Sheet-like nonwoven fibre materials

Abstract

The invention relates to sheet-like nonwoven materials, to processes for producing these materials and to the use thereof.

Description

[0001] Sheet-like nonwoven fibre materials

[0002] Field of the invention

[0003] The invention relates to novel additives for the treatment of sheet-like nonwoven fibre materials.

[0004] Prior art

[0005] Many textiles and also leather are environmentally problematic since use is made, as starting materials or in their production, of various components that are not biobased, have a high CO2 footprint and permit neither recycling nor composting at the end of use. Novel materials are being developed at the moment, such as mycelium leather, hemp leather or pineapple leather. These materials are currently in their development phase and still have inadequate optical and mechanical properties and inadequate durability. A treatment with biobased and biodegradable additives would be desirable, in order to increase the performance of the materials and at the same time to meet their sustainability requirement and to offer an option for the end of use. Additionally desirable is a treatment with as few additives as possible, in order to improve the complexity of the production and post-processing process and the transparency along the value chain.

[0006] WO2022140330 and US202016904520 claim methods to produce a fungal biomass and to infiltrate it after growth with a polymer and / or a crosslinker in order to make it long-lasting. Various plasticizers are also listed in the patent applications. Only glycerol is used in the examples and an increase in flexibility, but also a reduced tensile strength, is described in the case of elevated concentrations of glycerol.

[0007] US20200392341 claims the production of a mycelium material consisting of cultivated mycelium material and a binder. In the examples, the plasticizing effect is shown by a reduction in flexural strength, but usually accompanied by reduced tear strength, and in addition the plasticizers Tween 20 (Polysorbate 20) and Tween 80 (Polysorbate 80) are not 100% biobased.

[0008] WO2023237869 discloses a fungal material comprising fungal biomass, a polysaccharide-based matrix; a plasticizer; an emulsifier and optionally a diluent. In the results there are examples where only glycerol is used as plasticizer, which results in materials that are water-sensitive and therefore not durable. It is therefore necessary according to the invention to add a more complex mixture of at least one emulsifier and optionally a further plasticizer. There is no discussion of mechanical properties.

[0009] Appels et al., in their publication “Fungal mycelium classified in different material families based on glycerol treatment” in Commun. Biol. 3, 334 (2020), describe material properties of materials made from fungal mycelium which have been treated with various aqueous solutions having various glycerol contents. A significant increase in deformability is accompanied by reduced tensile strength. In addition, the plasticizing effect does not last long, since brittle materials with reduced deformability are obtained again after a few weeks in the case of treatment with glycerol. Object

[0010] Despite the developments in the field of plant-based, fungus-based and bacterially obtained fashion materials, there is a lack of additives that improve the performance of the materials in order to qualify these materials for example for use in the fashion, furniture and automotive industries. Above all, the deformability, the tensile strength and the durability need to be improved, while the sustainability of the materials should be ensured by treatment with biobased additives and as few treatment steps as possible.

[0011] Achievement

[0012] The object has been achieved by the provision of sheet-like nonwoven materials containing polysaccharide- based fibres and polyglycerol derivatives, in particular polyglycerol and / or polyglycerol partial esters.

[0013] When adding various additives to polysaccharide-based fibres, in particular to a fungal biomass, containing or consisting of fungal mycelium, or to a fibre material, containing or consisting of hemp fibres, it was surprisingly found that specific polyglycerol derivatives increase the deformability or ductility of the material, with the tensile strength also being better maintained than in the case of the prior art glycerol. In addition, there is less migration of the additive. A further advantage is that the polyglycerol derivatives can be produced from biobased raw materials.

[0014] The sheet-like nonwoven materials contain

[0015] (a) 24.95% - 99.95% by weight of polysaccharide-based fibres and

[0016] (b) 0.05% - 15% by weight of polyglycerol and / or polyglycerol partial ester

[0017] (c) 0% - 75% by weight of further additional substances.

[0018] It is understood by a person skilled in the art that the weight ranges of components (a), (b) and (c) indicated in % by weight are based on the total weight of the sheet-like nonwoven material.

[0019] The sheet-like nonwoven materials according to the invention may contain polysaccharide-based fibres (a) selected from the group of fungal mycelia or cellulose-containing plant fibres or a combination thereof.

[0020] Preferably, the fungal mycelia are selected from the group of Ascomycota and Basidiomycota and the cellulose-containing plant fibres are selected from natural leaf, bast, grass, stalk, seed, fruit or wood fibres and combinations thereof.

[0021] Particularly preferred cellulose-containing plant fibres are selected from the group of fibres of flax, hemp, pineapple, bamboo, apple, cactus, kenaf, jute, cotton, sisal, rice straw or maize straw, agave, abaca, ramie, coconut palm and other palms, kapok, or broad-leaved or coniferous trees, and mixtures of these fibres.

[0022] A sheet-like nonwoven material should be understood to mean a fibre material that comprises a multiplicity of fibres. Preferably, the fibre material in the context of the present invention comprises, based on the total weight of the fibre material, a fibre proportion of at least 24.95% by weight to 99.95% by weight. The fibre material may in particular comprise a multiplicity of interfolded, crimped, entwined, fibrillated, branched or ramified fibres (or two or more thereof). A fibre should in particular be understood to mean a linear structure, in particular with a longitudinal shape.

