Composite polymeric materials, and products and methods of preparing the same

Abstract

The disclosure provides leather articles and a method for making leather articles comprising a substrate and a coating comprising a cellulose derivative having improved colorfastness to rubbing. The cellulose derivative may be methyl cellulose, ethyl cellulose, ethyl methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, ethyl hydroxyethyl cellulose, cellulose acetate, cellulose triacetate, cellulose propionate, cellulose acetate propionate, cellulose acetate butyrate, microcrystalline cellulose, cellulose nitrate, or cellulose sulfate.

Description

Casting to Film 1. Take 40 grams of prepared basecoat solution and pour in a silicon mold. 2. Place filled silicon mold in a convection oven for 12 hrs at 140 °C. 2023228916   22 Sep 2026 3. Remove mold from oven and allow film to equilibrate for 1 hr. 4. Remove film from silicon mold. Solution Preparation (Crust Adhesive Coat) 1. Add 414 grams of water to a container 2. Add 85 grams of low molecular weight silk solution to the solution and stir for 5 minutes. 3. Add 1.25 grams of Melios 09s11 crosslinker to the solution and stir for 5 minutes. Solution Preparation (Base Adhesive Coat) 1. Add 414 grams of water to a container 2. Add 85 grams of mid molecular weight silk solution to the solution and stir for 5 minutes. 3. Add 1.25 grams of Melios 09s11 crosslinker to the solution and stir for 5 minutes. Solution Preparation (Basecoat) 1. Add 1 kilogram of water to a container and heat to 60 °C. 2. Add 2.5 grams of gelatin and 5 grams of glycerol to the container and stir for 30 minutes. 3. Remove the solution from heat. 4. Add 10 grams of elastin to the solution and stir for 5 minutes 5. Add 10 grams of transglutaminase / maltodextrin powder and 170 grams of mid molecular weight silk solution into the solution and stir for 5 minutes. 6. Adjust the solution pH to 10 using ammonia. 7. Add 20 grams of TP Black E pigment from First Source Worldwide. Solution Preparation (Topcoat) 1. Add 500 mL of 100% ethanol to a container. 2. Add 8.3 grams of triethyl citrate and 13.5 grams of Prisorine (isostearic acid) to the solution and stir for 5 minutes. 3. Slowly, to prevent clumping, add 12.5 grams of ethyl cellulose to the solution and stir overnight (at least 12 hours). Note, make sure to stir in a covered vessel to prevent evaporation of ethanol and concentration of ethyl cellulose. Spray Coating on Fabric 1. On an unfinished leather skin, spray the crust adhesive coat using a 1.3 mm spray nozzle at a 45° cone pattern and 35-40 psi adding 1 gr / ft2 of 2023228916   22 Sep 2026 material. 2. Take the sample and dry in an oven at 130 °C for 30-60 seconds (until dry). 2023228916   22 Sep 2026 3. Next, spray the base coat onto the leather again using a 1.3 mm spray nozzle at a 45° cone pattern and 35-40 psi adding 1 gr / ft2 of material. 4. Take the sample and dry in an oven at 130 °C for 30-60 seconds (until dry). 5. Iron the sample using a roller iron at 98 °C under 50 kg / f pressure at a 6 m / min speed. 6. Apply two more coats of basecoat formula using steps 3 and 4. 7. Finally, spray the topcoat formula onto the leather using a 1.3 mm spray nozzle at a 45° cone pattern and 45-50 psi adding 1 gr / ft2 of material. 8. Take the sample and dry in an oven at 130 °C for 30-60 seconds (until dry). 9. Repeat steps 7-8 two more times. 