according to variant (i) can, for example, be a one- or two-dimensional textile structure or leather, in particular vegan leather. The term "fiber-containing substrate material" therefore includes, in particular:

[0040] ■ Textile sheet structures (two-dimensional textile structures) such as woven fabrics, knitted fabrics, crocheted fabrics, nonwovens, felts and braids;

[0041] ■ Textile linear structures (one-dimensional textile structures) such as yarns, threads, threads and filaments; as well as

[0042] ■ Leather, including genuine and vegan leather, hides and furs in both processed and unprocessed form. Alternatively, cellulose- and wood-based materials may be used as substrates according to variant (i), in particular:

[0043] ■ Paper, cardboard and handmade paper;

[0044] ■ Cellulose nonwovens and wallpaper-like sheet materials; as well as

[0045] ■ Solid wood, veneers and wood-based materials.

[0046] The natural capillary structure of cellulose and wood-based materials promotes controlled water flow and supports the formation of uniform crystal structures.

[0047] In an alternative embodiment, an inorganic and / or keratin-based material serves as the support material according to variant (ii).

[0048] For the purposes of this invention, "inorganic support material" means a support material that consists of at least 50% by weight, preferably entirely, of inorganic compounds. Inorganic compounds are defined as compounds that are not based on organic carbon compounds, in particular salts, minerals ("mineral support materials"), metals, metal oxides, and metal hydroxides. Carbonates and hydrogen carbonates are considered inorganic compounds for the purposes of this definition.

[0049] “Mineral substrates” include, in particular, porous rocks whose natural porosity and surface roughness provide attachment points for crystallization. Suitable rock types include, for example:

[0050] ■ Sedimentary rocks, especially sandstone and limestone; as well as

[0051] ■ Metamorphic rocks, especially slate and marble.

[0052] “Inorganic support materials” include, in particular, ceramic materials, such as:

[0053] ■ unglazed ceramics;

[0054] ■ porous technical ceramics;

[0055] ■ Terracotta; as well as

[0056] ■ Open-pored ceramic molded bodies.

[0057] Such ceramic materials enable near-surface crystal formation, with the crystal structure preferentially forming in microporous areas and roughness zones. "Inorganic support materials" also include, in particular, precious metals and / or alloys such as:

[0058] ■ Silver;

[0059] ■ Gold;

[0060] ■ Copper; as well as

[0061] ■ Brass.

[0062] In a preferred embodiment, the metallic support materials are roughened on the surface and / or provided with a porous, hydrophilic or fibrous surface layer to enable the formation of crystallization nuclei.

[0063] "Keratin-based" within the meaning of the invention is a material comprising keratin, preferably consisting of at least 50% of the structural protein keratin, and particularly preferably consisting entirely of keratin.

[0064] The term "keratin-based carrier materials" includes, in particular:

[0065] ■ Scales, especially fish scales and reptile scales;

[0066] ■ Hair, especially animal hair such as wool, fur hair and hide hair;

[0067] ■ Feathers, preferably bird feathers, in particular feather shafts, feather barbs (rami) and feather rays (radii); as well as

[0068] ■ other keratin-containing structures such as horn.

[0069] The crystals can grow in the pores, other depressions and / or on the outer surface of the above support material according to (i) or (ii) and form a firm bond with the support material.

[0070] A "crystallite" is a single-oriented region within a crystalline material, i.e., a crystal, in which the atoms are arranged in a regular, crystalline structure. Crystallites frequently form in polycrystalline materials, where the entire material consists of many such crystallites bordering one another in random orientations. The boundaries between the crystallites, known as grain boundaries, influence the mechanical and physical properties of the material. In contrast to polycrystalline materials, a "single crystal" consists of a single crystallite. According to the invention, the term "crystal" encompasses both single crystals and polycrystalline materials. The inventive method significantly reduces the effort required to produce decorative materials with crystal applications.The individual sewing, gluing, or other application of separately manufactured crystals, for example glass or plastic crystals, can be completely replaced by the method according to the invention. This results in comparatively low production costs.

[0071] Furthermore, the process according to the invention is particularly energy-efficient. The production of the crystallites does not require any process step that consumes a particularly large amount of energy, such as a melting step, which is necessary for the production of glass crystals. This makes the process resource-efficient and sustainable.

[0072] Furthermore, the high scalability is a particular advantage of the method according to the invention. While individually applied applications are difficult and / or costly and time-consuming to implement on a large scale, the present invention offers simple scalability and can also be used in industrial production.

[0073] Bringing at least a portion of the fiber-containing, preferably textile, carrier material from step b) into contact with the crystallizable solution from step a) at a crystallizable solution temperature of > 30 °C, preferably > 40 °C, improves the fiber bonding capacity, thereby positively influencing the crystallization of the dissolved substance and its adhesion to the carrier material. Particularly preferably, the crystallizable solution is heated to a temperature in the range of 60 to 100 °C, preferably 70 to 95 °C, and the carrier material is also contacted with the crystallizable solution within this temperature range. One of the key advantages is the increased accessibility of the fibers for crystallization. Swelling increases the surface area of ​​the fibers, which facilitates penetration by the crystallizable solution and enables nucleation and crystallization even between the fibers.

[0074] In a preferred embodiment, steps c) (bringing into contact) and d) (crystallization) take place in a container at least partially filled with the crystallizable solution.

[0075] The container material is preferably adapted to the process requirements. For example, stainless steel is particularly suitable for precise and homogeneous temperature control of the entire solution volume due to its excellent thermal conductivity. Alternatively, glass containers can be advantageous because they allow visual monitoring of crystal growth and permit the influence of light exposure on the process. Chemically inert plastics, such as polypropylene, are also conceivable. However, it should be noted that the potential release of particles, such as microplastics, as contaminants could impair the purity of the solution.

[0076] Furthermore, the geometry of the container and the extent of the free solution surface influence crystal formation and are adapted to the desired appearance of the crystals for process optimization.

[0077] The shape of the container determines the temperature and concentration zones within the solution, which in turn control the growth rate and morphology of the crystals. For example, more uniform growth conditions can be achieved in cylindrical or rounded containers, as the formation of zones with varying flow or temperature, such as those that can occur in the corners of rectangular containers, is minimized. This can lead to more controlled crystal growth on the substrate. Therefore, round, oval, or rounded containers are preferred.

[0078] The size of the free solution surface area influences the solvent's evaporation rate. A larger surface area means a higher evaporation rate, which accelerates crystallization through a faster increase in concentration. Conversely, slower, more controlled crystal growth, which often results in higher-quality and clearer crystals, can be achieved by reducing the free surface area.

[0079] To quantify this relationship, the surface area to volume ratio (A / V ratio) is used according to the invention. The "free solution surface" (= A) denotes that portion of the solution surface that is in direct contact with the surrounding atmosphere and is thus available for solvent evaporation. The solution volume is denoted by V. The method according to the invention can be carried out over a wide range of A / V ratios. In preferred embodiments, the A / V ratio lies in the range of 0.01 to 5.0 cm². -1 , more strongly preferred in the range of 0.05 to 2.0 cm -1 For applications where high optical quality, transparency and / or uniformity of the crystals is desired, an A / V ratio of < 0.3 cm is used. -1 A preferred size is a surface area to volume ratio of < 0.15 cm². A stronger preference is a surface area to volume ratio of < 0.15 cm². -1 , particularly preferably a range of 0.05 to 0.15 cm -1In this regime, crystal growth occurs over a longer period (typically 24 to 120 hours, depending on the solute and initial concentration), which favors the formation of crystals with lower defect density and increased clarity. For applications where rapid crystallization is desired, for example, to increase production throughput or to generate a large number of smaller crystals, an A / V ratio of > 0.5 cm⁻¹ is used. -1 preferred. A surface area to volume ratio of > 1.0 cm² is even more preferred. -1 , particularly preferred a range of 1.0 to 3.0 cm -1 In this regime, crystallization can be completed within 2 to 24 hours.

[0080] In a particularly advantageous embodiment, the support material is positioned at a specific minimum distance from the free surface of the crystallizable solution, this minimum distance applying to all areas of the support material intended for crystallization. It has been found that a minimum distance of preferably > 1 cm, more preferably > 3 cm, more preferably > 5 cm, and most preferably > 10 cm or > 12 cm from the solution surface promotes the formation of particularly large and clear crystals firmly anchored to the support material. This is because the thermal conditions are more stable and the concentration of the solute is more homogeneous at this depth than at the surface, where evaporation and faster cooling can lead to uncontrolled, spontaneous nucleation.A substantially horizontal orientation is preferred over a vertical one, as this exposes the support material to more homogeneous temperature and concentration conditions across its entire surface, resulting in more uniform crystal growth. In another advantageous embodiment, crystal growth is controlled by applying a cyclic temperature profile corresponding to wave-like temperature modulation. In this process, the temperature of the solution is increased by heating, preferably by at least 10 °C, and then subsequently decreased again.

[0081] Repeating such heating and cooling cycles promotes controlled crystal growth by, for example, dissolving smaller crystals during the heating phases and redepositing the material onto larger crystals during the cooling phases. Such a cycle might include, for instance, a brief increase to an upper temperature of up to 60 °C, subsequent cooling to a lower temperature of 20 °C, and then reheating to a holding temperature of around 30 °C. These cycles are preferably combined with a sufficiently large distance from the free surface.

[0082] In a further advantageous embodiment, the container, which is at least partially filled with the crystallizable solution, is at least partially covered in order to selectively influence the microclimate above the solution. A completely open container is susceptible to external disturbances such as air convection or ambient temperature fluctuations, which can impair crystal growth and degrade crystal quality. Complete coverage, on the other hand, can lead to an increased concentration of water vapor in the atmosphere above the solution, which can result in larger, but more irregular, crystals.

[0083] Preferably, the container is therefore only partially covered, with the degree of coverage preferably being 45 to 95%, more preferably 55 to 85%, and particularly preferably 60 to 80%. A cover of, for example, approximately 75% of the opening area represents an optimal compromise for stabilizing the microclimate while simultaneously allowing sufficient water vapor removal, resulting in controlled growth and high crystal clarity.

[0084] Additionally or alternatively, a water vapor-absorbing, porous material, such as a textile fabric like veil nettle, can be stretched over the opening of the container to regulate the moisture above the solution and at the same time offer a certain degree of protection against external influences.

