Moldable Composition

Abstract

The present invention relates to a moldable material containing a) at least one binder and b) at least one particulate filler material. The filler material includes a natural, non-porous filler material such as cork or coconut fiber. The present invention also provides products, such as modeling compounds, art materials, children's play materials, filler materials, building materials, packaging materials, insulating materials, and / or fire-retardant materials, that include or are made from the moldable material. Methods for making the moldable material are also provided.

Description

[Technical Field]

[0001] [Field of the Invention] The present invention relates to a moldable composition comprising a binder and at least one filler, the filler comprising a natural product. In particular, the present invention relates to such a material wherein the filler is a non-food product, such as a lignin-containing product, especially a suberin-containing product. [Background technology]

[0002] [Background of the invention] Moldable compositions are useful in a variety of applications, with children's play compositions such as doughs and molding clays being a very common use, but many other applications exist, including artistic endeavors such as sculpting, and industrial applications such as construction, acoustic or thermal insulation, and packaging.

[0003] Many moldable compositions are formed from at least one binder material and at least one filler. The filler provides bulk to the material and influences properties such as the density, compressibility, thermal properties, and acoustic properties of the composition. The binder primarily holds the composition together and may contribute properties such as strength and rigidity. Moldable materials containing fillers and binders may be moldable at room temperature or may require heating to become moldable and harden again upon cooling. Similarly, moldable materials may be permanently moldable or may "set" through actions such as drying, heating, or chemical reaction.

[0004] A variety of particulate materials have been used or proposed as all or part of the filler component in moldable materials, including inorganic fillers such as sand, chalk, mica, and glass, synthetic polymers such as resin beads, expanded polymer materials, and polymer microbubbles, and natural materials such as food flours such as wheat flour or rice flour.

[0005] Natural filler materials offer several potential advantages over inorganic and synthetic materials. They are generally easily and potentially inexpensively procured because they are often part of existing natural product industries; they have low biological impacts and / or well-established safety profiles, are typically biocompatible, and / or are relatively environmentally friendly in both procurement and disposal. The vast majority of natural product-based fillers are carbon-based and, because they were recently produced, serve to sequester carbon from the atmosphere. When such products reach the end of their useful life, the filler material can be easily disposed of because, as a natural product, natural decomposition mechanisms exist and environmentally compatible disposal is possible. Furthermore, the carbon released into the atmosphere in such processes does not exceed the amount of carbon captured in the production of the material, resulting in no net carbon release from the filler material. Summary of the Invention [Problem to be solved by the invention]

[0006] The most commonly used natural filler materials are food materials, i.e., edible materials such as starch or their derivatives. Typical examples are food flours such as wheat flour and rice flour. These types of flours form the basis for many of the simplest molding compositions, such as simple flour-and-water pastes. However, such fillers have several drawbacks. First, they are generally permeable to the binder material (e.g., water). This means that the surface binding effect is not achieved until the filler is saturated with the binder. With other binder materials, the permeability of the filler may not necessitate immediate "saturation," but the permeability of the filler allows the binder to gradually penetrate the filler, which can lead to gradual drying and loss of cohesion in the composition, even if the binder itself is not dry but simply absorbed by the filler particles. While convenient, it is also preferable to limit the use of edible materials that may be consumed by humans or animals in the production of non-food products, such as modeling compositions. [Means for solving the problem]

[0007] The present inventors have searched for alternative naturally occurring filler materials suitable for use in molding compositions, particularly materials that are not composed of or made from edible materials such as starch. Unfortunately, many common particulate natural materials perform poorly when used as filler materials. In particular, many natural particulate materials, such as grain flours, wood chips, sawdust, and paper dust, tend to absorb binder materials immediately or gradually over time. As a result, moldable materials may require large amounts of binder or may gradually lose binder from the filler surface due to absorption. This can cause the material to lose cohesion and moldability over time during use or storage.

[0008] In view of the above, it would be a significant advantage to provide a formable material comprising a natural or naturally derived filler material that does not absorb binder material beyond a surface layer and / or that can maintain cohesiveness and formability during use and / or storage. The present inventors have surprisingly determined that moldable materials formed using particles of closed-cell natural materials absorb binder only at the surface, thus requiring less binder and / or not losing cohesion due to binder absorption. [Brief explanation of the drawings]

[0009] [Figure 1] Figure 1 is a scanning electron micrograph of the surface of a cork sample, showing the closed-cell nature of the material.* [Figure 2] Figure 2 shows a scanning electron micrograph (A) and a transmission electron micrograph (B) of an oak wood sample.** [Figure 3] FIG. 3 shows a scanning electron micrograph of an untreated corncob sample. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Summary of the Invention] In a first aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: a) at least one binder; b) at least one particulate filler material.

[0011] In particular, said filler material is a natural filler material, in particular a non-porous filler material such as a closed-cell filler material.

[0012] A highly suitable filler material for use in all aspects of the present invention is cork.

[0013] The moldable materials of the present invention are useful in a variety of technologies. In particular, the present disclosure provides, in various aspects, modeling compounds, art materials, children's play materials, filler materials, building materials, packaging materials, insulating materials, and / or fire retardant materials that comprise, consist essentially of, or consist of the moldable compositions described in any aspect or embodiment herein.

[0014] The moldable materials of the present invention can be produced by combining a suitable binder material (as described in any suitable embodiment herein) with a particulate filler material (as described in any suitable embodiment herein). Accordingly, in a corresponding aspect, the present disclosure provides a method for forming a moldable material as described in any aspect or embodiment herein, the method comprising combining a binder material with a particulate filler material.

[0015] [Brief description of the drawing] Figure 1 is a scanning electron micrograph of the surface of a cork sample, showing the closed-cell nature of the material. * Figure 2 shows a scanning electron micrograph (A) and a transmission electron micrograph (B) of an oak wood sample.** FIG. 3 shows a scanning electron micrograph of an untreated corncob sample. ***

[0016] * Image courtesy of Nicola Angeli / MUSE. This file was uploaded by MUSE (Science Museum of Trento) in collaboration with Wikimedia Italia. -MUSE, CC BY-SA 3.0, https: / / commons.wikimedia.org / w / index.php?curid=48378572 ** Image courtesy of McKDandy from English Wikipedia - CC BY 2.5, https: / / en.wikipedia.org / wiki / Vessel_element# / media / File:Hardwood_Pores.jpg *** Cropped from image by Linna Suo, Xiangyang Sun, and Weijie Jiang. Credit: Public Library of Science (PLOS) - CC BY 4.0, https: / / doi.org / 10.1371 / journal.pone.0064550.g001

[0017] [Detailed Description of the Invention] The moldable materials of the present disclosure comprise two key components: a binder component and a particulate, non-porous (especially closed-cell) filler component. The filler material is particularly a natural filler material.