[0023] Preferably, the fibre material comprises organic fibre material. Organic fibre material should be understood to mean natural fibre materials, regenerated fibres, fungal mycelium or wood fibres. This means in particular that the fibre material can already occur in nature in a fibrous state (naturally obtained) and / or it can be converted into a fibrous structure by way of a treatment step (naturally obtainable) and / or it can be cultivated. Among the organic materials, plant fibre materials, fungal mycelium materials and also animal fibre materials, such as leather fibre materials, wool fibre materials and silk fibre materials, are suitable in particular.

[0024] The object was able to be achieved by polyether polyols, preferably polyglycerols, obtained by way of the condensation of one or more polyols, preferably glycerol, or by reaction products of the polyether polyols, preferably polyglycerols, with aliphatic, saturated or unsaturated, linear or branched mono-, di- or polyfunctional carboxylic acids having 2 to 40 carbon atoms, preferably 4 to 26 carbon atoms, particularly preferably having 6 to 22 carbon atoms, or corresponding acyl donors.

[0025] The polyether polyols, preferably polyglycerols (b), or the polyether polyol partial esters obtained via esterification / transesterification, preferably the polyglycerol partial esters (b), may be prepared petrochemically. Preferably, however, they are prepared from renewable raw materials.

[0026] The partially petrochemical polyglycerol partial esters may also be prepared via a chemical reaction of carboxylic acids with glycidyl ethers of glycerol or of polyglycerol.

[0027] As generally known in the art, the term "partial ester" denotes a type of ester in which a part of the hydroxyl (-OH) groups of a polyol, i.e. a molecule with multiple hydroxyl groups such as e.g. a polyglycerol, forms ester groups with carboxylic acids or their derivatives, and another part of the hydroxyl groups of the polyol remains as free hydroxyl groups. A partial ester is thus an ester in which not all available hydroxyl groups of a polyol have been converted into ester linkages. This results in a molecule in which some free hydroxyl groups remain.

[0028] As generally known in the art, the term “polyglycerol” denotes a polymer comprising glycerol units which are linked together through ether bonds. In the context of the present invention, the term “polyglycerol” may also be understood to mean a polyglycerol mixture which may in particular contain glycerol oligomers and glycerol. Any glycerol proportion should therefore also be taken into consideration when calculating amounts, masses and the like. Owing to its polymeric nature, the polyglycerol may be a mixture of various compounds. Polyglycerol may have ether bonds between two primary, one primary and one secondary, or else two secondary alcohol positions of the glycerol monomers. For this reason, the polyglycerol base skeleton usually does not consist exclusively of linearly linked glycerol units, but may also comprise branches and rings. For details, see for example “Original synthesis of linear, branched and cyclic oligoglycerol standards”, Cassel et al., J. Org. Chem. 2001 , 875-896.

[0029] Suitable for the condensation reaction for preparing the polyether polyols, preferably the polyglycerols, is at least one polyol or else a mixture of at least two polyols selected from the group of 1 ,10-decanediol, 1 ,12-dodecanediol, 1 ,2-hexanediol, 1 ,2-octanediol, 1 ,2-pentyleneglycol, 1 ,4- bis(hydroxymethyl)cyclohexane, 1 ,5-pentanediol, 2,2,4-trimethyl-1 ,3-pentanediol, 2,2-bis(4- hydroxycyclohexyl)propane, 2,2-dimethyl-1 ,3-propanediol (neopentyl glycol), 2,4-diethyl-1 ,5-pentane, 2,5- dimethyl-3-hexyne-2,5-diol, 2-buty l-2-ethy 1-1 ,3-propanediol, 2-buty l-2-ethy 1-1 ,3-propanediol, 2-ethy 1-1 ,3- hexanediol, 2-methyl-1 ,3-propanediol, 2-methyl-2-propyl-1 ,3-propanediol, 2-methyl-2-propyl-1 ,3- propanediol, 2-sec-butyl-2-methyl-1 ,3-propane, 3-hexyne-2,5-diol, ditrimethylolpropane, isosorbide, pinacol, tricyclodecane diethanol, tripentaerythritol, 1 ,2-butylene glycol, 1 ,2-propylene glycol, 1 ,3-butylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,4-sorbitan, 1 ,5-sorbitan, diglycerol, dipentaerythritol, erythritol, glycerol, triglycerol, tetraglycerol, pentaglycerol, isomalt, lactitol, maltitol, mannitol, pentaerythritol, sorbitol, trimethylolethane, trimethylolpropane, xylitan, xylitol, and preferably one of the polyols is glycerol.

[0030] Very particularly preferably, glycerol is exclusively used as polyol.

[0031] The polyglycerols (b) according to the invention may have a content of cyclic oligomers, that is to say oligomers containing one or more rings, of 0% by weight to 50% by weight. The polyglycerols according to the invention comprise preferably 1 .0% by weight to 50% by weight, particularly preferably 3.0% by weight to 30% by weight. It is understood by a person skilled in the art that the weight ranges indicated in % by weight are based on the total weight of the polyglycerols.

