Dispersion processing aids for the formation of a leather material

[0001] The present application claims priority to and the benefit of U.S. application 62/275,503, “Dispersion Processing Aids for the Formation of a Leather Material” (filed Jan. 6, 2016), the entirety of which application is incorporated herein by reference for any and all purposes.

[0002] The disclosure relates to formed leather products and their method of manufacture, particularly, a leather substrate formed in part or in whole from waste leather.

[0003] Conventional leather is formed by tanning animal hides. The tanning process treats an animal hide with a variety of substances to improve and maintain leather's desirable physical characteristics for use in clothing, upholstery, luggage and like applications. The most desirable physical characteristics of tanned leather include appearance, feel, resilience to stretching, longevity, treatability with a variety of surface conditioning finishes and natural drape.

[0004] Leather's desirable characteristics are attributed in part to its being a fibrous, semi-porous material made up of an entangled, open matrix of resistant collagen fibers. Collagen fibers make up majority of leather's composition. Collagen fibers are made up of constituent collagen fibril bundles made up in turn by smaller elongated strands of collagen protein known as collagen fibrils.

[0005] The tanning process is directed primarily toward collagen fibers to fix chemically reactive sites between adjacent collagen molecules. This links the matrix of resistant collagen fiber bundles, leaving tanned leather pliable, and occupies reactive sites that otherwise would allow leather to degrade and rot. The tanning process likewise removes other compounds from the hide that may be susceptible to degradation and/or perform other functions in the hide that may be replaced with other materials.

[0006] Obtaining natural leather is problematic due to supply hide having varying qualities, tanning process costs, varying hide costs over time among other challenges.

[0007] The leather harvesting, tanning and preparation process produces waste leather byproducts in leather scraps and shavings. If not otherwise used, the waste leather is disposed of by landfill or incineration, creating a negative environmental impact.

[0008] Artificial leather products containing waste leather, such as bonded leather, attempt to emulate natural leather. Bonded leather is synthetic leather formed by embedding shredded leather particles into various binding materials. The shredded leather and binding material substance may be applied onto a fabric backing carrier.

[0009] Bonded leather type synthetic leathers lack the above-noted desirable characteristics of natural leather. This is due to synthetic leathers lacking the continuous matrix of resistant collagen fiber bundles found in natural leather.

[0010] The failure of known artificial and synthetic leathers that contain shredded leather particles is that the individual particles do not physically interact to reproduce or emulate the characteristics of a continuous piece of natural leather having an entangled matrix of resistant collagen fibers. Most notably, artificial and synthetic leathers suffer as lacking desirable tensile strength qualities, other strength qualities and esthetic attributes.

[0011] In tests applied by a conventional tensometer, artificial and synthetic leather samples of 0.010 to 0.080 inch thickness were subjected to pulling stresses under tension to failure. Measurement of maximum applied force before failure was recorded and calculated as maximum tensile strength PSI measurements ranging generally from about 790 pounds per square inch (PSI) to about 1750 PSI.

[0012] Likewise, given the inherently variable makeup of organic animal hides and tanning treatments, the tensile strength qualities of tanned natural leather can vary widely. The tensile strength of representative natural tanned leathers were found to vary from about 2000 to 3200 PSI depending on leather quality, mechanical treatments and coatings applied to the leather.

[0013] Processes for forming other types of formed leather substrates containing shredded and fibrillated collagen leather fibers derived from waste derived leather are known. A challenge with these processes is the inability to achieve high levels of fibril dispersion so that subsequently formed leather substrates have the potential for fibril to fibril entanglement. Other challenges are that formed interim wet lap products are difficult to dewater and represent a limit to the degree of fibril dispersion which can be achieved in a final leather substrate product. Wet lap may refer to a sheet comprising the dispersion, where particles or fibers are suspended in a fluid (i.e., a slurry) and the wet lap may be pressed or otherwise manipulated to eliminate at least a portion of the fluid.

