Coating composition for porous substrates

Abstract

The present invention relates to a bio-based or at least partially bio-based coating composition for porous substrates such as textiles. The composition comprises polyester and cellulose ester and is manufactured using a melt-kneading method. Furthermore, the present invention relates to a method for coating or laminating a porous substrate using the coating composition of the present invention.

Description

[Technical Field]

[0001] This invention relates to compositions comprising a mixture of polyester and cellulose ester, and to coatings comprising such compositions. More particularly, this invention relates to such coatings on porous substrates, and to methods for coating or laminating such coating compositions onto porous substrates. This invention also relates to the use of such coated or laminated porous substrates. [Background technology]

[0002] In many applications, protective and defensive properties are required, and if the substrate itself does not possess such properties, these are usually imparted by different types of coating layers. In particular, various porous substrates generally have low defensive properties, so protective coatings are necessary to improve product lifespan and overall product characteristics. The improved properties obtained by coatings enable applications where, for example, the substrate needs to be protected from water, light, and oxygen. For example, textile coatings are commonly used to impart desirable properties to textiles, such as stain resistance, wind resistance, fire resistance, oil resistance, and water resistance.

[0003] Porous substrates requiring protective properties generally have a polymer coating layer to improve their physical properties. This coating layer is typically made from fossil-derived plastics. Porous substrates made from fibrous materials such as natural fibers are known to be coated with common coating materials such as polyvinyl chloride (PVC), acrylic resin, and polyurethane. Fluorofunctional plastic films and treatment agents are also used, including, for example, fluorosiloxanes or perfluoroalkyl and polyfluoroalkyl compounds (PFAS). While these materials possess many desirable properties, they all have the drawback of being toxic and / or fossil-derived. PVC contains various hazardous chemicals and additives that are harmful to both human health and the environment. In this respect, acrylic is a better alternative, but acrylic is also fossil-derived and, furthermore, does not offer properties as superior to PVC, for example, in terms of tactile feel and stain resistance. Additionally, the manufacture of polyurethane requires the use of hazardous chemicals.

[0004] The use of biopolymers is an attractive alternative to these plastic coatings, and bio-based or at least partially bio-based laminate films have been studied for coating various porous substrates. However, there is still room for improvement in terms of the bio-based content, protective properties, and lifecycle of coated products. [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention aims to solve at least some of the problems of the prior art. In particular, the present invention provides an environmentally friendly alternative to the solutions of the prior art.

[0006] The object of the present invention is to provide a new type of coating composition and coating for porous substrates, particularly fiber-based porous substrates, such as textiles. [Means for solving the problem]

[0007] Accordingly, according to a first aspect, the present invention relates to a coating composition comprising a completely or partially bio-based polyester and cellulose ester, particularly a mixture of polyester and cellulose ester.

[0008] According to a second aspect, the present invention relates to a coating formed from the above-mentioned coating composition.

[0009] According to a third aspect, the present invention relates to the above-mentioned coating on a porous substrate. The coating composition can form a coating, i.e., a coating layer, on a porous substrate by coating or laminating it.

[0010] According to a fourth aspect, the present invention relates to a method for coating or laminating a porous substrate using the above-mentioned coating composition.

[0011] Accordingly, the present invention is based on a coating composition comprising polyester and cellulose ester, particularly a mixture of polyester and cellulose ester, and is particularly suitable for porous substrates, preferably a bio-based coating composition. The composition of the present invention is obtained by melt-kneading polyester and cellulose ester together, and the composition thus obtained is applied to a substrate by coating or lamination to form a protective coating layer, and in particular improves the protective properties of the substrate.

[0012] By using a melt compounding process, effective mixing and uniform heat distribution are obtained, enabling efficient mixing of polyester and cellulose ester, and forming a biopolymer composition of polyester and cellulose ester.

[0013] The coating composition of the present invention, by combining biodegradable polyester with cellulose ester, can form a thin, flexible coating layer that preferably has protective properties against water and dirt.

[0014] The coating layer formed by the coating composition of the present invention can be a single-layer or multi-layer coating. In one embodiment, the composition of the present invention provides a single-layer coating with excellent water repellency. Because a single-layer coating is thinner than a multi-layer coating, it requires fewer raw materials to form a uniform coating, making it more economical and environmentally friendly. Furthermore, the thinness of the coating layer improves the flexibility of the coating.

[0015] In particular, the present invention is characterized by the matters described in the independent claims. Several specific embodiments are provided in the dependent claims. [Effects of the Invention]

[0016] Several advantages can be obtained by using the present invention. In particular, the method of the present invention preferably provides a bio-based and recyclable coating composition for porous substrates. The coating composition of the present invention is generally homophase. Furthermore, the composition is preferably manufactured entirely or at least partially from renewable and / or biodegradable raw materials and is free from harmful chemicals. Recycled raw materials can also be used in the composition.

[0017] Accordingly, the present invention provides a porous material having a coating composition that maintains excellent protective / defensive properties combined with biodegradability and / or recyclability. In particular, the coating composition improves the water resistance and stain resistance of the porous substrate. Furthermore, the combination is washable at temperatures up to at least 40°C. As a result, the coating or laminated porous substrate of the present invention has an improved service life. The present invention is particularly suitable for improving the service life of porous substrates made of natural fibers. Accordingly, the coating composition is particularly suitable for fiber-based porous materials such as various textiles, including tablecloths, clothing, and fabric upholstery.

[0018] The coating composition of the present invention is suitable for use as a relatively thin coating layer on hard and soft substrates. By applying the composition of the present invention to a bio-based, biodegradable, recyclable and / or compostable porous substrate, the present invention ensures the recyclability of the entire material in accordance with the requirements of a circular economy, particularly the chemical recycling method.

[0019] Therefore, the present invention provides a coating composition and its coating, which have durability, are washable, have defensive and flexibility, particularly for porous substrates. The coating composition may be partially or completely transparent.

[0020] Furthermore, melt extrusion does not require dissolving polyester and cellulose ester in a solvent, and enables processing of different viscosities. Therefore, the method of the present invention can form a composition without using a solvent by using melt kneading by melt extrusion, which is environmentally friendly. Overall, melt extrusion not only provides high flexibility, enables efficient mixing and a continuous process with a short residence time, but also enables economical production of a small amount of special materials.

[0021] Next, embodiments will be described in more detail.

Embodiments for Carrying Out the Invention

[0022] "Room temperature" refers to a temperature of about 15 to 30 °C, particularly 15 to 25 °C, for example about 23 °C.

[0023] In this specification, the term "about" refers to a value that is ±5% of the stated value. In this specification, the term "about" refers to the actual given value and an approximate value of the given value that can be reasonably inferred by those skilled in the art, including an approximate value resulting from experimental conditions and / or measurement conditions related to the given value.

[0024] In this specification, the term "biodegradable" is used in relation to materials such as polyesters, biopolymer compositions, or coating compositions, and especially when applied to their organic parts, it has the conventional meaning of a material that can be broken down (decomposed) by the action of microorganisms, bacteria, fungi, or both. Decomposition can proceed through aerobic and anaerobic processes, and typically ends with the production of carbon dioxide from organic matter. Biodegradation generally occurs in the presence of water. The biodegradation of organic matter is affected by ambient temperature and pH, and may take several days, months, or even years to complete.

[0025] The present invention relates to a coating on a porous substrate, the coating being formed from a composition comprising a mixture of polyester, particularly biopolyester, and cellulose ester.

[0026] In a preferred embodiment, the polyester is bio-based by weight of at least 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95 percent, i.e., the polyester is 35 to 100% bio-based. Preferably, the polyester is 100% bio-based. This amount is calculated from the total weight of the polyester.

[0027] In this context, the term "coating composition" refers to a composition suitable for use as a coating composition. Such a coating composition can be applied to a substrate by any known method, in particular by conventional coating methods that form the coating composition as a layer only on the surface of the substrate, i.e., by providing it on the substrate in a molten state and then cooling it, or as a laminate.

[0028] The terms "coating" and "coating layer" are used synonymously to refer to a layer formed from a coating composition on a porous substrate. The coating of the present invention can have any thickness, but is preferably as thin as possible to provide the desired properties. In preferred embodiments, the thickness of the coating is less than 100 μm, more preferably less than 80 μm, for example less than 50 μm. The thickness can be, for example, 20 to 100 μm.

