Method for manufacturing collagen yarn

Abstract

The invention relates to a method for producing a collagen yarn (Y) comprising the steps of providing collagen fibres (CF)-spinning the collagen fibres (CF) into a yarn (Y) and-tanning the yarn (Y) after the yarn (Y) is spun.

Description

[0001] This application is a divisional application, and its corresponding parent application is a Chinese application with an application date of December 20, 2019, application number 201980092255.6, and invention name “Method for manufacturing collagen yarn”. Field of the Invention

[0002] The present invention relates to the manufacture of collagen-based yarns. Background of the Invention

[0003] Leather is used in a wide variety of applications, including furniture, shoes, clothing, bags, and automotive applications. The demand for leather products continues to increase, and given the economic and environmental costs of producing leather, new methods are needed to meet this demand. In addition, users and manufacturers are increasingly demanding technical and aesthetic products that incorporate natural ingredients and exhibit superior strength, uniformity, and aesthetic properties. However, one challenge is that fiber sources often exhibit substandard properties, such as strength and durability, when used. The present invention advantageously addresses these needs and interests. Summary of the Invention

[0004] The present invention relates to a method for producing collagen yarn, comprising the following steps:

[0005] - Provide collagen fibers

[0006] - spinning the collagen fibers into yarn; and

[0007] -Tanned yarn after it has been spun.

[0008] The inventors of the present invention have discovered that by spinning natural collagen fibers into yarn and tanning the yarn after it has been spun, several advantages can be obtained, such as relatively high tensile strength, elasticity, and regularity.

[0009] The tanning process described may also be referred to as post-tanning within the scope of the present invention in terms of the process flow, since the tanning in question is carried out after the collagen-based yarn has been manufactured. Post-tanning in the present context does not necessarily refer to how a skilled person would understand the terminology generally applied to, for example, chrome tanning, including retanning, dyeing and fat liquoring, or whether the collagen of the yarn has been previously tanned. It simply means that the tanning is carried out according to the claimed terminology, i.e., after the yarn has been spun.

[0010] Unless otherwise stated, reference to tanning in the embodiments or explanations of the present invention will refer to the above-mentioned post-tanning, ie tanning performed after the yarn is manufactured according to the definition of claim 1.

[0011] Advantages of tanning yarns according to the present invention include, for example, a homogenizing process because the material is homogenous compared to non-woven animal hides. In animal hides, variations in collagen organization exist in animals of different species, animals from different regions, and animals of different ages and sexes. These variations and differences affect the physical properties of the hide, resulting in differences in the leather products produced from the hide. The collagen organization structure varies with the thickness of the leather, with the top - grain side of the hide consisting of a fine network of collagen fibrils, while the deeper part (dermis) consists of larger fiber bundles.

[0012] According to the present invention, these differences have been minimized, making it possible to apply the correct amount of tanning agent, obtain a tanning process that is faster than leather tanning, and obtain a more predictable result of the tanning process (for example in terms of color). Equally attractive is that the final product can contain different amounts of tanning agent, and the probability that the tanning agent used will actually have the desired effect on collagen is much greater.

[0013] In the present invention, fiber can refer to, for example, tightly packed collagen fibrils that can form fibers, which can include natural collagen fibers, short fibers, and filaments, and can also include additives. The fiber in the present invention can also be shorter than a full-length yarn, or be made of one or more continuous strands (filaments), wherein each filament extends over the entire length of the yarn.

[0014] In one embodiment of the invention, the tanning of the yarn is a retanning.

[0015] The collagen-based yarn provided (as described above) can, in principle, be formed based on untanned collagen forming part of the yarn. However, it is preferred that the tanning performed is not only a post-tanning but also a re-tanning. This means that re-tanning here refers not only to the tanning process performed after the yarn is provided, but also to the tanning of yarns in which the collagen has been treated with a tanning agent before being formed into the yarn.

[0016] Retanning is particularly advantageous because adding fresh chrome to aged wet blue creates new cationic sites that may help fix anionic agents later in the process. More fundamentally, the isoelectric point will shift to a higher value, so that at any pH, the charge on the yarn will be less anionic and more cationic than that of unretanned yarn. This also affects the reactivity to tanning agents (which are usually anionic).

[0017] An advantage of the retanning process of the present invention may be that, due to the fact that the fibers may have been tanned before spinning, the use of tanning agents may be significantly reduced compared to a tanning process. Furthermore, also due to the fact that the fibers may have been tanned before spinning, and due to the open fiber structure of the yarn compared to the more compact fiber structure of leather, the time spent in the retanning process may also be advantageously shorter.

[0018] Tanning as used within the scope of the present invention may be applied, for example, to chrome tanning processes and includes tanning, dyeing and fatliquoring processes. However, in this context, it is understood to be the tanning process after the fiber has been made into yarn. The fiber may or may not have been tanned before manufacture.

[0019] Tanning is the process of converting perishable organic materials into a stable material that resists decay caused by spoilage bacteria. During the tanning process, the proteins in the fabric are converted into a stable material that allows the fabric to remain flexible while resisting decay. The fabric is stabilized in its "open" form by reacting some of the collagen with complexing ions of chromium or other tanning agents.

[0020] In an embodiment of the present invention, when the fabric is dried after wet treatment, greasing can be applied to prevent fiber adhesion. A secondary effect can be to control the softness imparted to the yarn and / or fabric. One consequence of lubrication can be an effect on the strength of the yarn and / or fabric. Greasing can be performed using self-emulsifying, partially sulfated, or sulfonated (sulfited) oils, which can be animal oils, vegetable oils, mineral oils, or synthetic oils. This step can also include processing to impart the desired degree of water resistance to the yarn and / or fabric.

[0021] In one embodiment of the present invention, collagen fibers are reconstructed staple fibers produced from a plurality of mechanically divided or ground protein fibrils.

[0022] In one embodiment of the present invention, the step of tanning the yarn is performed after the step of spinning the collagen fibers (CF) into yarn (Y) and before the step of processing the yarn (Y) into fabric (F).

[0023] In one embodiment of the present invention, the step of tanning the yarn is performed after the step of spinning the collagen fibers (CF) into the yarn (Y) and after the step of processing the yarn (Y) into the fabric (F).

[0024] In an advantageous embodiment of the invention, the two types of tanning methods specified according to the invention can also be combined, i.e. two tanning process steps are performed, one for the first tanning of the yarn before the fabric is made and the other for further tanning after the fabric is made.

[0025] In one embodiment of the invention, the tanning of the yarn comprises chemically altering the protein structure of the yarn.

[0026] The yarn tanning process chemically alters the protein structure by displacing water from the spaces between protein fibers and binding these fibers together. Tanning changes the spacing between protein chains in collagen from Increase to

[0027] In one embodiment of the invention, the chemical alteration of the yarn protein structure comprises subjecting the yarn to at least one tanning agent.

[0028] Tanning agents may include chrome tannins, including chromium salts such as chromium sulfate; vegetable tannins, including pyrogallol- or pyrocatechin-based tannins, for example valonea, mimosa, ten, tara, oak, pine, sumach, quebracho and chestnut tannins; aldehyde tannins, including glutaraldehyde and oxazolidine compounds, synthetic tannins (syntans), including aromatic polymers, polyacrylates, polymethacrylates, copolymers of maleic anhydride and styrene, condensation products of formaldehyde with melamine or dicyandiamide, lignin and natural flours; fish oils and other oils.

[0029] In one embodiment of the present invention, the tanning agent comprises an acid.

[0030] In one embodiment of the present invention, the tanning agent comprises a chromium salt, such as a chromium (III) salt.

[0031] During the chrome tanning process, chrome alum and chromium (III) sulfate are used. Chromium (III) sulfate may dissolve to produce chromium (III) hexahydrate cations, which undergo a process called hydroxylation at higher pH, resulting in polychromium (III) compounds that are active during tanning and cross-link with collagen subunits. The result of chrome treatment of yarn is that it appears light blue (called "wet blue").

[0032] In one embodiment of the present invention, the tanning agent comprises tannin.

[0033] The vegetable tanning process uses raw / natural tannins, available in liquid or powder form, obtained from different parts of the plant, including wood, bark, fruit, fruit pods, and leaves. The most common tannins come from chestnut branches, whitewood, tara fruit pods, Catechu, Chinese gallnut, Turkish gallnut, Gambier, Myrobalan, Oakwook, Sumac, and Valonia oak.

[0034] In one embodiment of the present invention, the tanning agent comprises a synthetic tanning agent.

[0035] The term syntan refers to a range of synthetic tanning agents. This class of agents is quite wide, but generally they are aromatic, such as hydroxy and sulphonate derivatives, so some general principles can be derived about their function.

[0036] In one embodiment of the present invention, the tanning agent comprises a combination for wet white tanning.

[0037] Wet white leather is made from a combination of synthetic tannins, vegetable tannins, glutaraldehyde, and minerals such as aluminum, titanium, and zirconium.

[0038] In one embodiment of the invention, the step of tanning the yarn precedes and / or includes acidification to the desired pH value.

[0039] In this context, the desired pH is a pH that promotes or facilitates the penetration of the tanning / retanning agent into the yarn and / or yarn fibers.