10. Iron the sample using a roller iron at 98 °C under 50 kg / f pressure at a 5 m / min speed. Performance Testing Methods Film Testing All films were tested in house qualitatively based on bendability, stretch, elasticity, and water drop resistance. Each test was performed on a scale of 1- 4 with 1 being the worst and 4 being the best. -For bendability, the film was creased in two directions if the film could not bend it was given a score of 1 and if it could crease without leaving a mark it was given a score of 4. -For stretch, the film was pulled into opposite directions, if it broke without any elongation, it was given a score of 1 and if it could elongation past twice its size it was given a score of 4. -For elasticity, the film was stretched, if it could not stretch any distance without permanently deforming it was given a score of 1 and if it could stretch to twice its length and still recover its shape it was given a score of 4. -For water drop resistance, a drop of water was applied to the surface using an eye dropper, if the film immediately dissolved it was given a score of 1 and if no change occurred after the water was applied and evaporated it was given a 2023228916   22 Sep 2026 score of 4. Leather Testing All leather coated samples were tested using the Veslic test to ensure colorfastness to rubbing and bally flex test to ensure adhesion between all layers and to prevent cracking. The Veslic test follows the ISO 11640 testing procedure and the bally flex test follows the ISO 5402 testing procedure. Test Results Film Test Results All film test results can be seen in Table 1. From the film testing data, the silk / elastin / gelatin formulation crosslinked by transglutaminase gives the best films. In all formulations, activated silk (AS-105) and gelatin are present to give the film structure and body. Glycerol is also added to the film as a plasticizer to add bendability. Originally, Etocas 200 (a highly ethoxylated castor oil) was added to make the film soft as seen in experiments 1-3, however, the bendability was sometimes subpar, and the films had little to no stretch and elasticity as well as poor water resistance. To increase water resistance and stretch Etocas 200 was substituted with Span 120 (sorbitan isostearate). This increased the water resistance, however, just like Etocas 200 it was lacking in stretch elasticity as seen in experiments 4-5. Elastin was used to increased stretchability and transglutaminase was tested to improve elasticity. AS seen through experiments 7-18, stretchability and elasticity were greatly improved when elastin and transglutaminase was added. To find the optimal concentrations standard curves were made for each ingredient as can be seen in experiments 19-36, leaving the optimal ratio to be 0.25:1:1 Gelatin to Transglutaminase to Elastin. With the optimal ratio identified, the optimal concentration of total non-silk solids in the solution was investigated resulting in an optimal concentration of 2.75% additives. Leather Coating For each leather coating experiment, four layers were applied. First an adhesive layer consisting of low molecular weight activated silk (AS-104) and Melios-09s11 crosslinker was applied to the leather crust. Next the basecoat was applied at a 3 g / ft2 application rate. Then an adhesive layer 2023228916   22 Sep 2026 between the basecoat and topcoat consisting of mid molecular weight activated silk (AS-105) and Melios-09s11 was applied to the surface. And finally, the topcoat was sprayed on the surface. 2023228916   22 Sep 2026 # Study Additive 1 Additive 2 Additive 3 Additive 4 Additive 5 Bend Stretch Elasticity WD Note 1 Etocas Study 0.5% Gelatin 0.25% glycerol 1% Etocas - - 3 2 1 2 2 0.5% Etocas 4 2 0 2 3 0.25% Etocas 4 2 1 1 4 Span Study 0.25% Gelatin 0.5% glycerol 1% Span 0.25% Tween 0.95% Ethanol 2 0 0 3 5 0.5% Span 4 2 1 3 6 0.25% Span 4 2 1 2 7 TG and Elastin Study 0.25% Gelatin 0.5% glycerol 1% TG 0.25% Tween - 4 4 3 2 O 8 0.5% TG 4 4 3 2 O 9 0.25% TG 3 2 1 2 O 10 2% Elastin 4 4 4 2 HE 11 1% Elastin 4 4 4 - HE 12 0.5% Elastin - - - - NF 13 1% TG 1% Elastin 0.25% Tween 4 3 2 2 14 0.5% TG 4 3 2 2 15 0.25% TG 4 3 3 2 S 16 