[0032] The polyglycerols (b) according to the invention preferably have an average degree of polymerization N of 2.0 to 20, more preferably 2.5 to 16 and even more preferably 2.6 to 12.

[0033] The average degree of polymerization of the polyglycerol N is calculated via its hydroxyl value (OHV, in mg KOH / g) according to the formula N = (112200 - 18*OHV) / (74*OHV - 56100).

[0034] Suitable methods for determining the hydroxyl value are in particular those according to DGF C-V 17 a (53), Ph. Eur. 2.5.3 Method A and DIN 53240.

[0035] The polyether polyols, or the polyglycerols (b), produced via condensation reaction as described above, may be used directly as additive.

[0036] In addition, the polyether polyols, or polyglycerols (b), also constitute the precursor for the polyether polyol partial esters, or polyglycerol partial esters (b), according to the invention.

[0037] If the polyether polyol partial esters, or the polyglycerol partial esters, are prepared by esterification or transesterification from a mixture of polyols comprising polyglycerol, it is preferable that at least one further polyol or at least one further polymer from the condensation of one or more polyols is selected or is obtained from the group of 1 ,10-decanediol, 1 ,12-dodecanediol, 1 ,2-hexanediol, 1 ,2-octanediol, 1 ,2-pentyleneglycol, 1 ,4-bis(hydroxymethyl)cyclohexane, 1 ,5-pentanediol, 2,2,4-trimethyl-1 ,3-pentanediol, 2,2-bis(4- hydroxycyclohexyl)propane, 2,2-dimethyl-1 ,3-propanediol (neopentyl glycol), 2,4-diethyl-1 ,5-pentane, 2,5- dimethyl-3-hexyne-2,5-diol, 2-buty l-2-ethy 1-1 ,3-propanediol, 2-buty l-2-ethy 1-1 ,3-propanediol, 2-ethy 1-1 ,3- hexanediol, 2-methyl-1 ,3-propanediol, 2-methyl-2-propyl-1 ,3-propanediol, 2-methyl-2-propyl-1 ,3- propanediol, 2-sec-butyl-2-methyl-1 ,3-propane, 3-hexyne-2,5-diol, ditrimethylolpropane, isosorbide, pinacol, tricyclodecane diethanol, tripentaerythritol, 1 ,2-butylene glycol, 1 ,2-propylene glycol, 1 ,3-butylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,4-sorbitan, 1 ,5-sorbitan, dipentaerythritol, erythritol, isomalt, lactitol, maltitol, mannitol, pentaerythritol, sorbitol, trimethylolethane, trimethylolpropane, xylitan and xylitol, preferably isosorbide, 1 ,2-butylene glycol, 1 ,2-propylene glycol, 1 ,3-butylene glycol, 1 ,3-propanediol, 1 ,4- butanediol, 1 ,4-sorbitan, 1 ,5-sorbitan, dipentaerythritol, erythritol, isomalt, lactitol, maltitol, mannitol, pentaerythritol, sorbitol, trimethylolethane, trimethylolpropane, xylitan and xylitol.

[0038] Polyether polyol partial esters that are preferred according to the invention are obtainable by esterification or transesterification of mixtures of polyether polyols comprising polyglycerol, where polyglycerol accounts for preferably at least 20% by weight, more preferably at least 40% by weight and even more preferably at least 60% by weight, especially preferably at least 80% by weight, based on all polyols. It is thus understood by a person skilled in the art that the values indicated in % by weight are based the total weight of all polyols.

[0039] The preferred polyether polyol partial esters are preferably obtainable by esterification or transesterification of polyether polyols or mixtures of at least two polyols with at least one fatty acid, or with mixtures of at least one fatty acid and at least one mono-, di- or polyfunctional carboxylic acid (polycarboxylic acids) or acyl donors derived therefrom.

[0040] Any acyl group donors may be used according to the invention. These are, for example, carboxylic esters or carboxylic acids themselves and mixtures thereof.

[0041] As an alternative to polyether polyol partial esters, use may also be made of polyol ether polyols, as described in detail in WO2019042696 as foaming aids or foam stabilizers in aqueous polymer dispersions. For the further description of such polyol ether polyols as an alternative to polyether polyol partial esters in the context of the present invention, reference is made in full to this document. In the context of the entire present invention, the term “polyether polyols” also includes the alkoxylated adducts thereof that can be obtained by reaction of a polyol ether with alkylene oxides, such as ethylene oxide, propylene oxide and / or butylene oxide. In the context of the entire present invention, the term “polyether polyols” also includes polyether polyol partial ester-polyether polyol hybrid structures that are produced by O-alkylation of polyether polyol partial esters or by esterification of polyether polyols according to WO2019042696.