[0040] When chromium is introduced, the pH must be very acidic to ensure that the chromium complex is small enough to fit between the fibers and residues of collagen. Once the desired level of chromium penetration into the material is achieved, the pH of the material is raised again to facilitate this process (alkalinization). It should be noted that alkalinization in this article is more intended to encompass the process of increasing the pH value, rather than necessarily obtaining an alkaline pH final value. Therefore, alkalinization in this application can also be understood as deacidification.

[0041] The pH may be, for example, lowered (eg to pH 2.8-3.2) to allow penetration of the tanning agent, and after penetration the pH may be raised to fix the tanning agent (eg pH 3.6-4.2 or higher for chrome).

[0042] In one embodiment of the present invention, the step of tanning the yarn comprises fixing the tanning agent at a pH between 3.6 and 6.2 without prior acidification to a pH between 2.2 and 3.6.

[0043] According to an advantageous embodiment of the invention, the fixing of the tanning agent can be carried out without previously subjecting the yarn to acidification, since in some cases yarns based on textiles of collagen fibers can be manufactured without particular regard to penetration, as it is a requirement associated with conventional tanning of animal hides.

[0044] Another advantage of the present invention is that the pH adjustment step is faster than when adjusting the pH during conventional tanning of leather, since the fabric will react to the acid due to its more accessible conformation.

[0045] In one embodiment of the invention, the step of yarn tanning includes subsequent deacidification.

[0046] Considering that alkalization is essentially understood as an increase in the pH value after the tanning agent has penetrated into the yarn and / or the yarn fibers, alkalization can also be referred to as neutralization.

[0047] When the chromium is introduced, the pH must be very acidic to ensure that the chromium complexes are small enough to fit between the fibers and residues of collagen. Once the desired level of chromium penetration into the material is achieved, the pH of the material is raised again to allow the tanning agent to set.

[0048] Neutralization is the process of raising the pH after the main tanning step and before the start of the aftertanning reaction to adjust the charge on the leather. The final pH may be lower than the normal neutral pH (pH 7). This mechanism relies on sufficient alkalizing power to raise the pH to the desired level. Neutralization and alkalization are used interchangeably in this article.

[0049] The pH may be lowered to allow penetration of the tanning agent and after penetration the pH may be raised to fix the tanning agent.

[0050] Another advantage of the present invention is that the pH adjustment step is faster than when adjusting the pH during conventional tanning of leather, since the fabric responds to the acid due to its more penetrable structure.

[0051] In one embodiment of the invention, the tanning process includes temperature regulation.

[0052] The pH adjustment (increase) during the tanning process is usually accompanied by a gradual increase in temperature up to 50 degrees Celsius.

[0053] In one embodiment of the invention, the tanning process includes process pressure regulation.

[0054] According to one embodiment of the present invention, the portion of the tanning process involving the tanning agent may be performed at elevated pressure.

[0055] In one embodiment of the present invention, the tanning process comprises at least one drying step.

[0056] In one embodiment of the invention, the tanning of the yarn comprises mechanically processing the yarn.

[0057] During the drying process, the fibers may stick together resulting in a stiffer product and a mechanical step may be required to soften the yarn / fabric.

[0058] In one embodiment of the invention, mechanically processing the yarn comprises tumbling the yarn.

[0059] In one embodiment of the present invention, tumbling refers to the process of rotating the yarn / fabric in a narrow, tall, rotating barrel. The purpose of tumbling is to soften the fibers that would otherwise stick together during drying and make the yarn / fabric feel stiffer. The short rods and shape of the barrel enhance the movement of the yarn / fabric.

[0060] Stacking also makes the yarn / fabric softer by softening the fibers. A stacker (stacking machine) has two plates with ridges and opposing grooves. Continuous vibration ensures the product is pressed into the grooves by the ridges, causing the fibers to stretch. Stacking also enhances patterns and reduces looseness.

[0061] In one embodiment of the present invention, tanning of the yarn increases the temperature resistance of the yarn.

[0062] In one embodiment of the present invention, the hydrothermal stability is at least 70 degrees Celsius.

[0063] Hydrothermal stability measures a material's resistance to heat and moisture. In the case of collagen, fur, or leather, it's the effect of heat on a water-saturated material. The shrinkage temperature (Ts) of a fur or leather is a measure of hydrothermal stability. This method involves suspending a test piece in water as a strip. The water is then heated at a rate of 2 degrees Celsius per minute. The shrinkage temperature is recorded when the sample visibly shrinks.

[0064] In one embodiment of the present invention, the tanning process is performed at a temperature ranging from about 30 degrees Celsius to about 50 degrees Celsius.

[0065] Another advantage of the present invention is that the temperatures are lower compared to conventional tanning which is carried out at temperatures up to 60 degrees Celsius because the fibers in the yarn / fabric are more open and exposed compared to leather.

[0066] In one embodiment of the present invention, the tanning of the yarn is a continuous process performed by drawing the yarn through the tanning compound using rolls.

[0067] The yarns would likely stick together if treated like fabric and leather, so instead they are processed in a bath as a continuous process.

[0068] In one embodiment of the present invention, the collagen fibers (CF) are natural collagen fibers.

[0069] In one embodiment of the present invention, the collagen fibers (CF) are reconstructed fibers based on native collagen.

[0070] In one embodiment of the present invention, the collagen fibers (CF) are reconstructed fibers based on native collagen, and wherein the reconstructed fibers comprise at least 40% by weight of native collagen.

[0071] In one embodiment of the present invention, the collagen yarn comprises at least 40% collagen by weight.

[0072] In one advantage of the present invention, the collagen yarn can contain more weight of collagen and can contain at least 50% weight of collagen, for example 60% weight of collagen, for example 70% weight of collagen, for example 80% weight of collagen, for example 90% weight of collagen, for example 99% weight of collagen.

[0073] In one embodiment of the present invention, the collagen yarn further comprises non-collagenous proteins.

[0074] In one embodiment of the present invention, the collagen yarn further comprises 1 to 60% by weight of a non-collagenous material.

[0075] An advantage of the present invention is that collagen yarns can be hybridized with proteins other than collagen, resulting in great flexibility in production and the possibility of making yarns and fabrics with a wide variety of different properties.

[0076] In one embodiment of the present invention, the collagen yarn further comprises 1 to 60% by weight of natural and / or synthetic textile fibers.

[0077] In one embodiment of the present invention, the methods described herein may include the application of functional ingredients, which may include but are not limited to polymers, resins, dyes, stains, or paints.

[0078] In one embodiment of the present invention, the yarn is post-processed.

[0079] Post-processing is understood in this context to be any yarn treatment process, including but not limited to processes for making fabrics, including knitting, weaving, etc.; and further processes such as dyeing, impregnation and stabilizing the product.

[0080] In one embodiment of the present invention, the method comprises the step of post-processing the yarn (Y) into a fabric (F).

[0081] An advantage of the present invention is that yarn can be processed into the fabric that can be used in any way that the fabric made with natural fiber is used, and can be similar to leather in appearance and feel.The fabric processed by yarn has the advantage of using different methods to process, such as knitting, weaving, crocheting (crocheting), felting (felting), plaiting (braiding), braiding (plaiting) or other textile production methods known in the art, and fabric will be understood as cloth or other materials made by any of these methods within the scope of the present invention.The fabric manufactured can be similar and use in the case of being applicable to textiles and can show the characteristics with extensive multiple intensity, pliability and / or stretchability.Fabric also can show different characteristics in whole piece fabric.By selecting and adjusting fiber content and manufacturing process step, the fabric manufactured can be improved aspect softness, pliability, surface texture, elasticity, thickness or other functions.

[0082] Another advantage of the present invention is that the yarn can be processed into a fabric with a high degree of uniformity and flexibility. Fabrics made from natural collagen fibers have much less variation in appearance and physical properties than materials produced directly from animal hides.

[0083] In one embodiment of the present invention, the step of post-processing the yarn (Y) into the fabric (F) is performed by weaving.

[0084] Weaving is understood in the present invention to be a textile production method in which two different sets of yarns or threads are interwoven at right angles to form a fabric.

[0085] In one embodiment of the present invention, the step of post-processing the yarn (Y) into the fabric (F) is performed by knitting.

[0086] Knitting is understood in the present invention to be a method of producing textiles by looping one or more continuous yarns.

[0087] In one embodiment of the invention, the post-processing step comprises ironing.

[0088] In one embodiment of the present invention, the post-processing step comprises dyeing.

[0089] In one embodiment of the present invention, dyeing is performed at pH 5-11, preferably at pH 6-8.

[0090] In one embodiment of the present invention, dyeing is performed at pH 3-8, preferably pH 5-6.

[0091] In embodiments of the present invention, there may be additional dyeing steps, and any suitable dye may be used on any type of fabric, regardless of the background color, even though the final effect may be affected by previous processes. The application of dye solutions or pigments to impart a rich, opaque color may be done in a drum, or the dye may be sprayed or applied to the leather surface manually or by machine (pad dyeing, roller coating).

[0092] In one embodiment of the present invention, the post-processing step comprises impregnation.