[0014] The interim wet lap products of these processes also tend to have low wet lap strengths. This presents possessing challenges with manipulating interim wet lap products in large scale production processes using known paper-type processing machines. During transition of the interim wet lap from wire mesh sections of paper-type processing machines, the wet lap tends to break reducing process efficiency and making it very difficult or impossible to produce the end product on a large scale.

[0015] Thus, there is a need for an improved formed leather product that is created from available waste leather by-products that reproduces desirable physical characteristics of natural leather. The improved leather product should reproduce the collagen fiber matrix that is found in natural leather, have predicable physical characteristics including high tensile strength, desired elastic properties for a range of end applications and treatability by conventional leather conditioning substances. The process of creating the improved leather product should allow improved de-watering of interim wet lap products and have good wet lap strength to facilitate physically manipulating interim wet lap products.

[0024] Disclosed is a formed leather product created from commonly-available waste leather byproducts and its method of manufacture. The formed leather product reliably reproduces desirable physical characteristics of natural leather including high tensile strength and desired elastic properties for end applications and treatability by conventional leather conditioning substances.

[0025] The improved leather product includes a formed leather substrate containing a matrix formed by collagen fibrils. The collagen fibril matrix is formed from entangled collagen fibrils derived from collagen fibril bundles and collagen fibers found in naturally occurring leather.

[0026] The formed leather substrate is formed by obtaining leather waste and physically processing the waste by shredding or grinding to create leather particles of desired size as provided herein. The leather particles are combined with water to form a leather particle/water mixture (also, referred to as a particle/water mixture herein). The mixture is processed to allow collagen fibril bundles within the particles to absorb a quantity of water. The water absorption swells and partially distresses the collagen fibril bundles. Distressing of the collagen fibril bundles may refer to the fibril bundles of the leather particles separating or partially separating from one another. For example, ends of individual collagen fibrils may begin to separate from among the collagen fibril bundles. The partially distressed bundles are particularly susceptible to mechanical dispersion. Mechanical dispersion of the swollen, partially distressed fibril bundles extracts a high yield of constituent collagen fibrils from the bundles to the particle/water mixture. Water is then removed from the mixture through a series of dewatering steps to form a leather substrate product containing a matrix of collagen fibrils, bundles and fibers.

[0027] The process allows improved de-watering of interim wet lap products. Formed interim wet lap products have improved wet lap strength to facilitate physically manipulating the interim wet lap products.

[0028] Leather products containing the collagen fibril matrix substrate have improved tensile strength qualities over known artificial and synthetic leathers. In tests by conventional tensometer, samples of leather substrate products are subjected to pulling stresses under tension to failure to determine maximum applied force measurements before failure. Measurements recorded and calculated as maximum tensile strength were well above known artificial and synthetic leathers and many natural tanned leather samples.

[0029] Leather products containing the collagen fibril matrix substrate share the desirable physical characteristics of conventional leather and may be treated by leather mechanical enhancement techniques such as embossing, calendaring, staking, tumbling and so forth.

[0030] The formed leather substrate and its method of manufacture are disclosed herein.

[0031] Other objects and features of the leather substrate will become apparent as the description proceeds, especially when taken in conjunction with the accompanying drawing sheets illustrating aspects of the leather substrate.

[0032] A process of forming a leather substrate may comprise collecting a portion of leather source material (such as leather waste); shredding and screening the leather waste material to provide leather material particles comprising collagen fiber bundles; combining the leather material particles with a portion of a fluid or water to provide a water/leather material particle or a fluid/leather material particle solution; allowing collagen fiber bundles of the leather material particles to absorb at least a portion of the fluid or water; shearing the leather material particles; dispersing the leather material particles; forming a wet lap or pulp comprising the leather material particles; removing at least a portion of the fluid or water from the fluid/leather material particle solution or from the water/leather material particle solution.

[0033] In some aspects, a process of forming a leather substrate may comprise manipulating a leather material to form leather material particles; combining the leather material particles with a fluid to form a leather material solution; adding a polymer latex to the leather material solution; adding a dispersion aid; and removing at least a portion of the fluid from the leather material solution to form a leather substrate.