[0042] For production of the polyether polyol partial esters, it is possible to use monocarboxylic acids and / or polyfunctional di- and / or polycarboxylic acids. Preferred carboxylic acids used to produce the polyether polyol partial esters according to the invention correspond to the general form R-C(O)OH, where R is a monovalent aliphatic, saturated or unsaturated hydrocarbon radical having 2 to 40 carbon atoms, preferably 4 to 26, particularly preferably 6 to 22, carbon atoms. Especially preferred here are carboxylic acids selected from butyric acid (butanoic acid), caproic acid (hexanoic acid), caprylic acid (octanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), palmitic acid (hexadecanoic acid), stearic acid (octadecanoic acid), arachidic acid (eicosanoic acid), behenic acid (docosanoic acid), lignoceric acid (tetracosanoic acid), palmitoleic acid ((Z)-9-hexadecenoic acid), oleic acid ((Z)-9-hexadecenoic acid), elaidic acid ((E)-9-octadecenoic acid), cis-vaccenic acid ((Z)-11- octadecenic acid), linoleic acid ((9Z,12Z)-9,12-octadecadienoic acid), alpha-linolenic acid ((9Z,12Z,15Z)- 9,12,15-octadecatrienoic acid), gamma-linolenic acid ((6Z,9Z,12Z)-6,9,12-octadecatrienoic acid), dihomo- gamma-linolenic acid ((8Z,11Z,14Z)-8,11 ,14-eicosatrienoic acid), arachidonic acid ((5Z,8Z,11Z,14Z)- 5,8,1 1 ,14-eicosatetraenoic acid), erucic acid ((Z)-13-docosenoic acid), nervonic acid ((Z)-15-tetracosenoic acid), ricinoleic acid, hydroxystearic acid and undecenylic acid, and mixtures thereof, such as rapeseed oil acid, soya fatty acid, sunflower fatty acid, peanut fatty acid and tall oil fatty acid.

[0043] Preference is given in particular to natural fatty acids that can be prepared on the basis of naturally occurring vegetable or animal oils and have preferably 2-40 carbon atoms, in particular 4-26, particularly preferably 6-22, carbon atoms. Natural fatty acids are generally unbranched and usually consist of an even number of carbon atoms. Any double bonds have cis configuration. Examples are: palmitoleic acid, pelargonic acid (obtainable from the ozonolysis of oleic acid), isostearic acid (obtainable for example as a byproduct in the process of catalytic dimerization of unsaturated C18 fatty acids to obtain dimer acid), 12-hydroxystearic acid, dihydroxystearic acid, petroselic acid, gadoleic acid, eicosapentaenoic acid and docosahexaenoic acid.

[0044] Carboxylic esters used with preference according to the invention as acyl group donor are selected from esters based on alkanols and polyols having up to 6 carbon atoms, particularly preferably having up to 3 carbon atoms, very particularly preferably glycerol esters.

[0045] Carboxylic esters used with particular preference according to the invention as acyl group donor are selected from triglycerides, in particular short-chain triglycerides (C4-C10), natural fats and oils, particularly preferably selected from the group comprising coconut fat, palm kernel oil, olive oil, palm oil, argan oil, castor oil, linseed oil, babassu oil, rapeseed oil, algal oils, sesame oil, soya oil, avocado oil, jojoba oil, safflower oil, almond oil, cottonseed oil, shea butter, sunflower oil, cupuagu butter and oils having a high proportion of polyunsaturated fatty acids (PUFAs). Sorbitan esters, monoglycerides and diglycerides, in particular containing the acyl groups described hereinbelow, may likewise preferably be used.

[0046] Preferably according to the invention, the acyl group donor is selected from carboxylic acids, preferably fatty acid acyl group donors, which in particular provide an acyl group selected from the group of acyl groups of natural fatty acids.

[0047] Preferably, polycarboxylic acids (di-, tri- or polycarboxylic acids) are selected from the group of aconitic acid, agaric acid, 1 ,2,3,4-butanetetracarboxylic acid, citric acid, ethene-1 ,1 ,2,2-tetracarboxylic acid, isocitric acid, propane-1 ,2, 3-tricarboxylic acid or trimesic acid.

[0048] The polycarboxylic acid used is preferably short-chain and / or long-chain dicarboxylic acids. In the context of the present invention, the term “short-chain dicarboxylic acid” should be, in particular, understood to mean dicarboxylic acids having 4 to 18, preferably 4 to 14, particularly preferably 6 to 10, carbon atoms.

[0049] It is preferable according to the invention if the short-chain dicarboxylic acid used is selected from aliphatic, linear dicarboxylic acids, in particular succinic acid, maleic acid, tartaric acid, malic acid, fumaric acid, sorbic acid, a-ketoglutaric acid, glutaric acid, itaconic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and brassylic acid; particular preference is given to itaconic acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.

[0050] In the context of the present invention, the term “long-chain dicarboxylic acid” should be, in particular, understood to mean dicarboxylic acids having 20 to 44, preferably 30 to 40, particularly preferably 34 to 38, carbon atoms.

[0051] Particular preference is given in the context of the present invention to “long-chain dicarboxylic acids” selected from those obtainable from the dimerization of oleic acid and / or linoleic acid. The mixtures obtainable from such a process known as dimer fatty acids can comprise not only the long-chain acyclic and cyclic dicarboxylic acids but also, to a minor extent, polymeric fatty acids (trimeric and higher functional). The functionality of the mixture obtainable from the dimerization of oleic acid and / or linoleic acid should preferably not exceed, on molar average, a value of 2.4. For the production and use of dimer fatty acids and the physical and chemical properties thereof, reference is also made to the publication "The Dimer Acids: The chemical and physical properties, reactions and applications", Ed. E.C. Leonard; Humko Sheffield Chemical, 1975, Memphis, Tenn.