[0029] In the context of this invention, the terms "bio" and "bio-based" refer to polymers chemically synthesized from biological materials or produced from natural resources completely biosynthesized by living organisms.

[0030] In one embodiment, the coating composition is bio-based in a proportion of at least 40, 45, 50, 55, 60, 65, 70, 75, or 80% by weight. In a preferred embodiment, the coating composition is bio-based in a proportion of 40 to 80%. This amount is calculated from the total weight of the coating composition.

[0031] The substrate to be coated or laminated may be any porous material. In this invention, the term "porous" refers to a material that is permeable to gases, liquids, oils or greases, or combinations thereof. Typically, porous materials are provided in the form of sheets, boards, plates, or webs.

[0032] In one embodiment, the porous material includes fibrous material, typically in the form of a sheet, board, plate, or web. Examples of porous materials used in embodiments of this technology include textiles such as tablecloths, fabrics, protective textiles, and interior textiles, as well as consumer devices such as watch straps or heart rate monitors. The textile as the porous substrate of the present invention can be made from natural fibers or artificial fibers, and preferably from natural fibers.

[0033] In a preferred embodiment, the base material is a woven or nonwoven fabric or sheet, and in particular is a woven or nonwoven fabric or sheet made from natural fibers such as plant fibers (e.g., cellulose, cotton, hemp, flax, ramie, jute, coconut) or animal fibers (e.g., wool, silk).

[0034] Therefore, the substrate is preferably bio-based. A "bio-based substrate" generally refers to a material obtained from bio-derived materials such as biomass (e.g., carbohydrate materials, lignocellulose materials, and especially carbohydrate materials and lignocellulose materials in the form of fibrous materials), protein materials, lipid-containing materials, and combinations thereof. Typically, such materials are biodegradable, recyclable, repulpable, and / or compostable.

[0035] In one embodiment, the porous material includes natural fibers such as lignocellulose fibers, cellulose fibers, or combinations thereof.

[0036] In one embodiment, the substrate contains natural fibers such as cellulose fibers, lignocellulose fibers, or combinations thereof, in an amount of 50 to 100% by weight, particularly 75 to 100% by weight, calculated from the total weight of the fibrous material in the substrate, preferably from the total weight of the substrate.

[0037] In one embodiment, the base material includes a combination of natural fibers and artificial fibers. Examples of artificial fibers include synthetic fibers such as polyester and acrylic, as well as regenerated fibers such as those produced by the viscose method or lyocell method, or other synthetic fibers including materials derived from polysaccharides. In one embodiment, the base material contains 10 to 75% by weight of natural fibers and 90 to 25% by weight of artificial fibers, calculated from the total weight of the base material.

[0038] In one embodiment, the porous substrate includes a plastic, i.e., a thermoplastic material.

[0039] The polyester in the coating composition of the present invention can be any polyester, and in particular can be a biodegradable polyester. It may be a commercially available grade polyester or one produced using a well-known polymerization route. In a preferred embodiment, the polyester is a thermoplastic polyester. The polyester particularly imparts mechanical strength to the composition.

[0040] In the present invention, one or more types of polyester can be used. For example, two different types of polyester can be used in the coating composition. In one embodiment, the one or more types of polyester are selected from the group consisting of polylactic acid, polylactide, polybutylene succinate, polybutylene succinate adipate, polyhydroxyalkanoate, polyhydroxybutyrate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(butylene adipate-co-terephthalate), polyethylene furanoate, polycaprolactone, and combinations thereof. These compositions can provide advantageous properties in terms of biodegradability, flexibility, and barrier properties of the composition.

[0041] Furthermore, or alternatively, the composition comprising a mixture of polyester and a cellulose ester comprises a mixture of cellulose ester and two or more polyesters, where each of the two or more polyesters is independently selected from the group consisting of polylactic acid, polylactide, polybutylene succinate, polybutylene succinate adipate, polyhydroxyalkanoate, polyhydroxybutyrate, poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(butylene adipate-co-terephthalate), polyethylene furanoate, and polycaprolactone, and combinations thereof. Having two or more polyesters may be advantageous in terms of the biodegradability, flexibility, and barrier properties of the composition.

[0042] According to a preferred embodiment, the polyester is polybutylene succinate (PBS) and / or polybutylene succinate adipate (PBSA), particularly PBSA. Preferably, at least 80% by weight, more preferably at least 90% by weight, of the polyester is polybutylene succinate and / or polybutylene succinate adipate.

[0043] In one embodiment, the composition contains at least 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% by weight of polyester, calculated from the total weight of the composition.

[0044] In one embodiment, the composition contains up to 95, 90, 85, 80, 75, 70, 65, 60, 55, or 50% by weight of polyester, calculated from the total weight of the composition.

[0045] In a preferred embodiment, the composition contains 40 to 95% by weight, preferably 45 to 85% by weight, and more preferably 50 to 70% by weight of polyester, calculated from the total weight of the composition.

[0046] In another preferred embodiment, the composition contains 30 to 95% by weight, preferably 30 to 65% by weight, and more preferably 30 to 50% by weight of polyester, calculated from the total weight of the composition.

[0047] Furthermore, or alternatively, the composition may contain 25 to 95% by weight of polyester, preferably 25 to 60% by weight, 30 to 65% by weight, or 25 to 50% by weight of polyester, more preferably 30 to 60% by weight or 30 to 50% by weight of polyester, based on the total weight of the composition.

[0048] The melting points of the one or more types of polyester used in the present invention are typically in the range of 40 to 300°C, preferably in the range of 80 to 250°C, and most preferably in the range of 120 to 200°C.

[0049] Preferably, the one or more types of polyester have a melt flow index in the range of 1 g / 10 min to 50 g / 10 min, preferably in the range of 5 g / 10 min to 25 g / 10 min, for example, 10 g / 10 min. The melt flow index is measured by a measurement method that includes filling a capillary tube maintained at a temperature of 190°C with plastic polyester granules. A piston and a 2.16 kg weight are placed on top of the granules. Under the action of the weight, the molten polyester is pushed out of the capillary tube over a certain period of time to obtain the melt flow index.

[0050] The cellulose ester in the coating composition of the present invention can be any cellulose ester. According to a preferred embodiment, the cellulose ester is selected from the group consisting of cellulose acetate (CA), cellulose acetate butyrate (CAB), cellulose acetate propionate (CAP), or mixtures thereof. In a preferred embodiment, the cellulose ester is CAP or CAB, or a combination thereof. The cellulose ester can be used in particular to improve the transparency of the composition and mechanical properties such as flexibility and durability.

[0051] In one embodiment, the composition contains at least 10, 15, 20, 25, 30, 35, 40, or 45% by weight of cellulose ester, calculated from the total weight of the composition.

[0052] In one embodiment, the composition contains up to 45, 40, 35, 30, 25, 20, 15, or 10% by weight of cellulose ester, calculated from the total weight of the composition.

[0053] In a preferred embodiment, the composition contains 10 to 60% by weight, preferably 20 to 50% by weight, more preferably 25 to 45% by weight, for example 30 to 40% by weight of cellulose ester, calculated from the total weight of the composition.

[0054] According to one embodiment, a portion of the cellulose ester in the composition can be replaced with polyethylene (PE), preferably bio-based PE, or polyethylene terephthalate (PET), preferably bio-based PET, or polypropylene (PP), preferably bio-based PP, or thermoplastic polyurethane (TPU), preferably bio-based TPU, or polyamide (PA), preferably bio-based PA, or a mixture thereof. Preferably, the amount of PE, PET, PP, TPU, PA, or a mixture thereof in the coating composition is a maximum of 50% by weight, or a maximum of 25% by weight, for example, 1 to 20% by weight, more preferably 5 to 10% by weight, of the total weight of the coating composition. PE, PET, PP, TPU, and / or PA can be used to further improve the elastic and mechanical properties of the composition. PE, PET, PP, TPU, and / or PA can be used to further improve the adhesion to the substrate, processability, washability and abrasion resistance, optical properties and tactile properties, and / or thermal stability of the composition, and combinations thereof.