[0018] The particulate, non-porous (especially closed-cell) filler component is critical to the present invention because many of the important attributes of the products of the present disclosure can be attributed to the non-porous (especially closed-cell) filler material and its interaction with the binder material. The non-porous and / or closed-cell nature of the filler material is an important feature of the present invention because it allows for a more efficient filler-to-binder ratio and improves the long-term properties of the material. In preferred embodiments, the filler material is free or substantially free of porous material.

[0019] In one important embodiment, the non-porous (e.g., closed-cell) filler material is a natural material. As used herein, the term "natural material" refers to the filler material being sourced from at least one living (or formerly living) entity. For example, the natural material may be sourced from an organism that was alive at some point in the past 20 years. In particular, preferred natural materials are typically sourced (or are sourceable) from living (or formerly living) organisms, such as plants, animals, fungi, protists, and / or prokaryotic microorganisms. Highly suitable organisms include plants and fungi, particularly plants (e.g., trees). Natural products are preferably obtained from their producing organisms by physical, chemical, and / or biological methods. Physical methods, such as mechanical separation, heating, grinding, and cutting, are highly effective and generate minimal waste. Biological methods, such as the use of microorganisms and / or enzymes, are suitable for some natural products and typically generate relatively little waste with an adverse environmental impact. Chemical methods may also be used but are generally less preferred due to the potentially greater environmental impact of the waste products generated. Natural products that can be separated by physical and / or biological methods are preferred, such as cork and coconut fiber.

[0020] In a preferred embodiment, the non-porous (e.g., closed-cell) filler material is not an inorganic material (e.g., not a mineral). In a preferred embodiment, the non-porous (e.g., closed-cell) filler is free or substantially free of metals and / or metal ions (e.g., alkali metal ions such as sodium ions). In one embodiment, the filler material contains less than 20% by weight (e.g., 0-20% by weight) or less than 20% by volume (e.g., 0-20% by volume) of inorganic material (e.g., a mineral material). Typically, this is less than 10% by weight, e.g., less than 5% by weight, or less than 10% by volume, e.g., less than 5% by volume.

[0021] In one embodiment, the non-porous natural filler material may be compressible. Compressibility means that the filler material can be compressed to 90% of its length in its longest direction and recover to at least 95% (e.g., 95-100%) of its original length within 24 hours. In one embodiment, the compressible natural material is such that a 10 mm square of the natural material can be compressed to 90% of its length in one direction with a force of 1000 N or less (e.g., 25-1000 N), preferably 500 N or less or 300 N or less.

[0022] A valuable property of compressible natural materials as filler materials in various embodiments of the present invention is that compression of the material can temporarily redistribute the binder material on the filler material surface. This results in a material that is cohesive when compressed, but does not feel sticky or sticky to the touch. Thus, in one embodiment, the filler material comprises or consists of at least one compressible natural material, and the composition of any aspect or embodiment of the present invention is cohesive when compressed with manual pressure, but does not feel sticky or sticky to the touch.

[0023] When this type of material is compressed into small "blocks" (e.g., blocks 1-10 cm in each dimension) by hand, extrusion, or using small molds, the resulting blocks exhibit cohesive properties when pressed together but do not stick to hands or surfaces.

[0024] In one embodiment, small blocks formed from the material of the present invention can be adhered to one another by pressing them together, but do not stick to hands and / or work surfaces. In a corresponding embodiment, small blocks formed from the material of the present invention can be adhered to one another by pressing them together with manual force, but do not adhere to one another solely by stacking them together.

[0025] Among plant-derived natural products, tree-derived products are highly relevant because trees offer many environmental benefits, such as carbon sequestration from the atmosphere, soil stabilization, and resistance to land "desertification." Materials that can be harvested without destroying the trees offer the added advantage of not compromising these properties. Cork and coconut fiber are examples of materials that can be harvested from trees without killing them; cork is the renewable outer bark layer, and coconut fiber is formed around the fruit / seed of the plant.

[0026] An important attribute of non-porous / closed-cell filler materials suitable for use in the present invention is that they should have limited absorption of binder material. This is believed to be related to the non-porous / closed-cell nature of the filler material. Without being bound by theory, this is believed to reduce the weight of binder required to coat the filler material and also reduce or prevent "drying out" of the moldable composition due to absorption of the binder material into the bulk of the filler material. Therefore, it is highly desirable that the particulate filler materials of the present invention be "closed-cell" filler materials. As used herein, "closed-cell" filler materials refer to materials that are non-porous or substantially non-porous.

[0027] The closed-cell filler materials referred to in all aspects and embodiments herein may be non-porous natural materials. In particular, non-porous materials desirably contain no surface pores greater than 2 μm in diameter (e.g., 2-200 μm) and having a depth greater than 100 μm (e.g., 100 μm-1 cm), and preferably no pores greater than 1 μm in diameter extending to a depth greater than 50 μm. A material is considered to be pore-free on its surface if the surface area of ​​the material made up of pores of the above sizes is less than 10% or 5% (e.g., 0-5% or 0.00001-5%), preferably less than 1%. In one embodiment, this may be less than 0.1% of the surface area.