[0093] In a favorable embodiment of the present invention, the fabric of tanning and / or retanning can be mechanically and / or chemically finished.Mechanical finishing can be used for polishing fabric to produce shiny or matte surface, ironing and pressing fabric to have flat, smooth surface, embossing fabric to provide 3D printing or pattern, or tumbling fabric to provide more obvious particles and smooth surface.Chemical finishing may relate to applying film, natural or synthetic coating or other fabric processing.Fabric finishing can be natural or synthetic polymer and / or colorant applied on the fabric surface and in the fabric surface, to produce uniform surface, wear resistance, water resistance etc.For example, the mixture of acrylic polymer, fluoropolymer and acrylic polymer, and / or the silicone polymer of different molecular weight can be used for imparting water resistance and feel finishing.Finishing can be carried out by spraying and / or roller coating or other applications relevant to finishing.The final performance of fabric may have added stabilizing and / or lubricating substances in tanning, retanning and / or post-tanning process.

[0094] In one embodiment of the present invention, fewer chemicals are used in the manufacturing process compared to traditional leather tanning.

[0095] One advantage of the present invention is that the fabric produced can exhibit uniformity, including uniform thickness and uniform distribution of reactive compounds, such as chemicals and / or tanning agents. This uniformity can result in reduced use of hazardous chemicals, such as chrome, and the reuse of chrome-tanned hides in the manufacturing process can result in an overall reduction in the use of chrome and compounds associated with the chrome tanning process.

[0096] In one embodiment of the present invention, manufacturing is performed with 10% less weight of chemicals.

[0097] In one embodiment of the present invention, manufacturing is performed with 25% less chemicals by weight.

[0098] In one embodiment of the present invention, the fabric has a tensile strength higher than 10 kPa.

[0099] In some embodiments, the tensile strength of the fabric is greater than 1 MPa, or more preferably greater than 10 MPa, or even more preferably greater than 50 MPa.

[0100] Tensile strength, also known as ultimate tensile strength or tensile testing, is the ability of a material to withstand a load that causes it to stretch and break when grips are attached to the ends of a sample and pulled apart. Fabrics can be tested on a textile tensile testing machine.

[0101] In one embodiment of the present invention, the fabric has a shrinkage temperature exceeding 70 degrees Celsius.

[0102] In one embodiment of the present invention, the fabric has an elastic modulus greater than 100 kPa.

[0103] In some embodiments, the fabric has an elastic modulus of 100 kPa to 1000 MPa.

[0104] The elastic modulus is a number that characterizes a fabric's ability to resist elastic deformation when subjected to stress. An object's elastic modulus is defined as the slope of its stress-strain curve in the elastic deformation region. Rigid materials will have a high elastic modulus, which can be measured using a texture analyzer.

[0105] In one embodiment of the present invention, the fineness of the fibers of the yarn is less than 10 dTex.

[0106] In one embodiment of the present invention, the fineness of the yarn is in the range of about 10 Tex to 300 Tex.

[0107] In one embodiment of the present invention, when the yarn contains at least 10% by weight of a tanning agent before retanning, the tanning agent content in the collagen fibers increases during retanning of the yarn.

[0108] In another embodiment, the tanning agent content of the collagen fibers is increased during retanning of the yarn when the yarn contains at least 10% by weight of tanning agent before retanning, and wherein the collagen fibers contain at least 1% by weight of tanning agent provided to the fibers before retanning.

[0109] In one embodiment of the present invention, the tanned yarn is fatliquored and wound into a plurality of yarn spools. In one embodiment of the present invention, the yarn is incorporated into an item.

[0110] In some embodiments, the produced yarn will be incorporated into articles including, but not limited to, furniture, clothing, shoes, socks, handbags, luggage, purses, jewelry, or other consumer, commercial, or industrial products.

[0111] In one embodiment of the present invention, the fabric is to be used in an article.

[0112] In some embodiments, the fabrics produced are used in articles including, but not limited to, furniture, clothing, shoes, socks, handbags, luggage, purses, jewelry, or other consumer, commercial, or industrial products.

[0113] In one embodiment of the present invention, leather yarn is manufactured according to the present invention and wherein the yarn is tanned.

[0114] In the present context, leather yarn is understood to be a yarn which is based at least on collagen and / or collagen fibrils.

[0115] An advantage of providing leather yarn as tanning material ready for optional further manufacturing is that the final properties of the yarn are essentially known before the fabric or fabric item is manufactured.

[0116] The leather yarn according to the present invention, wherein the yarn is wound on a plurality of yarn reels before dyeing.

[0117] One advantage of winding the yarn on a reel is that the undyed yarn can then be used as a flexible stock item that can be dyed to order.

[0118] In one embodiment of the present invention, the leather yarn according to the present invention, wherein the collagen fibers have a tenacity greater than 3 g / denier, such as at least 5 g / denier, such as at least 7 g / denier.

[0119] In one embodiment of the present invention, the amount of tanning agent in the leather yarn fabric comprising collagen fibers and a tanning agent is less than that of tanned leather having the same volume.

[0120] In one embodiment of the present invention, the amount of tanning agent in the leather yarn fabric comprising collagen fibers and tanning agent is less than 10% by volume of the fabric, for example less than 8% by volume, for example less than 5% by volume, for example less than 2% by volume of the fabric or for example less than 1% by volume.

[0121] In one embodiment of the invention, the amount of tanning agent in the leather yarn fabric comprising collagen fibers and tanning agent is less than 10% by weight of the yarn, such as less than 8% by weight, such as less than 5% by weight, such as less than 2% by weight or such as less than 1% by weight.

[0122] The leather yarn fabric according to the present invention, wherein the leather yarn is made according to the present invention.

[0123] In one embodiment of the invention, the amount of tanning agent in the leather yarn comprising collagen fibers and tanning agent is less than 10% by weight of the yarn, for example less than 8% by weight, for example less than 5% by weight, for example less than 2% by weight or for example less than 1% by weight.

[0124] The leather yarn fabric according to the present invention comprises leather yarns made according to the present invention.

[0125] In one embodiment of the present invention, the leather yarn fabric according to the present invention, wherein the collagen fibers have a tenacity greater than 3 g / denier, such as at least 5 g / denier, such as at least 7 g / denier.

[0126] In one embodiment of the invention, the leather yarn comprises collagen fibers and a tanning agent, wherein the amount of tanning agent is less than 10% by weight of the yarn, such as less than 8% by weight, such as less than 5% by weight, such as less than 2% by weight or such as less than 1% by weight.

[0127] In the present context, leather yarn is understood to be a yarn which is based at least on collagen and / or collagen fibrils.

[0128] In one embodiment of the present invention, the leather yarn fabric comprises the leather yarn according to the present invention, wherein the leather yarn is produced according to the present invention.

[0129] In one embodiment of the present invention, a leather shoe comprises a sole (SO) and an upper (UP),

[0130] The upper UP is at least partially made of leather fabric.

[0131] The leather fabric is produced based on the leather yarn of the present invention,

[0132] In one embodiment of the present invention, the leather shoe according to the present invention comprises the leather fabric according to the present invention, and the leather fabric is applied to the upper of the shoe.

[0133] In one embodiment of the present invention, the shoe leather fabric is used as the shoe lining SL or as a part of the shoe lining.

[0134] Shoe lining is the material on the inside of a shoe that, in some applications, comes into contact with the entire foot: the sides, top, and heel, or at least some of these parts of the foot. One purpose of the lining is to cover the interior seams of the shoe and extend the life of the shoe. Linings made according to the present invention can provide cushioning and comfort to the foot or wick away moisture.

[0135] As a result, leather fabric linings feel soft against the skin and conform to the shape of the foot over time. They are also durable, allowing air to flow and moisture to evaporate. While leather is the highest-quality material for linings, some shoes, particularly athletic shoes, do not use leather linings due to the extra weight it adds. The present invention facilitates such use because leather fabric can offer all or many of the advantages of conventional leather but at a lower weight, thereby increasing its application, for example, in athletic shoes. It also reflects the realization that the incorporated dye can be closely matched to the fabric, for example, in terms of dosage, as opposed to conventional leather, where such processes are time-consuming and difficult to control for the desired final color.

[0136] In summary, it is noted that the leather fabric provided according to the present invention is very breathable, and that the shoe provided according to the present invention is not only relatively resistant to discoloration, but can also be used as an outer layer and optionally an inner layer of a shoe, thereby providing a shoe whose upper is very breathable compared to traditional shoe fabrics.

[0137] In one embodiment of the present invention, the leather yarn according to any one of the preceding claims, wherein the yarn comprises at least 1% by weight of the yarn of a tanning agent and at least 0.1% by weight of the yarn of a dye.

[0138] In one embodiment of the invention the leather yarn according to any one of the preceding claims, wherein the yarn comprises 1-10% by weight of the yarn of a tanning agent and 0.1-10% by weight of the yarn of a dye in at least 0.1% by weight of the yarn.

[0139] The present invention also relates to a fatliquor leather yarn, wherein the leather yarn has been tanned and not dyed.

[0140] The present invention also relates to a fatliquor leather yarn, wherein the leather yarn is untanned and undyed.

[0141] In one embodiment of the present invention, fatliquor leather yarn is produced according to the present invention.

[0142] In one embodiment of the present invention, the fatliquor leather yarn according to the present invention is untanned and undyed.