[0085] In a preferred embodiment of the invention, the crystallizable solution is mixed at least sectionally, preferably continuously, during step d). Alternatively or additionally, the crystallizable solution is mixed at least sectionally, preferably continuously, for a period of less than 1 h, preferably less than 30 min, more preferably less than 10 min, and most preferably less than 5 or even 2 min before contact in step c). In a particularly preferred embodiment, such mixing takes place before contact, and no further mixing occurs subsequently in step d). This minimizes the number of crystallization nuclei.

[0086] Preferably continuous mixing of the crystallizable solution in step d) enables controlled crystallization by keeping the reaction conditions constant throughout the entire volume of the solution. This applies in particular to the temperature and the degree of saturation, or the concentration of the substance in the solution. Other conditions, such as pH value or additive distribution, are also kept homogeneous by the preferably continuous mixing.

[0087] The preferably continuous mixing thus prevents, for example, local supersaturation points that can lead to uncontrolled crystal formation. Furthermore, this results in uniform crystal nucleation, which enables uniform growth. This leads to crystal patterns with a particularly homogeneous appearance.

[0088] Preferably, mixing is carried out using at least one mixing device, which is particularly preferably placed within the crystallizable solution. Exemplary mixing devices allow for mechanical mixing of the solution, mixing of the solution by generating turbulence or shear forces, by shaking or vibration, or by ultrasound.

[0089] The mixing device can be implemented in various designs and can be based on either active or passive mixing principles. Active mixing devices use mechanical or electrical components such as agitators, screw mixers, turbines, or rotor-stator systems to achieve targeted mixing of the components.

[0090] Alternatively, the mixing device can also be designed passively, i.e., without moving parts, for example, in the form of a static mixer. In this variant, mixing is achieved through the fluid dynamics of the components and the integration of stationary mixing elements within the device. Such a passive device can be advantageous for achieving homogeneous mixing without generating excessive turbulence, which can negatively affect nucleation.

[0091] The process stability is also increased by the preferably continuous mixing, which prevents unwanted deposits on container walls or other container surfaces that come into contact with the solution. This ensures that the concentration or saturation level of the solution remains controllable, and thermoregulation, which occurs, for example, via the container walls, can be transferred to the solution without hindrance, thus saving energy costs.

[0092] Furthermore, the mixing device and / or the container in which the crystallizable solution is contacted with the carrier material can optionally be combined with additional functions, such as temperature control by a temperature sensor.

[0093] The mixing device is preferably selected from the group consisting of agitators such as propeller stirrers, paddle stirrers, or anchor stirrers; magnetic stirrers; or shaking machines, preferably linear shakers or orbital shakers. These mixing devices are easy to install and can be scaled relatively easily. They ensure constant mixing, which enables controlled crystallization and thus the production of a high-quality and uniform hybrid material.

[0094] Preferably, the mixing device is placed within the crystallizable solution. This is particularly preferred if the crystallizable solution is provided in containers in step a).

[0095] The crystallization according to the invention is particularly preferably carried out by means of the cooling method. Here, the solution capable of crystallizing is cooled over a preferably precisely controlled temperature-time profile. For this purpose, devices for temperature regulation, also called thermocouples, preferably heating and / or cooling plates, can be used, which are preferably mounted inside a container holding the solution capable of crystallizing or outside of it, preferably directly on the walls or the bottom of the container.

[0096] The temperature-time profile is a crucial parameter for controlling crystal quality. A high initial temperature (temperature of the crystallizable solution at the first contact in step c), preferably in the range of 80 to 90 °C, is initially advantageous to provide a sufficiently saturated solution. During the subsequent cooling process, it has been shown that the cooling rate significantly influences the crystal morphology. While steep, rapid cooling can lead to an irregular and "fractured" crystal structure, controlled, slow cooling yields a higher-quality result. The final temperature to which the solution is cooled during step d) typically corresponds to ambient temperature or a chilled temperature. In preferred embodiments, the final temperature is in the range of 15 °C to 35 °C, and more preferably in the range of 20 °C to 30 °C.The average cooling rate is preferably in the range of 0.1 to 2.0 °C / h, more preferably in the range of 0.2 to 1.0 °C / h, and particularly preferably in the range of 0.3 to 0.8 °C / h.

[0097] A particularly advantageous temperature-time profile involves controlled, stepwise cooling over an extended period, for example, 48 to 120 hours or more, including one or more holding phases at constant intermediate temperatures. This stepwise process enables slow and controlled crystal growth, which, by minimizing defects in the crystal structure, results in very clear crystals with fine dispersion and particularly stable and deep adhesion or rooting in the substrate. Specifically, at least one heating plate is attached to the bottom of the container so that sedimenting crystals can be dissolved. This ensures a sufficient concentration or saturation level of the solution during crystallization, as any unneeded free crystals can be dissolved and made available for generating the hybrid material.

[0098] In a preferred embodiment, the thermocouples are controllable and can be combined with temperature sensors. The temperature sensors can send constant feedback to a control element, which in turn controls the thermocouples to maintain a constant temperature or a specific temperature profile. This is particularly important for controlled crystal growth and a homogeneous appearance of the hybrid material.

[0099] Other sensors such as conductivity sensors (conductometers), pH meters, refractometers and / or ion-selective electrodes can also be used in the process according to the invention and, together with appropriate control devices, keep the conditions homogeneous during the controlled crystallization.

[0100] To monitor and control the crystal growth process, the concentration of potassium aluminum sulfate or other water-soluble salts in the process water can be determined. This measurement is preferably performed indirectly via physical parameters that correlate with the salt concentration.

[0101] In a preferred embodiment, the double salt content is determined using a conductivity meter by measuring the electrical conductivity of the aqueous system. Since potassium aluminum sulfate and similar double salts dissociate into their ionic components in aqueous solution, the electrical conductivity of the water increases proportionally to the ion concentration. Conductivity measurement thus allows for an indirect determination of the salt concentration. Quantitative evaluation is performed using a previously generated calibration curve, which is created using defined reference solutions with known concentrations of the respective double salt. In this way, the current salt content in the process water can be reliably monitored and reproducibly adjusted.

[0102] This measurement method is particularly suitable for continuous or semi-continuous use, as it is robust, fast, and requires no additional chemical reagents. Refractometric methods are not suitable for determining potassium aluminum sulfate or similar inorganic double salts, as these only minimally affect the refractive index of water. Refractometers are primarily designed for measuring organic solutes, especially sugars or alcohols.

[0103] For higher analytical accuracy or for reference determination, laboratory-based methods can be used, in particular:

[0104] • Titration methods (e.g. sulfate or aluminium determination),

[0105] • photometric methods,

[0106] • spectrometric methods such as ICP-OES or AAS.

[0107] These methods allow for a direct and highly precise determination of the respective ions, but are associated with higher equipment and time costs.

[0108] The process can be precisely regulated using the employed control elements, all process steps can be documented, and thus potential production errors can be minimized. This reduces the resulting scrap, which offers significant advantages for the sustainability of producing such hybrid materials. It also reduces production costs and increases efficiency.

[0109] In a further advantageous embodiment, crystal growth after step d) can be selectively terminated and the crystal surface sealed. For this purpose, the hybrid material is preferably brought into contact with a second crystallizable solution containing a second solute different from the first. This second solute crystallizes on the surface of the already formed crystals and forms a terminating layer that prevents and thus terminates further growth of the primary crystals. This layer can, for example, be a thin, dense polycrystalline layer that encloses and seals the underlying crystals. In this way, the final crystal size can be controlled and the surface of the hybrid material can be modified with regard to its properties, such as hardness, chemical resistance, or optical appearance.

[0110] In a preferred embodiment, the method comprises a further step e) in which the at least one crystal produced in step d) is coated. Coating is a process in which one or more layers of a material are applied to a surface to modify or improve its properties. Preferably, the coating is carried out by means of spray coating, dip coating, spin coating, or powder coating.

[0111] The coating is preferably applied with a polymer material, in particular a poly(meth)acrylate (PMA) such as polymethyl(meth)acrylate (PMMA). PMA and PMMA coatings are optically clear and offer high light transmission, which is why they do not obscure the advantageous characteristics of crystals and ensure high optical aesthetics. PMMA also forms a hard and resistant layer that protects against mechanical defects such as scratches and has hydrophobic properties, so that water is repelled, which is advantageous against external influences such as humidity or moisture. The coating material is preferably selected from the following groups:

[0112] Organic coating materials

[0113] Organic coating materials offer versatile protective and functional properties for solids, particularly against moisture, chemicals, or abrasion. Suitable materials can be selected from the group consisting of polyurethanes (PU), which create elastic and durable surfaces; epoxy resins, known for their high hardness and chemical resistance; silicone polymers, characterized by temperature and UV resistance; and acrylic resins, frequently used for decorative or weather-resistant coatings.

[0114] Bio-based and / or compostable coating materials

[0115] Bio-based and / or compostable coatings offer sustainable alternatives to conventional materials and are therefore particularly preferred. Suitable materials can be selected from the group consisting of polysaccharides such as starch and cellulose, which are biodegradable and versatile; proteins such as casein and soy protein; as well as polylactic acid (PLA) and other bio-based polyesters, which are distinguished by high transparency and good mechanical properties.

[0116] Inorganic coating materials

[0117] Inorganic coating materials offer excellent protection against heat, corrosion, and abrasion, and are therefore particularly suitable for technical applications. Examples from this group include aluminum oxide (Al₂O₃) and zirconium oxide (ZrO₂) for wear protection, titanium dioxide (TiO₂) for UV protection and self-cleaning properties, and silicon dioxide (SiO₂), which serves as a transparent, chemically resistant protective layer. Metallic coating materials

[0118] Metallic coatings protect solids from corrosion, improve their mechanical properties, or provide electrical conductivity. Suitable materials can be selected from the group consisting of zinc and aluminum, precious metals such as gold, silver, and platinum; as well as copper and nickel, which are used in functional applications.

[0119] Hybrid coating materials

[0120] Hybrid coatings combine organic and inorganic components to meet specific requirements. Examples include materials from the group consisting of sol-gel coatings made of silicates and organic polymers; nanostructured coatings containing nanoparticles such as titanium dioxide (TiO2), zinc oxide (ZnO), or silicon dioxide (SiO2), which offer improved mechanical, optical, or thermal properties; and hybrid polymers that combine chemical resistance and flexibility.

[0121] Functional coating materials

[0122] Functional coatings impart specific properties to solids, such as self-cleaning, conductivity, or thermal insulation. Suitable materials can be selected from the group consisting of hydrophobic and superhydrophobic coatings, for example, based on fluorinated polymers; electrically conductive materials such as indium tin oxide (ITO) or graphene; heat-insulating layers, for example, based on ceramics or aerogels; and thermochromic or photochromic coatings, which change their properties depending on temperature or light.