0.5% TG 2% Elastin 4 4 3 1 NH 17 1% Elastin 4 4 3 1 18 0.5% Elastin 4 4 3 1 19 Elastin Standard Curve 0.25% Gelatin 0.5% glycerol 0.5% TG 4% Elastin 0.25% Tween 3 4 2 3 20 2% Elastin 4 4 3 2 21 1% Elastin 4 4 3 2 22 0.5% Elastin 4 3 3 2 23 0.25% Elastin 4 3 2 1 24 0.125% Elastin 3 2 1 1 25 TG Standard Curve 0.25% Gelatin 0.5% glycerol 2% TG 1% Elastin 0.25% Tween 4 3 2 2 S 26 1% TG 4 3 3 1 S 27 0.5% TG 4 3 3 2 S 28 0.25% TG 4 3 2 2 NH 29 0.125% TG 4 4 3 2 30 0.0625% TG 4 4 3 2 2023228916   22 Sep 2026 31 Gelatin Standard Curve 2% Gelatin 0.5% glycerol 1% TG 1% Elastin - 1 0 0 1 32 1% Gelatin 1 1 0 1 33 0.5% Gelatin 4 4 3 1 34 0.25% Gelatin 4 4 3 1 35 0.125% Gelatin 4 4 2 1 36 0.0625% Gelatin 2 2 2 1 37 Non-Silk Solid Mass Standard Curve 1% Gelatin 2% glycerol 4% TG 4% Elastin - 2 1 1 2 38 0.5% Gelatin 1 % glycerol 2% TG 2% Elastin 3 2 1 2 39 0.375% Gelatin 0.75% glycerol 1.5% TG 1.5% Elastin 3 3 3 2 40 0.25% Gelatin 0.5% glycerol 1% TG 1% Elastin 4 4 3 1 41 0.0625% Gelatin 0.125% glycerol 0.25% TG 0.25% Elastin 1 1 1 1 Table 32. Film casting qualitive assessments. Each film contains 0.85% Activated Silk (AS-105). Ingredient abbreviations (Tween = Tween 80, TG = Transglutaminase + Maltodextrin, Etocas = Etocas 200, Span = Span 120). Note abbreviations (NH = Non homogenous, NF = No film formed, S = Sticky, HE = Highly elastic, O = Opaque). Also, WD is an abbreviation for water drop. 2023228916   22 Sep 2026 # Basecoat Additives Topcoat Additive Veslic Test (After 300 Cycles) 1 - - - - - - 3.33 % TEC 1.67% ISA P 2 0.25% Gel 0.25% Gly 0.5% E200 0.25% T80 1% Eth - 3.33 % TEC 1.67% ISA P, TD (50 cycles) 3 0.25% Gel 0.25% Gly 0.5% E200 0.25% T80 1% Eth ^B 3.33% TEC 1.67% ISA P, TD (50 cycles) 4 0.25% Gel 0.25% Gly 0.5% E200 0.25% T80 1% Eth - 2.5 % TEC 5% S120 NP 5 - - - - - - 2.5% TEC 5% S120 NP 6 0.25% Gel 0.25% Gly 0.5% S120 0.25% T80 1% Eth 0.25%Melio 09s11 2.5 % TEC 5% S120 NP, TD 7 0.25% Gel 0.25% Gly 0.5% S120 0.25% T80 1% Eth 0.25% Bayhydur 2.5 % TEC 5% S120 NP, RI 8 0.25% Gel 0.25% Gly 0.5% S120 0.25% T80 1% Eth 0.25% Glutaraldehyde 2.5 % TEC 5% S120 NP, RI 9 0.25% Gel 0.25% Gly 0.5% S120 0.25% T80 1% Eth 0.25% Rodalink 3315 2.5 % TEC 5% S120 NP 10 0.25% Gel 0.25% Gly 0.5% S120 0.25% T80 1% Eth 0.25% Rodalink R77 2.5 % TEC 5% S120 NP, RI 11 0.25% Gel 0.25% Gly 0.5% S120 0.25% T80 1% Eth 0.25% Azaridine 2.5 % TEC 5% S120 NP, RI 12 0.25% Gel 0.25% Gly 0.25% TG 1% Elastin ^B ^B 2.5 % TEC 5% S120 NP Table 33. Wet Veslic data from leather spray coat experiments. All basecoat layers have 0.85% AS-105 and all topcoat layers have ethyl cellulose in them. The ingredient abbreviations are (Gel = Gelatin, Gly = glycerol, S120 = Span 120, T80 = Tween 80, E200 = Etocas 200, Eth = Ethanol, TG = Transglutaminase, TEC = Triethyl Citrate, and ISA = Isostearic Acid, Rice Quat. = Quaternized Rice Protein). The result abbreviations are (P = Pigment detected on scrubbing pad, NP = No pigment detected on scrubbing pad, TD = Topcoat began to detach, and RI = Rub indent present) 2023228916   22 Sep 2026 # Basecoat Additive Topcoat Additive Bally Flex Test (8000 cycles) 1 0.25% Gel 0.25% Gly 0.5% E200 0.25% T80 1%Eth 3.33% TEC 1.67% ISA TD 2 0.25% Gel 0.25% Gly 0.5% E200 0.25% T80 1%Eth 2.5 % TEC 5% S120 TD 3 ^B ^B ^B ^B ^- 3.33% TEC 1.67% ISA SD 4 - — — - - 2.5 % TEC 5% S120 SD 5 0.25% Gel 0.25% Gly 0.5% S120 0.25% T80 1%Eth 3.33% TEC 1.67% ISA SD 6 0.25% Gel 0.25% Gly 0.5% S120 0.25% T80 1%Eth 2.5 % TEC 5% S120 SD 7 0.25% Gel 0.5% Gly 0.25% TG 1% Elastin - - - NSF 8 - - - - - - - NSF 9 0.25% Gel 0.5% Gly 0.25% TG 1% Elastin - 2.5 % TEC 5% S120 NSF Table 34. Bally flex data from leather spray coat experiments. All basecoat layers have 0.85% AS-105 and all topcoat layers have ethyl cellulose in them. The ingredient abbreviations are (Gel = Gelatin, Gly = glycerol, S120 = Span 120, T80 = Tween 80, E200 = Etocas 200, Eth = Ethanol, TG = Transglutaminase, TEC = Triethyl Citrate, and ISA = Isostearic Acid). The test result abbreviations are (NSF = No significant 5 Failure, SD = Slight Detachment, and TD = Total Detachment) 422 2023228916   22 Sep 2026 Veslic Test Results All Veslic test results can be seen in Table 32. For both samples with no basecoat and Etocas 200 as the main additive, if the topcoat contains isostearic acid it will rub off causing pigments to leach onto the scrubbing pad as can be seen in experiments 1-3. However, if Span 120 is used in the topcoat it will stay on up to 300 cycles as can be seen in experiments 4-5. If Span 120 is used in the basecoat with a crosslinker, the topcoat will prevent the pigment from leaching onto the scrubbing pad. However, the surface of the leather becomes deformed after rubbed (except for the use of Rodalink 3315 crosslinker) and the use of a petrochemical derived crosslinker makes this formulation not 100% biobased. But, if elastin is used with a transglutaminase, no pigment leeches out as well as the surface remains unaltered as can be seen in experiment 12. The use of elastin and transglutaminase also makes the formulation 100% biobased. Bally Flex Test Results All bally flex test results can be seen in Table 33. The use of Etocas 200 in the basecoat causes samples to undergo total topcoat detachment from the basecoat at 8000 cycles as can be seen in experiments 1-2. Furthermore, by removing Etocas 200 from the basecoat the samples do not undergo total detachment, however, they still experience slight detachment as can be seen in experiments 3-4. Even experiments which contain Span 120 in the basecoat undergo slight detachment as can be seen in experiments 5-6. But samples containing elastin and transglutaminase in the basecoat do not undergo any form of detachment up to 8000 cycles. All patents, patent applications, and published references cited herein are hereby incorporated by reference in their entirety. While the methods of the present disclosure have been described in connection with the specific embodiments thereof, it will be understood that it is capable of further modification. Further, this application is intended to cover any variations, uses, or adaptations of the methods of the present disclosure, including such departures from the present disclosure as come within known or customary practice in the art to which the methods of the present disclosure pertain. 2023228916   22 Sep 2026 Example 22. Basecoat and Topcoat Components for Coating System Below are examples of the amount of various products that may be included in the topcoat and basecoat in accordance with a coating system described herein. Table 35. Basecoat and Topcoat Grams per sq. ft. Component Product CAS % in formulation Grams solids in 1 Liter Final Solution Solid Grams in 1 Gram of Application Volume Minimum application ml / sq. ft Total Grams per sqft L5267 basecoat Biopur 3015 11.3% 112.5 0.1125 2 0.225 AS 104 0.3% 2.5 0.003 2 0.005 Top coat CAS % in formulation Grams solids in 1 Liter Final Solution Solid Grams in 1 Gram of Application Volume minimum application ml / sq. ft Total Grams per sqft L0822 topcoat Ethyl cellulose 200 (Ethocel Standard 200 Industrial) 9004 57-3 2.50% 25 0.025 2 0.05 Methoxy Propanol 107 98-2 97.50% 975 0.975 2 1.95 Example 23. BIOPUR 3015 Adhesive Study The minimum viable amount of BIOPUR 3015 needed to pass the adhesion test was evaluated. Table 36. Amount of BIOPUR 3015 Needed to Pass the Adhesion Test Sample        Basecoat Topcoat Topcoat Penetration Solvent Scotch Tape Test J 1 10% BIOPUR 3015 2.5 % EC Methoxy Poor Pass J 2 5% BIOPUR 3015 2.5 % EC Methoxy Medium Pass 2023228916   22 Sep 2026 J 3 2.5% BIOPUR 3015 2.5 % EC Methoxy Good Pass J 4 1% BIOPUR 3015 2.5 % EC Methoxy Good Pass J 5 0.5% BIOPUR 3015 2.5 % EC Methoxy Good Pass J 6 0.1% BIOPUR 3015 2.5 % EC Methoxy Good Fail* J 7 0.05% BIOPUR 3015 2.5 % EC Methoxy Good Fail As can be seen in Table 36, the cutoff for passing the scotch tape test is around 0.5% BIOPUR 3015. To further evaluate variations in performance, water resistance was measured by adding a drop of water to the surface and observing if it absorbs into the leather over a period of 5 minutes. Sample Basecoat Topcoat Water drop without scratch Water drop with scratch (control) J 1 10% BIOPUR 3015 2.5 % EC Partial Deformation Deformation J 2 5% BIOPUR 3015 2.5 % EC Deformation Deformation J 3 2.5% BIOPUR 3015 2.5 % EC Deformation Deformation J 4 1% BIOPUR 3015 2.5 % EC Deformation Deformation J 5 0.5% BIOPUR 3015 2.5 % EC Deformation Deformation J 6 0.1% BIOPUR 3015 2.5 % EC Deformation Deformation 2023228916   22 Sep 2026 J 7 0.05% BIOPUR 3015 2.5 % EC Deformation Deformation A study was then performed adding different numbers of layers of 10% BIOPUR 3015. Sample Basecoat Topcoat Water drop without scratch Water drop with scratch (control) J 1 10% BIOPUR 3015 (4 g / sf | 1g / sf per layer) 2.5 % EC Partial Deformation Deformation J 9 10% BIOPUR 3015 (8 g / sf | 1g / sf per layer) 2.5 % EC No Deformation Deformation J 10 10% BIOPUR 3015 (12 g / sf | 1g / sf per layer) 2.5 % EC No Deformation Deformation J 11 10% BIOPUR 3015 (16 g / sf | 1g / sf per layer) 2.5 % EC No Deformation Deformation To better understand the effects activated silk has on the topcoat adhesion. An adhesive layer with BIOPUR 3015 and the minimum amount of silk needed to reach 80% biobased was made. Sample Basecoat Topcoat Topcoat Solvent Scotch Tape Test Water Drop test K 1 1% BIOPUR 3015 | 0.17% AS 14A(4 g / sf | 1g / sf per layer) 2.5 % EC Methoxypropanol Fail* Fail K 2 1% BIOPUR 3015 | 0.17% AS 105TS(4 g / sf | 1g / sf per layer) 2.5 % EC Methoxypropanol Fail* Fail 2023228916   22 Sep 2026 References The following documents may be referenced as sources of data Document Description of Document EBN-SOP-TXTL-035 Veslic Testing Procedures (developed according to ISO 11640). ETHOCEL™ Standard 200 Industrial Ethylcellulose Technical Data Sheet for ETHOCEL™ Standard 200 Industrial Ethylcellulose All patents, patent applications, and published references cited herein are hereby incorporated by reference in their entirety. While the methods of the present disclosure have been described in connection with the specific embodiments thereof, it will be understood that it is capable of further modification. Further, this application is intended to cover any variations, uses, or adaptations of the methods of the present disclosure, including such departures from the present disclosure as come within known or customary practice in the art to which the methods of the present disclosure pertain. The term “comprising” as used in this specification and claims means “consisting at least in part of”. When interpreting statements in this specification and claims which include the term “comprising”, other features besides the features prefaced by this term in each statement can also be present. Related terms such as “comprise” and “comprises” are to be interpreted in similar manner. In this specification where reference has been made to patent specifications, other external documents, or other sources of information, this is generally for the purpose of providing a context for discussing the features of the invention. Unless specifically stated otherwise, reference to such external documents is not to be construed as an admission that such documents, or such sources of information, in any jurisdiction, are prior art, or form part of the common general knowledge in the art.