[0055] Furthermore, or alternatively, one or more polyesters in the composition may be replaced with polyethylene (PE), preferably bio-based PE, or polyethylene terephthalate (PET), preferably bio-based PET, or polypropylene (PP), preferably bio-based PP, or thermoplastic polyurethane (TPU), preferably bio-based TPU, or polyamide (PA), preferably bio-based PA, or a mixture thereof. Preferably, the amount of PE, PET, PP, TPU, PA, or a mixture thereof in the coating composition is a maximum of 50% by weight or a maximum of 25% by weight, for example, 1 to 20% by weight, more preferably 5 to 10% by weight, of the total weight of the coating composition. PE, PET, PP, TPU, and / or PA can be used to further improve the adhesion of the composition to the substrate, elasticity, mechanical properties, processability, washability and abrasion resistance, optical properties and tactile properties, and / or thermal stability, and / or combinations thereof.

[0056] Furthermore, or alternatively, the composition comprises or contains a mixture of one or more polyesters, a cellulose ester, and at least one selected from polyethylene (PE), preferably bio-based PE, polyethylene terephthalate (PET), preferably bio-based PET, polypropylene (PP), preferably bio-based PP, thermoplastic polyurethane (TPU), preferably bio-based TPU, and polyamide (PA), preferably bio-based PA, or a mixture of any combination thereof. Preferably, the amount of PE, PET, PP, TPU, and / or PA, or a mixture thereof in the coating composition is up to 50% by weight, or up to 25% by weight, for example, 1 to 20% by weight, more preferably 5 to 10% by weight, of the total weight of the coating composition. PE, PET, PP, TPU, and / or PA can be used to further improve the adhesion of the composition to the substrate, elasticity, mechanical properties, processability, washability and abrasion resistance, optical properties and tactile properties, and / or thermal stability, and / or combinations thereof.

[0057] Furthermore, or alternatively, the composition comprises a mixture of one or more polyesters, a cellulose ester, and a thermoplastic polyurethane (TPU), preferably a bio-based TPU, wherein the amount of TPU in the coating composition is preferably up to 50% by weight, or up to 25% by weight, or 5-50% by weight, 25-50% by weight, or 1-20% by weight, more preferably 5-10% by weight, of the total weight of the coating composition. The TPU can be used to further improve the adhesion of the composition to the substrate, elasticity, mechanical properties, processability, washability and abrasion resistance, optical properties and tactile properties, and / or thermal stability, and / or combinations thereof.

[0058] Furthermore, or alternatively, the composition may contain 5-50% by weight, 25-50% by weight, or 1-20% by weight of TPU based on the total weight of the coating composition.

[0059] According to a preferred embodiment, the coating composition of the present invention has a single-phase structure. In the present invention, the term "single-phase" means a material having a uniform composition throughout that cannot be mechanically separated into different materials.

[0060] In one embodiment, the weight ratio of the polyester to the cellulose ester in the composition is 1:99 to 99:1, for example, 10:99, 99:10, 20:80, 80:20, 30:70, 70:30, or 50:50.

[0061] According to a preferred embodiment, the weight ratio of the polyester to the cellulose ester in the composition is in the range of 50:50 to 70:30.

[0062] According to one embodiment, the composition of the present invention further includes additives, particularly plasticizers such as glycerol, polyethylene glycol, triethyl citrate, tributyl citrate, acetyl tributyl citrate, etc., vegetable oils such as soybean oil, linseed oil, tall oil, castor oil, canola oil, etc., or modified versions thereof, such as maleic, acrylic, vinyl, succinic, epoxidized, or hydroxylated vegetable oils, or other vegetable ester oils or resins such as epoxidized soybean oil, maleicized soybean oil, or epoxidized linseed oil, etc., or any combination thereof. The plasticizer particularly improves the flexibility and adhesion of the coating. In particular, maleicized soybean oil can improve the compatibility between one polyester (or two or more polyesters) and a cellulose ester, and / or improve the mechanical properties of the composition. That is, maleicized soybean oil can be used as a compatibilizer and plasticizer in the composition.

[0063] According to one embodiment, the plasticizer is a vegetable oil, particularly a functionalized vegetable oil such as male-oxidized soybean oil.

[0064] In a preferred embodiment, the plasticizer is malein-oxidized soybean oil, where the coating composition further comprises malein-oxidized soybean oil. Malein-oxidized soybean oil is a modified soybean oil in which some of the unsaturated bonds are converted to cyclic dicarboxylic acids.

[0065] Accordingly, according to a preferred embodiment, the coating composition further contains a plasticizer, preferably malein-oxidized soybean oil, in an amount of 1 to 20% by weight, more preferably 2 to 10% by weight, for example, 3 to 7% by weight, calculated from the total weight of the composition.

[0066] According to one embodiment, the composition of the present invention further comprises additives, particularly lubricants such as stearic acid, stearates such as calcium stearate, magnesium stearate, etc., and / or natural waxes such as carnauba wax, soybean wax, beeswax, sugarcane wax, cassava wax, candelilla wax, rice bran wax, berry wax, myrica fruit wax, or laurel wax, etc., and / or synthetic waxes such as polyamide wax, stearamides such as ethylene-bis-stearamide (EBS) wax (bio-based or synthetic), ethylene-bis-oleamide wax, polyethylene wax, Fischer-Tropsch wax, fatty acids and modified fatty acids, hybrid waxes, etc., or any mixture thereof.

[0067] Accordingly, according to a preferred embodiment, the composition further comprises a lubricant, such as stearamide or stearate, preferably calcium stearate, zinc stearate, or ethylene-bis-stearamid, or a mixture thereof. In one embodiment, the amount of lubricant, preferably stearate or stearamid, is calculated from the total weight of the composition to be 0.05 to 10% by weight, preferably 0.1 to 8% by weight, for example, about 0.1 to 3% by weight or 0.1 to 1% by weight. The lubricant particularly affects the processability of the composition. Stearates and stearamids, such as EBS, are particularly suitable for improving processability by preventing the coating composition from unnecessarily adhering to processing equipment without coloring the coating composition.

[0068] Furthermore, or alternatively, the composition further comprises a plasticizer and a lubricant, wherein the plasticizer is maleic soybean oil, and the lubricant is, for example, stearamide or stearate, preferably calcium stearate, zinc stearate, or ethylene-bis-stearamide, or a mixture thereof, and a portion of the cellulose ester in the composition is replaced with thermoplastic polyurethane (TPU).

[0069] Furthermore, or alternatively, the composition further comprises or contains maleated soybean oil and a lubricant, wherein a portion of the cellulose ester in the composition is replaced with thermoplastic polyurethane (TPU).

[0070] Furthermore, or alternatively, the composition further comprises or contains maleic soybean oil, a lubricant, and thermoplastic polyurethane (TPU).

[0071] In one embodiment, the composition further comprises a polysiloxane. In a preferred embodiment, the polysiloxane is provided in liquid form. The term “liquid” in the present invention also includes a solution. Thus, according to the present invention, a material is liquid if it is liquid by itself or dissolved or at least dispersed in a medium, preferably a solvent. Polysiloxanes are beneficial because they can impart hydrophobicity to the composition, improve the water-repellent and water-resistant properties of the composition, and improve the stain-resistant, chemical-resistant, and abrasion-resistant properties of the composition.

[0072] In one embodiment, the composition contains polysiloxane in an amount of 0.05 to 10% by weight, preferably 0.1 to 3% by weight, for example, about 2% by weight, calculated from the total weight of the composition.

[0073] In one embodiment, the composition does not contain polysiloxane.

[0074] In one embodiment, the polysiloxane mixture is formed by mixing one or more different silane monomers. The silane is preferably hydrolyzed with an aqueous solution of an acid, where the acid is preferably an organic acid. The acid content in the aqueous solution is typically in the range of 0.5 to 5 mol%, for example, 1 mol%.

[0075] In one embodiment, the polysiloxane mixture is made from silane monomers having at least one functional group. Preferably, the monomer is selected from the group consisting of methyltriethoxysilane (MTEOS), dimethyldiethoxysilane (DMDEOS), 3-glycidoxypropyl-trimethoxysilane (GPTMS), bis(triethoxysilyl)ethane (BTESE), methyltrimethoxysilane (MTMS), phenyltrimethoxysilane (PTMS), and (3-aminopropyl)triethoxysilane (APTES), ethoxytrimethylsilane (ETMS), and combinations thereof.