[0123] Preferably, the substance dissolved in the crystallizable solution is a salt.

[0124] The salt is preferably selected from the following groups:

[0125] Inorganic salts containing alkali and alkaline earth metal ions

[0126] Inorganic salts containing alkali and alkaline earth metals are particularly well-suited for crystallization due to their high solubility in water and clear crystal structures. Suitable compounds can be selected from the group consisting of nitrates such as sodium nitrate (NaNO3), potassium nitrate (KNO3), and calcium nitrate (Ca(NO3)2); chlorides such as sodium chloride (NaCl), potassium chloride (KCl), and calcium chloride (CaCl2); and sulfates such as sodium sulfate (Na2SO4), potassium sulfate (K2SO4), and calcium sulfate (CaSO4). Carbonates such as sodium carbonate (Na2CO3), potassium carbonate (K2CO3), and calcium carbonate (CaCO3) also fall into this category. Transition metal salts

[0127] Transition metal salts are often colored and form interesting geometric crystal structures, making them particularly suitable for aesthetic applications. Examples of suitable compounds can be selected from the group consisting of sulfates such as copper sulfate (CuSO4), iron sulfate (e.g., FeSO4), nickel sulfate (NiSO4), and zinc sulfate (ZnSO4); chlorides such as iron chloride (FeCl3), cobalt chloride (CoCl2), and nickel chloride (NiCl2); and nitrates such as silver nitrate (AgNO3), iron(II) nitrate (Fe(NO3)3), and cobalt nitrate (Co(NO3)2).

[0128] Aluminum salts and complexes

[0129] Aluminum salts and their hydrous complexes are particularly well-suited for crystallization and offer stable, symmetrical structures. Suitable compounds can be selected from the group consisting of aluminum sulfate (Al₂(SO₄)₃), potassium aluminate (Ka₂O₂), potassium aluminum sulfate (Ka₂(SO₄)₂, known as alum), and ammonium aluminate (NH₄Al₂(SO₄)₂).

[0130] Halides

[0131] Halide salts crystallize readily from solutions and often form clear, prismatic crystals. Suitable compounds can be selected from the group consisting of sodium halides such as sodium fluoride (NaF), sodium chloride (NaCl), and sodium bromide (NaBr); potassium halides such as potassium iodide (Kl) and potassium chloride (KCl); and magnesium halides such as magnesium chloride (MgCl₂).

[0132] Organic salts

[0133] Organic salts, composed of organic acids and bases, are excellent for crystallization and often exhibit interesting optical properties. Suitable compounds can be selected from the group consisting of acetates such as sodium acetate (CH3COONa), potassium acetate (CH3COOK), and calcium acetate (CH3COO)2Ca; formates such as sodium formate (HCOONa) and potassium formate (HCOOK); citrates such as sodium citrate (Na3C6H5O7) and potassium citrate (K3C6H5O7); and tartrates such as potassium hydrogen tartrate (tartaric acid).

[0134] Double salts and complex salts

[0135] Double salts and complex salts often crystallize in symmetrical and aesthetically pleasing structures. Suitable compounds can be selected from the group consisting of alums such as potassium aluminum alum (KAI(SO4)2-12H2O) and ammonium iron alum (NH4Fe(SO4)2-12H2O), as well as Tutton's salts such as magnesium ammonium sulfate (Mg(NH4)2(SO4)2-6H2O) and zinc ammonium sulfate (Zn(NH4)2(SO4)2-6H2O).

[0136] Rare earths and their salts

[0137] Rare earth salts offer unique optical and crystallographic properties that make them particularly interesting. Suitable compounds can be selected from the group consisting of lanthanide salts such as lanthanum chloride (LaCl3), neodymium nitrate (Nd(NO3)3), and europium sulfate (Eu2(SO4)3), as well as yttrium salts such as yttrium chloride (YCl3) and yttrium sulfate (Y2(SO4)3).

[0138] Hydrates and salts containing water of crystallization

[0139] Salts containing water of crystallization are particularly well-suited for crystallization because they often form clear and stable crystals. Suitable compounds can be selected from the group consisting of copper sulfate pentahydrate (CuSO4-5H2O), magnesium sulfate heptahydrate (MgSO4-7H2O), and zinc sulfate heptahydrate (ZnSO4-7H2O).

[0140] Salts with special optical properties

[0141] Some salts exhibit optical properties such as fluorescence or birefringence and are ideally suited for specific applications. Suitable compounds can be selected from the group consisting of calcium fluoride (CaF₂), sodium fluoride (NaF), and lithium fluoride (LiF).

[0142] The salt is particularly preferred as an alum, i.e., a sulfuric acid double compound corresponding to the composition M'M'^SO^ * 12 H2O, where M 1 for a monovalent metal cation and M 111 for a trivalent metal cation. Preferably M 1 Potassium or sodium, with a stronger preference for potassium. M 111Aluminum, chromium, cobalt, or iron are preferred, with aluminum or chromium being more preferred, particularly aluminum. Alums are skin-friendly substances that are also frequently used in deodorants and aftershaves. They are characterized by their antibacterial and anti-inflammatory properties, which is why they are particularly used in natural cosmetics. Thus, alums are also particularly suitable for textiles, as they generally do not cause skin reactions in the wearer. Furthermore, alums are sustainable substances because they occur naturally and do not need to be synthetically produced, unlike plastics, for example. In addition, the growth time of alum crystals is relatively short compared to other crystals. Together, these properties are advantageous for the use of alum crystals to produce a hybrid material according to the invention.Alums are also water-soluble, which makes them easy to recycle and thus contributes further to sustainability.

[0143] Preferably, the crystallizable solution contains potassium aluminum sulfate dodecahydrate (potassium alum) and / or chromium(III) potassium sulfate dodecahydrate (chromium alum). Particularly preferably, the crystallizable solution contains only one of the aforementioned substances. Potassium alum forms colorless, transparent, high-purity, cubic crystals, while chromium alum forms dark violet, octahedral crystals. Both substances lead to aesthetically pleasing crystals that can grow with good definition and offer an elegant appearance.

[0144] Preferably, the salt contains < 1 atomic % of metals with a density > 5 g / cm³ 3This corresponds to the definition of a "heavy metal" according to the textbook "Metal Technology Handbook", 56th edition, Europa Lehrmittel, p. 268: Table 1: Classification of non-ferrous metals. Examples include copper, iron, and zinc. Due to environmental considerations, the content of such metals in the hybrid material should be kept as low as possible.

[0145] In a preferred embodiment of the invention, the content of metals having a density > 5 g / cm³ is 3 The aluminum content is less than 0.5 atomic percent, particularly preferably less than 0.2 atomic percent, and most preferably less than 0.1 atomic percent. Preferably, the content of aluminum, lithium, beryllium, strontium, and boron is individually and / or summed within the aforementioned ranges.

[0146] In a preferred embodiment, the concentration of the dissolved, crystallizable substance in the crystallizable solution in steps a) and / or c) and / or d) is 0.1–1 g / ml, preferably 0.2–0.9 g / ml, more preferably 0.3–0.85 g / ml. Depending on the temperature of the solution, this can correspond to an unsaturated, saturated, or supersaturated solution.

[0147] Preferably, the ratio of solute to solvent is 1:1 to 1:14, more preferably 1:2 to 1:13, more preferably 1:5 to 1:12, and most preferably 1:6 to 1:11 or even 1:7 to 1:10 or 1:7.5 to 1:10. Alternatively, the ratio of solute to solvent is 1:1 to 1:10, more preferably 1:2 to 1:8, more preferably 1:5 to 1:8, and most preferably 1:6 to 1:8 or even 1:7 to 1:8.

[0148] By carefully selecting the solute-to-solvent ratio, different aesthetic effects and crystal morphologies can be achieved. A ratio in the upper concentration range, for example 1:7.5, leads to relatively rapid growth with a larger crystal volume. A slightly lower concentration, such as a ratio of 1:8, slows down growth and results in finer crystals with a clearly defined structure and uniform deposition. Further reducing the concentration to a ratio of 1:9 produces a fine and very clear crystal structure, although the spatial distribution of the crystals may be slightly irregular, which encourages the formation of unusual shapes. A ratio of 1:10, in turn, leads to the formation of very small, crystalline microstructures, which are ideal for creating subtle, diffuse surface effects.

[0149] Preferably, an unsaturated solution is provided in step a), and / or step c), and / or step d). This allows for very controlled crystal growth, as crystal formation proceeds more slowly than with saturated or supersaturated solutions. Furthermore, unsaturated solutions are less prone to spontaneously forming crystal nuclei. Instead of many small crystals, fewer, larger crystals are more likely to form, which is particularly desirable for the decorative purposes of the hybrid material.

[0150] Preferably, the degree of saturation of the crystallizable solution in step a) and / or step c) and / or step d) is 60 - 95%, preferably 70 - 90%, more preferably 75 - 85%.

[0151] In an alternative embodiment, a saturated solution is provided in step a) and / or step c) and / or step d). While an unsaturated solution can favor the growth of single, large crystals, the use of a saturated solution is particularly advantageous for industrial-scale applications, as it allows for high process control and reproducibility, making the process more efficient and cost-effective.

[0152] It is particularly preferred that the saturation level of the solution be kept largely constant during the crystallization process. To ensure such constant saturation, the process can, for example, be carried out in a system with two or more containers. Crystallization takes place in a first container, while a second container holds a supply solution that is continuously or on demand fed into the first container. The supply solution is preferably also saturated or even supersaturated to compensate for the material consumption caused by crystallization and to keep the saturation level in the first container constant. This enables continuous operation and a high yield.

[0153] Preferably, step a) comprises the following sub-steps: ai) Providing a mass m of a solvent, preferably water;

[0154] a2) Weighing a mass mk of a crystallizable substance, preferably an alum, into the solvent;

[0155] optional: as) Heating the solvent to a temperature T ;

[0156] optional: a<0 Mixing of the solvent and the crystallizable substance.

[0157] In a preferred embodiment, the solvent is heated in step a) to a temperature T of 30–80°C, preferably 30–70°C, more preferably 30–60°C. Preferably, the temperature is also in the above range, at least partially, in steps c) and d).

[0158] In another preferred embodiment, the solvent is maintained in a temperature range of 20-50 °C in steps a) and / or c) and / or d). This is particularly useful in the evaporation method, where crystallization takes place without active temperature changes by evaporating the solvent and thus increasing the concentration of the crystallizable substance at a largely constant ambient temperature.