[0028] Because closed-cell filler materials are nonporous, they desirably contain no surface pores greater than 2 μm in diameter (e.g., 2-200 μm) and having a depth greater than 100 μm (e.g., 100 μm-1 cm), and preferably no pores greater than 1 μm in diameter extending to a depth greater than 50 μm. A closed-cell filler material is considered to be pore-free if the surface area of ​​the material is made up of pores of the above sizes, which accounts for less than 10% or 5% (e.g., 0-5% or 0.00001-5%), preferably less than 1%. In one embodiment, this may be less than 0.1% of the surface area. As used herein, a "closed-cell" material generally refers to a material having gas-containing cells that do not allow liquids or similar non-gaseous fluids (e.g., binders) to pass from one cell to an adjacent cell. Some materials, such as cork, allow small amounts of gas to pass between cells, but this is irrelevant to the present invention, as it does not affect the absorption of the binder (which is typically a fairly viscous liquid). In one embodiment, the non-porous material is a closed-cell material consisting of gas-containing cells that do not allow liquid (especially binders such as any of those described herein) to pass from one cell to the next.

[0029] In one embodiment, the natural material is a multicellular material. A multicellular material is a material composed of sealed gas-filled cells, with a plurality of cells adjacent to each other across a common wall. In one embodiment, a 10 mm square multicellular natural material contains at least 10,000 (e.g., 10,000 to 100,000,000) cells, preferably at least 50,000 or at least 500,000 gas-filled cells. Generally, the closed-cell materials described herein are multicellular materials.

[0030] Referring to Figure 1 herein, cork is an example of a natural material with a "closed-cell" structure. As is evident from Figure 1, cork has very low porosity (in the pore size range greater than 1 μm, e.g., 1 μm to 200 μm). Many other natural materials, including those typically considered impermeable, such as wood, actually have "open" surfaces with significant densities of pores greater than 1 μm. This is true even for relatively dense woods, as exemplified in Figure 2, which shows a micrograph of an oak wood sample. Cork is therefore a highly suitable filler material for all aspects and embodiments of the present invention.

[0031] Cork, which is porous and does not meet the definition of "non-porous" as described herein, is not suitable as a non-porous filler material. The filler preferably does not include porous cork. The filler preferably includes commercial grade 1 or 2 cork. Porous cork is not a common type of cork, and the term "cork" is not typically used to refer to porous materials. Therefore, the term "cork" as used herein follows its natural definition and does not encompass porous materials.

[0032] In one embodiment, the filler material comprises at least 10% suberin (eg, 10-50% suberin).

[0033] Another material with very low porosity (excluding cut ends of the fibers) is coir (coconut fiber), which may form a further suitable filler material for all applicable aspects and embodiments of the present invention, particularly in lengths of 1 mm or greater (e.g., 1 mm to 30 cm, e.g., 2 mm to 50 mm or 5 mm to 20 mm).

[0034] In a preferred embodiment, the filler material comprises closed-cell coir. Reference is made to the SEM image of coir in Tran et al.'s Industrial Crops and Products 65 (2015) 437-445 (see FIG. 2), incorporated herein by reference. This image demonstrates the closed-cell nature of coir. As is evident from this image, coir contains multiple small pockets (i.e., lumens, as described in the literature) between each of its elementary fibers, and these pockets are confined to the coir's internal cross-section. Thus, "pores" are only present at the cut ends of the coir, and these pores are not open to the fiber structure but only extend to the depth of a single closed cell within the material. Thus, coir is also a closed-cell material as described herein.

[0035] In one embodiment, the particulate filler material comprises, consists essentially of, or consists of a material comprising cellulose (including hemicellulose) and / or lignin. In particular, the filler material may be a material comprising at least 10% by weight of cellulose (including hemicellulose) and at least 10% by weight of lignin.

[0036] In another embodiment, the particulate filler material is free (or substantially free) of absorbent (porous) materials. Preferably, the particulate filler material comprises less than 10% by weight of porous polysaccharide materials. Porous polysaccharide materials include wood chips / flour, corn fiber, and starch (e.g., starch fiber).

[0037] The filler is preferably not a human food-grade material. In one embodiment, the filler material preferably does not contain significant nutritional value as a human food. In one embodiment, the filler material does not contain more than 20% starch by weight (e.g., 0-20% by weight or 0.0001-20% by weight). In one embodiment, the filler is not a food flour. In particular, the filler is not a flour or other particulate material derived from cereals or quinoa, and thus is not, for example, wheat flour, rice flour, quinoa, or related products. This has two advantages: such food materials tend to be porous and therefore do not easily form stable, low-binder materials such as those that can be formed from cork, coir, or other closed-cell materials. It is also preferable not to use human food-grade materials for non-food applications.

[0038] In certain embodiments, the filler is free or substantially free of polysaccharide food additives such as xanthan gum and / or cellulose gum.

[0039] In a preferred embodiment applicable to all aspects of the invention, the filler material comprises, consists essentially of, or consists of bark, a bark product, or a bark layer. In a preferred embodiment, the filler comprises, consists essentially of, or consists of all or a portion of the periderm layer of bark. In one embodiment, the filler may comprise, consist essentially of, or consist of lithidome.

[0040] In one embodiment, the natural filler material (e.g., cork or coconut fiber) has a density of about 30-500 g / L. Preferably, it is about 50-250 g / L, 80-220 g / L, or 60-180 g / L. A typical cork density of about 100-175 g / L is very suitable.

[0041] A typical density of (unmilled) coconut fiber, about 100-200 g / L, is very suitable.

[0042] In a further preferred embodiment, the filler may comprise, consist essentially of, or consist of cork.

[0043] In particularly preferred embodiments, the filler comprises, consists essentially of, or consists of non-porous, closed-cell cork (as defined in any preferred embodiment herein).

[0044] In another preferred embodiment, the filler comprises, consists essentially of, or consists of non-porous, closed-cell coir (as defined in any preferred embodiment herein).

[0045] In another preferred embodiment, the filler comprises, consists essentially of, or consists of a mixture of non-porous closed-cell coir and non-porous closed-cell cork (both as defined herein in any preferred embodiment).

[0046] Bark is only present in woody plants, and is not present on the stems of herbaceous plants or young plants. The bark referred to in this specification is the bark of the mature stem of a woody plant, and therefore typically preferably includes the periderm (cork, cork cambium, cork cortex), the cortex, and the phloem. All layers of the bark may be used as appropriate, but the periderm, especially the cork layer, is particularly preferred in the present disclosure.