[0143] Fatliquoring can advantageously be carried out on the yarn after tanning the yarn.

[0144] Finishes can also be applied to the fibers, collagen yarns, and / or collagen fabrics in the process. These may include wax surface finishes to improve water resistance, harden the surface, and protect its color. Finishes may include solvents, adhesives, plasticizers, pigments, and specialized waxes.

[0145] Furthermore, relevant polishes and / or processes suitable for treating yarn textiles can be applied to the method.

[0146] The present invention also relates to a leather fabric produced from the leather yarn according to the invention.

[0147] In one embodiment of the present invention, the leather fabric is made of leather yarn, wherein the leather yarn is provided based on a solution of protein molecules.

[0148] In one embodiment of the present invention, the leather fabric is made of leather yarn, wherein the leather yarn is provided based on a suspension of protein fibrils.

[0149] More specifically, this application relates to

[0150] 1. A method for producing collagen yarn (Y), comprising the following steps:

[0151] -Provide collagen fibers (CF)

[0152] - spinning the collagen fibers into yarn (Y), and

[0153] - Tanning the yarn (Y) after it has been spun.

[0154] 2. The method according to item 1, wherein the tanning of the yarn is retanning.

[0155] 3. The method according to any of the preceding items, wherein the collagen fibers are reconstructed fiber staples produced on the basis of a plurality of mechanically subdivided or ground protein fibrils.

[0156] 4. A method for producing collagen yarn (Y) according to any one of the preceding items, wherein the step of tanning the yarn is carried out after the step of spinning the collagen fibers into yarn (Y) and before the step of processing the yarn (Y) into fabric (F).

[0157] 5. A method for manufacturing collagen yarn (Y) according to any one of the preceding items, wherein the yarn tanning step is carried out after the step of spinning collagen fibers into yarn (Y) and after the step of processing the yarn (Y) into fabric (F).

[0158] 6. A method according to any of the preceding items, wherein the tanning of the yarn comprises chemically altering the protein structure of the yarn.

[0159] 7. Method according to any of the preceding items, wherein the chemical modification of the protein structure of the yarn comprises subjecting the yarn to at least one tanning agent.

[0160] 8. The method according to any one of the preceding items, wherein the tanning agent comprises an acid.

[0161] 9. The method according to any one of the preceding items, wherein the tanning agent comprises a chromium salt, such as a chromium (III) salt.

[0162] 10. The method according to any of the preceding items, wherein the step of tanning the yarn precedes and / or comprises acidification to the desired pH value.

[0163] 11. The method according to any of the preceding items, wherein the step of tanning the yarn comprises penetrating the tanning agent at a pH of 2.2-3.6.

[0164] 12. The method according to any of the preceding items, wherein the step of tanning the yarn comprises fixing the tanning agent at a pH of 3.6-6.2.

[0165] 13. The method according to any of the preceding items, wherein the step of tanning the yarn comprises fixing the tanning agent at a pH of 3.6-6.2 without prior acidification to a pH of 2.2-3.6.

[0166] 14. Method according to any of the preceding items, wherein the step of tanning the yarn comprises subsequent deacidification.

[0167] 15. Method according to any of the preceding items, wherein the tanning process comprises temperature regulation.

[0168] 16. Method according to any of the preceding items, wherein the tanning process comprises process pressure regulation.

[0169] 17. Method according to any of the preceding items, wherein the tanning process comprises at least one drying step.

[0170] 18. The method according to any of the preceding clauses, wherein tanning the yarn comprises mechanically treating the yarn.

[0171] 19. The method according to any of the preceding clauses, wherein mechanically treating the yarn comprises tumbling the yarn.

[0172] 20. The method according to any of the preceding items, wherein tanning the yarn increases the temperature resistance of the yarn.

[0173] 21. The method of any preceding item, wherein the hydrothermal stability is at least 70 degrees Celsius.

[0174] 22. The method according to any of the preceding items, wherein the tanning process is carried out at a temperature in the range of about 30 degrees Celsius to about 50 degrees Celsius.

[0175] 23. Method according to any of the preceding items, wherein tanning the yarn is a continuous process by drawing the yarn through the tanning compound with the aid of rollers.

[0176] 24. The method according to any of the preceding items, wherein the collagen fibers (CF) are native collagen fibers.

[0177] 25. The method according to any of the preceding items, wherein the collagen fibers (CF) are reconstructed fibers based on native collagen.

[0178] 26. The method according to any of the preceding items, wherein the collagen fibers (CF) are reconstructed fibers based on native collagen and the reconstructed fibers comprise at least 40% by weight of native collagen.

[0179] 27. A method according to any of the preceding items, wherein the collagen yarn comprises at least 40% collagen by weight.

[0180] 28. The method of any of the preceding items, wherein the collagen yarn further comprises a non-collagenous protein.

[0181] 29. A method according to any preceding item, wherein the collagen yarn further comprises 1-60% by weight of non-collagenous proteins.

[0182] 30. The method according to any of the preceding items, wherein the collagen yarn further comprises 1-60% by weight of natural and / or synthetic textile fibers.

[0183] 31. A method according to any of the preceding items, wherein the yarn is post-processed.

[0184] 32. The method according to any of the preceding items, wherein the method comprises the step of post-processing the yarn (Y) to form a fabric (F).

[0185] 33. The method according to item 32, wherein the step of post-processing the yarn (Y) into a fabric (F) is carried out by weaving.

[0186] 34. The method according to item 32, wherein the step of post-processing the yarn (Y) into the fabric (F) is carried out by knitting.

[0187] 35. Method according to any of the preceding items, wherein the post-processing step comprises ironing.

[0188] 36. The method according to any of the preceding items, wherein the post-processing step comprises dyeing.

[0189] 37. The method according to any of the preceding items, wherein dyeing is performed at pH 5-11, preferably pH 6-8.

[0190] 38. The method according to any of the preceding items, wherein the dyeing is performed at pH 3-8, preferably pH 5-6.3.

[0191] 39. The method according to any of the preceding items, wherein the post-processing step comprises impregnation.

[0192] 40. A method for manufacturing collagen yarn (Y) according to any one of the preceding steps, wherein the manufacturing is carried out with less chemical consumption than conventional leather tanning.

[0193] 41. A method for manufacturing collagen yarn (Y) according to item 40, wherein the manufacturing is carried out with 10% less weight of chemicals.

[0194] 42. A method for manufacturing collagen yarn (Y) according to items 40-41, wherein the manufacturing is carried out using 25% less weight of chemicals.

[0195] 43. The method according to any of the preceding items, wherein the fabric has a tensile strength higher than 100 kPa.

[0196] 44. The method according to any of the preceding items, wherein the fabric has a shrinkage temperature exceeding 70 degrees Celsius.

[0197] 45. The method of any of the preceding items, wherein the fabric has an elastic modulus greater than 100 kPa.

[0198] 46. ​​Method according to any of the preceding items, wherein the fineness of the fibers of the yarn is less than 10 dtex.

[0199] 47. The method according to any of the preceding items, wherein the fineness of the yarn is in the range of about 10 to 300 TeX.

[0200] 48. A method according to any of the preceding items, wherein the content of tanning agent in the collagen fibres is increased during retanning of the yarn, wherein at least 10% by weight of the tanning agent is contained in the yarn before retanning.

[0201] 49. A method according to any of the preceding clauses, wherein the tanned yarn is fatliquored and wound into a plurality of yarn spools.

[0202] 50. Use of a yarn produced according to the method of any of the preceding items, wherein the yarn is incorporated into an article.

[0203] 51. Use of a fabric comprising the artificial yarn according to any one of the preceding items, wherein the fabric is to be used in an article.

[0204] 52. Leather yarn produced according to any one of steps 1 to 49, wherein the yarn is tanned.

[0205] 53. The leather yarn of claim 52, wherein the yarn is wound onto a plurality of yarn spools prior to dyeing.

[0206] 54. The leather yarn according to items 52-53, wherein the collagen fibers have a tenacity greater than 3 g / denier, such as at least 5 g / denier, such as at least 7 g / denier.

[0207] 55. A leather yarn fabric comprising collagen fibers and a tanning agent, wherein the amount of tanning agent is less than an equivalent volume of tanned leather.

[0208] 56. Leather yarn fabric comprising collagen fibers and a tanning agent, wherein the amount of tanning agent is less than 10% by volume of the fabric, such as less than 8% by volume, such as less than 5% by volume, such as less than 2% by volume or such as less than 1%.

[0209] 57. Leather yarn fabric comprising collagen fibers and a tanning agent, wherein the amount of tanning agent is less than 10% by weight of the yarn, such as less than 8% by weight, such as less than 5% by weight, such as less than 2% by weight or such as less than 1% by weight.

[0210] 58. The leather yarn fabric according to any one of items 55-57, wherein the leather yarn is made according to any one of items 1-50.

[0211] 59. A leather yarn fabric according to item 56, wherein the tenacity of the collagen fibers is greater than 3 grams per denier, such as at least 5 grams per denier, such as at least 7 grams per denier.

[0212] 60. Leather yarn comprising collagen fibers and a tanning agent, wherein the amount of tanning agent is less than 10% by weight of the yarn, such as less than 8% by weight, such as less than 5% by weight, such as less than 2% by weight or such as less than 1% by weight.