[0052] Suitable reaction conditions for the esterification or transesterification are temperatures between 120°C and 260°C and atmospheric pressure or else reduced pressure in a range between 20 mbar and 800 mbar, in particular between 50 and 500 mbar. The esterification or transesterification may be carried out in the presence of catalytic amounts of a base, in particular selected from metal hydroxides, metal oxides and metal carbonates such as NaOH, Ca(OH)2, KOH, Zn(OH)2, CaO, ZnO, Na2CO3, CaCOs or K2CO3, or catalytic amounts of an acid, in particular sulfuric acid, phosphoric acid, phosphinic acid, methanesulfonic acid, ethanesulfonic acid or para-toluenesulfonic acid. Corresponding processes can be found in standard chemistry textbooks such as Rompp.

[0053] Polyglycerol partial esters that are preferred according to the invention preferably have an acid value (AV) of 0.005-50 mg KOH / g, more preferably 0.01-25 mg KOH / g. Suitable methods for determining the acid value are in particular those according to DGF C-V 2, DIN EN ISO 2114, Ph. Eur. 2.5.1 , ISO 3682 and ASTM D 974.

[0054] The polyglycerol partial esters (b) preferably have a hydroxyl value of 10-900 mg KOH / g, more preferably 300-850 mg KOH / g. Suitable detection methods for determining the hydroxyl value are in particular those according to DGF C-V 17 a (53), Ph. Eur. 2.5.3 Method A and DIN 53240. Polyglycerol partial esters that are preferred according to the invention preferably have a saponification value of 30-300 mg KOH / g, more preferably 50-150 mg KOH / g. Suitable detection methods for determining the saponification value are in particular those according to DGF C-V 3, DIN EN ISO 3681 and Ph. Eur. 2.5.6.

[0055] Very particular preference is given to polyglycerols and polyglycerol partial esters, especially polyglycerol hexanoate, polyglycerol caprylate, polyglycerol pelargonate, polyglycerol caprate, polyglycerol laurate, polyglycerol myristate, polyglycerol palmitate, polyglycerol palmitoleate, polyglycerol isostearate, polyglycerol stearate, polyglycerol 12-hydroxystearate, polyglycerol oleate, polyglycerol undecylate, polyglycerol undecylenate, polyglycerol linoleate, polyglycerol arachinate and polyglycerol behenate, and mixtures of these substances.

[0056] The sheet-like nonwoven material according to the invention may also contain additional substances (c) such as auxiliaries or additives, including crosslinking agents, processing aids (for example drainage aids), binders, dispersants, blowing agents, drying agents, wetting agents, foaming aids or foam stabilizers, flocculants, viscosity reducers, thickeners, flame retardants, plasticizers, compatibilizers, fillers, pigments, matting agents, catalysts, antioxidants, stabilizers, such as hydrolysis or UV stabilizers, and the like.

[0057] Advantageously, the crosslinkers are selected from the group of citric acid, tannic acid, silicic acid, adipic acid, succinic acid, extracted vegetable tannins, glyoxal, and mixtures thereof.

[0058] Also provided according to the invention is a process for producing sheet-like nonwoven materials, comprising the process steps of

[0059] I. bringing the fibres or the sheet-like nonwoven material into contact with a 0.5-100% by weight mixture of the polyglycerol or polyglycerol partial ester in water or other solvents,

[0060] II. at temperatures between 15°C and 50°C,

[0061] III. optionally adding further additional substances,

[0062] IV. optionally stirring or mixing over a period of 1 min to 48 h.

[0063] It is understood by a person skilled in the art that the weight ranges of I. indicated in % by weight are based on the total weight of the mixture of the polyglycerol or polyglycerol partial ester in water or other solvents.

[0064] Polyglycerol or polyglycerol partial esters may be used in pure form, but preferably as a mixture in aqueous or other suitable solvents.

[0065] The contacting may be performed by means of insertion, mixing, spraying or brushing or application by means of rollers or rolls.

[0066] The process according to the invention also includes the preparation of the polyglycerol partial ester (b). This is effected by esterification or transesterification of polyglycerol with at least one fatty acid or polycarboxylic acid or acyl donors derived therefrom. In particular, the fatty acids here are selected from the group of linear or branched, unsaturated or saturated fatty acids having 2 to 40 carbon atoms. There is a broad field of application for the use of the sheet-like nonwoven materials according to the invention. It has been found that the materials according to the invention are suitable as leather substitute. Preferably, they may be used in the fashion, furniture and automotive industries.

[0067] The present invention is also characterized by the following items:

[0068] 1. Sheet-like nonwoven material containing at least

[0069] (a) polysaccharide-based fibres

[0070] (b) a polyglycerol and / or polyglycerol partial ester.