[0047] Cork is an impermeable, buoyant material composed of the cork layer of bark tissue in woody plants. Cork cell walls contain a waxy substance called suberin, which protects the stem from water loss and insect infestation, as well as from bacterial and fungal spore infection. The cells within cork trap air-like gases, giving cork its low density, elasticity, insulating properties, and flame resistance. Cork's impermeability, buoyancy, elasticity, and flame resistance make it useful for a variety of products. Cork is found in the bark of most woody plants, but it is typically harvested from certain tree species, particularly cork oak (Quercus suber) and Quercus variabilis.

[0048] The cork referred to herein may be any form of cork, but is preferably cork from the cork oak (Quercus suber) or Quercus variabilis. Typically, cork contains suberin (about 40%), lignin (about 22%), cellulose and hemicellulose (about 18%), waxes, and other materials.

[0049] In one embodiment, the filler material may contain at least 10% by weight (eg, 10-60%) suberin, for example, 15-50% by weight or 30-45% by weight suberin.

[0050] The filler materials utilized in various aspects and embodiments of the present invention are particulate materials.

[0051] Typical sizes of particulate materials correspond to "sand" sizes. These can have an average particle size of 50 μm to 5 mm (e.g., 63 μm to 5 mm), preferably 95 μm to 3 mm. Particle sizes can also include gravel- or pebble-sized fillers with an average particle size of up to about 10 mm. When referring to individual particles, size generally refers to the smallest diameter (i.e., the diameter along the shortest axis). Fillers can be "unimodal," "bimodal," or "multimodal," in that filler particles of one size or two or more sizes can be present. For example, a fine filler with an average particle size of less than 100 μm can be used in combination with a coarser filler with a particle size of 1 mm or greater (e.g., 1 to 10 mm or 1 mm to 5 mm). Such a bimodal mixture of fillers can allow for better coating of larger particles and improve binder properties. Typically, in such cases, the larger particle size filler is a closed-cell filler. Obviously, all filler materials of all particle sizes may be formed from one or more closed-cell fillers. When bimodal fillers are used, in one embodiment, the maximum value of the first particle size may be at least twice (e.g., 2 to 100 times) the maximum value of the second particle size. In such cases, if the two sizes of particles have similar densities (e.g., ±50%), in one embodiment, the filler component may comprise at least 60% by weight, preferably at least 75% by weight, of the larger filler size. With such a distribution, regardless of the relative densities of the fillers, in one embodiment, the filler component may comprise at least 60% by volume (e.g., 75% by volume) of the larger filler particles.

[0052] In one embodiment, the molding composition may include a "large" filler, which may comprise at least one closed-cell particulate filler described herein, and a "small" filler, which may be a closed-cell particulate filler or another filler type. The "large" filler may have an average particle size of 300 μm to 10 mm, e.g., 500 μm to 5 mm. The "small" filler may have an average particle size of 0.1 μm to 100 μm, e.g., 0.5 μm to 50 μm or 1 to 30 μm. The small and large filler particles may be the same filler material or different filler materials.

[0053] In one embodiment, at least 20% by weight (e.g., 20-100% by weight), such as at least 30% by weight or at least 50% by weight (e.g., 50-100%) of the filler component in the moldable composition is closed-cell filler. This is preferably at least 60% or at least 75%, e.g., at least 80%, at least 90%, or at least 95%. In one embodiment, substantially 100% of the filler material is closed-cell filler.

[0054] In a further embodiment, at least 30% by volume of the filler component in the moldable composition is closed-cell filler, preferably at least 40% by volume or at least 60% by volume, e.g., at least 70% by volume, at least 80% by volume, or at least 90% by volume. In one embodiment, substantially 100% of the filler material is closed-cell filler.

[0055] In particularly preferred embodiments, the filler comprises more "large" fillers than "small" fillers. The ratio of "large" to "small" fillers is preferably in the range of 55:45 to 90:10 by weight or volume. Ratios of "large" to "small" fillers in the range of 60:40 and 75:25 by weight and / or in the range of 75:25 to 90:10 by volume are particularly preferred.

[0056] In certain embodiments, the filler comprises a natural non-porous filler material and at least one additional filler material, which may comprise an inorganic filler and / or a polymer filler. In certain embodiments, the filler may comprise the natural non-porous filler material and at least one additional filler material in a weight or volume ratio of 55:45 to 90:10. The ratio of the non-porous filler material to the additional filler material is particularly preferably in the range of 60:40 to 75:25 by weight and / or 75:25 to 90:10 by volume.

[0057] The additional filler material may be any suitable inert material, but is typically a particulate material such as at least one inorganic filler and / or at least one polymer filler. Suitable materials include sand, glass (e.g., borosilicate glass), silica, calcium carbonate, and other "inorganic" materials such as minerals; and polymers, including natural polymers, semi-synthetic polymers, and synthetic polymers. Natural polymers can include polyphenolic and polysaccharide fillers, including lignin- and cellulose-type fillers such as wood flour, and carbohydrate-type fillers such as wheat flour, rice flour, or corn flour. Synthetic polymers include polyolefins (e.g., polystyrene, polyethylene, or polypropylene), polyesters (e.g., polyethylene terephthalate (PET), polybutyrate), polyamides, polyurethanes, and mixtures thereof. Foam materials also include hollow glass microspheres and foamed polymers (polymer foams), such as foamed latex, polyurethane foam, foamed PVC, foamed polystyrene, or foamed polyethylene, and copolymers containing any of these. One particularly suitable foam material is "Expancel," a copolymer of vinylidene chloride, acrylonitrile, and methyl methacrylate, typically formulated with isobutene as the blowing agent.

[0058] In alternative embodiments, the "large" fillers are free of or substantially free of inorganic or mineral fillers (e.g., natural or industrial minerals such as kaolin, silica, and / or perlite). In preferred embodiments, the non-porous filler material is free of or substantially free of inorganic natural or industrial minerals such as kaolin, silica, and / or perlite. In certain embodiments, the filler is free of or substantially free of inorganic industrial minerals such as kaolin, silica, and / or perlite, especially kaolin.

