Formable composition

Abstract

【Solution】The present invention is a) at least one polyester homopolymer or copolymer having a melting point of 40 to 70 °C, such as polycaprolactone; and b) at least one softening agent having a molecular weight of 50 to 500 amu, such as carbonate, benzyl ester or benzoic acid; A composition comprising The composition exhibits a melting point or softening point in the range of 30 to 45 °C, A composition is provided. Typically, component a) is present in 25 to 95% by weight of components a) and b); Component b) is present in 5 to 75% by weight of components a) and b). The composition may further comprise a filler. The present invention further provides a modeling compound comprising the composition of the present invention, and a method for producing the composition.

Description

Technical Field

[0001] Field of the Invention The present invention relates to modeling compositions, and more particularly to modeling compositions that can be solidified into a permanent shape but can be re-softened for reuse. Compositions that are safe for children to use have been of particular interest.

Background Art

[0002] Background of the Invention Various types of modeling clays and the like for making figures and sculptures have long been known in the art, on the one hand for artistic purposes and on the other hand as children's playthings and educational materials.

[0003] Formable or moldable compositions are known to consist only of "binder"-type materials such as polymers, softeners and other "active" materials, or such compositions may include inert "filler" materials that mainly function as extenders. The filler can be obtained by applying a coating of binder on at least one filler, and the filler is formed of particles or granules.

[0004] Polymeric modeling clays have long been known in the art as children's playthings or educational materials. EP2646996A2 discloses a play modeling dough of a composition that is easily malleable and non-drying so that the model can be reformed and the dough can be reused. A drawback inherent in this type of composition is that it cannot be cured and thus cannot be used, for example, as a toy or model to be used or decorated, a landscape for a railway model, or a decoration such as an aquarium. US5498645A discloses a moldable modeling dough composition that forms a solid when dried and can be used for some robust articles. However, the solidification of the composition is irreversible. Thus, this composition cannot be made flexible again and cannot be reprocessed once dried.

[0005] WO2006101440 discloses a material composition having at least two solid phases, namely a soft phase that can be easily deformed at a temperature below the melting point of the binder and a hard phase that can be recycled into a deformable state. One major drawback of this composition is that a cured structure can only be achieved at a temperature above the melting point of the binder, which is in the range of 60 to 120 °C. As a result, to create a hard figure, the material has to be baked in an oven or heated with the aid of a heat gun, which not only takes time but is also not suitable for children's use and requires strict adult supervision. Another drawback is that if a soft material is desired again, the hard figure has to be heated and then the composition kneaded during cooling to become soft at room temperature. Again, this heating process is not suitable for children's use, and the latter operation requires handling high-temperature materials for a long time, which takes a significant amount of time and effort.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0007] Generally, there are two broad classifications of modeling compositions; compositions intended to maintain malleability and compositions that can be dried or cured to give a permanent shape. The former type can be reused because it remains malleable, but being soft, it does not produce a robust, rigid or elastic shape. This type cannot be used to produce permanent and robust objects. The latter type, once formed, can be dried or cured to a rigid or elastic final shape, but the drying or curing process usually cannot be reversed or can only be reversed with difficulty, so it cannot be easily reused. Further, plastic-type compositions typically require heat to cure, so young children cannot cure them without strict supervision.

[0008] It would be advantageous to provide a material that can be easily formed or shaped by hand, can adopt a robust or elastic shape, and can be reused an unlimited number of times. It would be further advantageous if all steps could be carried out under sufficiently mild conditions such that young children do not require strict supervision to avoid the risk of injury.

Means for Solving the Problem

[0009] Accordingly, there is a need in the art to realize a composition for mainly play and educational purposes that is easily deformable at room temperature and blood temperature, does not require excessive processing, and can be cured and recycled at a temperature low enough for children to handle. Also, this composition should have little adhesion to the surroundings, have an attractive and comfortable structure, and be suitable for children to handle.