[0071] 2. Sheet-like nonwoven material according to item 1 , containing

[0072] (a) 24.95% - 99.95% by weight of polysaccharide-based fibres

[0073] (b) 0.05% - 15% by weight of polyglycerol and / or polyglycerol partial ester

[0074] (c) 0% - 75% by weight of further additional substances.

[0075] 3. Sheet-like nonwoven material according to item 1 , wherein the polysaccharide-based fibres (a) are selected from the group of fungal mycelia or cellulosic plant fibres or a combination thereof.

[0076] 4. Sheet-like nonwoven material according to item 3, wherein the polysaccharide-based fibres (a) are selected from fungal mycelia from the group of Ascomycota and Basidiomycota and the cellulose- containing plant fibres are selected from natural leaf, bast, grass, stalk, seed, fruit or wood fibres and combinations thereof.

[0077] 5. Sheet-like nonwoven material according to item 4, wherein the cellulose-containing plant fibres are selected from the group of fibres of flax, hemp, pineapple, bamboo, apple, cactus, kenaf, jute, cotton, sisal, rice straw or maize straw, agave, abaca, ramie, coconut palm and other palms, kapok, or broad-leaved or coniferous trees, and mixtures of these fibres.

[0078] 6. Sheet-like nonwoven material according to item 1 , wherein the underlying polyglycerols (b) have an average degree of polymerization N of 2.0 to 20, preferably 2.5 to 16 and very particularly preferably 2.8 to 12.

[0079] 7. Sheet-like nonwoven material according to any of the preceding items, wherein the underlying polyglycerols have a content of cyclic oligomers, that is to say oligomers containing one or more rings, of 1 .0% by weight to 50% by weight.

[0080] 8. Sheet-like nonwoven material according to item 1 , wherein the polyglycerol partial esters (b) have an acid value of 0.005-50 mg KOH / g.

[0081] 9. Sheet-like nonwoven material according to item 1 , wherein the polyglycerol partial esters (b) have a hydroxyl value of 10-900 mg KOH / g. 10. Sheet-like nonwoven material according to item 1 , wherein the polyglycerol partial esters (b) have a saponification value of 30-300 mg KOH / g.

[0082] 11 . Process for producing sheet-like nonwoven materials according to item 1 , comprising the process steps of

[0083] I. bringing the fibres or the sheet-like nonwoven material into contact with a 0.5-100% by weight mixture of the polyglycerol or polyglycerol partial ester in water or other solvents,

[0084] II. at temperatures between 15°C and 50°C,

[0085] III. optionally adding further additional substances,

[0086] IV. optionally stirring or mixing over a period of 1 min to 48 h.

[0087] 12. Process for producing sheet-like nonwoven materials according to item 1 , wherein in step I. the contacting is performed by means of insertion, mixing, spraying, brushing or application by means of rollers or rolls.

[0088] 13. Process for producing sheet-like nonwoven materials according to item 1 , wherein the polyglycerol partial esters (b) are obtained by esterification of polyglycerol with at least one fatty acid or diacid or polyacids or acyl donors derived therefrom.

[0089] 14. Process for producing sheet-like nonwoven materials according to item 1 , wherein the polyglycerol partial esters (b) are obtained by esterification of polyglycerol with at least one fatty acid, preferably a linear or branched, unsaturated or saturated fatty acid having 2 to 40 carbon atoms.

[0090] 15. Use of the sheet-like nonwoven material according to item 1 as leather substitute or textile, in the fashion, furniture and automotive industries.

[0091] Examples

[0092] All stated percentages relating to the compositions or formulations refer to % by weight based on the total weight of the respective composition, unless expressly stated otherwise.

[0093] Example 1 : Polyqlycerol

[0094] Commercially available polyglycerol-3 (Spiga Nord S.p.A, Italy).

[0095] Example 2: Polyqlycerol partial ester 1 of polyqlycerol and capric acid

[0096] A mixture of 105.8 g of commercially available polyglycerol-4 (Spiga Nord S.p.A; Italy) and 26.5 g of capric acid (99%) was heated to 240°C over the course of 3 h with stirring and introduction of N2 and the water formed was continuously distilled off until an acid value of < 2.0 mg KOH / g had been reached. The product obtained had an acid value (AV) of 0.5 mg KOH / g, a saponification value (SV) of 65 mg KOH / g and a hydroxyl value (OHV) of 790 mg KOH / g. Example 3: Polyqlycerol partial ester 2 of polyqlycerol, palmitic acid, stearic acid and behenic acid

[0097] A mixture of 2102 g of glycerol and 24.2 g of 45% aqueous potassium hydroxide solution was heated to 240°C at 400 mbar over the course of 1 hour and the water formed was continuously distilled off. As soon as the reaction mixture had reached a refractive index of > 1.4900 (typically after 20-21 h at 240°C), the pressure was slowly reduced to 50 mbar and further water and excess glycerol were distilled off at 240°C until the remaining mixture had a hydroxyl value of 880 mg KOH / g.