[0034] A leather substrate formed according to the method disclosed herein wherein the leather substrate exhibits a tear resistance of greater than about 20 Newtons when tested in accordance with ASTM D 4704.

[0035] In some aspects, this disclosure relates to leather products formed from waste leather materials and their method of manufacture and to the manufacture of a leather substrate material from waste leather materials. Particularly, the disclosure relates to the use of dispersion processing aids that prevent undesired agglomeration or clumping of intermediate particle/water mixtures during manufacturing steps. The disclosed dispersion processing aids allow processing of particle/water mixtures with reduced agglomeration or clumping while maintaining adequate dewatering in later manufacturing process steps.

[0036] Use of the disclosed dispersion processing aids assists in manufacturing a leather substrate material by formation steps including flowing or piping particle/water mixtures between different vessels for processing steps by avoiding agglomeration or clumping that may block passageways and/or result in undesired leather to water ratios during processing steps.

[0037] The dispersion processing aids may be used in leather substrate formation processes described generally in the present disclosure.

[0038] Collected leather waste is physically processed by shredding or grinding to create leather particles of desired size. The desired size may refer to particle size that provides an apparently even dispersion of leather particles in the leather particle/water mixture. That is the desired size may provide a non-agglomerated pieces or leather particles.

[0039] Then, the leather particles are combined with water to form a particle/water mixture. This mixture is subjected to physical mixing or agitation by mechanical dispersion devices.

[0040] Dispersion processing aids may be added to the particle/water mixture. A potential dispersion processing aid may be a polyvinyl alcohol. Potential polyvinyl alcohols may be partially hydrolyzed to a degree greater than 95%, and having a viscosity of greater than 500 centipoise (cP). A potential polyvinyl alcohol may be manufactured from vinyl acetate monomers (VAM), polymerized into polyvinyl acetate and then converted to polyvinyl alcohol. Potential polyvinyl alcohols of this kind may be a Selvol™ brand Polyvinyl Alcohol 325 or Selvol™ brand Polyvinyl Alcohol 325 produced by Sekisui Specialty Chemicals.

[0041] Another potential dispersion processing aid may be a cross-linked polyacrylate polymer. Potential cross-linked polyacrylate polymers may be within classes of superabsorbent polymers (SAPs). That is, polymers capable of absorbing and retaining large amounts liquid relative to their own mass. A potential cross-linked polyacrylate polymer of this kind may be a Carbopol™ brand Polymer produced by The Lubrizol Corporation.

[0042] Another potential dispersion processing aid may be a low molecular weight polysaccharide such as sucrose and polysaccharides derived from cellulose for example sodium carboxymethylcellulose. A low molecular weight polysaccharide may have a molecular weight as low as about 150 grams per mole, or about 180 grams per mole (g/mol). Low molecular weight polysaccharides may include up to about 5000 g/mol, or up to about 1000 g/mol, or up to about 500 g/mol for example.

[0043] Leather substrates may be formed by processes described generally in the present disclosure. Leather waste may be a source material for the materials used to form the leather substrates described herein. As described herein, leather waste is physically processed by shredding or grinding to create leather particles of desired size. The desired size may refer to particle size that provides an apparently even dispersion of leather particles in the leather particle/water mixture. That is the desired size may provide a non-agglomerated pieces or leather particles. For example, the leather waste may be processed in a cutting, grinding, or shredding machine that allows a continuous thorough shearing or cutting of the leather to provide generally uniform sized particles. In a specific example, the leather is cut or ground in machinery and screened through apertures of approximately 3/32 of an inch in diameter to provide generally uniform leather particle pieces. However, the leather particles may not necessarily be the same size or same size and shape. The leather particles may be combined with water to form a particle/water mixture. In various aspects, the particle/water mixture have a particle content of less than 10 wt. %. The particle/water mixture may have a particle content of about 6 wt. %. The particle/water mixture is then diluted to a particle content of about 2% by the addition of a selected processing aid as described herein.