[0059] Highly suitable "small" fillers include finely divided calcium carbonate or silica. Such fillers serve to increase the bulk of the binder component without significantly affecting the texture of the binder or moldable material. This type of finely divided filler ("small filler") can have an average particle size of less than 20 μm (e.g., 0.5-20 μm), preferably less than 10 μm (e.g., 1-10 μm). Average particle sizes of 0.5-8 μm or 2-20 μm are highly suitable for such small fillers, which may be comprised of any of the filler materials disclosed herein, particularly inorganic fillers such as silica or calcium carbonate. Such small filler particles may be used alone as fillers (when formed from closed-cell filler materials) but are more typically used in combination with larger (closed-cell) filler materials.

[0060] Silica fillers, particularly hydrophobized silica fillers, are highly preferred mineral fillers for use as "small fillers" and, in combination with closed-cell fillers, form part of the filler component of the present invention. Such small particle silica fillers may be added in amounts of about 1 to 30% by weight of the total components in the composition. When such a filled composition is then added to a larger amount (e.g., a larger volume) of another filler (see below for typical filler amounts), the small filler can provide a volume-increasing effect and potentially improve the binding effect of the binder without requiring more binder (e.g., polymers or other components such as softeners).

[0061] In one advantageous embodiment, the various products of the present invention may contain both "small fillers," such as hydrophobized fumed silica fillers or small-particle calcium carbonate fillers, and closed-cell fillers of any of the types described herein. This provides benefits to the resilience and toughness of the binder, particularly when the small filler (e.g., hydrophobized fumed silica filler) is used at levels of about 5-30% by weight (e.g., 10-25% or 5-15%) of the total filler and binder components. Preferred hydrophobized fumed silica fillers may include a variety of particle sizes, including agglomerates of small particles. Typical agglomerated fumed silica particles may have a minimum size ranging from 1 to 100 μm, preferably about 5 to 50 μm.

[0062] All fillers, especially mineral fillers including glass, sand, silica, alumina, and other mineral fillers, may be surface treated. Many surface treatments are useful for improving various properties, such as performance and / or appearance. One preferred surface treatment is a hydrophobic surface treatment to "hydrophobize" the surface of the filler. Thus, surface-treated (e.g., hydrophobized) glass, sand, silica, and / or alumina form preferred fillers in the present invention. Suitable surface treatments, particularly for silica-containing fillers, include treatment with 0.05 to 0.2% by weight of the filler of an alkoxysilane or silylalkanoate.

[0063] The moldable materials of the present invention include at least one filler (including natural closed-cell fillers) and at least one binder material. The ratio of binder material to filler material can vary widely depending on the intended use of the moldable material. For example, the binder to filler ratio can range from 1:99 to 99:1 by weight to 1:99 to 99:1 by volume. This ratio can vary depending on the nature of the binder, the nature of the filler, and the purpose of the material. For example, binder:filler ratios of 2:98 to 98:2 or 5:95 to 95:5, either by weight or volume, can be suitable, although ratios of 90:10 to 10:90 and 75:25 to 25:75 can also be suitable. When the filler consists of a natural closed-cell filler (generally 50-100% of the total filler volume) and, optionally, another low-density filler such as hollow glass or polymer microspheres or expanded polymer foam, the binder is generally the larger component by mass, and the binder:filler ratio can be 50:50 to 98:2 by weight, e.g., 60:40 to 95:5 or 70:30 to 90:10.

[0064] If the filler component contains natural closed-cell fillers (typically 50-99% of the total filler volume) and additional fillers such as inorganic (e.g., silica) or polymer fillers, the total filler density will be higher than the above. In such cases, the binder:filler ratio by weight may be 90:10 to 10:90, for example, 60:40 to 40:60 or 70:30 to 30:70.

[0065] In a preferred embodiment, the amount of filler in the composition is greater than the amount of binder on a weight basis. In a particularly preferred embodiment, the weight ratio of filler to binder is in the range of 51:49 to 90:10, for example, 51:49 to 75:25. Also, in a preferred embodiment, the amount of filler in the composition is greater than the amount of binder on a volume basis. In a particularly preferred embodiment, the volume ratio of filler to binder is in the range of 51:49 to 95:5, for example, 60:40 to 92:8. The filler / binder volume ratio is particularly preferably in the range of 70:30 to 95:5, for example, 80:20 or 90:10. One potentially valuable application of the material of the present invention is its use in flame retardants. Natural fillers, such as cork, have high thermal insulation properties and natural flame retardancy and can be used directly in the material of the present invention. The flame retardancy of the material can be further improved by adding a secondary filler material, particularly an inorganic / mineral filler. Thus, in one embodiment, the present invention provides a flame retardant material as described in any embodiment or aspect herein, which contains at least one particulate natural closed-cell filler and, optionally, at least one mineral filler. Suitable closed-cell fillers include cork. Suitable mineral fillers include any of those described herein, such as silica (e.g., sand) and / or calcium carbonate.

[0066] In the moldable compositions and all aspects and embodiments of the present invention, a binder material is required.

[0067] Binders suitable for use in all aspects and embodiments of the present invention include silicone-based binders, polyester binders, polyamide binders, and substituted aliphatic polymer binders. In particular, polyesters such as polycaprolactone (optionally copolymerized with lactic acid monomers) and substituted aliphatic polymers such as polyvinyl acetate (homopolymer or copolymer) are included. Silicone binders include polyalkylsiloxane binders, optionally crosslinked with materials such as alkylsilylalkanoates.

[0068] In a preferred embodiment, the binder component comprises less than 10% by weight, e.g., less than 5% by weight, of polysaccharides (e.g., cellulose, starch). In a further preferred embodiment (which can be combined with the above), the binder component comprises less than 10% by weight, e.g., less than 5% by weight, of polyethers (e.g., polyethylene glycol). In a preferred embodiment, the binder is free or substantially free of polysaccharides and polyethers.

[0069] In one embodiment, the moldable material of the present invention does not contain (or is substantially free of) cellulose in solution. For example, the material of the present invention may contain less than 5% by weight (e.g., 0-5%) cellulose in solution.