[0098] A mixture of the thus obtained polyglycerol (360.0 g) and glycerol (47.82 g) having a hydroxyl value of 1000 mg KOH / g, a mixture of stearic acid and palmitic acid in a 1 :1 ratio (m / m; 334.19 g), behenic acid (28.0 g) and Na2COs (3.75 g) was heated to 240°C over the course of 3 h with introduction of nitrogen, and the mixture was then stirred at this temperature and the water formed was removed continuously until an acid value of < 1.0 mg KOH / g had been reached. The product obtained had an acid value (AV) of 0.5 mg KOH / g, a saponification value (SV) of 94 mg KOH / g and a hydroxyl value (OHV) of 435 mg KOH / g.

[0099] Cultivation of the fungal mycelium

[0100] Fungal mycelium of Schizophyllum commune wild-type, strain 4-39 (MATA41 MATB41 , CBS 341.81) was obtained by a slightly modified procedure from “Appels et al., “Fungal mycelium classified in different material families based on glycerol treatment” in Commun. Biol., 3, 334 (2020)”:

[0101] A piece of fungal mycelium from the edge region of a 7-day-old colony of Schizophyllum commune wildtype, strain 4-39 (MATA41 MATB41 , CBS 341.81) was cultivated in a 50 ml Greiner centrifuge tube with 20 ml of Schizophyllum commune minimal medium (Dons et al., “Characterization of the genome of the basidiomycete Schizophyllum commune” in Biochim. Biophys. Acta - Nucleic Acids and Protein Synthesis, 563, 100-112 (1979)) with exclusion of light at 30°C and 50 rpm for 5 days.

[0102] The mixture was then treated with 100 ml of Schizophyllum commune minimal medium for 30 seconds at 18 000 rpm in a Waring blender (Waring Laboratory, Torrington, England) and subsequently incubated for 24 hours in a 250 ml Erlenmeyer flask at 30°C and 200 rpm. Thereafter, the mixture was treated once again for 30 seconds at 18 000 rpm in a Waring blender and an aliquot of 1 g (wet weight of fungal mycelium) was mixed with 1 I of Schizophyllum commune minimal medium in a 2 I Erlenmeyer flask and left to grow for 7 days at 30°C and 200 rpm with exclusion of light.

[0103] The fungal biomass obtained was then isolated by filtration (using a cheesecloth) and washed with three times the volume of demineralized water. Subsequently, the fungal biomass was resuspended in 500 ml of dH2O and homogenized for 6 seconds using an immersion blender. The mixture was filtered through Miracloth® and the residue, the fungal biomass, was left to dry at room temperature between two cellophane films on a smooth surface.

[0104] The tensile tests of experiments A1-A3 were carried out at room temperature. For the tensile tests of experiments A1-A3, at least three tensile specimens (according to DIN 53504 S2) per batch, i.e. per treated fungal biomass, were cut out of the dried material.

[0105] The preload force was set at 0.5 N and measurement was performed at a speed of 10 mm min1. All experiments for inserting the fungal biomass were repeated at least three times per additive. All stated tensile values and elongations at break are therefore average values of at least 9 measurements.

[0106] To determine the migration of the additive, the respective sample was cut into pieces with a size of 1 cm x 1 cm and the pieces were stored for 24 h at 60°C and 15% relative humidity. Blotting paper (VWR, type 703) was also stored under the same conditions for 24 h. The stored samples were then placed between two stored pieces of blotting paper and covered with two glass plates (7.5 cm x 10 cm) and weighted down with a 1.75 kg weight. Everything was stored at 60°C and 15% relative humidity and the loss of mass of the samples after 6 hours was evaluated.

[0107] Comparative Example A1 :

[0108] The dried fungal biomass was placed in 100 ml of an aqueous solution containing 4 g of glycerol at room temperature for 6 hours at 50 rpm. The treated sample was subsequently left to dry at room temperature between two cellophane films. Tensile strength: 5.2 MPa; elongation at break: 2.2%. Migration test: Weight loss after 6 h: 0.8%.

[0109] Example A2:

[0110] The dried fungal biomass was placed in 100 ml of an aqueous solution containing 4 g of mixture according to Example 1 at room temperature for 6 hours at 50 rpm. The treated sample was subsequently left to dry at room temperature between two cellophane films. Tensile strength: 6.2 MPa; elongation at break: 6%. Weight loss after 6 h: 0.1 %.

[0111] Example A3:

[0112] The dried fungal biomass was placed in 100 ml of an aqueous solution containing 4 g of mixture according to Example 2 at room temperature for 6 hours at 50 rpm. The treated sample was subsequently left to dry at room temperature between two cellophane films. Tensile strength: 6.5 MPa; elongation at break: 25.3%. Weight loss after 6 h: 0.3%.

[0113] The elongation at break characterizes the deformability, or ductility, of the material. The higher the value obtained, the higher the ductility of the material. The higher the tensile strength, the higher the mechanical tensile stress that a material withstands. The treatment with glycerol (Comparative Example A1) results in the most significantly reduced tensile strength of all Examples A1-A3 and in poor ductility. Good ductility (elongation at break) with simultaneously good tensile strength is obtained with the mixtures according to Example 1 and 2. In addition, after 6 hours the highest weight loss can be observed in the case of the samples treated with glycerol (Comparative Example A1), which indicates migration of the glycerol out of the material. Less weight loss is observed in the case of Examples A2 and A3 according to the invention, which indicates less migration of the additive out of the material.