[0044] The resulting mixture is subjected to physical mixing or agitation by mechanical dispersion devices. Potential dispersion devices may be refiners such as double disk refiners or conical refiners as known in the paper manufacturing processes. Other potential dispersion devices may be beaters as conventionally known in paper processing machinery, such as Hollander-type beaters.

[0045] A polymer latex is added to the particle/water mixture and mixed into the particle/water mixture using standard industrial mixing equipment such a LIGHTNIN™ brand mixer produced by SPX Corporation. Exemplary polymer latex may include an acrylic latex polymer such as acrylonitrile latex polymer. Polymer latex may further include, but is not limited to acrylonitrile-butadiene styrene (ABS), styrene-butadiene styrene, acrylonitrile-ethylene-butadiene-styrene, methyl methacrylate-butadiene styrene, polybutadiene, or styrene acrylonitrile latex polymers, among others. In some aspects, the polymer latex comprises about 50% polymer.

[0046] The polymer latex is absorbed by leather material within the particle/water mixture. The physical mixing/agitation is maintained until the supernatant liquid is clear, substantially clear, appears visibly clear, or appears substantially clear to an observer.

[0047] In some aspects, an ionic salt or may be added to the water/leather particle mixture. Added salts may include salts of magnesium, strontium and calcium. In particular, added salts may include: magnesium chloride MgCl₂ and hydrated forms thereof, calcium chloride CaCl₂, magnesium sulfate Mg₂SO₄ and hydrated forms thereof, strontium chloride SrCl₂, and hydrated forms thereof. Other salts may also be effective, not limited to the above listed divalent cationic salts, including: barium chloride BaCl₂, iron(II) chloride FeCl₂, magnesium bromide MgBr₂, and magnesium iodide MgI₂, for example. Ionic salts may be included so as to provide a water/leather particle mixture comprising up to about 25 wt. % of one or more ionic salts. In one example, the water/leather particle mixture comprises about 2% CaCl2 and 2.5% MgCl₂.6H₂O (magnesium chloride hexahydrate).

[0048] In additional leather substrate formation steps, the particle/water mixture is then dewatered. In steps particularly related to paper making processes, the particle/water mixture is dewatered to form a wet lap slurry that is transferred to a sheet mold or like screen. The screen allows water to drain from the particle/water wet lap slurry consisting of about 0.75% leather particle solids.

[0049] Use of the disclosed dispersion processing aids greatly reduces the time needed to obtain acceptable wet lap dewatering and/or leather substrate materials produced by this method have greater strength and tear resistance than conventionally formed waste leather materials.

[0050] FIG. 1 is a magnified cross-sectional view of conventional tanned leather 10. Leather 10 is made up by numerous elongate, entangled collagen fibers 12 that cooperate to form an open tanned leather matrix 14.

[0051] FIG. 2 is a cross-sectional representational view of a single collagen fibril bundle 16 segment made up of constituent elongated bundles of collagen fibrils 18. It is understood that FIG. 2 is a representational view and that in naturally-occurring collagen fibril bundles, the constituent elongated bundles of collagen fibrils would not be aligned in uniform, parallel formation.

[0052] The disclosed leather substrate is formed from processing collected scrap leather byproducts derived from conventional leather processing steps.

[0053] Collected scrap leather byproducts are ground or shredded into particles 20 of desired size containing leather material including fibril bundles 16. Collagen fibril bundles 16 are subjected to water absorption and distressed though swelling steps described below to form swollen fibril bundles 22. Swollen fibril bundles 22 contain quantities of absorbed water 23 that partially fibrillates the bonds between adjacent collagen fibrils 18. Distressed swollen fiber bundle segments 22 contain fibrillated constituent collagen fibrils 18′ as shown in FIG. 5.

[0054] The water absorption likewise distresses and partially fibrillates the bonds between adjacent collagen fibers 12 in a particle 20.

[0055] Swollen fiber bundle segments 22 are subjected to mechanical dispersion steps to extract elongate constituent collagen fibrils 18. Collagen fibrils 18 are collected and processed to form collagen fibril matrix 24 as detailed below.