Claims

1. A composite comprising a first polymeric macromolecular species or polymer and a second polymeric macromolecular species or polymer having a characteristic selected from:i. a portion of the first polymeric macromolecular species or polymer and a portion of the second polymeric macromolecular species or polymer are physically and / or chemically entangled;ii. a portion of the first polymeric macromolecular species or polymer are physically and / or chemically crosslinked;iii. a portion of the second polymeric macromolecular species or polymer are physically and / or chemically crosslinked;iv. a portion of the first polymeric macromolecular species or polymer are chemically and / or physically integrated into a portion of the second polymeric macromolecular species or polymer;v. a portion of the first polymeric macromolecular species or polymer and a portion of the second polymeric macromolecular species or polymer are not separable;vi.   a portion of the first polymeric macromolecular species or polymer and / ora portion of the second polymeric macromolecular species or polymer are cross-linked;vii.   a portion of the first polymeric macromolecular species or polymer and / ora portion of the second polymeric macromolecular species or polymer are partially organized and / or crystallized;viii. a portion of the first polymeric macromolecular species or polymer and a portion of the second polymeric macromolecular species or polymer cannot be delaminated; andix. a portion of the first polymeric macromolecular species or polymer and a portion of the second polymeric macromolecular species or polymer are self-assembled,wherein the second polymeric macromolecular species or polymer comprises ethyl cellulose having a degree of substitution of 0.5 to 1, 1 to 1.5, 1.5 to 2, 2 to 2.5, or 2.5 to 3.2023228916   06 Oct 20262. The composite of claim 1, wherein a portion of the first polymeric macromolecular species or polymer in the composite has a second structure different than a first structure of the first polymeric macromolecular species or polymer and / or wherein a portion of the second polymeric macromolecular species or polymer in the composite has a second structure different than a first structure of the second polymeric macromolecular species or polymer.

3. The composite of any one of claims 1 to 2, wherein a portion of the first polymeric macromolecular species or polymer in the composite has a second structure different than a first structure of the first polymeric macromolecular species or polymer, and a portion of the second polymeric macromolecular species or polymer in the composite has a second structure different than a first structure of the second polymeric macromolecular species or polymer.

4. The composite of any one of claims 1 to 3, wherein the first polymeric macromolecular species or polymer comprises a protein component.

5. The composite of claim 4, wherein the protein component comprises one or more of silk fibroin proteins or fragments, collagen, elastin, gelatin, corn zein, wheat gluten, pectin, chitin, casein, and / or whey.

6. The composite of any one of claims 1 to 3, wherein the first polymeric macromolecular species or polymer comprises a biodegradable polymer.

7. The composite of any one of claims 1 to 3, wherein the first polymeric macromolecular species or polymer comprises one or more of a polyurethane component.

8. The composite of any one of claims 1 to 3, wherein the first polymeric macromolecular species or polymer comprises a poly lactic acid (PLA) component, a poly(lactic-co-glycolic acid) (PLGA) component, or both.

9. The composite of any one of claims 1 to 8, wherein the ethoxyl content in ethyl cellulose is from 45.0% to 49.5%, from 45.0% to 46.0%, from 45.0% to 47.0%, from 47.0% to 48.0%, or from 48.0% to 49.5%.2023228916   06 Oct 202610. The composite of any one of claims 1 to 9, wherein a second structure of the ethyl cellulose comprises a degree of crystallinity of less than 100%.

11. The composite of any one of claims 1 to 9, wherein a second structure of the ethyl cellulose comprises a degree of crystallinity of between about 5% and less than about 100%.

12. The composite of any one of claims 1 to 9, wherein a second structure of the ethyl cellulose comprises a degree of crystallinity of between about 10% and about 20%, between about 20% and about 30%, between about 30% and about 40%, between about 40% and about 50%, between about 50% and about 60%, between about 60% and about 70%, between about 70% and about 80%, between about 80% and about 90%, between about 90% and about 99%, or between about 90% and about 100%.