Advantages of the Invention

[0010] The inventors have surprisingly established a specific class of polymer-based compositions that have a sharp transition between hard and soft near body temperature. Such compositions are thus re-formable at a temperature suitable for use by children and form a robust material when cooled. This material can be reused without long-term intervention such as kneading. BRIEF DESCRIPTION OF THE DRAWINGS

[0011]

Figure 1

[0012] SUMMARY OF THE INVENTION In a first aspect, the present invention provides a) at least one polyester homopolymer or copolymer having a melting point of 40 to 70 °C; and b) at least one plasticizer having a molecular weight of 50 to 500 amu; comprising a composition, the composition exhibits a melting point (or softening point) within the range of 30 to 45 °C (e.g., 35 to 40 °C), component a) is present at 25 to 95% by weight of components a) and b); component b) is present at 5 to 75% by weight of components a) and b), providing a composition.

[0013] The composition may be a pure polymer / plasticizer composition or a filled composition. Thus, in one embodiment, the composition further comprises c) at least one filler.

[0014] The plasticizer typically comprises at least one alcohol; at least one carbonyl; at least one ether; at least one organic acid; at least one halogen; at least one nitro and / or at least one aromatic moiety.

[0015] Preferred polymers are caprolactone-based and / or lactide- or glycolide-based polyesters as described herein.

[0016] Preferred plasticizers include those having at least one benzyl alcohol, benzyl ester, benzyl ether, and / or acyl benzoate moiety, including those described herein. Dibenzoate plasticizers are highly preferred.

[0017] In one embodiment, the present invention provides a filled composition comprising components a), b), and c) as described above and further described herein.

[0018] In a further embodiment, the composition may optionally comprise component d) at least one silicone oil.

[0019] In a further embodiment, the composition e) a pigment; f) glitter; g) mica or coated mica; h) a fragrance; i) a preservative may optionally comprise at least one optional component selected from

[0020] In a further aspect, the present invention provides a method for forming a composition according to any embodiment herein, the method comprising: I) heating component a) to a temperature of 30-70°C, II) mixing into component b); III) optionally, mixing into component c) and / or components d)-h) if present; and IV) cooling the resulting mixture to ambient temperature; Steps I), II), and III) may be performed sequentially or simultaneously.

[0021] One exemplary embodiment of this aspect involves heating and mixing components a) and b) together at a temperature above the melting temperature of component a), then mixing in component c) and / or components d) - h), if present, and cooling to ambient temperature.

[0022] A further exemplary embodiment of this aspect (where component c is present) involves mixing component c) with component b), then heating and mixing in component a), and cooling to ambient temperature.

[0023] In a further embodiment, the present invention i) a step of heating the composition described herein in water, wherein the water is at a temperature of 42°C or less (e.g., 35 - 42°C); ii) a step of forming the composition into a desired shape (e.g., by pouring into a mold, press extrusion, rolling, or freehand shaping); and iii) a step of cooling the composition (e.g., in ambient air, in water at ambient temperature, in cooled air (e.g., in a refrigerator or household freezer), or in cooling water such as ice water) to provide a method for forming a three - dimensional shape.

[0024] Brief Description of the Drawings Figure 1 shows the melting temperature of a polycaprolactone copolymer (PCL(90%) - co - PLA(10%)) as the amount of plasticizer added increases. The plasticizers used were dipropylene glycol dibenzoate and benzoic acid ester (Benzoflex 988).

[0025] Detailed Description of the Invention The present invention provides a moldable or malleable composition that can be formed at a slightly elevated temperature and becomes hard and / or elastic upon cooling to ambient temperature. Such a composition may consist of only a polymer and a plasticizer material (plus optional additives), or may include a polymer, a plasticizer, and a filler (plus optional additives).