[0056] The collagen fibril matrix 24 is made up of a number of individual collagen fibrils 18 derived from collagen fiber bundles 12. Each collagen fibril 18 has an elongate body having a cross-sectional diameter generally less than 10 micrometers, and a length generally many times its diameter, each collagen fibril physically engaged and entangled with adjacent collagen fibrils to form collagen fibril matrix 24. Collagen fibril matrix 24 contains a plurality of fine gaps 26 between adjacent collagen fibrils 18 to form an overall open and porous matrix structure.

[0057] Methods of forming leather substrates containing collagen fibril matrix 24 are described below.

[0058] The flowchart of FIG. 7 discloses a method 28 of producing a leather substrate containing the collagen fibril matrix from leather byproduct.

[0059] Starting at step 30, leather byproduct waste is collected. Potential byproduct leather waste could be scrap leather waste byproducts produced in tanning processing steps or leather waste from articles manufacture from tanned leather.

[0060] At step 32, byproduct leather waste is shredded or ground and screened to form de-agglomerated byproduct particles 18 of a desired size. Particles are passed through a screen having screen apertures of a selected size to assure collected particles 18 are of a like selected size.

[0061] At step 34, collected particles 18 are mixed with a quantity of water to form a particle/water mixture.

[0062] Particles 20 become swelled with water from the particle/water mixture. Particle swelling is a result of particle collagen fibril bundles absorbing water from the particle/water mixture to form swollen fibril bundle segments 22 at step 36. The swollen fibril bundle segments are partially distressed, causing partial separation of constituent fibrils which allows improved bundle dispersion in later processing steps.

[0063] At step 38, the particle/water mixture is sheared and dispersed by a dispersion device. The dispersion device subjects particles 20 within the particle/water mixture to shear forces that separate collagen fibrils 18 from particle collagen fibril bundles 16. The dispersion process shreds particles 20 and further distresses particle collagen fibril bundles to separate collagen fibrils 18 from particle collagen fibril bundles 12.

[0064] Potential dispersion devices may be refiners such as a double disk refiner or conical refiner as are known in the paper manufacturing processes. Other potential dispersion devices may be beaters as conventionally known in paper processing machinery, such as Hollander-type beaters.

[0065] At step 38 dispersion of the particle/water mixture is conducted for a period of time required to obtain desired fibril dispersion.

[0066] At step 40, water is removed from the particle/water mixture to form a substrate wet lap.

[0067] Water is further removed from the substrate wet lap to form a leather substrate by steps known in conventional paper manufacturing using machinery as known to convert wet paper pulp to a dried paper product. For instance, draining of the particle/water mixture to form a substrate wet lap may be effected through use of a Fordriner-type machine having various pressing and drying operations as explained in greater detail below.

[0068] At step 42, water is removed from the substrate wet lap to form a leather substrate containing primarily by-weight of solids and a remainder by-weight of water. As water is removed from the substrate wet lap, separated collagen fibrils 18 within the particle/water mixture physically interact with each other. As adjacent fibrils become physically engaged with each other, leather substrate collagen fibril matrix 24 is formed at step 44. Step 52 water removal may be effected through use of a Fordriner-type machine as explained in greater detail below.

[0069] FIG. 8 illustrates an apparatus 100 for producing a leather substrate in accordance with the steps shown in the FIG. 7 flowchart. Apparatus 100 may include elements commonly found in Fordriner-type paper processing machines.

[0070] In apparatus 100, waste leather 102 is selected and physically processed by shredding or grinding in shredder or grinder 104. Waste leather 102 is selected as described in step 30 of the FIG. 8 flowchart.

[0071] Initially collected waste leather 102 may come in the form of scraps from other leather tanning and treatment processes. Shredder or grinder 104 initially de-agglomerates shavings that may have become clumped due to water content or are compacted during bailing or other packaging methods and also grinds larger particles to a desired size.

[0072] Physical processing by shredding or grinding forms initially shredded leather particles 106. Initially shredded leather particles 106 are screened through screening machine 108 to select leather particles 20 of a desired size and to screen out unwanted waste that may have passed through shredder 104 as described in step 32 above.