[0213] 61. Leather yarn fabric comprising the leather yarn according to any one of items 52-60, and wherein the leather yarn is made according to any one of items 1-49.

[0214] 62.Leather shoes include soles (SO) and uppers (UP).

[0215] wherein the upper (UP) is at least partially composed of leather fabric,

[0216] The leather fabric is produced based on the leather yarn produced according to any one of the above items 1 to 49.

[0217] 63. The leather shoe according to item 62, wherein the leather shoe comprises the leather fabric according to 55-58, and wherein the leather fabric is applied to the upper of the shoe.

[0218] 64. Leather shoe according to items 62-63, wherein the leather fabric is used as a shoe lining (SL) or as a part of a shoe lining.

[0219] 65. Fatliquor leather yarn, wherein the leather yarn is tanned and undyed.

[0220] 66. Fatliquor leather yarn produced according to any one of items 1 to 49.

[0221] 67. Fatliquor leather yarn according to any one of items 1 to 49, wherein the leather yarn is untanned and undyed.

[0222] 68. Leather fabric made from the leather yarn according to items 65 to 67.

[0223] 69. Leather fabric made from leather yarn according to item 68, wherein the leather yarn is provided based on a solution of protein molecules.

[0224] 70. Leather fabric made from leather yarn according to item 68, wherein the leather yarn is provided based on a suspension of protein fibrils. BRIEF DESCRIPTION OF THE DRAWINGS

[0225] The present invention will be described below with reference to the accompanying drawings, in which:

[0226] Figure 1A and 1B An example of collagen fibers (CF) being twisted and spun into yarn (Y) before the tanning process (TP) is shown.

[0227] Figure 2A and 2B An example of collagen fibers (CF) being twisted and spun into yarn (Y) and rope (CO) before the tanning process (TP) is shown.

[0228] Figure 3 shows the manufacture of a fabric according to an embodiment of the present invention,

[0229] Figure 4 shows an example of processing collagen fibers (CF) and (Y) by tanning according to an embodiment of the present invention,

[0230] Figure 5 Shown is a shoe according to an embodiment of the present invention,

[0231] Figure 6A -D shows different tanning strategies within the scope of the present invention, and wherein

[0232] Figure 7 Another advantageous embodiment of the invention is shown. Specific implementation plan

[0233] In the description and claims, unless otherwise indicated, percentage values ​​relating to amounts of material are weight percentages (wt.%) based on the total weight of the filament or staple fiber in question. The word "comprising" can be used as an open term, but also includes the closed term "consisting of."

[0234] As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0235] As used herein, "at least one" is intended to mean one or more, ie, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0236] The term "collagen" refers to any of at least 28 different known collagen types, each of which performs a different function in animals. The main component of skin is type I collagen, although other types of collagen can also be used to form leather. Collagen is a protein, which means that it is made up of amino acids. These can be divided into alpha-amino acids and beta-amino acids. Each of them is characterized by a terminal amino group and a terminal carboxyl group that participate in peptide linkage, as well as side chains attached to a methylene group in the center of the molecule. When amino acids are linked together to form proteins, they create an axis or "backbone" for the polymer, from which the side chains extend. The content and distribution of side chains determine most of the properties of any protein.

[0237] The term "collagen fibrils" refers to nanofibers composed of triple helices of collagen molecules (tropocollagen). Fibrils may have diameters between 10 and 100 nanometers and are not typically found alone, but rather as part of a more complex, multilayered structure. Each fibril can interlock with its neighboring fibrils to form collagen fibers. Collagen fibrils may be derived from wood shavings, leather pulp, and / or tanned hides, including waste from the tanning process, and unfinished and finished leather scrapings. Collagen fibers can come from various sources, but are typically derived from the skin.

[0238] The term "collagen fiber" refers to tightly packed collagen fibrils that exhibit a high degree of alignment in the fiber direction and are typically longer than they are wide. Changes in the organization or cross-linking of fibrils and fibers can provide strength to the material. Collagen fibers can include staple fibers or filaments. Fibers can be reconstructed fibers and can include other materials besides collagen.

[0239] The term "staple fiber" refers to fibers having discrete lengths and that can have any composition. Staple fibers can be provided, for example, by dividing collagen-based filaments into discrete staple fibers of a certain length. The length can vary depending on the application. In this context, the length should be selected to allow the staple fibers to be subsequently spun into yarns. The staple fibers can be further processed to provide articles, such as yarns or nonwovens.

[0240] The term "reconstructed" fiber refers to short fibers produced from a plurality of mechanically broken protein fibrils. Reconstructed fibers can be formed by directing a protein suspension through a nozzle onto a surface for drying. The suspension is dried to remove water and solvent from the suspension, thereby forming the reconstructed fibers, for example, on the surface of a conveyor belt or drum.

[0241] This method for producing fibers based on protein fibril reconstruction is described, for example, in WO 2018 / 149950 or WO 2018 / 149949 for use in connection with collagen.

[0242] Other starting materials can of course also be added to the collagen, thereby promoting reconstructed fibers based on a mixture of fibrils originating from collagenous materials such as leather and fibrils originating from, for example, a cellulosic source.

[0243] The term "wool" refers to staple fibers or fibers of a fluffy material or reconstructed natural-based fibers. The term wool may also be used as natural fiber-based wool or staple wool.

[0244] As used herein, the term "manufacturing process" may refer to a process in which fibers are formed into an uneven network of raw wool based on natural fibers and a process through carding preparation and carding, wherein carding includes fiber cleaning, opening, mass reduction, mixing, homogenization and structuring, i.e., disentanglement and intermixing of fibers to produce a continuous web or sliver suitable for subsequent processing, such as spinning.

[0245] The term "sliver" as used herein is a long bundle or rope of fibers, typically used for spinning, produced by combing or combining fibers and then pulling them into a long strip with the fibers aligned in parallel. Slivers may be slightly twisted and are considered to be loose, soft, robe-like textile fibers.

[0246] Spinning is the process of twisting drawn fiber bundles together to form yarn, which can be processed using ring spinning or other systems, including air-jet, open-end, and vortex spinning. Ring spinning is the most common method of spinning fibers, and yarn is made through a continuous process in which roving is first drawn down using drawing rollers, then spun and wound onto a rotating spindle, which is in turn contained in an independently rotating ring flyer. The term roving refers to the long, narrow fiber bundles produced during the process of making spun yarn from fibers. Their main use is as fibers ready for spinning, but they can also be used in specialized types of knitting or other manufacturing processes.

[0247] Yarn is a long, continuous length of interlocking fibers suitable for making fabrics. Yarn can be spun from a variety of materials, including variations of collagen fibers, but within the scope of this invention, yarns may also include a certain amount of natural and synthetic fibers. The direction in which the yarn is spun is called twist, which is classified as S twist or Z twist depending on the spinning direction. Twist is measured in TPI (twists per inch or turns per inch). Two or more spun yarns can be twisted together or plied to form a thicker yarn. The term "plies" refers to the process used to create a strongly balanced yarn, which is accomplished by twisting two or more strands of yarn together and placing them together. Filament yarns are continuous, long fibers that are twisted or combined together. Multiple filament yarns can be combined to create yarns with different textures. Spun yarns can contain a single type of fiber, a mixture of various yarn types, or a blend of natural and synthetic fiber yarns.

[0248] Yarns can also be used to create fabrics by weaving, a method of producing materials in which two different sets of yarns are interwoven at right angles to form a fabric. The lengthwise yarns are called the warp, and the widthwise yarns are called the weft (or filling). The method by which these threads are interwoven affects the fabric's properties. The three basic weaves are plain, twill, and satin, but specialized weaves such as pile, jacquard, dobby, and leno are also possible, requiring special loom attachments for their construction.

[0249] Yarn can also be used to create fabrics through knitting, which produces multiple loops of yarn called stitches in a linear or tubular form. Knitting has multiple active stitches, and knitted fabrics consist of continuous rows of intermeshing loops. Different types of yarn (fiber type, texture, and twist), needle gauge, and stitch type can be used to activate different properties in knitted fabrics, such as texture, weight, appearance, warmth, color, water resistance, integrity, conductivity, and other possible properties.

[0250] The yarn may also undergo any other manufacturing process including, but not limited to, crocheting, braiding, and / or knotting.

[0251] Tanning is a common method for treating leather and can be applied to the present invention. Depending on the chemical compounds used, the color and texture of the fabric may change. The technical definition of tanning is well known in the art, but in short, according to Anthony D. Covington's "Tanning Chemistry," Chapter 10, the only strict definition of tanning is the conversion of perishable organic materials into a stable material that is resistant to biochemical attack. Tanning involves multiple steps and reactions, depending on the starting material and the final product.