[0026] Component a) of the composition is at least one polyester polymer, and suitable polymers include homopolymers and / or copolymers, generally having a melting point of 42 to 70 °C. Preferred melting point ranges include 45 to 65 °C or 48 to 62 °C. A particularly suitable melting point range is 52 to 63 °C. The polymer of component a) typically has an average (preferably weight average) molecular weight of 5 to 200 kD, for example 10 to 100 kD, preferably 25 to 100 or 25 to 50 kD. The polymer of component a) may have a melt flow index of 2 to 100 g / 10 min, preferably 3 to 70 g / 10 min, for example 5 to 10 g / 10 min. MFI is typically measured according to ASTM D1238 and / or ISO1133. Typically, the temperature for MFI measurement of component a) is 80 °C for polymers with MW less than 50 KD (e.g., 35 KD and below, preferably 25 KD and below), and 160 °C for polymers with MW exceeding 25 KD (e.g., exceeding 35 KD, preferably 50 KD and above).

[0027] Polymers suitable for component a) include homopolymers and copolymers. Both may be formed from or may be formable from caprolactone monomers. In particular, in one embodiment, the polymer of component a) may comprise, consist essentially of, or consist of at least one polycaprolactone homopolymer. In other embodiments, component a) may comprise, consist essentially of, or consist of at least one polycaprolactone copolymer. Such copolymers may usually be present with other polyester materials and / or may be formed from or may be formable from another ester or alcohol-functionalized organic acid. Suitable alcohol-functionalized organic acids that may form suitable comonomers include lactic acid and / or glycolic acid or acids of the following formula (II).

[0028]

Chemical formula

[0029] In the formula, each of R5 and R6 is independently selected from H; CH3; a branched or linear alkyl or alkenyl group having 2 to 8 carbon atoms; and m is from 1 to 8, preferably from 1 to 5.

[0030] Lactic acid (m = 1, R5 = H, R6 = CH3); and Glycolic acid (m = 1, R5 = H, R6 = H) are preferred examples.

[0031] When a caprolactone copolymer is used, preferably at least 50% by weight (e.g., 50 - 90% or 50 - 95%) of the monomers is caprolactone and the remainder is one or more other monomers of formula II. Preferably, the caprolactone content is at least 60% or at least 75%, preferably at least 85%. Correspondingly, the non-caprolactone monomers of formula II may be present in about 2 - 50% by weight, preferably 4 - 30% or 5 - 20% by weight of the polymer.

[0032] Preferred homopolymers are caprolactone homopolymers. In one embodiment, component a) may comprise, consist essentially of, or consist of at least one caprolactone homopolymer.

[0033] Preferred copolymers are copolymers of caprolactone and lactide (e.g., 60 - 95% by weight caprolactone and 5 - 40% by weight lactide). In one embodiment, component a) may comprise, consist essentially of, or consist of at least one copolymer of caprolactone and lactide.

[0034] The polyester homopolymer or copolymer for use as component a) in all aspects of the present invention may have any suitable molecular weight. Typical number average molecular weights may be from 3,000 to 200,000, preferably from 10,000 to 120,000 or from 20,000 to 100,000. In one embodiment, a polymer with an MW of about 40,000 to 80,000 is used.

[0035] The polymer component a) is typically present in an amount of at least 25% by weight of components a) and b). This may be, for example, from 28% to 95% by weight, from 30% to 70% by weight, or from 32% to 65% by weight of components a) and b).

[0036] For both homopolymers and copolymers in all aspects of the present invention, the ends of the polymer may be substituted with any suitable functionality. This may be to adjust the properties or reactivity of the polymer, or may be the result of the polymerization process. In particular, at least one end of the polymer chain can contain the residue of any suitable initiator. Common initiator residues include alternative esters (such as esters of diols such as C2 - C8 diols). These will be particularly common at the acid ends of the polyester chain. Particularly useful diols as initiators include ethylene glycol, propylene glycol, butylene glycol or pentylene glycol. Butylene glycol esters at the ends of the polyester are particularly common.