[0073] Alternatively, a grinder may be used having an integrated screen to select processed leather particles having desired size criteria.

[0074] Leather particles 20 are next mixed with water 23 in a mixing chest or mixing tank 110 to form a water/leather particle mixture 112 containing a percentage of leather particles by-weight as described in step 34 above.

[0075] Next, leather particle collagen fibril bundles absorb water 23 from the particle/water mixture to form swollen fibril bundles 22 at step 38.

[0076] Next, water/leather particle mixture 112 is delivered to a dispersion tank 116. Dispersion tank 116 includes a dispersion refiner 118, such as a double disk refiner, a conical refiner or Hollander-type beater as is known in the paper manufacturing art.

[0077] Dispersion refiner 118 subjects leather particles 20 within mixture 112 to shear dispersion forces as described in step 40 above.

[0078] Alternatively, water/leather particle mixture 112 may be separately delivered to a dispersion device and returned to mixing tank 110 for processing before drying steps are undertaken.

[0079] Water is next separated from mixture 112 to form a wet lap slurry 122.

[0080] Wet lap slurry 122 is transferred from dispersion tank 116 to processing machine 124 for dewatering as described in step 50 above.

[0081] Processing machine 124 may be a Fourdrinier-type machine typically used in the making of paper having a head box 125 and a transfer assembly 126 including wire mesh section 128, one or more wet presses 130, dryer cans 132 and calendaring rollers 134.

[0082] Initially, wet lap slurry 122 is transferred to proceeding machine head box 125 and to wire mesh section 128 wire mesh endless belt 136. Wire mesh endless belt 136 is made up of a wire meshing to allow initial draining of wet lap slurry 122 and is driven by rollers 138. Vacuums 140 may be used to assist in dewatering wet lap slurry 122.

[0083] Dewatering by wire mesh section 128 sufficiently dewaters wet lap slurry 122 to form wet lap 142. Wet lap 142 is transferred further along transfer assembly 126 from wire mesh section 128 to one or more wet presses 130 for additional mechanical dewatering by presses 144. Wet lap 142 is further transferred along assembly 126 from wet presses 130 to drier section 132 for final dewatering by drying. Drier section 132 may include a heated felt dryer known in the paper making art.

[0084] At this point in the process, wet lap 142 has been sufficiently dewatered to form a leather substrate 148 having desired moisture content and containing a collagen fibril matrix 24 as described in steps 52 and 54 above.

[0085] It should be appreciated that the present disclosure can include any one up to all of the following aspects:

[0086] Aspect 1. A method of forming a leather substrate material comprising:

[0087] manipulating a leather material to form leather material particles;

[0088] combining the leather material particles with a fluid to form a leather material solution;

[0089] adding a polymer latex to the leather material solution;

[0090] adding a dispersion aid to the leather material solution;

[0091] agitating the leather material solution; and

[0092] removing at least a portion of the fluid from the leather material solution to form a leather substrate wherein the leather substrate exhibits a tear resistance of greater than about 20 Newtons when tested in accordance with ASTM D 4704.

[0093] Aspect 2. The method of aspect 1, further comprising adding an ionic salt.

[0094] Aspect 3. The method of aspect 1, wherein the leather material comprises waste leather collected from tanning waste.

[0095] Aspect 4. The method of aspect 1, wherein agitating the leather material solution comprises physically mixing the leather material solution.

[0096] Aspect 5. The method of aspect 1, wherein manipulating the leather material comprises grinding or reducing the leather material to a particulate form.

[0097] Aspect 6. The method of aspect 1, further comprising adjusting pH of the leather material solution.

[0098] Aspect 7. The method of aspect 1, wherein the ionic salts include magnesium chloride, calcium chloride, magnesium sulfate, strontium chloride, barium chloride, iron(II) chloride, magnesium bromide, and magnesium bromide, or a combination thereof.

[0099] Aspect 8. The method of aspect 1, wherein the adding the ionic salt to the leather material solution effects an ionic salt content of up to about 25%.