[0252] In the case of collagen, side chains largely determine its reactivity and its ability to be modified through stabilizing reactions during tanning during leather production. Furthermore, the chemical nature of the backbone, defined by the peptide linkages, provides multiple, distinct reactive sites that can be exploited in some tanning processes. During the tanning process, collagen modification due to the chemistry of the tanning agent can influence various aspects of the material's properties. The hydrophilic-hydrophobic balance of leather can be significantly affected by the tanning agent's chemistry by altering the relationship between the leather and the solvent, which in turn affects the equilibrium of any reagents between the solvent and the substrate. Furthermore, the site of reaction between the reagent and collagen may affect the collagen's isoelectric point, thus potentially leading to a different relationship between pH and the charge on the leather. The lower the isoelectric point, the more anionic or less cationic the charge on the hide at any pH; the higher the isoelectric point, the more cationic or less anionic the charge on the hide at any pH. Furthermore, the relative reactivity of the protein's side chains and backbone may determine the type of reaction, and thus the degree of stability achieved in the tanned leather. The fastness of the reagent can be influenced by the interaction between the reagent and the substrate.

[0253] Hydrothermal stability can be measured in this context by the shrinkage temperature (Ts) of the hide. This is the temperature at which the energy input (heat) exceeds the existing hydrogen bonding energy of the collagen structure, causing the helical structure to disintegrate. The shrinkage temperature of untanned hides is typically around 65°C. Ts can be increased during the tanning process.

[0254] As used herein, decitex (dtex) is a unit of linear density of continuous filament or yarn, equal to 1 / 10 tex.

[0255] refer to Figure 1A 、 1B 2A and 2B are schematic diagrams showing a method according to an embodiment of the present invention.

[0256] Further embodiments are Figure 3 -6, and all of these embodiments can be understood based on Figures 1-2 and the following discussion.

[0257] Back to Figure 1A and 1B , which illustrate some principles of advantageous embodiments of the present invention, Figure 1A Shows the mechanical components throughout the entire process, Figure 1B The process flow timeline is shown, showing spinning, tanning and post-processing as process steps. Initially, bundles of collagen fibers (CF) are spun into yarn (Y) as slivers, then tanned and then post-processed.

[0258] Suitable collagen fiber materials that can be used as the basis for the yarns, fabrics and their final products of the present invention include, for example, yarns based on collagen fibers, which are made based on, for example, natural collagen fibers, their staple fibers, or staple fibers of reconstructed filaments, or reconstructed filaments, biologically grown collagen fibers, and synthetic collagen fibers.

[0259] Examples of suitable natural collagen fibers can be provided, for example, by the loosening method described in EP 1 736 577 B, or can be made into fibers as described, for example, in WO 2018 / 149950, WO 2018 / 149949 or US 3,556,969, or WO 2017 / 142896 or 2007 / 225631A1. According to the latter, the collagen fibers should be loosened from the provided nonwoven structure.

[0260] Collagen fibers in this context are generally understood as fibers comprising collagen in an amount of at least 20% by weight of the fibers, such as at least 40% by weight of the fibers, such as at least 60% by weight of the fibers, such as at least 80% by weight of the fibers.

[0261] Collagen fibers in this context have several benefits for use in the present invention, such as providing stretch to the final fabric made according to the provisions of the present invention.

[0262] A yarn is understood here to be a minimal structure of bundled collagen fibers extending in a longitudinal direction. The extension of the bundled structure can in principle be infinite, although this is of course not a real-world application.

[0263] exist Figure 1A and Figure 1B In this embodiment, relatively short staple fibers of collagen-based fibers, i.e., short fibers containing collagen, are used, thereby facilitating the application of spinning to produce a fiber structure that is more longitudinally strong. However, it should be emphasized that this embodiment can be produced based on collagen fibers in the form of filaments, and Figure 2A 、 2B The embodiments are more based on the use of short fibers.

[0264] Spinning involves twisting drawn fiber strands or slivers together to form yarn. This can be done using ring spinning or other systems, including air-jet spinning, open-end spinning, and vortex spinning. Ring spinning is a method of spinning fibers into yarn using a continuous process, in which roving is first attenuated using draw rollers, then spun and wound onto a rotating spindle, which is contained within an independently rotating ring. The yarn can be twisted in either an S or Z direction, depending on the spinning direction. Spun yarn can contain a single fiber type, a blend of various yarn types, or a blend of natural and synthetic fibers.

[0265] The tanning (TE) device in this context is provided for at least chemically modifying the collagen of the yarn (Y). The tanning process itself is well known to the skilled person and can be carried out in a variety of ways, as long as a wet tanning process step is involved and a chemical reaction is obtained between the tanning agent and the collagen of the yarn.

[0266] The tanning step shown can in principle encompass a tanning process design and be performed on yarns where the collagen of the rope has not been previously tanned. However, it is preferred to consider the tanning step as a retanning step, i.e. the collagen fibers subjected to the tanning step have previously been treated with a tanning agent.

[0267] It should be noted, however, that the preferred tanning operation is best described as a so-called post-tanning, comprising at least one wet processing step involving a single chemical process or a combination of chemical processes.

[0268] Post-processing can be any processing of the yarn, including but not limited to processes for making fabrics including knitting, weaving, etc., as well as further processes such as dyeing, impregnation, functionalization and stabilization of the product.

[0269] It should be noted that Figure 1A and 1B The embodiment shown is exemplary. Other ways of providing a yarn suitable for post-processing may be applied, such as providing a yarn provided by weaving or knitting.

[0270] A yarn is understood here to be a minimal structure of bundled collagen fibers extending in a longitudinal direction. The extension of the bundled structure can in principle be infinite, although this is of course not a real-world application.

[0271] refer to Figure 2A and 2B , mechanical parts penetrate Figure 2B The corresponding process flow is shown in the process flow timeline, showing spinning, tanning and post-processing as process steps. Initially, bundles of collagen fibers (CF) are spun into yarn (Y) as slivers, and then two or more spun yarns can be twisted together or plied to form a thicker yarn or rope (CO). The term plying refers to the process used to create a strongly balanced yarn, which is done by twisting two or more yarns with each other and putting them together, with the strands twisted together in the opposite direction to the spinning. The spun yarn can contain a single type of fiber, a mixture of various types of yarns, or a blend of natural fiber yarns with synthetic fiber yarns.

[0272] exist Figure 2A and Figure 2B In this embodiment, relatively short collagen fibers, i.e. short fibers comprising collagen, are used, which facilitates the application of spinning to produce a longitudinally stronger fiber structure, here referred to as a rope (CO), although a rope (CO) can also be understood in the prior art and according to the present invention as a yarn, a reinforced yarn.

[0273] After the rope (CO) is provided, it is treated in a tanning step using a tanning equipment (TE).

[0274] In the present context, a tanning (TE) device is provided for at least chemically modifying the collagen of the rope (CO). Such tanning processes are well known to the skilled person and can be carried out in various ways, as long as a wet tanning process step is involved and a chemical reaction is achieved between the tanning agent and the collagen of the yarn / rope.

[0275] The tanning step shown can in principle encompass a tanning process design and be performed on ropes / yarns, wherein the collagen of the yarn / rope has not been previously tanned. However, it is preferred to consider the tanning step as a retanning step, that is to say that the collagen fibers subjected to the tanning step have previously been subjected to a tanning agent.

[0276] It should be noted however that preferred tanning operations are best described as so called post-tanning, ie involving at least one wet processing step involving a single chemical process or a combination of chemical processes.

[0277] Post-processing can be any process of the yarn or rope (CO), including but not limited to the process of making fabrics, including knitting, weaving, etc.; and further processes such as dyeing, impregnation, functionalization and stabilization of the product.

[0278] It should be noted that Figure 2A and 2B The embodiment shown is exemplary. Other methods can be used to provide yarns and ropes suitable for post-processing, for example, by weaving or knitting the provided yarns. Figure 2A 、 2B and Figure 1A 、 1B The difference between is basically the way the final rope-like structure is built; as a yarn (Y) or as a cord (C).

[0279] In other words, the post-tanning according to the invention can be carried out, for example, on yarn or further processed yarn, such as rope, or, for example, on fabric.

[0280] Finally, the yarn or rope can usually be processed into fabric (F), see Figure 3 , fabrics made from yarn or cord can have the advantages of being processed using different methods. The figures suggest a woven structure, but it should be noted that the figures are also intended to illustrate methods such as knitting, crocheting, felting, plaiting, rope braiding, or other textile production methods known in the art.

[0281] The fabric (F) within the scope of the present invention may comprise different fibers and / or yarns such as, but not limited to, wool, cellulose, polyester, silver, elastomer, and the like.

[0282] The fabric may be tanned after fabric manufacture is complete, or if the yarn is post-tanned before fabric manufacture but after yarn manufacture, no further tanning process may be performed.

[0283] It should be noted that Figure 3 The embodiment shown is exemplary. Other ways of providing the fabric may be applied.

[0284] It should also be noted that generally, the term post-tanning may refer to conventionally understood post-tanning when applied, including retanning, i.e. a tanning process within the understanding of conventional retanning with respect to the chemical products, processing temperature, processing pH value, etc. applied. In other words, if the collagen fibers have been chemically modified to a certain extent in an earlier tanning process, the tanning method of the present invention will therefore generally include within the scope of the present invention at least the conventional retanning that is applied to the yarn or fabric in question. It should be noted here that "conventional" in no way means that retanning has previously been applied to yarn according to the provisions of the present invention. This simply means that the technician can find relevant guidance in the conventional retanning process when designing the tanning process of the present invention.