[0076] According to one embodiment, the polysiloxane mixture is formed in the presence of an acid selected from the group of inorganic acids, including nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and boric acid, or an acid selected from the group of organic acids, including lactic acid, acetic acid, formic acid, citric acid, oxalic acid, uric acid, itaconic acid, fumaric acid, succinic acid, biosuccinic acid, gluconic acid, glutamic acid, malic acid, maleic acid, 2,5-franzicarboxylic acid, 3-hydroxypropionic acid, glucaric acid, aspartic acid, levulinic acid, and combinations thereof.

[0077] One or more organic acids can be used simultaneously. The acid acts as a catalyst during the hydrolysis reaction. Furthermore, since the acid also reacts with the polyester and / or the cellulose ester, the compatibility between the polysiloxane and the polymer matrix, i.e., the polyester and cellulose ester, is improved.

[0078] In a preferred embodiment, the silane mixture is pre-treated before being mixed with the polyester and cellulose ester, i.e., a polysiloxane mixture is formed.

[0079] According to one embodiment, the composition of the present invention further comprises inorganic colorants and / or fillers, particularly inorganic fillers such as ash, minerals, mineral sludge, clay, ceramics, and other inorganic materials including, for example, calcium carbonate, kaolin, talc, gypsum, chalk, mica, wollastonite, glass, silica, alumina, titania, and other inorganic oxides, crushed stone, concrete, and other materials such as stone and sand, diatomaceous earth, metal hydrates such as aluminum hydrate, calcium hydrate, geopolymers, etc.

[0080] According to one embodiment, the composition includes organic agents, particularly organic fillers and colorants, such as wood, and plant-based materials and parts and by-products thereof, such as legumes such as soybeans, bean husks, wheat husks, rice husks, seaweed, algae, natural resins and gums, carbon, carbon black, biocarbon, ward, willow and other tree bark, onion peels and other plant peels, lemon, turmeric root, cotton, hemp, flax, pulp, wood fibers and all other natural fibers, as well as their components, such as lignocellulose, lignin, suberin, polysaccharides, such as natural polysaccharides such as cellulose, starch and hemicellulose, nanocellulose, and derivatives thereof, and any combination thereof.

[0081] According to one embodiment, the composition of the present invention further comprises a chain extender and / or crosslinking agent, such as an epoxy, peroxide, epoxy, amine, or acrylic functionalized chain extender. In a preferred embodiment, the amount of the chain extender / crosslinker, particularly the amount of the epoxy functionalized chain extender or peroxide, preferably the amount of the epoxy functionalized chain extender, is less than 1.0% by weight or less than 0.5% by weight, preferably 0.01 to 0.7% by weight, 0.05 to 0.7% by weight, or 0.01 to 0.2% by weight, calculated from the total weight of the composition. Furthermore, or alternatively, the amount of the chain extender / crosslinker, particularly the amount of the epoxy functionalized chain extender, is 0.01 to 0.7% by weight, calculated from the total weight of the composition. The chain extender / crosslinker can be used to increase the viscosity of the composition. For example, in some applications, such as film applications, a higher viscosity, i.e., a composition with lower fluidity, may be preferred. Furthermore, the chain extender / crosslinker improves the durability of the composition by forming bonds between polymer chains. In a preferred embodiment, such components are added to the composition of the present invention after the silane-modified polyester has been formed in another process step. In another embodiment, such components may be added to the composition in the final stage of a reaction extrusion process in which the siloxane and polyester have already reacted primarily.

[0082] According to one embodiment, the composition of the present invention further comprises stabilizers, such as light stabilizers, ultraviolet stabilizers, antioxidants, heat stabilizers, or flame retardants, or mixtures thereof. Furthermore, or alternatively, the antioxidant is selected from tris(2,4-di-tert-butylphenyl) phosphite (e.g., Irgaphos 168), pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (e.g., Irganox 1010), and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1076). Furthermore, or alternatively, the flame retardant is selected from organic phosphates and aluminum compounds. These compositions are beneficial because they can improve the processability of the composition.

[0083] Therefore, in one embodiment, the composition includes the following auxiliary agents: - Inorganic colorants and / or fillers, especially inorganic fillers, such as ash, minerals, mineral sludge, clay, ceramics, and other inorganic materials including, for example, calcium carbonate, kaolin, talc, gypsum, chalk, mica, wollastonite, glass, silica, alumina, titania, and other inorganic oxides, crushed stone, concrete, and other materials such as stone and sand, diatomaceous earth, metal hydrates, such as aluminum hydrate, calcium hydrate, geopolymers, etc., or any combination thereof. - Additives, especially plasticizers, such as glycerol, polyethylene glycol, triethyl citrate, tributyl citrate, acetyl tributyl citrate, etc., vegetable oils, such as soybean oil, linseed oil, tall oil, castor oil, canola oil, etc., or modified versions thereof, such as maleic, acrylic, vinyl, succinic, epoxidized, or hydroxylated vegetable oils, or other vegetable ester oils or resins such as epoxidized soybean oil, maleicized soybean oil, or epoxidized linseed oil, or any combination thereof. - Organic fillers or colorants, such as wood or plant-based materials or parts or by-products thereof, such as legumes such as soybeans, bean husks, wheat husks, rice husks, seaweed, algae, natural resins and gums, carbon, carbon black, biocarbon, ward, willow and other tree bark, onion peels and other plant peels, lemon, turmeric root, cotton, hemp, flax, pulp, wood fibers and all other natural fibers, and their components, such as lignocellulose, lignin, suberin, polysaccharides, such as natural polysaccharides such as cellulose, starch and hemicellulose, nanocellulose, and their derivatives, and any combination thereof. - Chain extenders and / or crosslinking agents, such as epoxy, peroxide, amine, or acrylic functionalized chain extenders, - Lubricants, such as stearamide and stearate, such as calcium stearate, magnesium stearate, etc., and natural waxes, such as carnauba wax, soybean wax, beeswax, sugarcane wax, cassava wax, candelilla wax, rice bran wax, berry wax, myrica fruit wax, laurel wax, etc., or any mixture thereof, and - Stabilizers, such as light stabilizers, UV stabilizers, antioxidants, heat stabilizers, or flame retardants, or any mixture thereof. It may further include at least one of the following.

[0084] Furthermore, or alternatively, the lubricant may be selected from stearic acid; stearates selected from calcium stearate and magnesium stearate; natural waxes selected from carnauba wax, soybean wax, beeswax, sugarcane wax, cassava wax, candelilla wax, rice bran wax, berry wax, myrica fruit wax, and laurel wax; and synthetic waxes selected from polyamide wax, ethylene-bis-stearamide (EBS) wax (bio-based or synthetic), ethylene-bis-oleamide wax, polyethylene wax, Fischer-Tropsch wax, fatty acids and modified fatty acids, and hybrid waxes; or any mixture thereof.

[0085] According to one embodiment, the composition contains the above-mentioned auxiliary agent in a total amount of up to 10, 8, 5, 3, or 1% by weight, calculated from the total weight of the composition, for example, 0.1 to 10 or 1 to 10% by weight, preferably 0.5 to 5% by weight.

[0086] According to one embodiment, at least a portion of the components of the coating composition are recycled components. The polyester and cellulose ester components can be manufactured from fully or partially recycled polymers. In one embodiment, at least 50% by weight of the total weight of the polyester and cellulose ester is recycled. Plasticizers, which are optionally used as additives, can be manufactured using waste or auxiliary materials, fully or partially.

[0087] According to a preferred embodiment, the composition contains neither water nor any other solvent.

[0088] In one embodiment, the coating composition comprises a combination of polyester, a cellulose ester, and a plasticizer such as male-oxidized soybean oil.

[0089] Therefore, according to one embodiment, the composition is - 40-75% by weight, preferably 50-70% by weight of polyester, - 20-50% by weight, preferably 25-45% by weight of cellulose ester, - 2-10% by weight of a plasticizer, preferably maleated soybean oil It includes, preferably, consists of, The aforementioned amount is calculated from the total weight of the composition.

[0090] Furthermore, or alternatively, the composition may be: - 30-75% by weight, preferably 30-65% by weight, more preferably 30-50% by weight of polyester, - 20-50% by weight, preferably 25-45% by weight of cellulose ester, - 2-10% by weight of a plasticizer, preferably maleated soybean oil. - 0.05 to 10% by weight, preferably 0.1 to 1% by weight of a lubricant, preferably zinc stearate and / or calcium stearate, and - Optionally, 0.1 to 10% by weight, preferably 0.5 to 5% by weight, of any one or more of the additives disclosed herein. It includes, preferably, consists of, The aforementioned amount is calculated from the total weight of the composition.