[0159] In a preferred embodiment, the carrier material is a textile structure, preferably a one-dimensional textile structure. A one-dimensional textile structure has a linear shape and is extended in only one direction to a large extent. These can preferably be filaments, threads, yarns, twines, ropes, or cords.

[0160] Filaments, as defined in the invention, are continuous fibers made of natural or synthetic materials. Natural filaments, such as silk, occur in their original form, while synthetic filaments are produced by extrusion. They are characterized by a uniform, smooth structure and are particularly suitable for fine, uniform textiles. Filaments can be used individually or bundled into filament yarns to achieve different properties such as strength and elasticity.

[0161] According to the invention, threads are linear structures produced by spinning fibers or filaments. They consist of one or more strands of fibers that are loosely or tightly connected. Threads are versatile and can be used for sewing, embroidery, or weaving. They are usually thin and flexible, but can exhibit varying degrees of strength and texture depending on the material chosen. Yarns are threads made from spun fibers, consisting either of short fibers (staple yarn) or filaments (filament yarn). They form the basis for most textile surfaces, such as woven and knitted fabrics. Yarns can be single- or multi-twisted to achieve specific properties.

[0162] According to the invention, twisted yarns are produced by the targeted twisting of two or more yarns together, resulting in a robust and durable one-dimensional textile structure. Twisting improves the strength, uniformity, and resistance of the material. They can offer particularly decorative effects when different colors or materials are combined.

[0163] Preferably, the one-dimensional textile structures comprise twisted or braided fiber materials. These offer a particularly large surface area for crystal attachment, thus ensuring stable growth across the entire structure.

[0164] Preferably, one-dimensional textile structures overgrown with crystals are used as starting materials for further processing into two- or three-dimensional textile structures. These two- or three-dimensional textile structures are preferably decorative textiles, especially lace. This enables the production of particularly high-quality and elegant textile embellishments that find a wide range of applications in the areas of clothing, fashion accessories, home textiles, and similar products.

[0165] Alternatively, the textile structure is a two-dimensional textile structure. A two-dimensional textile structure is a textile sheet that extends in length and width and has a small thickness. Preferably, the two-dimensional textile structure is obtained through techniques such as braiding, interlacing, weaving, felting, or interlacing.

[0166] In a preferred embodiment, the two-dimensional textile structure is at least partially, and preferably completely, in a form selected from the group consisting of nonwovens, knitted fabrics, woven fabrics (especially plain weaves), or twill fabrics such as denim, gabardine, twill, or serge; braids, nonwovens, or mixtures thereof. The two-dimensional textile structure is particularly preferably in the form of a woven or braided fabric. Crystal growth is influenced by the weave structure. A looser weave (e.g., plain weave or open twill weave) promotes the stability and growth of the crystals because the more open weave structure offers more space for crystal formation and enables better adhesion to the fiber surface. These weave types therefore favor uniform and stable crystal growth across the entire textile surface.In contrast, a tight and stable weave (as in twill or satin weave) inhibits the penetration of crystals into the fabric and ensures slow growth. Such a weave means that the crystals can only form on one side of the fabric (if fully immersed in the crystallizable solution, the inside must be prepared accordingly). This significantly simplifies wearing the woven textile, as the crystal growth remains on the outer surface of the material, preventing the formation of bothersome crystals on the inside. This property is particularly advantageous when the textile is used for garments or accessories where comfort and visual appeal are important.

[0167] According to the invention, a nonwoven fabric is understood to be a structure made of fibers of limited length, continuous fibers (filaments), or cut yarns of any kind and origin, which have been joined together in some way to form a fiber layer and bonded together in some way. This excludes the interlacing or entanglement of yarns, as occurs in weaving, knitting, crocheting, lacemaking, braiding, and the manufacture of tufted products. This definition corresponds to the standard DIN EN ISO 9092. According to the invention, the term nonwoven fabric also includes felt fabrics. Films and papers, however, are not considered nonwoven fabrics.

[0168] For the purposes of this invention, braiding is understood to mean the regular interlacing of several strands of flexible material. The difference from weaving lies in the fact that in braiding, the threads are not fed at right angles to the main direction of the product.

[0169] Particularly preferred within the scope of the invention is the use of a textile structure in the form of a woven fabric. According to the invention, a woven fabric is understood to be a textile surface structure consisting of two thread systems, warp (warp threads) and weft (weft threads), which, when viewed from the woven surface, intersect in a patterned manner at an angle of exactly or approximately 90°. Each of the two systems can be composed of several types of warp or weft (e.g., ground, pile, and filler warp; ground, binding, and filler weft). The warp threads run longitudinally in the direction of the woven fabric, parallel to the fabric edge, and the weft threads run transversely, parallel to the fabric edge. The threads are joined to form the woven fabric primarily by friction. In order for a woven fabric to be sufficiently resistant to shifting, the warp and weft threads must usually be woven relatively densely. Therefore, with few exceptions, woven fabrics also have a closed appearance. This definition corresponds to the standard DIN 61100, Part 1.In a further advantageous embodiment, targeted pattern formation is achieved by producing the fabric itself from at least two different types of threads that differ in their surface properties, in particular their hydrophilicity. For this purpose, hydrophilic and hydrophobic threads are selectively interwoven as warp and / or weft threads.

[0170] During contact with the aqueous, crystallizable solution, the hydrophilic threads wet the solution, while the hydrophobic threads repel it. Consequently, nucleation and subsequent crystal growth occur preferentially or exclusively on the hydrophilic thread regions, while the hydrophobic regions remain largely or completely crystal-free. In this way, precise and durable crystal patterns can be created that are an integral part of the fabric structure and exhibit high resistance.

[0171] In a preferred embodiment, the thickness of the two-dimensional textile structure is 0.1 to 10 mm, more preferably 0.1 to 5 mm, particularly preferably 0.1 to 2 mm, and most preferably 0.2 to 1 mm.

[0172] Alternatively, the textile structure can also be three-dimensional. Three-dimensional textile structures are textiles that, in addition to length and width, also possess a significant thickness (> 3 cm, preferably > 5 cm) and thus offer particular aesthetic and functional advantages for garments. Examples include spacer fabrics, which create voluminous yet lightweight effects, or shaped knits, which assume three-dimensional forms during production. Their special properties allow for the realization of creative designs that can appear both voluminous and three-dimensional as well as soft and flowing.

[0173] The basis weight (grammage) of the substrate material, preferably the textile structure, is in a preferred embodiment 50 to 500 g / m². 2 , preferably 65 to 450 g / m² 2 , especially preferred 80-300 g / m² 2 , preferably 90-150 g / m² 2 Due to its low basis weight, crystals can adhere particularly easily.

[0174] In a preferred embodiment, the carrier material, preferably the textile structure, has a segmentally varying basis weight. It preferably consists of several segments whose basis weight varies between the segments. The strength of crystal adhesion is influenced by the basis weight. The higher the permeability, i.e., the lower the basis weight, the better the crystal adhesion. This is at least partly due to the capillary effect, which ensures that in segments with a lower basis weight, the liquid of the solution can penetrate the fabric more intensively, allowing for more pronounced crystal formation.

[0175] In a preferred embodiment, the carrier material, preferably the textile structure, has a segment-varying basis weight, wherein the carrier material comprises at least two segments whose basis weights vary in a ratio of 1:2, more preferably 1:4, particularly preferably 1:5 and most preferably 1:10 to each other.

[0176] In another preferred embodiment, the surface of the support material, preferably the textile structure, is at least partially modified before contact with the crystallizable solution. Surface modification means that the surface is altered by external physical or chemical methods. Preferably, the surface modification is the result of mechanical processing, more preferably by roughening, grinding, or brushing, especially by roughening. This also improves the adhesion of the crystals to the processed regions of the surface, thereby controlling the growth of the crystallites.

[0177] In a preferred embodiment, the method according to the invention comprises, as a partial step of step b), i.e., the provision of a fiber-containing carrier material, the impregnation of a linear textile structure and the production of the carrier material used in step b), which is a two- or three-dimensional textile structure comprising the impregnated linear textile structure.

[0178] Preferably, the linear textile structure is a textile structure selected from the group consisting of fibers, filaments, yarns, threads and yarns.

[0179] Impregnation is preferably carried out with a water-repellent impregnating agent, more preferably with a wax-based impregnating agent.

[0180] According to the invention, wax is understood to mean natural or artificially produced substances that are malleable at 20°C, solid to brittle-hard, have a coarse to fine crystalline structure, are translucent to opaque in color but not glassy, ​​melt above 40°C without decomposition, are slightly liquid (i.e., low viscosity) just above their melting point, have a strongly temperature-dependent consistency and solubility, and can be polished under slight pressure. This corresponds to the definition in Römpp Chemie Lexikon, 10th edition, 1999, Georg Thieme Verlag. A distinction can be made between natural waxes, chemically modified waxes, and synthetic waxes.In a preferred embodiment of the invention, the wax material is selected from the group of natural waxes, particularly preferably from the group of vegetable waxes, in particular candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, montan wax.

[0181] In another preferred embodiment, the natural wax is selected from the group consisting of animal waxes and mineral waxes, in particular from the group consisting of beeswax, shellac wax, spermaceti, lanolin (wool wax), preen grease, ceresin, ozokerite (earth wax).

[0182] Natural waxes offer the advantage of not being petroleum-based and thus contributing to the sustainability and biodegradability of the hybrid material.

[0183] In another embodiment, the wax is selected from the group consisting of chemically modified waxes or synthetic waxes, in particular from the group consisting of montan ester waxes, sasol waxes, paraffins, hydrogenated jojoba waxes, polyalkylene waxes, polyethylene glycol waxes.

[0184] In a further advantageous embodiment, the hybrid material and / or at least one, more preferably more than 50%, even more preferably more than 80%, and particularly preferably substantially all (> 95%) of the crystals and / or Kristal Lite of the hybrid material are provided with a hydrophobic surface coating exhibiting a lotus effect. This coating increases water and dirt repellency, improves resistance to moisture and environmental influences, and extends the service life of the hybrid material.

[0185] For the purposes of this invention, a lotus effect is understood to be a superhydrophobic surface whose properties are based on a combination of low surface energy and a specific micro- and / or nanostructural surface roughness. The coating is preferably applied as a film that functionally complements the existing crystalline surface structure without significantly impairing its optical appearance, crystal morphology, or haptics.