[0037] The compositions of all aspects of the present invention include a softening agent component b). Such a softening agent may be any suitable material that serves to lower the melting point (or melting point range) of the polymer component a) to meet the range discussed herein. Suitable softening agent materials typically contain at least one functional group, particularly at least one oxygen-containing functional group. Suitable softening agents typically contain at least one alcohol, at least one carbonyl (e.g., carbonate, ketone, aldehyde or ester); at least one ether; at least one epoxide, at least one organic acid, at least one halogen, at least one nitro and / or at least one aromatic moiety. Many aromatic moieties are suitable, but benzyl groups are typically effective. Terephthalate groups contain "benzoic acid" type functionality and are particularly suitable in the form of esters such as diesters with C2-C12 alkyl alcohols.

[0038] Alcohols containing polyols can form effective softening agents as all or part of component b). These may include C2-C12 diols and oligomers of diols (such as di- or triethylene glycol, or di- or tripropylene glycol). The diol may be esterified with one or two organic acids (particularly C2-C12 alkyl organic acids) to yield mono- or diesters.

[0039] Organic acids containing diacids (such as C2-C12 organic diacids) can also form suitable softening agents and can be used as the free acid, as mono- or diesters with suitable alcohols (e.g., C2-C12 alkyl alcohols or diols), or as oligomers with C2-C8 alkyl diols such as ethylene glycol or propylene glycol. Fatty acids such as C6-C20 fatty acids and their esters (e.g., esters with C2-C6 alcohols containing diols and polyols such as glycerol) can also be used.

[0040] "Carbonates" such as propylene carbonate (compounds having a carbonic acid ester moiety) can also form suitable plasticizers as all or part of component b). Suitable carbonates include cyclic alkylene carbonates (e.g., C2-C12 cyclic carbonates), linear alkyl carbonates (e.g., R5-O-CO-O-R6, where R5 and R6 are independently linear or branched C1-C12 alkyl groups), or aryl carbonates (e.g., R7-O-CO-O-R8, where R7 and R8 are independently C5-C10 aryl or heteroaryl groups, such as phenyl groups), including cyclic or linear alkyl and / or aryl carbonates. Dicarbonates such as C2-C12 dialkyldecarbonates (e.g., dimethyldicarbonate or diethyldicarbonate) are also suitable. Examples of suitable carbonates include diphenyl carbonate, ethylene carbonate, trimethylene carbonate, dimethyldecarbonate, propylene carbonate, and mixtures thereof. A preferred carbonate is propylene carbonate.

[0041] In a preferred embodiment, component b) may comprise or consist of at least one carbonate. In a more preferred embodiment, component b) may comprise at least one carbonate in addition to other plasticizers such as benzyl esters (e.g., as described herein).

[0042] In one embodiment, the softening agent may comprise at least one benzyl alcohol, at least one benzyl ester, at least one benzyl ether and / or at least one benzoyl moiety. All aromatic moieties containing a benzyl moiety may be optionally substituted with at least one alcohol, at least one carbonyl, at least one ether, at least one organic acid, at least one halogen, and / or at least one nitro moiety. The alkyl group and / or alkenyl group may also form a substituent on any of the aromatic moieties containing a benzyl moiety. Suitable alkyl groups and / or alkenyl groups can include, for example, linear, branched or cyclic C1-C12 alkyl groups and / or alkenyl groups, preferably C1-C4 alkyl groups and / or alkenyl groups. Clearly, the alkenyl group will have at least 2 carbons and the cyclic group will have at least 3 atoms in the ring.

[0043] One of the highly preferred components that can form all or part of component b) is a dibenzyl moiety, preferably a dibenzyl ester linked by a polyalkylene oxide chain. Suitable compounds include at least one compound selected from the compounds of formula (i) below:

[0044]

Chemical formula

[0045] Wherein Each of R1 and R2 is independently selected from H; Cl; F; Br; NO2; CH3; C2-C8 branched or linear alkyl or alkenyl groups; Each of R3 and R4 is independently selected from H; Cl; F; Br; CH3; C2-C8 branched or linear alkyl or alkenyl groups; m is an integer from 1 to 10; n is an integer from 1 to 10.