[0070] In one embodiment, the silicone binder may comprise a polyalkylsiloxane, such as polydimethylsiloxane (e.g., hydroxy-terminated PDMS). Any suitable siloxane or mixture thereof may be used, including those having a MW of 1 kD to 50 kD, e.g., 2 kD to 30 kD. A mixture of at least one low MW (e.g., 1 to 10 kD) siloxane and one higher MW (e.g., 12 to 30 kD) siloxane constitutes a preferred embodiment. The crosslinking of the siloxane binder may be by partial covalent bonding, such as with a silylalkanoate (e.g., triacetoxysilane) or an alkoxysilane (e.g., trimethoxysilane or triethoxy(2,4,4-trimethylpentyl)silane). Alternatively, or in addition, the crosslinking may be by a boron compound (e.g., a boron compound such as boric acid or sodium borate, or a boron-containing ceramic or glass such as borosilicate glass). In one embodiment, both boron crosslinking and covalent crosslinking may be used in combination.

[0071] It has been discovered that moldable compositions formed from closed-cell natural particulate fillers can be effectively coated with binder using less binder than is required for other natural filler materials. Furthermore, it is believed that the closed-cell or non-porous nature of the filler particles limits binder absorption, thus reducing binder migration from the particle surface over time and "drying out" the material.

[0072] The binder typically contains additional optional components such as a softener and / or an anti-tack agent. The amount of softener and / or anti-tack agent in binder component a) depends on the nature of the polymer. When a softener is included, its amount is typically less than 80% by weight of component a), with the remainder being the polymer. The softener content may be 1 to 50% by weight or 5 to 35% by weight.

[0073] The binder may be permanently flexible or may be "hardened" by drying, heating, or curing (e.g., with UV light). Similarly, the binder may be flexible at room temperature or may require heating to become flexible. In one embodiment, the binder may be rigid at 20°C but flexible at 42°C.

[0074] Some preferred examples of binders for component a) include: i) 30-70% of a polyvinyl acetate homopolymer, polyvinyl acetate copolymer (e.g., with at least one other vinyl ester), or mixtures thereof, and 30-70% of at least one hydroxylated or esterified softener (such as at least one glycerin ester and / or a C10-C22 branched or linear alkyl alcohol (e.g., monol, diol, or triol)); ii) 20-80% of at least one polyester homopolymer or copolymer (e.g., at least one caprolactone homopolymer or copolymer) and 20-80% of at least one softener (e.g., MW 50-500 amu), where suitable softeners may include at least one benzyl alcohol, benzyl ester, benzyl ether, and / or acyl benzoate moiety; or iii) at least one covalently crosslinked siloxanyl polymer, optionally further crosslinked with up to 5 wt. % (e.g., 0 or 0.01 wt. % to 5 wt. %), in particular up to 0.5 wt. % (e.g., 0 or 0.01 to 0.5 wt. %, e.g., 0.1 to 0.3 wt. % or 0.15 to 0.25 wt. %) of boron. iv) at least one non-covalently crosslinked siloxanyl polymer (i.e., a polymer having no covalent crosslinks) crosslinked with up to 5 wt. % (e.g., 0 or 0.01 to 5 wt. %, e.g., 0.01 to 0.5 or 2 wt. % or 0.1 to 1.0 wt. %) of boron.

[0075] The binder ii) may be rigid at 20°C but flexible at 42°C.

[0076] In all of the above embodiments i)-iv), all percentages are by weight based on the binder material.

[0077] In all embodiments utilizing boron crosslinking, the amount of boron refers to the amount of boron available for crosslinking. In the case of simple compounds such as boric acid, this is the total amount present, but in the case of boron present as part of the matrix of a glass or ceramic material, it is the amount available (as in the Examples). For example, in borosilicate glass spheres, the boron at the center of the particle is less available, and the amount of "available" boron is about 4000-8000 ppm by weight. About 5000 ppm is a typical amount. In all aspects of the present invention, the products and compositions may include at least one of a variety of optional ingredients, such as: c) pigments; d) glitter; e) Mica or coated mica; f)Fragrance; g) preservatives; and / or h) Flame retardants.

[0078] Each optional ingredient provides useful and valuable benefits in certain embodiments and for certain applications, and may be independently selected and used individually or, where technically feasible, in any combination. Although the various ingredients are described herein separately for clarity, they may also be used in combination to impart desirable properties to the compositions of the present invention.

[0079] Examples of each of these additives are well known to those skilled in the art. Glitters referred to herein include plastic film-based glitters (e.g., polystyrene film glitters) or plastic-free glitters (e.g., TiO, fluorophlogopite, tin dioxide, or mixtures thereof).

[0080] When additional components c) to h) or other additional components are contained, each is typically contained in an amount of 5% by weight or less (e.g., 0.01 to 5%) of the total composition, preferably 2% by weight or less or 1% by weight or less.

[0081] In one embodiment, the present disclosure provides a method for producing any of the moldable materials of the present invention. A suitable method may include, for example, forming a suitable binder component a) (e.g., as described herein) and, after heating or dissolving the binder, mixing the binder or binder solution with particulate filler component b), thereby at least partially coating the filler particles with the binder. Optionally, the material may then be dried to remove the solvent.

[0082] A moldable material should be moldable at low temperatures. In a preferred embodiment, the moldable material is moldable between room temperature and 50°C, e.g., in the range of 18-45°C, e.g., 21-42°C or 25-37°C. As used herein, "moldable" is defined as being capable of being flexibly deformed without the application of undue manual force (e.g., by manipulating the material in the user's hands).

[0083] As used herein, the terms "about," "around," "substantially," or "approximately" in connection with a numerical value or range of values ​​generally indicate that, while the specified numerical value or range is preferred, such numerical value may be varied to some extent without significantly affecting the properties of the relevant material, composition, method, or product. Those skilled in the art can typically readily determine the extent to which such numerical values ​​may be varied without impairing the important advantages of the present invention. As a general guideline, such numerical values ​​or the endpoints of such ranges referred to in conjunction with such terms may vary by ±20% or ±10%, preferably ±5%, and more preferably ±1%. A similar meaning may be construed for a composition "consisting essentially of" a particular component, which may contain, in addition to the specified component, up to 20% or up to 10%, preferably up to 5%, and most preferably up to 1% of other components. A composition described as comprising or consisting essentially of specific components includes a disclosure of a composition consisting solely of those components. Unless otherwise specified or the context requires otherwise, all percentages herein are by weight. Similarly, a material that is "substantially free" of another substance typically contains 20% or less (i.e., 0-20%) of that substance, and preferably contains 10% or less, 5% or less, 2% or less, or 1% or less of that substance. This can be a weight percentage or a volume percentage, as appropriate, but is most commonly a weight percentage, unless the context dictates otherwise.