[0091] According to another embodiment, the composition is - 40-75% by weight, preferably 50-70% by weight of polyester, - 20-50% by weight, preferably 25-45% by weight of cellulose ester, - 2-10% by weight of a plasticizer, preferably maleated soybean oil. - 0.05 to 10% by weight, preferably about 0.1 to 1% by weight of stearate, particularly zinc stearate and / or calcium stearate, and - Optionally, 0.1 to 10% by weight, preferably 0.5 to 5% by weight, of one or more of the above-mentioned auxiliary agents. It includes, preferably, consists of, The aforementioned amount is calculated from the total weight of the composition.

[0092] In one embodiment, the composition is - 50-70% by weight of polybutylene succinate, - 25-45% by weight of CAB or CAP, - 2-10% by weight of maleated soybean oil, and - 0.1-3% by weight of zinc stearate and / or calcium stearate Includes, The aforementioned amount is calculated from the total weight of the composition.

[0093] Furthermore, or alternatively, the composition may be: - 30-50% by weight of polyester, preferably polybutylene succinate; - 30-50% by weight of cellulose ester, preferably CAB or CAP; - 5-25% by weight of thermoplastic polyurethane; - 2-10% by weight of maleated soybean oil; - 0.2 to 1.0% by weight of a stearate lubricant, preferably zinc stearate and / or calcium stearate; - 0.2 to 1% by weight of a chain extender, preferably BASF Joncryl ADR 4468; and - 0.2 to 1% by weight of antioxidant It includes, preferably, consists of, The aforementioned amount is calculated from the total weight of the composition.

[0094] Furthermore, or alternatively, the composition may be: - 20-50% by weight of polyester, preferably polybutylene succinate; - 20-50% by weight of cellulose ester, preferably CAB or CAP; - 5-50% by weight of thermoplastic polyurethane; - 2-10% by weight of maleated soybean oil; - 0.2 to 1.0% by weight of a stearate lubricant, preferably zinc stearate and / or calcium stearate; - 0.2 to 1% by weight of a chain extender, preferably BASF Joncryl ADR 4468; and - 0.2 to 1% by weight of antioxidant It includes, preferably, consists of, The aforementioned amount is calculated from the total weight of the composition.

[0095] Furthermore, or alternatively, the composition may be: - 20-50% polyester by weight; - 20-50% by weight of cellulose ester; - 5-50% by weight of thermoplastic polyurethane; - 2-10% by weight of maleated soybean oil; - 0.2 to 1.0% by weight of additives, especially lubricants, such as stearic acid, stearate, such as calcium stearate, magnesium stearate, etc., and / or natural waxes, such as carnauba wax, soybean wax, beeswax, sugarcane wax, cassava wax, candelilla wax, rice bran wax, berry wax, myrica fruit wax, or laurel wax, etc., and / or synthetic waxes, such as polyamide wax, stearamide, such as ethylene-bis-stearamide (EBS) wax (bio-based or synthetic), ethylene-bis-oleamide wax, polyethylene wax, Fischer-Tropsch wax, fatty acids and modified fatty acids, hybrid waxes, etc., or any mixture thereof; - 0.2 to 1% by weight of a chain extender, preferably BASF Joncryl ADR 4468; and - 0.2 to 1% by weight of antioxidant It includes, preferably, consists of, The aforementioned amount is calculated from the total weight of the composition.

[0096] Furthermore, the present invention relates to a method for forming a coating composition comprising polyester and cellulose ester in a melt compounding process. The coating composition is characterized by all of the same embodiments as described above with respect to the coating composition.

[0097] Furthermore, the present invention relates to a method for forming a coating from the coating composition of the present invention.

[0098] In particular, the present invention relates to a method for coating or laminating a porous substrate with such a coating composition.

[0099] The method of the present invention includes preparing a polyester and a cellulose ester, mixing the polyester and the cellulose ester by melt extrusion in a melt compounding process to form a coating composition, and finally coating or laminating the surface of a porous substrate with the coating composition to form a coating.

[0100] According to one embodiment, the polyester and the cellulose ester can be mixed in a separate container before being supplied to the extruder, in which case the components are supplied together to the extruder.

[0101] In another embodiment, the polyester and the cellulose ester can be mixed in the extruder, that is, each component can be supplied to the extruder separately.

[0102] In a preferred embodiment, the polyester is provided in solid form, preferably as pellets. Since polyester typically absorbs some moisture from the air, and this moisture can cause decomposition of the material during processing at high temperatures, the pellets are typically dried before being mixed with the cellulose ester or before being fed into an extruder.

[0103] According to one embodiment, when the polyester contains two or more types of polyester, a polyester blend can be formed by melt-kneading the polyesters to form a single compound or at least a composite. In this case, the polyester is preferably dried overnight before melt-kneading, and then extruded at an extrusion temperature of about 200°C and a screw speed of about 50 to 350 rpm, preferably about 150 to 250 rpm.

[0104] According to another embodiment, several different types of polyester are manually mixed together before being fed into the extruder or inside the extruder.

[0105] Therefore, according to one embodiment, one or more separate polyester blends can be used, which are then mixed in an extruder.

[0106] The same applies to the cellulose esters; that is, in the case of a mixture of several different types of cellulose esters, they can be melt-mixed in a separate melt-blending process to form a single compound or at least a composite, or they can be manually mixed with polyester before or inside the extruder before being fed into the extruder.

[0107] According to a preferred embodiment, the cellulose ester is provided in solid form, preferably as a powder.

[0108] Therefore, in a preferred embodiment, both the polyester and the cellulose ester are solid, preferably provided as pellets and powders, respectively.

[0109] Therefore, according to one embodiment of the present invention, a method for producing a coating composition comprising polyester and cellulose ester is: - The process of preparing polyester, - Steps to prepare cellulose esters, - A step in the melt compounding process to mix the polyester and the cellulose ester. Includes.

[0110] A method for coating or laminating a porous substrate with such a coating composition further includes the step of coating or laminating the surface of the porous substrate with the coating composition to form a coating, and the method is - The process of preparing polyester, - Steps to prepare cellulose esters, - In the melt compounding process, a step of mixing the polyester and the cellulose ester by melt extrusion, and - A step of coating or laminating the reacted composition onto the surface of the porous substrate. Includes.

[0111] Extrusion in a melt compounding process according to the present invention includes supplying components to an extruder and heating the components, or at least the polyester and cellulose ester. Furthermore, or alternatively, extrusion in a melt compounding process according to the present disclosure includes supplying components to an extruder, mixing the components, and heating the components, or at least the polyester and cellulose ester. As already stated above, the polyester and the cellulose ester may be mixed before being supplied to the extruder, or they may be mixed in the extruder once they have melted.

[0112] Furthermore, or alternatively, the method further includes preparing a plasticizer which is maleic soybean oil, a lubricant which is such as stearamide or stearate, preferably calcium stearate, zinc stearate, or ethylene-bis-stearamide, or a mixture thereof, and a thermoplastic polyurethane (TPU), and mixing them with the polyester and the cellulose ester in a melt compounding process by melt extrusion.

[0113] Furthermore, or alternatively, when preparing the cellulose ester, a portion of the cellulose ester may be replaced with thermoplastic polyurethane (TPU), and the method further comprises preparing a plasticizer which is male-oxidized soybean oil, and a lubricant which is, for example, stearamide or stearate, preferably calcium stearate, zinc stearate, or ethylene-bis-stearamide, or a mixture thereof, and mixing the polyester and the cellulose ester in a melt compounding process by melt extrusion is equivalent to mixing the polyester, the cellulose ester, the TPU, the plasticizer, and the lubricant in a melt compounding process by melt extrusion.

[0114] Furthermore, or alternatively, mixing the polyester and the cellulose ester in a melt compounding process by melt extrusion includes preparing a plasticizer which is maleic soybean oil; a lubricant which is such as stearamide or stearate, preferably calcium stearate, zinc stearate, or ethylene-bis-stearamide, or a mixture thereof; and a thermoplastic polyurethane (TPU), and mixing the polyester and the cellulose ester with the plasticizer, the lubricant, and the TPU in a melt compounding process by melt extrusion.