[0285] Figure 4 Another embodiment of the present invention is described. This embodiment relates to processing collagen fibers (CF) into yarn (Y) and tanned fabric (TF); or processing collagen fibers (CF) into yarn (Y) and tanned yarn (TY).

[0286] According to the process flow diagram, collagen fiber (CF) is spun into yarn (Y) through a yarn spinning process (YSP). Thereafter, the yarn (Y) can be tanned, usually in a retanning / tanning process (TP) to form tanned yarn (TY).

[0287] Alternatively, the produced yarn (Y) may alternatively be processed in a fabric manufacturing process (FMP) into a collagen yarn (Y) based fabric (F) and subsequently processed in a tanning process (TP) into a tanned fabric (TF).

[0288] Technically, it is also possible to perform tanning after the yarn (Y) is provided and then add a further tanning step (not shown) when the already tanned yarn (TY) is processed into fabric (not shown) during the fabric manufacturing process. This is possible, but not necessarily expected, as one tanning step is usually sufficient.

[0289] The spinning process (YSP) involves twisting drawn fiber strands or slivers together to form yarn, which can be processed using ring spinning or other systems including air-jet spinning, open-end spinning, and vortex spinning. Ring spinning is a method of spinning fibers to make yarn in a continuous process, in which the roving is first attenuated using draw rollers, then spun and wound onto a rotating spindle, which is contained in an independently rotating ring. The direction of the yarn can be either S-twist or Z-twist, depending on the spinning direction. The spun yarn can contain a single type of fiber, a blend of various types of yarn, or a blend of natural and synthetic fiber yarns.

[0290] The tanning step shown can in principle be performed on ropes / yarns that have not been tanned beforehand. However, if the collagen fibers that undergo the tanning step have been previously treated with a tanning agent, then the tanning step is preferably considered a retanning step.

[0291] It should be noted however that preferred tanning operations are best described as so called post-tanning, ie involving at least one wet processing step involving a single chemical process or a combination of chemical processes.

[0292] It should be noted that Figure 4 The illustrated embodiments are exemplary.

[0293] Figure 5Another embodiment of the present invention is described. This embodiment comprises a shoe (S) comprising a sole (SO) and an upper (UP).

[0294] The upper (UP) can be formed entirely of the textile fabric provided by the present invention. The upper (UP) can also include a shoe lining (SL).

[0295] The shoe lining (SL) is the material on the inside of the shoe that, in some applications, comes into contact with the entire foot: the sides, top, and heel, or at least some of these parts. One purpose of the lining is to cover the interior seams of the shoe and extend the life of the shoe. A shoe lining (SL) made according to the present invention can provide cushioning and comfort to the foot or wick away moisture.

[0296] As a result, leather fabric linings feel soft against the skin and conform to the shape of the foot over time. They are also durable and allow air to flow, allowing moisture to evaporate. While leather is the highest-quality material for linings, some shoes, particularly athletic shoes, do not use leather linings due to the extra weight it adds. The present invention facilitates such use because leather fabric can offer all or many of the advantages of conventional leather but at a lower weight, thus increasing its application, for example, in athletic shoes. It also reflects the realization that the incorporated dye can be perfectly matched to the fabric, for example, in the opposite amount to conventional leather, where such processes are time-consuming and difficult to control the desired final color.

[0297] In summary, it is noted that the leather fabric provided according to the present invention is very breathable, and that the shoe provided according to the present invention is not only relatively resistant to discoloration, but can also be used as an outer layer and optionally an inner layer of a shoe, thereby providing a shoe whose upper is very breathable compared to traditional shoe fabrics.

[0298] The upper (UP) may be formed entirely or partially from a single layer of the leather fabric of the present invention, or it may be multi-layered, comprising a layer of the leather fabric of the present invention and further optionally comprising a lining (SL).

[0299] The single-layer leather fabric of the present invention may, for example, form the vamp, quarter or tongue of the upper (UP).

[0300] The leather fabric of the present invention may be oriented toward the outside and / or the inside of the shoe.

[0301] If multi-layered, the multi-layer structure of the upper portion may include one or more layers of the leather fabric of the present invention and at least one reinforcing layer, for example composed of another material.

[0302] Multiple layers of fabric can be laminated together.

[0303] If laminated, the multiple layers of fabric of the upper portion (UP) may include a reinforcing fabric bonded to the leather fabric of the present invention.

[0304] The reinforcing fabric provides strength to the laminate, allowing the leather layer to be thinned while the overall laminate is flexible. The reinforcing fabric is therefore relatively thin and has high tensile strength, high tear strength and low elongation at break.

[0305] Suitably, the basis weight of the reinforcing fabric is less than 150 g / m 2 , usually less than 100g / m 2 , more typically below 75g / m 2 , most usually less than 60g / m 2 .

[0306] A suitable method for measuring the basis weight of reinforcement fabrics is ASTM D3776.

[0307] Suitably, the ultimate tensile strength (breaking strength) of the reinforcing fabric is above 5 kN / m, more typically above 10 kN / m, or even above 15 kN / m.

[0308] The ultimate tensile strength, expressed in kN / m, is the force required to break a 1 m wide sample of material. A suitable test for measuring the ultimate tensile strength of reinforcing fabrics is ISO 3376:2011. An alternative test particularly suitable for testing the tensile properties of polymer matrix composites is ASTM D3039.

[0309] Suitably, the reinforcement material has an elongation at break (ie the elongation of the fabric when stretched to its breaking point) of less than 5%, typically less than 4%, or even less than 3%.

[0310] A suitable test for measuring elongation at break is ISO 3376: 2011. Another alternative test that is particularly suitable for testing the elongation properties of polymer matrix composites is ASTM D3039.

[0311] Suitably, the reinforcing material has a tear strength higher than 25N, typically higher than 50N, or even higher than 75N.

[0312] A suitable method for measuring the tear strength of reinforcing materials is ISO 3377-1:2011. Another alternative test particularly suitable for testing the tear strength of polymer matrix composites is Mil-C-21189 10.2.4.

[0313] As is clear from the above properties, reinforcing fabrics have a very low basis weight (and therefore are usually very thin) but typically have very high tensile and tear strengths. Suitable materials that meet these requirements include fabrics having at least one layer comprising high strength fibers.

[0314] "High strength fiber" refers to a fiber having an ultimate tensile strength greater than 1500 MPa. A suitable test for measuring the ultimate tensile strength of a fiber is ASTM D3822.

[0315] Typical high-strength fibers include carbon fibers or high-tensile-strength polymer fibers. Suitable high-tensile-strength polymer fibers include polyethylene (particularly UHMWPE), polyaramid, polybenzoxazole, and polyarylate.

[0316] Suitable high strength fibers that can be used in the reinforcement fabric thus include carbon fibers; UHMWPE fibers such as those available from DSM or available from Honeywell Polyaramid fibers, such as those available from DuPont Polybenzoxazole fibers, such as those available from Toyobo and polyaromatic esters, such as those available from Kuararay, Inc.

[0317] In this regard, UHMWPE is "ultra-high molecular weight polyethylene," sometimes also referred to as high modulus polyethylene (HMPE) or high performance polyethylene (HPPE). UHMWPE is typically characterized by having an intrinsic viscosity of at least 4 dl / g, ideally at least 8 dl / g. Typically, the intrinsic viscosity is less than 50 dl / g, often less than 40 dl / g.

[0318] A suitable method for measuring intrinsic viscosity is ASTM D1601-2004 (decalin at 135°C, dissolution time 16 hours, DBPC as antioxidant, amount 2 g / l solution, by extrapolating the viscosity measured at different concentrations to zero concentration).

[0319] At least one layer of the reinforcing fabric comprising high-strength fibers may be woven or non-woven. However, in order to benefit from the strength properties of the fibers, typically the at least one layer will comprise high-strength fibers having a specific orientation, such as a woven (including single-weave), unidirectional or multidirectional fabric.

[0320] Typically, the reinforcing fabric will comprise at least one layer of parallel high strength fibers. The parallel high strength fibers may optionally be embedded in a resin matrix.

[0321] The multi-layer fabric including the leather fabric of the present invention may, for example, form a toe portion, a waist portion, or a tongue of an upper (UP).

[0322] The leather fabric of the present invention may be oriented toward the outside and / or the inside of the shoe.

[0323] Figures 6A-6D Different ways of applying color within the scope of the present invention are disclosed, and while some embodiments are shown, other embodiments may also be applicable.

[0324] Figure 6A An exemplary embodiment of the present invention is shown.

[0325] Referring to the figure, collagen fibers (CF) are first subjected to acidification (ACI), as described above. Next, the collagen fibers (CF) undergo a tanning process / retanning (TP), followed by alkalization (BAS). The collagen fibers then undergo a dyeing step (D) to obtain dyed collagen fibers, which are then spun into yarn (Y) via a spinning process (YSP). The dyed collagen-based yarn can then be processed into fabric (F).

[0326] This embodiment illustrates that collagen fibers can be subjected to a tanning process (TP), wherein the collagen fibers are first subjected to acidification and application of a tanning agent. This can be a retanning, or even a first tanning is also possible. After application of the tanning agent, the collagen fibers are alkalized and then dyed, the details of which are described elsewhere in the specification. The dyed fibers are then spun and possibly made into fabrics. Other processes can be applied in this process, for example, fatliquoring and optional further tanning are possible.