[0084] When referring to the density of a particulate material herein, bulk density is intended, where the context allows. Density is typically the density of the material "as used," rather than material that has been crushed or ground to a powder before measurement.

[0085] [Example]

[0086] [Table 1] JPEG2025537890000003.jpg168139

[0087] Example 1 - PVAc Binder (i) 52.6 g of B500 / 40VL was melted and mixed with 36.5 g of Isofol 20, 4.6 g of MCT 60, and 6.4 g of Triacetin.

[0088] (ii) 42.6 g of the above binder (i) was mixed with 57.4 g of Cork (0.5-1.0) to obtain a cohesive, moldable material with a soft, pliable texture, flowing properties, and a "lifelike" appearance.

[0089] (iii) 57.1 g of the above binder (i) was mixed with 42.9 g of Cork (0.2-0.5) to obtain a cohesive, moldable material with a soft, pliable texture, flowing properties, and a "lifelike" appearance.

[0090] (iv) 52.6 g of B500 / 40VL was melted and mixed with 36.5 g of Isofol 20, 8.3 g of MCT 60, and 6.4 g of Triacetin to obtain a slightly modified, softer binder (compared to binder (i)). 76.3 g of this binder was mixed with 23.7 g of Cork (0.2-0.5) to obtain a cohesive, moldable material. This material is less fluid than (ii) and (iii), and therefore less "lifelike" in appearance. Due to the higher binder volume ratio, the texture is doughy, but its softer texture allows it to be easily molded into shaped architectural structures.

[0091] Example 2 - PCL Binder 36 g of CAPA 6500 was melted and mixed with 64 g of Benzoflex 988 to obtain binder (v). This binder (v) was then mixed with either (vi) 35 g to 15 g of cork (0.5-1.0%) or (vii) 35 g to 15 g of cork (0.2-0.5%). Both materials (vi and vii) were moldable at approximately 40°C, where the binder was in the molten phase. After the structures were formed, they were allowed to stand and cool to room temperature, solidifying into rigid structures. The heating and molding process could be repeated to form new solid structures.

[0092] Both materials (vi and vii) exhibited slight stickiness to the hands in the melt phase (above 40°C), which could be countered by adding approximately 1% by weight of AK10 to the material.

[0093] Example 3 - Silicone Binder Preparation (viii) was prepared by crosslinking 397 g of C2T with 3.5 g of ES23. The reaction occurred while mixing the two components at a temperature of approximately 130°C. Crosslinking resulted in a significant increase in viscosity. 530 g of CDS100 was then added to the reaction vessel and mixed. The reaction was deemed complete after 3 hours.

[0094] Formulations (ix), (x), and (xi) were obtained by mixing the appropriate amounts of the first four components (Table 2) at a temperature of approximately 60°C. Radiacid 0406 was then added, melted, and mixed properly. HCl (9%) was added to the mixture, and the water was evaporated. Finally, SnS was added if indicated in the recipe. After proper mixing, the texture of the final materials (ix), (x), and (xi) is dough-like, yet "lifelike." These materials can be used to build structures when compressed, yet have a fluffy appearance and flow when gently manipulated (without excessive compressive force).

[0095] [Table 2]

[0096] Example 4 - Comparison of cork with other natural filler materials Mixes xii through xx compare the properties of materials prepared using Type (i) binder (see Example 1) with various organic fillers. For comparison, Mix xxi was prepared using an inert sand filler. These mixes were corrected for different filler densities so that similar volume fractions (binder to filler) could be compared (Table 3).

[0097] The ratio (by volume) used was approximately 88:12 filler to binder. Sand (0.2) was surface treated before mixing with binder (i) to improve its compatibility with binder (i). First, an aqueous silane dispersion was prepared as follows.

[0098] 5 g of silane (0.5 g of BS1701 and 4.5 g of XL10) were weighed and mixed in a beaker using a magnetic stirrer. This silane (mixture) was added to an aqueous solution of 94.5 g of water and 0.5 g of HAc (24%) under vigorous stirring to obtain a course dispersion. · Mixing (vigorously) continued for approximately 30-60 minutes, after which it was brought into contact with heated sand (see below). Next, surface-treated sand, Sand(0.2)ST, was prepared. 5 kg of sand was heated to approximately 55-60°C in a stainless steel pot. Aqueous silane dispersion (100g - approximately 5% silane in water) was added to the hot sand under continuous mixing. · Mixing continued until the water evaporated and the sand was dry.

[0099] [Table 3]

[0100] Immediately after preparation, all materials were dough-like and had good moldability, making them suitable for modeling and children's play. The sawdust preparation had a slightly harder and less moldable texture than the other preparations. The cork-filled sample was soft and had a particularly pleasant feel and texture. On the other hand, the samples prepared with ground bare corncob and wood chips had a "hard" and less soft and smooth feel.

[0101] Already after 15 hours, some of the preparations showed noticeable changes. The inert sand filler and the cork-based filler appeared to be less affected by aging than the preparations with sawdust, wood chips, and ground bare corncob. All samples except those prepared with the inert sand or cork filler showed a continuous change in material properties over time.

[0102] Further investigation of sample (xix) revealed that, in particular, gradual changes over time resulted in the material being too "dry" and non-cohesive after 480 hours of storage to be useful. This "dry" sample had a "wet" appearance, but the binder was clearly not accessible at the filler particle surface. Small percentages of fresh additional binder were added to the "dry" sample. Properties were determined and compared with a freshly prepared reference sample. After six successive additions, corresponding to approximately 70% additional binder addition, the initial properties were restored. This indicates that a significant amount of the originally added binder had been absorbed by the filler particles and was no longer accessible.

[0103] Example 5 - Alternative Natural Non-Porous Filler Related to cork, coconut fiber also appears to have a non-porous surface structure. Fibers were manually cut with scissors and sieved to obtain size fractions with the majority of fibers between 1 mm and 5 mm in length—coconut fiber (1-5). The density of coconut fiber (1-5) was estimated by weighing the beaten mass. After adjusting the volume ratio (binder to filler) to a similar value as preparations xii-xxi, sample xxii was prepared (40 wt. % binder (i) and 60 wt. % coconut fiber (1-5)).