[0100] Aspect 9. The method of aspect 1, wherein the polymer latex comprises an acrylic polymer latex.

[0101] Aspect 10. The method of aspect 1, wherein the adding a polymer latex to the leather material solution effects a polymer content of about 25% combined leather material particles and latex polymer solids.

[0102] Aspect 11. A leather substrate material formed by a process comprising:

• • [0103] manipulating a leather material to form leather material particles;
  • [0104] combining the leather material particles with a fluid to form a leather material solution;
  • [0105] adding a polymer latex to the leather material solution;
  • [0106] adding a dispersion aid to the leather material solution; and
  • [0107] removing at least a portion of the fluid from the leather material solution to form a leather substrate.

[0108] Aspect 12. The leather substrate of aspect 11, wherein the leather substrate exhibits a tear resistance of greater than about 20 Newtons when tested in accordance with ASTM D 4704.

[0109] Aspect 13. The leather substrate of aspect 11, wherein manipulating the leather material comprises grinding or reducing the leather material to a particulate form.

[0110] Aspect 14. The leather substrate of aspect 11, further comprising adjusting pH of the leather material solution.

[0111] Aspect 15. The leather substrate of aspect 11, wherein the ionic salts include magnesium chloride, calcium chloride, magnesium sulfate, strontium chloride, barium chloride, iron(II) chloride, magnesium bromide, and magnesium bromide, or a combination thereof.

[0112] Aspect 16. The leather substrate of aspect 11, wherein the dispersion aid comprises a polysaccharide.

[0113] Aspect 17. The leather substrate of aspect 11, wherein the polymer latex comprises an acrylic polymer latex.

[0114] Aspect 18. The leather substrate of aspect 11, wherein the adding a polymer latex to the leather material solution effects a polymer content of about 25% combined leather material particles and latex polymer solids.

[0115] Aspect 19. The leather substrate of aspect 11, wherein the leather substrate exhibits a tear resistance of greater than about 20 Newtons when tested in accordance with ASTM D 4704.

[0116] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term “comprising” may include the aspects or aspects “consisting of” and “consisting essentially of.” Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.

[0117] As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a glass fiber” includes mixtures of two or more such glass fiber.

[0118] Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It is also understood that each unit falling within a range between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0119] As used herein, the terms “optional” or “optionally” mean that the subsequently described event, condition, component, or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

[0120] As used herein, the term or phrase “effective,” “effective amount,” or “conditions effective to” refers to such amount or condition that is capable of performing the function or property for which an effective amount is expressed. As will be pointed out below, the exact amount or particular condition required may vary from one aspect or aspect to another, depending on recognized variables such as the materials employed and the processing conditions observed. Thus, it is not always possible to specify an exact “effective amount” or “condition effective to” for each aspect or aspect encompassed by the present disclosure. However, it should be understood that an appropriate effective amount or condition effective to achieve a desired results will be readily determined by one of ordinary skill in the art using only routine experimentation.

[0121] As used herein, “fibrils” refers to fine fiberlike materials. Leather materials described herein may comprise fibrils which may associate together in bundles to form larger bundles, often described as leather bundles or leather fibers. The leather bundles or leather fibers or leather fiber bundles may be comprised of a subassembly of fibrils.

[0122] As used herein, “polymer latex” may refer to an aqueous colloidal distribution of polymer particles.

[0123] Disclosed are the components to be used to prepare disclosed compositions of the invention as well as the compositions themselves to be used within methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation cannot be explicitly disclosed, each is specifically contemplated and described herein. This concept applies to all aspects of this application including, but not limited to, steps in methods of making and using the compositions of the invention. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific aspect or combination of aspects of the methods of the invention.

[0124] References in the specification and concluding claims to parts by weight, of a particular component in a composition or article, denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a composition containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.

[0125] A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included. For example if a particular element or component in a composition or article is said to have 8% weight, it is understood that this percentage is relation to a total compositional percentage of 100%.

[0126] Each of the component starting materials disclosed herein are either commercially available and/or the methods for the production thereof are known to those of skill in the art.

[0127] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. Other aspects of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.