[0186] In a particularly preferred embodiment, the coating is biodegradable and / or at least partially bio-based. Suitable coating materials for generating a lotus effect are preferably based on bio-based silicate, polysaccharide, cellulose, or lignin derivatives; plant-based hydrophobic agents; modified fatty acids, fatty acid esters, or wax derivatives; or combinations thereof. Particularly preferred are alcohol- or water-based, fluorine-free coating systems that do not contain per- and polyfluoroalkyl substances (PFAS) and thus support the sustainability requirements of the hybrid material.

[0187] Alternatively, a silicone-based waterproofing agent can be used.

[0188] Preferably, the linear textile structure is treated by spraying, wash-in impregnation, or coating with the impregnating agent and / or by immersion in the impregnating agent. By impregnating with a water-repellent impregnating agent, parts of the textile structure that will later come into contact with the crystallizable solution can remain free from crystal nucleation, as long as the crystallizable solute is water-soluble. Nucleation of water-soluble crystallizable solutes preferably or exclusively occurs on polar surfaces, while non-polar surfaces are unable or less able to attach crystal nuclei. This allows for controlled crystal growth. Furthermore, it increases the material's resistance to external influences such as humid or wet environments.

[0189] This property can be used to integrate patterns and / or motifs into the hybrid material. For this purpose, at least two linear textile structures are preferably used, at least one of which is impregnated. A two- or three-dimensional textile structure is then produced from these linear textile structures, which is used for the further steps c) and d) of the process according to the invention. Preferably, the at least two linear textile structures are woven or braided together. In another preferred embodiment, an impregnated linear textile structure is used to embroider a pattern and / or motif onto a two- or three-dimensional textile structure. This creates more or less contiguous regions in which the impregnated linear textile structures are located within the final hybrid material.These regions are then largely or completely free of crystallites in the final hybrid material, while the remaining regions, which have non-impregnated linear textile structures, are covered with crystallites.

[0190] Alternatively, such pattern and / or motif formation can also be achieved by treating regions on the substrate, e.g., in the form of a textile structure, after step b) in such a way as to prevent crystal growth, preferably by making these regions inaccessible to the crystallizable solution, in particular by sealing. This can include the following process steps: applying boundary elements, preferably by gluing and / or sewing on boundary elements, in particular mold plates or even sections of the substrate itself; impregnating the region to be treated with a preferably water-repellent impregnating agent, in particular by waxing the region with wax or paraffin; foil plotting and / or applying chemical processes to seal the region, in particular nano-sealing and / or polymer-based sealing.This method has the advantage that precise patterns and / or motifs can be formed through crystal growth while simultaneously bringing the entire textile structure into contact with the crystallizable solution, for example, by immersion. While patterns and / or motifs can also be formed by adjusting the areas of the textile structure that come into contact with the solution, for example, through targeted wetting, these cannot achieve nearly the same level of precision as the methods described above.

[0191] In a further advantageous embodiment, crystal growth is controlled by mounting the substrate material onto a plate. Direct contact with the plate either prevents crystal growth on the side facing away from the substrate or influences it so that only flat crystals form there. This is particularly advantageous in the manufacture of garments, where, for example, the inside of the garments can be covered, thus preventing skin irritation and ensuring wearing comfort. A chemically inert and smooth surface, such as an acrylic glass plate, is preferably suitable as the plate.This method is particularly advantageous for sensitive or thin substrates compared to alternative coverings such as adhesive tapes, as stretching the substrate prevents damage to the textile structure that can occur when removing adhesives. Furthermore, this approach allows for precise and fixed positioning of the substrate within a container at least partially filled with the crystallizable solution when bringing the substrate into contact with the solution. This ensures, for example, that a defined distance to the solution surface is maintained.

[0192] In an alternative embodiment, crystal growth can also be controlled by the targeted application of light. It has been observed that crystals preferentially grow in the direction of the light source when exposed to light. Without committing to a specific theory, this effect could, for example, be due to locally increased evaporation rates of the solvent caused by the energy of the light, leading to local supersaturation and thus preferential nucleation and crystallization at that location. By targeted, directional irradiation with natural or artificial light—for example, using a lamp or a laser—crystal growth can therefore be directed into predefined areas or directions to create complex, three-dimensional crystal structures or patterns on the substrate.

[0193] Preferably, the fiber material of the carrier material is of plant or animal origin, or it consists of synthetic fibers made from natural polymers or polymers based on natural raw materials. This allows the proportion of natural components in the layered composite to be improved accordingly, thus enhancing its sustainability and biodegradability.

[0194] In a preferred embodiment, the carrier material comprises a natural fiber material, wherein the natural fiber material is preferably selected from the group consisting of seed fibers, bast fibers, leaf fibers, and animal fibers. Particularly preferred are those selected from the group consisting of cotton, animal wool, animal hair, silk, kapok, akon, poplar down, bamboo fiber, fiber nettle, hemp, hemp nettle, jute, urena, linen, ramie, kenaf, roselle, sunns, abutilon, pung, castor, sisal, abaca, curaua, fibe, ixtle fiber, arenga, afrik, hequen, fique, phormium, alfa, maguey, yucca, pitta, coconut, broom, hops, cattail reed, and bast.Natural fibers selected from the group consisting of cotton, animal wool, silk, and linen are particularly preferred, as these represent high-quality materials with special properties such as excellent skin-friendliness, superior temperature regulation, and good breathability, and are also exceptionally sustainable. Textured wool fabrics, such as Cheviot, a firm, robust wool fabric with a slightly coarse textured surface, are especially favored, particularly in the form of a twill weave.

[0195] Preferably, the chemical fibers are selected from natural polymers or polymers based on natural raw materials. Particularly preferred are those selected from the group consisting of viscose, modal, lyocell, curpo, cellulose acetates, protein fibers such as casein fibers, polylactides, alginates, chitin, bio-based polyamides, polyesters, and polyisoprene.

[0196] In another embodiment, the chemical fibers are selected from synthetic polymers from the group consisting of polyesters such as PET or PBT, polyamide, polyimide, polyamide-imide, aramid, poly(metha)acrylates, polyacrylic, polytetrafluoroethylene (PTFE), polyethylene, polypropylene, polychloride, PVC, elastane, polystyrene, polycarbonate, polyvinyl alcohol, vinylal, polyphenyl sulfide, melamine, polyurea, polyurethane, polybenzimidazole, polybenzo-xal.

[0197] Crystal growth on the substrate is significantly influenced by the adhesion of the crystals to the material, which in turn is determined by the surface properties, particularly the roughness and hydrophilicity of the material. The high hydrophilicity of substrates made of cotton or cotton jersey leads to very good and uniform wetting by the crystallizable solution, resulting in regular, fine crystal scattering on the surface. In contrast, the very smooth fiber surface of substrates made of silk, such as crepe de chine or raw silk, results in a lower density of defined adhesion points for crystallization. This leads to clear, but often irregularly scattered crystals, with raw silk in particular being able to promote the formation of large, extensive crystal clusters.For substrate materials such as springs, whose structure is based on hydrophobic keratin, the adhesion of the aqueous solution is naturally low, typically resulting in very slow growth and the formation of small, regular crystals. However, by using a higher concentration of the solute, the formation of large crystals can also be achieved on such hydrophobic surfaces.

[0198] In a particularly preferred embodiment, the solvent of the crystallizable solution comprises or is water, more preferably distilled or filtered water. According to the invention, distilled water is water that has been purified by distillation or demineralization to remove impurities such as salts, minerals, and other foreign substances. In a preferred embodiment, the solvent of the crystallizable solution is multiply distilled water, preferably double distilled (bi-distilled) water. The more multiple distillation stages, the purer the resulting water.

[0199] Particularly preferred is the solvent of the crystallizable solution a water-based solvent, i.e. a solvent with > 50 wt.%, preferably > 70 wt.% or even > 90 wt.% water content.

[0200] Mixtures of water with a less polar substance such as ethanol, isopropanol, or glycerol are particularly suitable for controlling solubility. This slows down the crystallization rate, allowing for precise control of crystal growth and improving crystal quality. The conductivity of the solvent in the crystallizable solution (excluding the solute) at 25°C is preferably 0.1–800 pS / cm, more preferably 0.1–200 pS / cm, particularly preferably 0.1–50 pS / cm or even 0.1–10 pS / cm, and most preferably 0.1–5 pS / cm. The lower the conductivity, the lower the ion concentration and thus the higher the purity of the distilled water.

[0201] Pure water is particularly suitable for the production of the hybrid material, as it promotes controlled crystallization. A lower concentration of dissolved salts or other substances increases the uniformity of crystal growth. Any substances present in the solvent, such as impurities, can disrupt crystal growth by causing local supersaturation or uncontrolled nucleation. Furthermore, a highly pure solvent allows for precise control of the saturation level of the crystallizable solution, thus achieving a high degree of reproducibility. The quality of the resulting crystallites can also be significantly improved by using highly pure solvents. Impurities in the solvent can be incorporated into the crystal structure during crystallization, leading to defects and potentially reducing the material's luster.

[0202] Preferably, in addition to the dissolved, crystallizable substance, a dye is added to the crystallizable solution, which influences the color of the resulting crystals, particularly preferably by incorporation into the crystal.

[0203] In a further preferred embodiment, at least one additional crystallizable substance can be added to the crystallizable solution, in addition to the dissolved crystallizable substance, to modify the physical, chemical, or optical properties of the resulting crystals. The crystallizable solution then comprises a mixture of a primary crystal-forming substance and at least one secondary property-modifying substance. During crystallization, the ions or molecules of the secondary substance are incorporated into the crystal lattice of the primary substance (co-crystallization), leading to the formation of a mixed crystal with modified properties such as hardness, solubility, chemical resistance, color, or luster.For example, the addition of iron sulfates to an alum solution can achieve a targeted coloration, while other co-crystallizates can affect the mechanical stability or water solubility of the crystals.

[0204] Furthermore, a growth modifier or nucleation inhibitor can be added to the crystallizable solution, preferably selected from the group consisting of polymers, surfactants, or chelating agents, particularly preferably sodium dodecyl sulfate (SDS) or ethylenediaminetetraacetate (EDTA). These additives prevent undesirable deposits in the crystal structure and / or prevent uncontrolled aggregation of the crystals.

[0205] The proportion of dye, growth modifier and / or nucleation inhibitor in the crystallizable solution is preferably 0.01 - 5 wt.%, more preferably 0.1 - 2 wt.%, particularly preferably 0.1 - 1 wt.% and most preferably 0.5 - 1 wt.%.

[0206] The simplest method for bringing the fiber-containing, preferably textile, carrier material into contact with the crystallizable solution is to immerse at least a part, preferably the entire carrier material. This is therefore a preferred embodiment of step c) of the method according to the invention.