[0115] The extruder used in the present invention is typically a twin-screw extruder, preferably a co-rotating twin-screw extruder. Twin-screw extruders have excellent mixing capabilities at the molecular level, enabling the production of homogeneous material compositions.

[0116] Preferably, the melt extrusion is carried out at a temperature higher than the melting points of both the polyester and the cellulose ester. According to a preferred embodiment, the melt extrusion is carried out at a temperature of at least 150°C, 160°C, 170°C, 180°C, 190°C, or 200°C, for example, about 200°C, for example, in the range of 150 to 250°C, or in the range of 180 to 220°C.

[0117] The screw speed used for the extrusion is preferably in the range of 50 to 350 rpm, more preferably in the range of 50 to 200 rpm or 50 to 250 rpm, and even more preferably in the range of 50 to 250 rpm, for example, 150 rpm.

[0118] During the extrusion process, the component is incorporated into the biopolymer composition.

[0119] In one embodiment, the mixture is formed into strands during the extrusion. In a further embodiment, the strands are optionally cooled in a water bath. Finally, the cooled strands are pelletized to form granules.

[0120] In one embodiment, the method includes providing the coating composition with further components such as additives or auxiliaries.

[0121] In a preferred embodiment, the method further includes providing the coating composition with a plasticizer, such as maleic soybean oil, and / or a lubricant, particularly a stearate, such as calcium stearate and / or zinc stearate. Preferably, any additives such as plasticizers and / or lubricants are mixed with the polyester and the cellulose ester by melt extrusion during the melt compounding process. The plasticizers and / or lubricants may be added to the extruder separately, or all or at least some of the components may be mixed together before being supplied to the extruder. For example, the lubricant may be supplied to the extruder by a side feeder and the plasticizer by a pump.

[0122] According to one embodiment, the method further comprises providing the coating composition with one or more types of polysiloxane. In a preferred embodiment, a liquid polysiloxane is mixed with solid polyester and cellulose esters, i.e., the polysiloxane and polyester and cellulose esters are mixed before melt kneading, the liquid polysiloxane mixture remains on the surface of the polyester and cellulose esters, and the reaction occurs during extrusion once the polyester and cellulose esters have melted.

[0123] According to another embodiment, liquid polysiloxane is mixed with molten polyester and cellulose ester using a liquid supply, and a reaction occurs during extrusion once the components are mixed with each other.

[0124] According to one embodiment, at least a portion of the components of the coating composition are already mixed before being supplied to the extruder.

[0125] According to one embodiment, the method of the present invention can be repeatedly applied to a biopolymer composition formed according to the present invention, and the properties of the composition can be further modified. For example, according to one embodiment, the composition can be combined with another polyester blend.

[0126] As described above, according to one embodiment, the molten biopolymer composition discharged from the extruder is granulated, for example, using a strand pelletizing or underwater pelletizing system. In strand pelletizing, one or more strands discharged from the extruder are cooled and solidified in a cooling water bath, and then cut into biopolymer granules using a pelletizing device. In underwater pelletizing, cutting is performed by a rotating blade immediately after the extruder die, and the molten polymer is cooled by circulating process water. After pelletizing, the polymer granules are preferably dried in a dryer or an air-circulating oven.

[0127] Next, the coating composition is coated or laminated onto the surface of the porous substrate.

[0128] In one embodiment, the polymer granules are melted again, for example, in a coating process such as hot-melt coating or extrusion coating, or in a film manufacturing process before lamination coating.

[0129] In one embodiment, the method of the present invention may include foaming the obtained composition to obtain a foamed coating composition. The composition can be foamed by any known foaming method, such as foam extrusion molding and chemical or physical foaming using carbon dioxide, nitrogen, pentane, or any combination thereof as a foaming agent. The foamed coating composition can then be coated or laminated onto a substrate as described above.

[0130] In one embodiment, the porous substrate is coated with the coating composition by hot-melt coating. In one embodiment, the granules of the coating composition are first melted, for example, in an extruder, and then the molten coating composition is transferred to the gap between two heated calender rolls. The molten coating is transferred from the rolls to the substrate, and then the coated substrate is smoothed by the calender rolls and pressure is applied to obtain a uniform, thin coating layer.

[0131] In another embodiment, the porous substrate is laminated with the coating composition. That is, the coating composition is first formed into a film of a desired thickness (e.g., 20 μm to 100 μm) using a film blow molding method or a film extrusion molding method. The formed film can then be laminated onto the surface of the porous substrate. In the thermal lamination method, the film to be laminated is attached to the substrate using a heated and pressurized roller, which is used to fuse the film onto the substrate.

[0132] One or both sides of the porous substrate can be coated or laminated. Alternatively, part or all of one or both sides can be coated or laminated.

[0133] In further embodiments, the coated or laminated surface of the porous substrate, i.e., the formed coating, can be further processed, in particular by pattern formation and / or perforation. In preferred embodiments, pattern formation and / or perforation is carried out by press working, particularly by press working with a pattern forming mold, a perforating roll, or an embossing roll.

[0134] According to one embodiment, an adhesive layer can be used between the porous substrate and the coating layer or laminate layer, particularly between the porous substrate and the laminate layer. Such an adhesive layer can be, for example, starch paste.

[0135] Furthermore, or alternatively, the composition further comprises an adhesion promoter. Examples of adhesion promoters include, but are not limited to, Coatosil and BYK, such as Coatosil 2287 (organofunctional silane ester, CAS number: 2897-60-1), BYK4509, BYK4510, BYK4511, BYK4512, etc. Including an adhesion promoter in the composition is beneficial because it improves the adhesion of the composition to the substrate.

[0136] Patterning and / or perforation can be performed with or without heating. Patterning can also be carried out with or without additive manufacturing and radiation hardening.

[0137] Pattern formation and / or perforation can be performed immediately after coating or lamination, or it can be performed later in a separate process.

[0138] According to one embodiment, the coating composition of the present invention can be further coated or laminated with a hard coating, i.e., a protective coating. The hard coating is particularly useful for protecting patterned and / or perforated surfaces. The hard coating can be any polymer hybrid coating, such as an acrylate or polysiloxane-based coating, that has good adhesion to the coating material and improves abrasion resistance.

[0139] Furthermore, the present invention relates to the use of porous substrates coated with the coating composition. Such coated substrates, particularly textile substrates, have various applications in consumer textiles such as tablecloths and interior textiles.

[0140] In general, the present invention can be used to produce porous substrates having a biopolymer coating, and can generally be used as an alternative to conventional methods for producing coated porous substrates.

[0141] It should be understood that the embodiments of the present invention disclosed herein are not limited to the specific structures, process steps, or materials disclosed herein, but extend to their equivalents as recognized by those skilled in the art. It should also be understood that the terms used herein are for the purpose of describing specific embodiments only and are not intended to limit them.

[0142] Throughout this specification, any reference to “one embodiment” or “embodiment” means that a particular feature, structure, or characteristic described in relation to that embodiment is included in at least one embodiment of the present invention. Therefore, where the expression “in one embodiment” or “in an embodiment” is used in various places throughout this specification, it does not necessarily refer to the same embodiment. For example, when numerical values ​​are referred to using terms such as “about” or “substantially,” the exact numerical values ​​are also disclosed.

[0143] In this specification, multiple items, structural elements, components, and / or materials may be presented in common lists for convenience. However, these lists should be interpreted as each element of the list being individually identified as a distinct and unique element. Accordingly, no individual element of such list should be interpreted as a de facto equivalent of any other element of the same list, solely on the grounds that it is presented in a common group, unless otherwise suggested. Furthermore, various embodiments and examples of the Invention may be referenced herein along with alternative examples of their various components. It should be understood that such embodiments, examples, and alternative examples should not be interpreted as de facto equivalents of each other, but rather as distinct and independent expressions of the Invention.

[0144] Furthermore, the described features, structures, or properties can be combined in any suitable manner in one or more embodiments. This specification provides numerous specific details, such as examples of length, width, shape, etc., to allow for a full understanding of the embodiments of the present invention. However, those skilled in the art will understand that the present invention can be implemented by omitting one or more of the specific details, or by using other methods, components, materials, etc.