13. The composite of any one of claims 1 to 9, wherein a second structure of the ethyl cellulose comprises a degree of crystallinity of less than about 99%, less than about 98%, less than about 97%, less than about 96%, less than about 95%, less than about 94%, less than about 93%, less than about 92%, less than about 91%, less than about 90%, less than about 89%, less than about 88%, less than about 87%, less than about 86%, less than about 85%, less than about 84%, less than about 83%, less than about 82%, less than about 81%, less than about 80%, less than about 79%, less than about 78%, less than about 77%, less than about 76%, less than about 75%, less than about 74%, less than about 73%, less than about 72%, less than about 71%, less than about 70%, less than about 69%, less than about 68%, less than about 67%, less than about 66%, less than about 65%, less than about 64%, less than about 63%, less than about 62%, less than about 61%, less than about 60%, less than about 59%, less than about 58%, less than about 57%, less than about 56%, less than about 55%, less than about 54%, less than about 53%, less than about 52%, less than about 51%, less than about 50% less than about 49%, less than about 48%, less than about 47%, less than about 46%, less than about 45%, less than about 44%, less than about 43%, less than about 42%, less than about 41%, less than about 40%, less than about 39%, less than about 38%, less than about 37%, less than about 36%, less than about 35%, less than about 34%, less than about 33%, less than about 32%, less than about 31%, less than about 30% less than about 29%, less than about 28%, less than about 27%, less than about 26%, less than2023228916   06 Oct 2026about 25%, less than about 24%, less than about 23%, less than about 22%, less than about 21%, less than about 20% less than about 19%, less than about 18%, less than about 17%, less than about 16%, less than about 15%, less than about 14%, less than about 13%, less than about 12%, less than about 11%, or less than about 10%.

14. The composite of any one of claims 1 to 13, wherein a concentration of the first polymeric macromolecular species or polymer closer to a first surface of the composite is higher than a concentration of the first polymeric macromolecular species or polymer closer to a second surface of the composite.

15. The composite of any one of claims 1 to 13, wherein a concentration of the second polymeric macromolecular species or polymer closer to a second surface of the composite is higher than a concentration of the second polymeric macromolecular species or polymer closer to a first surface of the composite.

16. The composite of any one of claims 1 to 15, wherein the composite has an increased water resistance compared to one of: i) a non-composite material comprising the first polymeric macromolecular species or polymer, but excluding the second polymeric macromolecular species or polymer, ii) a non-composite material comprising the second polymeric macromolecular species or polymer, but excluding the first polymeric macromolecular species or polymer, or iii) a non-composite material comprising the first polymeric macromolecular species or polymer and the second polymeric macromolecular species or polymer, wherein the polymeric macromolecular species or polymers are not physically and / or chemically molecularly entangled.

17. The composite of any one of claims 1 to 16, wherein the composite has an increased water vapor permeability compared to one of: i) a non-composite material comprising the first polymeric macromolecular species or polymer, but excluding the second polymeric macromolecular species or polymer, ii) a non-composite material comprising the second polymeric macromolecular species or polymer, but excluding the first polymeric macromolecular species or polymer, or iii) a non-composite material comprising the first polymeric macromolecular species or polymer and the second polymeric macromolecular species or polymer, wherein the polymeric macromolecular species or polymers are not physically and / or chemically molecularly entangled.2023228916   06 Oct 202618. An article comprising a substrate and a coating, the coating comprising the composite of any one of claims 1 to 17.

19. The article of claim 18, wherein the coating has a thickness between about 10 pm and about 1000 pm.

20. The article of any one of claims 18to 19, wherein:the amount of coating on the substrate is between about 0.01 g / ft2 and about 25 g / ft2;the amount of first polymeric macromolecular species or polymer in the coating onthe substrate is between about 0.001 g / ft2 and about 20 g / ft2; and / orthe amount of second polymeric macromolecular species or polymer in the coating on the substrate is between about 0.001 g / ft2 and about 15 g / ft2.

21. The article of any one of claims 18to 20, wherein the substrate comprises a leather material or a textile material.

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