[0207] Particularly preferably, the crystallizable solution is provided in step a) in a container such as a basin, tub, or dish. Subsequently, the support material provided in b) is at least partially, preferably completely, immersed in the crystallizable solution in step c). This allows for uniform wetting of the entire or at least the partially immersed support material and is therefore particularly efficient and scalable.

[0208] Preferably, the support material is immersed in the crystallizable solution for 2 to 140 h, or 1 min to 96 h, more preferably for 2 to 48 h, particularly preferably for 2 to 24 h, most preferably for 2 to 12 h or even 4 to 8 h. The longer the support material remains in the solution, the larger the crystals that can form. However, excessively long immersion results in the crystals growing unevenly and no longer producing a homogeneous appearance.

[0209] In another preferred embodiment, the crystallizable solution from step a) is brought into contact with the substrate from step b) by means of a screen printing process. For this purpose, the crystallizable solution is applied to specific areas of the substrate using stencils, resulting in precise, pattern-based crystallization and thus allowing for a wide range of design possibilities.

[0210] The crystallizable solution can also be brought into contact with the substrate by a spraying process. In this process, the crystallizable solution is applied to the surface of the substrate through nozzles or spray heads. This also enables pattern-based crystallization while simultaneously ensuring uniform wetting of the selected substrate areas.

[0211] In a particularly preferred embodiment, steps c) and d) proceed at least partially in parallel. Controlled crystallization occurs at least partially during contact with the support material.

[0212] In another preferred embodiment, crystallization is controlled by targeted structuring of the substrate material. For this purpose, hydrophilic and hydrophobic fibers or yarns, for example as warp and / or weft threads, are combined during the production of the textile structure in such a way that a pattern of zones with varying hydrophilicity is created. This method is applicable to one- and two-dimensional textile structures, from simple woven surfaces to complex Jacquard fabrics. Since crystallization from the aqueous solution preferentially occurs on the hydrophilic zones, the resulting crystal pattern follows the predefined textile structure. In this way, controlled, design-oriented crystallization patterns can be generated, which significantly expand the design possibilities of the hybrid material.

[0213] Such embodiments, which include applying the crystallizable solution to the support material, for example by spraying or screen printing, preferably include a further step of cooling the support material to promote or initiate controlled crystallization on the support material. Preferably, the contact of the support material with the crystallizable solution and the cooling of the support material can be carried out in several cycles to enable greater crystal formation.

[0214] In a preferred embodiment, the crystallizable solution is applied to the substrate material via a nozzle, which is cooled. Preferably, the nozzle temperature is 1–40°C, more preferably 1–30°C, more preferably 5–20°C, and most preferably 5–10°C. The temperature of the crystallizable solution before entering the nozzle is preferably 70–95°C, more preferably 75–90°C, and more preferably 80–85°C. Due to the temperature drop in the nozzle, controlled crystallization begins during application, so the process can also be considered an additive manufacturing technique or 3D printing. The solution, which has already crystallized at least partially, is then applied to the surface of the substrate material, where further controlled crystallization of the solid from the crystallizable solution to at least one crystal takes place.This technique allows for the highly targeted and precise application of crystal-shaped patterns to the substrate, thus generating particularly high-quality and complex hybrid materials.

[0215] Crystals formed from crystallizable solutions have the property of being able to redissolve in the appropriate solvent. Thus, new raw materials can be generated from previously used and no longer needed hybrid materials or from rejects, which can then be used for controlled crystallization to produce a new hybrid material.

[0216] Preferably, step a) of the method according to the invention therefore comprises the following sub-step ai): Dissolving at least one crystal of a hybrid material comprising a fiber-containing, preferably textile, carrier material on its surface with at least one crystal using a preferably aqueous solvent in order to obtain a crystallizable solution.

[0217] In particular, the dissolution of the at least one crystal in step ai) is carried out by means of heat. By increasing the temperature of the preferably aqueous solvent, the solubility of the crystal increases, whereby it can be effectively at least partially, preferably completely, dissolved from the hybrid material.

[0218] In a further preferred embodiment, step a) of the inventive process after sub-step ai) further comprises the subsequent sub-step a2): filtering the crystallizable solution from step ai). This removes impurities and insoluble crystals from the solution, so that a pure crystallizable solution can be provided for the production of the hybrid material.

[0219] The filtration of the crystallization solution can be carried out using various methods and aids to ensure efficient purification. For example, vacuum filtration can be performed using a filter medium such as filter paper, fiberglass mats, or synthetic membranes with a suitable pore size. Alternatively, gravity filtration can be used. This is particularly gentle and prevents premature crystallization.

[0220] Additionally, and preferably, filtration can be carried out using membrane filtration to effectively remove the finest particles and impurities. For higher solids concentrations in the solution, pressure filtration can be used to increase the filtration rate and ensure effective separation. Particularly for sensitive crystal structures, filtration with sheet filters or ceramic filters may be preferred to minimize mechanical stress during the process.

[0221] The selection of the appropriate method and auxiliary materials is preferably based on the properties of the crystallization solution, including viscosity, solids content and chemical composition, as well as the specific requirements for the purity and quality of the crystals obtained.

[0222] This reusability is particularly advantageous for the reprocessing of rejects. For example, if a final sealing or coating is omitted, defective or non-compliant crystallization areas can be mechanically removed from the substrate, dissolved in a solvent, and reintroduced into the crystallization process. This enables a completely closed material cycle without significant material loss and increases the sustainability and cost-efficiency of the process.

[0223] The invention further relates to a hybrid material produced according to one of the methods as described in claims 1-9 and above.

[0224] The invention further relates to a hybrid material, in particular for use as a clothing and / or fashion accessory component or as a clothing and / or fashion accessory, comprising:

[0225] A) a carrier material selected from:

[0226] (i) a fibrous, preferably textile, carrier material comprising one or more fibers, and / or

[0227] (ii) an inorganic and / or keratin-based support material, preferably a rock comprising pores; and

[0228] B) at least one crystal which

[0229] ■ in the case of (i) at least partially enveloping the circumferential surface of one or more fibers to more than 30%, preferably completely, and / or connecting at least two of the one or more fibers together,

[0230] ■ in the case of (ii) is at least partially arranged in one or more pores. The crystal is connected to the support material by crystallization on the surface. The circumferential surface of a fiber denotes the outer surface that completely surrounds the fiber. It corresponds to the area formed by the circumference of the fiber along its length. According to the invention, a section of the circumferential surface, i.e., an area along a partial length, is encased to more than 30%, preferably more than 50%, particularly preferably more than 70%, or even completely. Preferably, such a hybrid material is produced according to the inventive method as specified in claims 1-9 and above.

[0231] In a preferred embodiment, more than 5%, preferably more than 10% or more than 30%, more preferably more than 50%, even more preferably more than 70%, and most preferably more than 80% of all fibers of the hybrid material have such a coating. Preferably, such a hybrid material is produced according to the inventive method as specified in claims 1-9 and above.

[0232] The invention further relates to a hybrid material, in particular for use as a clothing and / or fashion accessory component or as a clothing and / or fashion accessory, comprising:

[0233] A) a carrier material selected from:

[0234] (i) a fibrous, preferably textile, carrier material comprising one or more fibers, and / or

[0235] (ii) an inorganic and / or keratin-based support material, preferably a rock comprising pores; and

[0236] B) at least one crystal arranged on the surface of the support material, which is connected to the support material and has a coating, preferably a polymethyl(meth)acrylate coating.

[0237] The crystal is bonded to the substrate material through crystallization on the surface.

[0238] Preferably, one, more preferably more than 50%, even more preferably more than 80%, and most preferably essentially all (> 95%) of the crystals and / or crystallites of the hybrid material have such a coating.

[0239] Coating is preferably carried out with a polymer material, in particular a poly(meth)acrylate (PMA) such as polymethyl(meth)acrylate (PMMA). PMA and PMMA coatings are optically clear and offer high light transmission, which is why they do not obscure the advantageous characteristics of crystals and ensure high optical aesthetics. PMMA also forms a hard and resistant layer that protects against mechanical defects such as scratches and has hydrophobic properties, so that it repels water, which is advantageous against external influences such as humidity or moisture.

[0240] The hybrid material can have the additional properties defined in claims 10-15 and subsequent and preceding.

[0241] The coating material is preferably selected from the following groups:

[0242] Organic coating materials

[0243] Organic coating materials offer versatile protective and functional properties for solids, particularly against moisture, chemicals, or abrasion. Suitable materials can be selected from the group consisting of polyurethanes (PU), which create elastic and durable surfaces; epoxy resins, known for their high hardness and chemical resistance; silicone polymers, characterized by temperature and UV resistance; and acrylic resins, frequently used for decorative or weather-resistant coatings.

[0244] Inorganic coating materials

[0245] Inorganic coating materials offer excellent protection against heat, corrosion, and abrasion, making them particularly suitable for technical applications. Examples from this group include aluminum oxide (Al₂O₃) and zirconium oxide (ZrO₂) for wear protection, titanium dioxide (TiO₂) for UV protection and self-cleaning properties, and silicon dioxide (SiO₂), which serves as a transparent, chemically resistant protective layer.

[0246] Bio-based and / or compostable coating materials

[0247] Bio-based and / or compostable coatings offer sustainable alternatives to conventional materials and are therefore particularly preferred. Suitable materials can be selected from the group consisting of polysaccharides such as starch and cellulose, which are biodegradable and versatile; proteins such as casein and soy protein; as well as polylactic acid (PLA) and other bio-based polyesters, which are distinguished by high transparency and good mechanical properties. Metallic coating materials

[0248] Metallic coatings protect solids from corrosion, improve their mechanical properties, or provide electrical conductivity. Suitable materials can be selected from the group consisting of zinc and aluminum, precious metals such as gold, silver, and platinum; as well as copper and nickel, which are used in functional applications.

[0249] Hybrid coating materials

[0250] Hybrid coatings combine organic and inorganic components to meet specific requirements. Examples include materials from the group consisting of sol-gel coatings made of silicates and organic polymers; nanostructured coatings containing nanoparticles such as titanium dioxide (TiO2), zinc oxide (ZnO), or silicon dioxide (SiO2), which offer improved mechanical, optical, or thermal properties; and hybrid polymers that combine chemical resistance and flexibility.