[0145] While the above embodiments illustrate the principles of the present invention in one or more specific applications, it will be apparent to those skilled in the art that numerous modifications can be made to the form, usage, and details of implementation without affecting the capability of the invention or departing from the principles and concepts of the present invention. Accordingly, the present invention is not limited to the claims.

[0146] The following non-limiting embodiments are intended to illustrate the advantages obtained by embodiments of the present invention. [Examples]

[0147] <Example 1> Preparation of Maleated Soybean Oil 1 8.93 kg of soybean oil, 1.25 kg of maleic anhydride, and 28.93 g of catalyst (Sn(Oct)) were added to the reactor. Nitrogen was then added to the reaction vessel as an inert gas. The reaction mixture was heated to 180°C while stirring. The maleic oxidation reaction was continued for 10-12 hours.

[0148] "Preparation of coating composition 1" 196 kg of commercially available grade polybutylene succinate (BioPBS FD92B) and 87 kg of cellulose acetate butyrate (CAB 381.05) were dried overnight in a circulating air dryer at 60°C, and then mixed together before melt-kneading. The resulting mixture was melt-kneaded using a twin-screw extruder at an extrusion temperature of 150°C to 170°C and a screw speed of 285 rpm. During the mixing process, 2 kg of a 1:1 mixture of calcium stearate and zinc stearate was supplied to the mixture using a side hopper. Furthermore, 15 kg of maleated soybean oil 1 was pumped into the extruder during the mixing process. The mixed material was extruded in strand form, cooled in a water bath, and pelletized into granules.

[0149] "Coating of the base material" Basis weight 185g / m 2 A cotton fabric substrate was coated with coating composition 1 using an extrusion coating method.

[0150] The coating composition was melted in an extruder at a temperature of 150°C to 170°C, extruded through a flat die onto the nip of a coating roll, and transferred to the fabric substrate. The coating roll spread the coating into a uniform layer, and the coating cured during cooling. The coating thickness was 80 to 150 g / m². 2 I obtained some cotton cloth.

[0151] <Example 2> "Preparation of Maleated Soybean Oil 2" 120 g of soybean oil, 25.2 g of maleic anhydride, and 120 μL of catalyst (Sn(Oct)2) were added to a beaker. Under a nitrogen atmosphere, the reaction mixture was heated to 200°C while stirring. The maleic oxidation reaction was continued for 6 hours.

[0152] "Preparation of coating composition 2" 148 kg of commercially available grade polybutylene succinate (BioPBS FD92B) and 135 kg of cellulose acetate propionate (CAP 482.05) were dried overnight in a circulating air dryer at 60°C. The dried polybutylene succinate and cellulose acetate propionate were mixed together with 15 kg of maleated soybean oil and 2 kg of a 1:1 mixture of calcium stearate and zinc stearate before melt-kneading. The resulting mixture was melt-kneaded using a twin-screw extruder at an extrusion temperature of 180°C to 200°C and a screw speed of 165 rpm. The compounded material was extruded in strand form, cooled in a water bath, and pelletized into granules.

[0153] "Coating of the base material" Basis weight 185g / m 2 The cotton cloth was coated with coating composition 2 using a hot melt coating. The granules of the coating composition were first melted in an extruder, and then the molten coating composition was placed in the gap between two calender rolls heated to a temperature between 165 and 175°C. The molten composition was transferred from the calender rolls to the cloth, and then the coating on the cotton cloth was further smoothed and pressure was applied to 75 to 120 g / m² using the next calender roll. 2 A cloth with a coating thickness was obtained.

[0154] The same experiment was conducted with other vegetable oils, such as castor oil and linseed oil, and similar results were obtained.

[0155] <Example 3> "Preparation of coating composition 3" 161 kg of commercially available grade polybutylene succinate (BioPBS FD92B) and 120 kg of cellulose acetate propionate (CAP 482.20) were dried overnight in a circulating air dryer at 60°C. The dried polybutylene succinate and cellulose acetate propionate were mixed with 18 kg of triethyl citrate (TEC) and 0.9 kg of a 1:1 mixture of calcium stearate and zinc stearate before melt-kneading. The resulting mixture was melt-kneaded using a twin-screw extruder at an extrusion temperature of 200°C and a screw speed of 200 rpm. The compounded material was extruded in strand form, cooled in a water bath, and pelletized into granules.

[0156] <Example 3b> "Preparation of coating composition 3b" 117 kg of commercially available grade polybutylene succinate (BioPBS FD92B), 117 kg of cellulose acetate propionate (CAP 482.05), and 45 kg of partially (46% by weight, the remainder non-biobased) bio-based thermoplastic polyurethane (TPU) were dried overnight in a circulating air dryer at 60-80°C. The dried polybutylene succinate, cellulose acetate propionate, and thermoplastic polyurethane were mixed with 3.0 kg of ethylene-bis-stearamide wax, 1.5 kg of tris(2,4-di-tert-butylphenyl) phosphite antioxidant, and 1.5 kg of epoxy functionalized chain extender (Joncryl ADR 4468) before melt kneading. The resulting mixture was melt kneaded using a twin-screw extruder at an extrusion temperature of 200°C and a screw speed of 200 rpm. Furthermore, 15 kg of maleic oxidized soybean oil 1 prepared in Example 1 was pumped into the extruder during the mixing process. The mixed material was extruded in strand form, cooled in a water bath, and pelletized into granules.

[0157] "Coating of base material 3c" Basis weight 185g / m 2The cotton cloth was coated with coating composition 3 using a hot melt coating. The granules of the coating composition were first melted in an extruder, and then the molten coating composition was placed in the gap between two calender rolls heated to a temperature between 165 and 175°C. The molten composition was transferred from the calender rolls to the cloth, and then the coating on the cotton cloth was further smoothed and pressure was applied to 75 to 120 g / m² using the next calender roll. 2 A cloth with a coating thickness was obtained.

[0158] "3D coating of substrate" Basis weight 185g / m 2 The cotton cloth was coated with coating composition 3b using a hot melt coating. The granules of the coating composition were first melted in an extruder, and then the molten coating composition was placed in the gap between two calender rolls heated to a temperature between 145 and 165°C. The molten composition was transferred from the calender rolls to the cloth, and then the coating on the cotton cloth was further smoothed and pressure was applied to 75 to 120 g / m² using the next calender roll. 2 A cloth with a coating thickness was obtained.

[0159] <Example 4> "Preparation of Mixture 1 (Polysiloxane Mixture)" 225 g of an aqueous solution of biosuccinic acid (1% by weight of biosuccinic acid diluted with deionized water) was gradually added to 1500 g of methyltriethoxysilane. Before use, the solution was mixed at room temperature for 12 hours.

[0160] "Preparation of Bio-Based Compound 4" 47.6 kg of commercially available grade polybutylene succinate (BioPBS FD92B) and 21.7 kg of cellulose acetate butyrate (CAB 381.05) were dried overnight at 60 °C in a circulating air dryer and then mixed together before melt-kneading. The resulting mixture was melt-kneaded using a twin-screw extruder at an extrusion temperature of 200 °C and a screw speed of 250 rpm. During the formulation, 0.45 kg of a mixture of calcium stearate and zinc stearate (1:1) was supplied to the formulation using a side hopper. Further, 3.75 kg of maleated soybean oil and 1.5 kg of a polysiloxane mixture (mixture 1) were pumped into the extruder during the formulation. The formulated material was extruded into strands, cooled in a water bath, and pelletized into granules.

[0161] "Coating of the substrate" Cotton cloth with a basis weight of 185 g / m 2 was coated with coating composition 4 using a hot-melt coating. The granules of the coating composition were first melted in an extruder, and then the melted coating composition was placed in the gap between two calendar rolls heated to a temperature between 165 and 175 °C. The melted composition was transferred from the calendar roll to the cloth, and then, on the next calendar roll, the coating of the cotton cloth was further smoothed and pressed to obtain a cloth with a coating thickness of 75 - 120 g / m 2 .