[0327] Different variations of this process are described below. However, it is important to note that the main differences in the process, not necessarily in the resulting end product, refer to the same process steps organized in a different logical sequence. Only the differences will be highlighted below.

[0328] Figure 6B An exemplary embodiment of the collagen fibers according to the invention undergoing a tanning process (TP) is shown, wherein the collagen fibers (CF) are first subjected to spinning (YSP). After spinning (YSP), the collagen fibers (CF) undergo acidification (ACI), application of a tanning agent (TP), alkalization (BAS) and dyeing (D). The tanning process (TP) can be a retanning or even a first tanning. The dyed collagen fiber-based yarn can optionally be manufactured into a fabric (F), and further processes, such as fatliquoring and optional further tanning, are possible.

[0329] Figure 6C An exemplary embodiment of the present invention's collagen fibers (CF) undergoing a tanning process (TP) is shown, wherein the collagen fibers (CF) are first spun (YSP) and manufactured into a fabric (F). The manufacture of the yarn into fabric is described in detail elsewhere in the specification. The fabric is then subjected to acidification (ACI), application of a tanning agent (TP), and alkalization (BAS), followed by dyeing (D).

[0330] Figure 6DThe process steps corresponding to Figure 2A Another exemplary embodiment of the process steps already described in B, but in this case the collagen fibers (CF) are first spun into a collagen-based yarn (Y) by a spinning process (YSP), the resulting yarn (Y) being subjected to a tanning agent (TP) and associated acidification (ACI) and alkalization (BAS) to promote the penetration of the tanning agent into the yarn (Y). The yarn (Y) is then manufactured into a fabric (F), which is subsequently dyed in a dyeing step (D).

[0331] The latter embodiment is generally considered to be a very advantageous embodiment of the present invention, because the semi-finished yarn can be manufactured in a durable and distributable state, for example in a relatively neutral standard color or a color that is simply a natural result of the tanning agent used. The standard color-dyed yarn (now considered a leather yarn) can be dyed later, for example after the fabric (F) is made. The basic point is that in traditional leather that is not produced from leather yarn, this process has never been attractive, because dyeing is a very complex and demanding step that usually has to be carried out in a tannery or at least in certain types of manufacturers, such as shoe manufacturers, who require leather of a certain color. This means at least that a large amount of dye is applied to the raw hide or a part of the raw hide, thereby limiting the use of the raw hide / leather applied.

[0332] The present invention, in some embodiments, facilitates that substantially all yarns can be produced in a certain color or in one or a few color appearances, which can then be dyed to the desired final color. In other words, the applied dye is applied and fixed for its intended purpose at a very late stage in the process, thereby reducing the risk of wasting or creating leather materials for storage that may not be important when they are to be used.

[0333] Figure 7 is an example of an embodiment of the present invention.

[0334] With reference to the figure, a collagen-based yarn (Y) is subjected to a tanning process T. The tanning process may, for example, include or be associated with a dye standardization step, such as pre-dyeing (PD).

[0335] After tanning and an optional color standardization process, the yarn is wound onto a reel (SP) or similar suitable structure to hold the yarn.

[0336] Thereafter, the yarn reel SP may be picked up for subsequent dyeing into a desired final color, eg red (RE), blue (BL) or yellow (YE).

[0337] The step of pre-dyeing or color standardization of the yarn is an optional step, however, it is a very advantageous step in which the color of the yarn reaches the same neutral base color, thereby optimizing the dyeing (D) process and improving the predictability associated with the final dyeing process. This is a new and very interesting aspect of the present invention, because collagen-based products such as leather require complex dyeing, and the results are often obtained through trial and error, and this embodiment of the present invention makes it possible to perform more predictable dyeing, regardless of the final color of the yarn.

[0338] Yarn color standardization, in this context, is generally understood as the process of achieving yarns with the same neutral base color. This can involve bleaching, pre-dyeing, bleaching, or other related processes to achieve a similar neutral base color. In other words, pre-dyeing may not necessarily involve the addition of dyes, as bleaching or other chemical treatments may be sufficient to provide the desired neutral base color.

[0339] According to a preferred embodiment of the present invention, the so-called neutral base color may include a color that can be dyed into different related colors, such as black, white, yellow, red and blue, by substantially the same dyeing process using only the color of the dye.

[0340] Collagen-based yarns can come from a variety of sources, such as raw hides, such as cow hides, other animal hides, leather waste or other collagen sources, and the base color may be different. Different treatments or processes of the raw hides, waste, etc. may change the color of the product and thus also change the initial color of the collagen-based yarn. In addition, the raw hide may have been treated with a tanning agent such as chrome tanning, which may provide a blue or gray yarn. Hides treated with vegetable tanning agents may have a whiter or more yellow appearance. Applying the same amount of dye to yarns of different base colors may result in irregular and unsightly results, and may be difficult to handle in the final product without additional dyeing, depending on the color that the final yarn is intended to have.

[0341] It should therefore be noted that, although very advantageous, providing a neutral substrate is very attractive because it is necessary to avoid producing the final leather / collagen-based yarn with an undesirable color. This type of problem is generally associated with traditional leather manufacturing. On the other hand, even if the waste raw materials have been dyed or at least partially in the blue color caused by, for example, chrome tanning that has been carried out, it is also possible to reuse these waste products to reconstruct collagen-based fibers, staple fibers, collagen-based yarns. In other words, the collagen material used as the basis for making staple fibers / filaments / yarns in the present invention may have very diverse inherent properties due to different sources. The term "spool" in this context refers to a physical object that is suitable for winding up yarn for storage or further processing. It can also be a cone, a reel or any other suitable object for winding up yarn. The process of winding up / winding the yarn can also be simply performed to provide a yarn ball that does not have a physical object around which the yarn is wound.

[0342] It is worth noting that the tanning process carried out before the yarn is provided on the reels facilitates subsequent dyeing to the desired final color / use color, and also allows the application of general yarn materials with leather properties that can be applied and benefited in the fabrics subsequently produced.

[0343] Another advantage is that the yarn, when wound, already has the desired tenacity, strength, or elastic properties required for the yarn being produced. In other words, the yarn being manufactured into fabric may benefit from the fact that the tanning has already taken place, so the yarn is less prone to breaking, or at least the yarn is easier to handle without the risk of breaking or weakening the yarn during the fabric manufacturing process.

[0344] Reference numerals

[0345] CF. Collagen fibers

[0346] Y. Yarn

[0347] TY. Tanned yarn

[0348] CO.Rope

[0349] TE.Tanning equipment

[0350] YSP.Spinning Technology

[0351] S.Shoes

[0352] UP. Upper

[0353] SO.Sole

[0354] SL.Shoe lining

[0355] F. Fabric

[0356] TP. Tanning process

[0357] TF. Tanned fabric

[0358] FMP. Fabric Manufacturing Process.

Claims

1. A method for producing collagen yarn (Y), comprising the following steps: -Provide collagen fibers (CF) - spinning the collagen fibers into yarn (Y), and - Tanning the yarn (Y) after spinning collagen fibers into the yarn, wherein the collagen fibers are derived from wood shavings, leather pulp, unfinished leather shavings, finished leather shavings, and / or tanned hides.

2. The method according to claim 1, wherein the tanning of the yarn is a retanning.

3. The method according to any one of the preceding claims, wherein the collagen fiber is a reconstructed short fiber produced on the basis of a plurality of mechanically divided or ground protein fibrils.

4. A method according to any one of the preceding claims, wherein tanning the yarn comprises mechanically treating the yarn.

5. A method according to any one of the preceding claims, wherein tanning the yarn is a continuous process by drawing the yarn through the tanning compound with the aid of rollers.

6. The method according to any one of the preceding claims, wherein the collagen fiber (CF) is a reconstructed fiber based on native collagen.

7. The method according to any one of the preceding claims, wherein the collagen yarn further comprises non-collagenous proteins.

8. The method according to any one of the preceding claims, wherein the method further comprises the step of post-processing the yarn (Y) to form a fabric (F).

9. The method according to any of the preceding claims, wherein the method further comprises a post-processing step comprising dyeing the collagen yarn.

10. A method according to any one of the preceding claims, wherein the tanned yarn is fatliquored and wound into a plurality of yarn spools.

11. Use of a yarn produced according to the method of any one of the preceding claims, wherein the yarn is incorporated into an article.

12. Use of the fabric according to claim 8 comprising the artificial yarn according to any one of claims 1 to 10, wherein the fabric is for an article.

13. Leather yarn produced according to any one of claims 1 to 10, which yarn is tanned.

14. Leather shoes, including soles (SO) and uppers (UP), wherein the upper (UP) is at least partially composed of leather fabric, The leather fabric is produced based on the leather yarn produced according to any one of claims 1-10.

15. The leather shoe according to claim 14, wherein the leather shoe comprises the leather fabric according to claim 8, and wherein the leather fabric is applied to a shoe upper or the leather fabric is used as a shoe lining (SL) or as a part of a shoe lining.

16. Fatliquored leather yarn produced according to any one of claims 1 to 10.

17. Leather fabric produced from a leather yarn according to claim 13, wherein the leather yarn is provided based on a suspension of protein fibrils.

Images