[0251] Functional coating materials

[0252] Functional coatings impart specific properties to solids, such as self-cleaning, conductivity, or thermal insulation. Suitable materials can be selected from the group consisting of hydrophobic and superhydrophobic coatings, for example, based on fluorinated polymers; electrically conductive materials such as indium tin oxide (ITO) or graphene; heat-insulating layers, for example, based on ceramics or aerogels; and thermochromic or photochromic coatings, which change their properties depending on temperature or light.

[0253] Preferably, the crystal comprises at least one crystallite, wherein the at least one crystallite has a diameter D Kx has the diameter D Kx 0.05 - 0.5 mm.

[0254] This size of crystallites has the advantage of forming particularly uniform and smooth surfaces, which is less common with larger crystallites. The crystallites in the hybrid material thus have a homogeneous appearance and a fine texture, resulting in a striking aesthetic effect with a high degree of elegance.

[0255] In a preferred embodiment, the at least one crystallite is part of a polycrystalline material, wherein the polycrystalline material has a diameter D px exhibits the diameter D px The dimensions are preferably 1 mm - 5 cm, more preferably 1 mm - 3 cm, particularly preferably 2 mm - 2 cm, and most preferably 2 mm - 8 mm. This ensures that the polycrystalline material has an optimal size for a particularly aesthetic appearance, without making the hybrid material too heavy and thus compromising wearing comfort.

[0256] Depending on their size, the crystallites can be determined using X-ray diffraction, electron microscopy, or light microscopy. Light microscopy is particularly suitable for the diameters specified here, as it is sufficiently precise and requires little effort. Image analysis software can be applied to digital images to determine the crystallite diameter. Suitable image analysis software includes, for example, ImageJ or MATLAB.

[0257] In a preferred embodiment, at least one, more preferably more than 50%, even more preferably more than 80%, and most preferably substantially all (> 95%) of the crystals and / or crystallites of the hybrid material exhibit a linear (directional) and / or total transmission in the visible wavelength range of > 30%, preferably > 50%, more preferably > 70% or > 80%, and most preferably > 90% or > 95%. This allows the material to appear to be of particularly high quality. The transmission is typically determined using a spectrophotometer according to ASTM D1003, ISO 13468, or equivalent methods.

[0258] In a preferred embodiment, at least one, more preferably more than 50%, even more preferably more than 80%, and particularly preferably substantially all (> 95%) of the crystals and / or crystallites of the hybrid material exhibit exceptionally high clarity and low turbidity. "Clarity" is the ability of a material to transmit light in a straight line with minimal scattering, which is crucial for the aesthetic quality of the hybrid material. Only clear crystals can effectively refract and reflect incident light to produce the desired brilliance and sparkle. "Turbidity" refers to the milky appearance of a transparent material caused by the scattering of light at microscopic defects or inhomogeneities in the crystal structure. A low degree of turbidity is therefore an essential quality characteristic for the crystals produced, as it indicates high crystal quality with few defects.The degree of turbidity is preferably quantified by the haze value, which is a measure of the light scattering that occurs when light passes through a transparent material. The haze value (H value) is defined as the ratio of scattered light to the total transmitted light, expressed as a percentage. A low haze value indicates high clarity, as only a small proportion of the light is scattered. Preferably, at least one, more preferably more than 50%, even more preferably more than 80%, and most preferably substantially all (> 95%) of the crystals and / or crystallites of the hybrid material have a haze value H of < 30%, < 20%, or < 15%, preferably < 10%, more preferably < 5%, particularly preferably < 4% or < 3%, and most preferably < 2% or even < 1%, determined according to ASTM D1003, for example, using an integrating sphere.

[0259] The invention further relates to a hybrid material, in particular for use as a clothing and / or fashion accessory component or as a clothing and / or fashion accessory, comprising:

[0260] A) a carrier material selected from:

[0261] (i) a fibrous, preferably textile, carrier material comprising one or more fibers, and / or

[0262] (ii) an inorganic and / or keratin-based support material, preferably a rock comprising pores; and

[0263] B) at least one crystal arranged on the surface of the support material, which is connected to the support material, wherein at least one, more preferably more than 50%, even more preferably more than 80%, and particularly preferably substantially all (> 95%) of the crystals and / or crystallites of the hybrid material have a haze value H of < 20% or < 15%, preferably < 10%, more preferably < 5%, particularly preferably < 4% or < 3%, and most preferably < 2% or even < 1%, determined according to ASTM D1003, for example by means of an integrating sphere.

[0264] The crystal is bonded to the substrate material through crystallization on the surface.

[0265] The aforementioned specification of the haze value can also be combined with the features described in claims 10-11 and 13-15, as well as the properties described above and below for coating, mechanical anchoring, and / or fracture resistance. Furthermore, the crystals and / or crystallites of the hybrid material can exhibit the transmission values ​​mentioned above.

[0266] Preferably, at least one, more preferably more than 50%, even more preferably more than 80%, and most preferably substantially all (> 95%) of the crystals and / or crystallites of the hybrid material have a size that allows visual perception with the naked eye. Preferably, the smallest dimension of the crystal, measured as the minimum Feret diameter, is at least 0.05 mm, more preferably at least 0.1 mm, more preferably at least 0.3 mm, and most preferably at least 0.5 mm or even at least 1 mm. This preferably applies to all embodiments according to the invention.

[0267] The crystal size is preferably determined by light microscopy or, for crystals > 1 mm, by calipers. The crystal diameter is considered to be the equivalent sphere diameter or the mean Feret diameter, determined from at least two orthogonal measurements.

[0268] The invention further relates to a hybrid material, in particular for use as a clothing and / or fashion accessory component or as a clothing and / or fashion accessory, comprising:

[0269] A) a carrier material selected from:

[0270] (i) a fibrous, preferably textile, carrier material comprising one or more fibers, and / or

[0271] (ii) an inorganic and / or keratin-based support material, preferably a rock comprising pores; and

[0272] B) at least one crystal arranged on the surface of the support material, which is bonded to the support material, wherein at least one, more preferably more than 50%, even more preferably more than 80%, and particularly preferably substantially all (> 95%) of the crystals and / or crystallites of the hybrid material exhibit improved mechanical stability, which is reflected in particular in the fracture toughness of the crystals produced according to the invention. Fracture toughness, quantified by the critical stress intensity factor Klc, is a measure of a material's resistance to unstable crack propagation. Higher fracture toughness is crucial for the durability and serviceability of the hybrid material, especially in textile applications, as it reduces the risk of chipping or fracture under mechanical stress. Preferably, the crystals have a Klc value of > 0.1 MPa / m.Preferably, the value is in the range of 0.15 to 0.5 MPa / m, particularly preferably in the range of 0.2 to 0.45 MPa / m, and most preferably in the range of 0.25 to 0.4 MPa / m. The fracture toughness can be determined using standard materials testing methods, for example, the indentation method (Vickers indentation test) according to established standards such as ASTM C1421 or ISO 28079, or by equivalent methods.

[0273] The crystal is bonded to the substrate material by crystallization on its surface. The aforementioned specification of fracture toughness can also be combined with the properties of the mechanical anchoring described below, the coating, the haze value, and the features described in claims 10-15. Furthermore, the crystals and / or crystallites of the hybrid material can exhibit the transmission values ​​mentioned above.

[0274] The invention further relates to a hybrid material, in particular for use as a clothing and / or fashion accessory component or as a clothing and / or fashion accessory, comprising:

[0275] A) a carrier material selected from:

[0276] (i) a fibrous, preferably textile, carrier material comprising one or more fibers, and / or

[0277] (ii) an inorganic and / or keratin-based support material, preferably a rock comprising pores; and

[0278] B) at least one crystal, wherein this crystal exhibits a high mechanical anchorage on the support material to which it is bonded. Preferably, at least one, more preferably more than 50%, even more preferably more than 80%, and most preferably substantially all (> 95%) of the crystals and / or crystallites of the hybrid material exhibit such a strong bond.

[0279] This strong bond results from the inventive growth process, in which the crystals not only adhere to the surface but also anchor themselves deeply within the fiber or pore structure of the substrate material. In the case of a fiber-containing, preferably textile, substrate material according to variant (i), this anchoring is particularly promoted by the swelling of the fibers upon contact with the crystallizable solution, with the crystals preferably enveloping individual filaments or fiber bundles and thus forming a form-fit connection with the substrate material. In the case of an inorganic or keratin-based substrate material according to variant (ii), the crystals grow into the pores and depressions, thereby creating a mechanical interlock. This superior anchoring leads to high abrasion and wear resistance, which is crucial for the serviceability of the hybrid material.The strength of this anchoring can be quantified using various standardized testing methods: ■ Abrasion resistance (Martindale method according to DIN EN ISO 12947-2): A sample of the hybrid material is rubbed against a standard wool fabric with a defined pressure. The movement follows a complex Lissajous pattern to simulate uniform wear from all directions. The number of abrasion cycles (rubs) until a defined change occurs—in this case, a crystal loss corresponding to 10 or preferably 25 wt.% of the crystalline material—serves as a measure of the abrasion resistance. Preferably, the hybrid material exhibits a resistance of > 500 abrasion cycles, preferably > 1,000 abrasion cycles, and particularly preferably > 2,000 abrasion cycles before a crystal loss corresponding to 10 or 25 wt.% occurs.

[0280] ■ Tensile adhesion strength (pull-off test according to DIN EN ISO 4624): A test stamp is bonded to the surface of the hybrid material. After the adhesive has cured, the stamp is pulled perpendicularly from the surface using a tensile testing machine, and the force required to pull a crystal and / or crystallite, or a defined area of ​​crystals and / or crystallites, perpendicularly from the substrate is measured. Preferably, the tensile adhesion strength of at least 10 wt.%, preferably 20 wt.% of the crystals of the hybrid material on the substrate is > 0.5 MPa, preferably > 1.0 MPa, and particularly preferably > 2.0 MPa.

[0281] ■ Cross-cut test (tape test based on DIN EN ISO 2409): An adhesive tape with a defined adhesive strength is pressed firmly onto the surface of the hybrid material and then quickly pulled off, and the quantity of detached crystals is visually assessed. This is a faster, qualitative method. Preferably, in a cross-cut test performed with an adhesive tape having an adhesive strength of (10 ± 1) N per 25 mm width, at least 70%, preferably 80%, particularly preferably 90% or even 95% of the crystals and / or crystallites remain on the surface of the hybrid material.

[0282] The aforementioned specification of fracture toughness can also be combined with the features described in claims 10-15. Furthermore, the crystals and / or crystallites of the hybrid material can exhibit the transmission and haze values ​​mentioned above, as well as a coating.