[0162] <Example 5> "Preparation of Bio-based Compound 5" 222 kg of commercially available grade polybutylene succinate (BioPBS FD92B) and 60 kg of cellulose acetate propionate (CAB 381.05) were dried overnight in a circulating air dryer at 60°C. The dried polybutylene succinate and cellulose acetate butyrate were mixed with 15 kg of polyethylene glycol 400 (PEG 400) and 1 kg of a 1:1 mixture of calcium stearate and zinc stearate before melt-kneading. The resulting mixture was melt-kneaded using a twin-screw extruder at an extrusion temperature of 200°C and a screw speed of 200 rpm. The compounded material was extruded in strand form, cooled in a water bath, and pelletized into granules.

[0163] "Coating of the base material" Basis weight 185g / m 2 The cotton cloth was coated with coating composition 5 using a hot melt coating. The granules of the coating composition were first melted in an extruder, and then the molten coating composition was placed in the gap between two calender rolls heated to a temperature between 165 and 175°C. The molten composition was transferred from the calender rolls to the cloth, and then the coating on the cotton cloth was further smoothed and pressure was applied to 75 to 120 g / m² using the next calender roll. 2 A cloth with a coating thickness was obtained.

Claims

1. A coating on a porous substrate, The coating is formed from a composition comprising a mixture of polyester and cellulose ester. The composition further comprises a plasticizer and a lubricant, such as stearamide or stearate, preferably calcium stearate, zinc stearate, or ethylene-bis-stearamide, or a mixture thereof. The aforementioned plasticizer is maleic soybean oil. A coating in which a portion of the cellulose ester in the composition is replaced with thermoplastic polyurethane (TPU).

2. The coating according to claim 1, wherein the substrate is a fiber-based material, such as a textile such as a tablecloth, fabric, protective textile, or interior textile, or a consumer device such as a watch strap or heart rate monitor belt.

3. The coating according to claim 1 or 2, wherein the polyester is selected from the group consisting of polylactic acid, polylactide, polybutylene succinate, polybutylene succinate adipate, polyhydroxyalkanoate, polyhydroxybutyrate, polycaprolactone, and combinations thereof, and preferably the polyester is polybutylene succinate.

4. The coating according to any one of the claims, wherein the composition contains 25 to 95% by weight of polyester, preferably 25 to 60% by weight of polyester, and more preferably 30 to 60% by weight of polyester, calculated from the total weight of the composition.

5. The coating according to any one of the claims, wherein the composition comprises 40 to 95% by weight, preferably 45 to 85% by weight, and more preferably 50 to 70% by weight of polyester, calculated from the total weight of the composition.

6. The coating according to any one of the claims, wherein the cellulose ester is cellulose acetate (CA), cellulose acetate butyrate (CAB), cellulose acetate propionate (CAP), or a mixture thereof.

7. The coating according to any of the claims, wherein the composition comprises 10 to 60% by weight, preferably 20 to 50% by weight, more preferably 25 to 45% by weight, for example 30 to 40% by weight, of cellulose ester, calculated from the total weight of the composition.

8. The coating according to any one of the claims, wherein the composition contains maleic soybean oil in an amount of 1 to 20% by weight, more preferably 2 to 10% by weight, for example 3 to 7% by weight, calculated from the total weight of the composition.

9. The coating according to any one of the claims, wherein the composition contains a lubricant, such as stearic acid, stearamide, or stearate, preferably calcium stearate, zinc stearate, or ethylene-bis-stearamide, or a mixture thereof, in an amount of 0.05 to 10% by weight, preferably 0.1 to 8% by weight, for example, about 0.1 to 3% by weight or 0.1 to 1% by weight, calculated from the total weight of the composition.

10. The coating according to any one of the claims, wherein the composition further comprises a polysiloxane or a mixture of polysiloxanes, preferably in an amount of 0.05 to 10% by weight, preferably 0.1 to 3% by weight, for example, about 2% by weight, calculated from the total weight of the composition.

11. The above composition may further contain the following auxiliary agents: - Inorganic colorants and / or fillers, especially inorganic fillers, such as ash, minerals, mineral sludge, clay, ceramics, and other inorganic materials including, for example, calcium carbonate, kaolin, talc, gypsum, chalk, mica, wollastonite, glass, silica, alumina, titania, and other inorganic oxides, crushed stone, concrete, and other materials such as stone and sand, diatomaceous earth, metal hydrates, such as aluminum hydrate, calcium hydrate, geopolymers, etc., or any combination thereof, - Additives, especially plasticizers, such as glycerol, polyethylene glycol, triethyl citrate, tributyl citrate, acetyl tributyl citrate, etc., vegetable oils, such as soybean oil, linseed oil, tall oil, castor oil, canola oil, etc., or modified versions thereof, such as maleic, acrylic, vinyl, succinic, epoxidized, or hydroxylated vegetable oils, or other vegetable ester oils or resins such as epoxidized soybean oil, maleicized soybean oil, or epoxidized linseed oil, or any combination thereof. - Organic agents, especially organic fillers or colorants, such as wood or plant-based materials or parts or by-products thereof, such as soybeans and other legumes, bean husks, wheat husks, rice husks, seaweed, algae, natural resins and gums, carbon, carbon black, biocarbon, ward, willow and other tree bark, onion peels and other plant peels, lemon, turmeric root, cotton, hemp, flax, pulp, wood fibers and all other natural fibers, and their components, such as lignocellulose, lignin, suberin, polysaccharides, such as natural polysaccharides like cellulose, starch and hemicellulose, nanocellulose, and their derivatives, and any combination thereof. - Chain extenders and / or crosslinking agents, such as epoxy, peroxide, amine, or acrylic functionalized chain extenders, - Lubricants, such as stearamide and stearate, such as calcium stearate, magnesium stearate, etc., and natural waxes, such as carnauba wax, soybean wax, beeswax, sugarcane wax, cassava wax, candelilla wax, rice bran wax, berry wax, myrica fruit wax and laurel wax, etc., or any mixture thereof, and - Stabilizers, such as light stabilizers, UV stabilizers, antioxidants, heat stabilizers, or flame retardants, or any mixture thereof. The coating according to any one of the claims, comprising at least one of the above.

12. The coating according to any of the claims, wherein the composition contains neither water nor any other solvent.

13. The composition is - 30 to 75% by weight, preferably 30 to 65% by weight, more preferably 30 to 50% by weight of polyester, - 20 to 50% by weight, preferably 25 to 45% by weight of cellulose ester, - 2 to 10% by weight of a plasticizer, preferably male-oxidized soybean oil. - 0.05 to 10% by weight, preferably 0.1 to 1% by weight of a lubricant, preferably zinc stearate and / or calcium stearate, and - optionally comprising 0.1 to 10% by weight, preferably 0.5 to 5% by weight, one or more of the auxiliary agents described in claim 11. The coating according to any of the claims, wherein the amount is calculated from the total weight of the composition.

14. The composition is - 50-70% by weight of polybutylene succinate and / or polybutylene succinate adipate, - 25-45% by weight of cellulose acetate butyrate and / or cellulose acetate propionate, - 2 to 10% by weight of maleated soybean oil, and - Consists of 0.1 to 3% by weight of zinc stearate and / or calcium stearate, The coating according to any of the claims, wherein the amount is calculated from the total weight of the composition.

15. A method for coating or laminating a porous substrate, - The process of preparing polyester, - Steps to prepare cellulose esters, - In the melt compounding process, a step of mixing the polyester and the cellulose ester by melt extrusion to form a coating composition, and - A step of forming a coating by coating or laminating the surface of the porous substrate with the coating composition. Includes, The method further includes the step of preparing a plasticizer which is maleic soybean oil, a lubricant which is such as stearamide or stearate, preferably calcium stearate, zinc stearate, or ethylene-bis-stearamide, or a mixture thereof, and thermoplastic polyurethane (TPU), and mixing them with the polyester and the cellulose ester in a melt compounding process by melt extrusion.

16. The method according to claim 15, wherein the composition is compounded in a twin-screw extruder, preferably with a screw speed during extrusion in the range of 50 to 350 rpm, for example, 150 rpm.

17. The method according to any one of claims 15 to 16, wherein the extrusion is carried out at a temperature higher than the melting points of the polyester and the cellulose ester, preferably 150°C or higher, for example, about 200°C.

18. The method according to any one of claims 15 to 17, wherein the porous substrate is coated with the coating composition by hot melt coating, or laminated with a film formed from the coating composition.

19. The method according to any one of claims 15 to 18, wherein the formed coating is patterned and / or perforated by press processing, preferably with a pattern forming mold, a perforating roll, or an embossing roll.

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