[0104] The density of coir, measured as a ground powder, is known to be in the range of 1.1 to 1.5 g / mL. In this specification, the density is calculated based on unground coconut fiber. The calculated density is less than 0.2 g / mL.

[0105] Material xxii had dough-like properties and a soft, "hairy" appearance. Due to the length of the fibers, there was resistance to molding and shaping. One way to combat this is to use shorter fibers or blend the coconut fiber with a particulate filler (e.g., inorganic or polymeric fillers or natural fillers such as cork).

[0106] Material xxiii was prepared by mixing equal volumes of Samples xiii and xxii. The 1:1 mixture, xxiii, retained a significant portion of the "hairy" appearance from xxii while incorporating many of the molding and shaping properties from xiii.

[0107] As with cork, the coconut fiber-filled samples maintained their properties over the storage times studied, with no changes observed after 15, 60, 240, or 480 hours.

[0108] When the sample was reexamined after one year, it still retained a workable and sculptible texture. After working (i.e., kneading) the material for a few minutes, the texture returned to one very similar to its original texture.

[0109] Example 6 - Alternative Silicone Binder The method of Example 3 was repeated using an alternative silicone-based binder, which is cross-linked only with boron (in the form of borosilicate glass spheres) and does not contain significant covalent cross-links.

[0110] Material (xxiv) (see table below), prepared with Cork (0.2-0.5), showed cohesiveness and utility, but had a "shorter" texture compared to material (x). (x) and (xxiv) are very similar in composition but differ in the balance of physical and covalent crosslinks. (x) has more covalent crosslinks in the network than (xxiv).

[0111] [Table 4]

[0112] Finally, sample (xxv) was prepared based on ground corn cob, the formulation being adjusted for the different filler density compared to the sample.

[0113] [Table 5]

[0114] Sample (xxv) based on Corncobs (0.2-1) was overly dry, exhibiting undesirable properties, in contrast to the corresponding sample (xxiv) based on Cork (0.2-0.5).

Claims

1. a) at least one binder; b) at least one particulate filler material; A moldable material, wherein the filler material comprises a natural non-porous filler material.

2. 10. The moldable material of claim 1, wherein said filler component b) comprises at least one natural, non-porous filler material.

3. 10. The moldable material of claim 1, wherein the filler component b) comprises at least one natural, non-porous filler material and at least one additional filler material selected from inorganic fillers and polymeric fillers.

4. 4. The moldable material of claim 3, wherein the ratio of the natural non-porous filler material to the at least one additional filler material is from 55:45 to 90:10 by weight or volume.

5. 10. The moldable material of claim 1, wherein the natural, non-porous filler material is free of industrial and natural minerals such as silica, kaolin, and perlite.

6. 10. The moldable material of claim 1, wherein the non-porous filler material comprises or consists of a closed-cell filler material.

7. 10. The moldable material of claim 1, wherein the filler material has less than 10% of its surface area comprised of surface pores greater than 2 microns in diameter having a depth greater than 100 microns.

8. The moldable material of claim 1 , wherein the non-porous filler material comprises at least one compressible natural material.

9. 10. The moldable material of claim 1, wherein the closed-cell filler material comprises at least 10% suberin.

10. 10. The moldable material of claim 1, wherein the filler material comprises or consists of bark or a bark derivative.

11. 10. The moldable material of claim 1, wherein the non-porous filler material comprises or consists of cork.

12. 10. The moldable material of claim 1, wherein the non-porous filler material comprises or consists of coconut fiber.

13. 10. The moldable material of claim 1, wherein the non-porous filler material comprises or consists of a mixture of cork and coconut fiber.

14. 10. The moldable material of claim 1, wherein the binder is selected from silicone-based binders, polyester binders, polyamide binders, substituted aliphatic polymer binders, and mixtures thereof.

15. The binder is i) 30 to 70% of a polyvinyl acetate homopolymer, a polyvinyl acetate copolymer, or a mixture thereof, and 30 to 70% of at least one hydroxylated or esterified softener; ii) 20 to 80% of at least one polyester homopolymer or copolymer of caprolactone and 20 to 80% of at least one softening agent (e.g., containing at least one benzyl alcohol, benzyl ester, benzyl ether, and / or acyl benzoate moiety); or iii) at least one covalently crosslinked siloxanyl polymer, optionally further crosslinked with up to 5 wt. % (e.g., 0.01-0.5 wt. %) boron; iv) at least one non-covalently cross-linked siloxanyl polymer cross-linked with up to 5 wt. % (e.g., 0.01-1.0 wt. %) boron.

16. 2. The moldable material of claim 1, wherein component a) is free or substantially free of polysaccharides (e.g., cellulose, starch) and / or polyethers (e.g., polyethylene glycol).

17. 10. The moldable material of claim 1, wherein said component a) is present at 2 to 98% by weight of said composition.

18. 10. The moldable material of claim 1, wherein said component b) is present at 2 to 98% by weight of said composition.

19. 2. The moldable material of claim 1, wherein component b) is greater in amount than component a) by weight and / or volume.

20. 2. The moldable material of claim 1, wherein the ratio of b) to a) is in the range of 51:49 to 95:5 by volume, for example 70:30 to 95:

5.

21. The composition comprises: c) pigments; d) glitter; e) mica or coated mica; f) fragrance; g) preservatives; and / or 10. The moldable material of claim 1, further comprising at least one optional ingredient selected from:

22. 10. The moldable material of claim 1, which is moldable at at least one temperature between 18 and 50°C.

23. An article of manufacture selected from modelling compounds, art materials, children's play materials, filler materials, building materials, packaging materials, insulating materials, and / or fire retardant materials, comprising, consisting essentially of, or consisting of a mouldable material according to any one of claims 1 to 22.

24. 23. Use of the moldable material of any one of claims 1 to 22 as a modelling compound, art material, children's play material, filler material, building material, packaging material, insulating material and / or fire retardant material.

25. 23. A method for forming the moldable material of any one of claims 1 to 22, comprising combining a binder material a) with a particulate filler material b), wherein a) and b) are as defined in any one of claims 1 to 22.

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