[0114] The tensile tests of experiments B1 -B4 were carried out at room temperature. Measurement was performed at a speed of 80 mm min1.

[0115] The values are each average values from the measurement of at least 5 tensile specimens (according to DIN 53504 S2). Comparative Example B1 :

[0116] A plant fibre material, containing hemp fibres, was obtained by a process according to DE102021119667. The material was placed in an aqueous solution containing 8% by weight of glycerol for 24 hours. The samples were subsequently removed from the bath and left to dry at room temperature for 24 hours. Tensile strength: 9.3 MPa; elongation at break: 25.8%.

[0117] Example B2:

[0118] A plant fibre material, containing hemp fibres, was obtained by a process according to DE102021119667. The material was placed in an aqueous solution containing 8% by weight of mixture according to Example 1 for 24 hours. The samples were subsequently removed from the bath and left to dry at room temperature for 24 hours. Tensile strength: 10.7 MPa; elongation at break: 23.1 %.

[0119] Example B3:

[0120] A plant fibre material, containing hemp fibres, was obtained by a process according to DE102021119667. The material was placed in an aqueous mixture containing 8% by weight of mixture according to Example 2 for 24 hours. The samples were subsequently removed from the bath and left to dry at room temperature for 24 hours. Tensile strength: 11 .3 MPa; elongation at break: 23.6%.

[0121] Example B4:

[0122] A plant fibre material, containing hemp fibres, was obtained by a process according to DE102021119667. The material was placed in an aqueous mixture containing 8% by weight of mixture according to Example 3 for 24 hours. The samples were subsequently removed from the bath and left to dry at room temperature for 24 hours. Tensile strength: 11.1 MPa; elongation at break: 21 .6%.

[0123] The elongation at break characterizes the deformability, or ductility, of the material. The higher the value obtained, the higher the ductility of the material. The higher the tensile strength, the higher the mechanical tensile stress that a material withstands. The treatment with glycerol (Comparative Example B1) results in the most significantly reduced tensile strength of all Examples B1-B4. Good ductility (elongation at break) with simultaneously good tensile strength is obtained with the mixtures according to Example 1-3.

Claims

Claims1. Sheet-like nonwoven material containing at least(a) 24.95% - 99.95% by weight of polysaccharide-based fibres(b) 0.05% - 15% by weight of polyglycerol partial ester(c) 0% - 75% by weight of further additional substances, wherein the weight ranges of components (a), (b) and (c) indicated in % by weight are based on the total weight of the sheet-like nonwoven material.

2. Sheet-like nonwoven material according to Claim 1 , wherein the polysaccharide-based fibres (a) are selected from the group of fungal mycelia or cellulosic plant fibres or a combination thereof.

3. Sheet-like nonwoven material according to Claim 2, wherein the polysaccharide-based fibres (a) are selected from fungal mycelia from the group of Ascomycota and Basidiomycota and the cellulose- containing plant fibres are selected from natural leaf, bast, grass, stalk, seed, fruit or wood fibres and combinations thereof.

4. Sheet-like nonwoven material according to Claim 3, wherein the cellulose-containing plant fibres are selected from the group of fibres of flax, hemp, pineapple, bamboo, apple, cactus, kenaf, jute, cotton, sisal, rice straw or maize straw, agave, abaca, ramie, coconut palm and other palms, kapok, or broad-leaved or coniferous trees, and mixtures of these fibres.

5. Sheet-like nonwoven material according to Claim 1 , wherein the polyglycerol partial esters (b) have an acid value of 0.005-50 mg KOH / g.

6. Sheet-like nonwoven material according to Claim 1 , wherein the polyglycerol partial esters (b) have a hydroxyl value of 10-900 mg KOH / g.

7. Sheet-like nonwoven material according to Claim 1 , wherein the polyglycerol partial esters (b) have a saponification value of 30-300 mg KOH / g.

8. Process for producing sheet-like nonwoven materials according to Claim 1 , comprising the process steps ofI. bringing the fibres or the sheet-like nonwoven material into contact with a 0.5-100% by weight mixture of the polyglycerol partial ester in water or other solvents,II. at temperatures between 15°C and 50°C,III. optionally adding further additional substances,IV. optionally stirring or mixing over a period of 1 min to 48 h.

9. Process for producing sheet-like nonwoven materials according to Claim 8, wherein in step I. the contacting is performed by means of insertion, mixing, spraying, brushing or application by means of rollers or rolls.

10. Process for producing sheet-like nonwoven materials according to Claim 8, wherein the polyglycerol partial esters (b) are obtained by esterification of polyglycerol with at least one fatty acid or diacid or polyacids or acyl donors derived therefrom.

11. Process for producing sheet-like nonwoven materials according to Claim 8, wherein the polyglycerol partial esters (b) are obtained by esterification of polyglycerol with at least one fatty acid, preferably a linear or branched, unsaturated or saturated fatty acid having 2 to 40 carbon atoms.

12. Use of the sheet-like nonwoven material according to Claim 1 as leather substitute or textile, in the fashion, furniture and automotive industries.