[0283] In a preferred embodiment, the crystal and / or the hybrid material has a total quantity U with n crystallites having diameters DKI, DK2, ... - D Kn on, where n > 10, and where a subset A with k crystallites with diameters DKI, DK2, ... - D K k a mean value of the diameters D KA exhibits, whose standard deviation O D KA D KA * 0.5, preferably ODKA D KA * 0.4, where k is preferably 10.

[0284] The smaller the standard deviation, the more uniform the aesthetic appearance of the hybrid material, as homogeneous crystallites ensure consistent light reflection and the surfaces appear calm and elegantly glossy. A small standard deviation also increases material stability, as weak points in the material structure are reduced and less prone to delamination. However, an excessively small standard deviation necessitates process conditions that allow for very little variation. This would require extremely precise control and execution of the processes, which would significantly increase the effort, reduce efficiency, and consequently, drive up costs dramatically.

[0285] The standard deviation of the mean of the diameters ODKA is therefore preferably ODKA > D KA * 0.02, more strongly preferred ODKA SD KA * 0.05 and most preferred ODKA SD KA * 0.1 .

[0286] Preferably, the hybrid material has a total quantity U with n > 50, particularly preferably n > 200 and most preferably n > 1000 crystallites.

[0287] In a preferred embodiment, the k crystals of the subset A are arbitrarily selected from the total set U. This results in a particularly homogeneous hybrid material, which is distinguished by its uniformity.

[0288] As previously described, light microscopy is particularly suitable for determining the standard deviation ODKA of the mean diameter, as it is sufficiently precise and can be used with minimal effort. Image analysis software can be applied to digital images to determine the crystallite or crystal diameter and thus ascertain the size distribution.

[0289] The invention further relates to various uses of the hybrid material according to the invention. Crystallization on the substrate material is highly controlled by the inventive process, resulting in a particularly appealing, homogeneous appearance for the final product, the hybrid material. Therefore, it can preferably be used as a material for manufacturing a garment, a fashion accessory, or a decorative item. According to the invention, garments, also called clothing, encompass all materials that, as an artificial covering, more or less closely surround the body of a human or animal. This includes headwear, especially hats, and shoes. According to the invention, fashion accessories are understood to be accessories for clothing. These are preferably belts, gloves, fans, parasols or umbrellas, bags, scarves, and jewelry.The hybrid material can also be used for home textiles such as curtains, cushion covers, blankets, throws, upholstery, or coverings. EXAMPLES.

[0290] The invention will now be further explained with reference to specific embodiments of manufacturing examples according to the invention for hybrid materials.

[0291] Production example 1

[0292] Twelve liters of water were brought to a boil, and 1.5 kg of alum were gradually stirred in until completely dissolved, resulting in a clear, crystallizable solution. This solution was then kept at this temperature and stirred for another five minutes.

[0293] In the next step, a woven wool fabric (weight: 300 g / m²) was used. 2 , natural wool, twill weave) completely immersed in the crystallizable solution.

[0294] To create the pattern motif in a targeted manner, a portion of the woven fabric was covered with a plate before immersion, thus preventing certain areas of the fabric from being accessible to the crystallizable solution.

[0295] After immersion of the material, the temperature of the crystallizable solution was gradually reduced to 30 °C over a period of 10 hours. Once this temperature was reached, it was slowly lowered to a target temperature of 25 °C over a period of 24 hours using temperature control. This temperature was maintained for at least a further 96 hours, during which intensive crystallization was observed. After this period, the hybrid material was removed from the crystallizable solution.

[0296] Production example 2

[0297] Twelve liters of water were brought to a boil, and 1.5 kg of alum were gradually stirred in until completely dissolved, resulting in a clear, crystallizable solution. This solution was then kept at this temperature and stirred for another five minutes.

[0298] In the next step, a woven wool fabric (weight: 120 g / m²) was used. 2 , natural wool, twill weave) completely immersed in the crystallizable solution.

[0299] To create the desired pattern, a portion of the woven fabric was covered with a plate before immersion, thus excluding certain areas of the fabric from the crystallizing solution. After immersion, the temperature of the crystallizing solution was gradually reduced to 30 °C over a period of at least 10 hours, preferably up to 48 hours.

[0300] Once this temperature was reached, the solution was heated to 40 °C for a short time (< 1 min) and then the temperature was lowered back to 30 °C. This cycle was repeated every 2 hours and carried out a total of five times to enable controlled and intensive crystal growth.

[0301] This cyclical temperature change optimizes crystal growth, resulting in the formation of dense crystals that can reach a diameter of up to 3 cm.

[0302] Production example 3

[0303] To prepare a solution suitable for crystallization, 6.5 liters of distilled water were heated to 90 °C. 812.5 g of potassium aluminum sulfate (alum) were stirred into the heated water until completely dissolved, resulting in a clear solution with a mixing ratio of 1:8. The solution was then poured into a shallow stainless steel basin with rounded corners, the material of which ensures homogeneous heat distribution by heating from below.

[0304] A textile support material was partially covered with a plate to create a specific pattern and then horizontally immersed in the solution. The support material was positioned at a depth of approximately 5 cm below the solution surface to create optimal growth conditions. To stabilize the microclimate above the solution, the container was covered to about three-quarters of its surface during the crystallization process.

[0305] Crystallization took place over a period of eight days using a specific temperature profile, with the container heated from below to maintain the solution concentration. For the first two days, the solution temperature was maintained at approximately 40 °C. On the following three days, the temperature was reduced to 28 °C and held constant. For the final two days of the process, the temperature was lowered to 20 °C before the finished hybrid material was extracted.

[0306] This gradual and controlled cooling process resulted in slow crystal growth and a hybrid material with excellent optical and mechanical properties. The resulting crystals exhibited high clarity with a haze value of approximately 3% and a transmission of approximately 95%. The fracture toughness of the crystals (Klc) was determined to be approximately 0.35 MPa / m. The deep and stable bonding within the textile structure resulted in a tensile bond strength exceeding 2.0 MPa.

Claims

Patent claims 1. A method for producing a hybrid material comprising a support material on the surface of which at least one crystal is arranged; wherein the support material is selected from: (i) a fibrous, preferably textile, carrier material, and / or (ii) an inorganic and / or keratin-based carrier material; the procedure comprises the following steps: a) Providing a crystallizable, preferably aqueous, solution comprising a solvent and a solute; b) Provision of the carrier material; c) Bringing at least a part of the support material from step b) into contact with the crystallizable solution from step a) at a temperature of the crystallizable solution of > 20 °C, preferably > 40 °C; d) Crystallizing at least a part of the solute from the crystallizable solution into at least one crystal on the surface of the support material brought into contact with the crystallizable solution in order to obtain the hybrid material.

2. The method according to claim 1, wherein the crystallizable solution is mixed at least sectionally, preferably continuously, during step d).

3. A method according to any of the preceding claims, wherein the method according to step d) comprises the following additional step: e) Coating the at least one crystal produced in step d), wherein the coating is preferably carried out with a polymethyl(meth)acrylate or poly(meth)acrylate.

4. A method according to any one of the preceding claims, wherein the carrier material is a fiber-containing, preferably textile, carrier material according to variant (i) and preferably has a surface structure with segment-varying basis weight.

5. A method according to any one of the preceding claims, wherein the fiber-containing, preferably textile, carrier material is a one-dimensional textile structure, preferably selected from the group consisting of filaments, threads, yarns, and twisted threads; or a two-dimensional textile structure, preferably selected from the group consisting of woven fabrics, nonwovens, knitted fabrics, nonwovens, felts, and braids, wherein the fiber-containing, preferably textile, carrier material is particularly preferably a one-dimensional textile structure and step b) comprises the following sub-step: bo) Impregnating the one-dimensional textile structure and producing a two-dimensional textile structure comprising the one-dimensional textile structure, wherein the impregnation is preferably carried out with a water-repellent impregnating agent, more preferably with a wax-based impregnating agent.

6. Method according to one of the preceding claims, wherein the carrier material is a fiber-containing, preferably textile, carrier material according to variant (i) and comprises a natural fiber material, wherein the natural fiber material is preferably selected from the group consisting of wool, cotton, silk and linen.

7. Method according to any of the preceding claims, wherein the crystallizable solution in step a) comprises distilled water as a solvent.

8. Method according to one of the preceding claims, wherein the contacting (in steps) is carried out by immersing at least a part, preferably the entire carrier material, such as the fiber-containing, preferably textile, carrier material, into the crystallizable solution.

9. Method according to any of the preceding claims, wherein step a) comprises the following sub-step: (ai) Dissolving at least one crystal of a hybrid material comprising a support material according to variant (i) and / or (ii) on the surface of which at least one crystal is arranged, with a preferably aqueous solvent to obtain a crystallizable solution.

10. Hybrid material produced according to one of the methods as described in claims 1-9.

11. Hybrid material, especially for use as a component of clothing and / or fashion accessories, comprising: A) a carrier material selected from: (i) a fibrous, preferably textile, carrier material comprising one or more fibers, and / or (ii) an inorganic and / or keratin-based support material, preferably a rock comprising pores; and B) at least one crystal which ■ in the case of the carrier material according to (i) at least partially encases the circumferential surface of one or more fibers to more than 30%, preferably completely, ■ in the case of the carrier material according to (ii) is at least partially arranged in a pore.

12. Hybrid material, especially for use as a component of clothing and / or fashion accessories, comprising: A) a carrier material selected from: (i) a fibrous, preferably textile, carrier material comprising one or more fibers, and / or (ii) an inorganic and / or keratin-based support material, preferably a rock comprising pores; and B) at least one crystal arranged on the surface of the support material, which is bonded to the support material and has a haze value H of < 20%.

13. Hybrid material according to claims 10-12, wherein the at least one crystal has at least one crystallite with a diameter DKX, wherein the diameter DKX is 0.05 - 0.5 mm, determined by X-ray diffraction, electron microscopy and / or light microscopy.

14. Hybrid material according to any one of claims 10-13, wherein the hybrid material comprises a total quantity U with n crystallites having diameters DKI, DK2, ... - D Kn exhibits, where is > 10, and where is a subset A with k crystallites with diameters DKI, DK2, ... - D K k a mean value of the diameters D KA exhibits a standard deviation of ODKA 0^7* 0.5, preferably ODKA SZ) Ki4 * 0.4, where k is preferably 10.

15. Hybrid material according to claim 14, wherein the k crystalline lite of the subset A are arbitrarily selected from the total set U.

16. Use of a hybrid material according to any one of claims 10-15 for the manufacture of a garment, a fashion accessory, a decorative article and / or an architectural design element.

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