[0046] In one embodiment, each of R1 and R2 is independently selected from H; CH3; a branched or linear alkyl or alkenyl group having 2 to 4 carbon atoms.

[0047] In a further embodiment, each of R3 and R4 is independently selected from H; CH3; and a branched or linear alkyl having 2 to 4 carbon atoms.

[0048] In a further embodiment, at least one of R3 and R4 is H, preferably each of R3 and R4 is H.

[0049] In a further embodiment, m is an integer from 2 to 3. In a further embodiment, n is an integer from 2 to 3.

[0050] The softening agent component b) is typically present in an amount of up to 75% by weight of components a) and b). This may be, for example, 5 to 75% by weight, 30 to 70% by weight or 35 to 68% by weight of components a) and b).

[0051] The softening agent component b) typically has a boiling point high enough to prevent significant loss of the softening agent by evaporation. In one embodiment, the softening agent may have a boiling point above 150 °C (e.g., 150 - 1000 °C), preferably above 200 °C or above 220 °C.

[0052] The composition of the present invention (in all its aspects) may include a filler material. The filler is different from the "binder" material of components a) and b) in that it does not require control of the melting point. When the binder material softens, the composition softens, but the binder material may include an inert filler that does not need to participate in such a transition for the entire composition to become malleable. The filler component is referred to herein as component "c)".

[0053] When the filler component c) is present, it is at least partially coated and encapsulated by components a) and b).

[0054] The filler (component c)) can be any suitable inert material, but will typically be a particulate material. Suitable materials include other "inorganic" materials such as sand, glass, minerals; and polymers including natural, semi-synthetic and synthetic polymers. Natural polymers may include polyphenol-based and polysaccharide-based fillers, including lignin and cellulose-type fillers such as wood flour, and carbohydrate-type fillers such as wheat flour, rice flour, and corn flour. Synthetic polymers include polyolefins (e.g., polystyrene, polyethylene, polypropylene), polyesters (e.g., polyethylene terephthalate (PET), polybutyrate), polyamides, polyurethanes, etc., and mixtures thereof. Foamed polymers (polymer foams) such as hollow glass microspheres, foamed latex, polyurethane foam, foamed PVC, foamed polystyrene, or foamed polyethylene, and foamed materials such as copolymers containing any of these. A particularly suitable foamed material is "Expancel", which is a copolymer of vinylidene chloride, acrylonitrile, and methyl methacrylate, and typically contains isobutene as a blowing agent.

[0055] In one embodiment, the filler material may be a biodegradable material such as polyester (e.g., polylactide). In such a case, the filler polyester typically has a melting point higher than the combined melting points of binder components a) and b). For example, the filler may have a melting point of 50 °C or higher (e.g., 50 - 200 °C). Polylactide polymers, polyglycolide polymers, or lactide / glycolide copolymers are suitable examples. Such polymers can be used as solid polymer particles or as foamed particles such as foamed beads. Such foamed beads can be formed by known methods such as the use of alkanes, air, CO2 blowing agents. BEWI's BioFoam is an example of a suitable polyester foamed filler. The particle size of such foams can be any of those indicated herein, such as 0.5 - 5 mm.

[0056] Generally, the filler material has a melting point higher than that of the binder material. Some fillers (e.g., glass or mineral fillers) do not melt under realistic use conditions, but polymer fillers (especially synthetic polymer fillers) generally have a melting point or decomposition temperature of at least 70 °C (e.g., 70 - 150 °C, such as 70 - 500 °C).

[0057] Typical examples of the filler component c) include sand fillers, glass fillers, polymer fillers, mineral fillers, or mixtures thereof. Typical sand fillers include quartz sand and / or silica sand. Thus, such "sand" can include coarse sand or gravel-sized particles. The typical "sand" indicated herein has an average particle size of 50 μm to 5 mm (e.g., 63 μm to 5 mm), preferably 95 μm to 3 mm, but sand also encompasses gravel and pebble-sized fillers with an average particle size up to about 10 mm, and these can also be used. When referring to individual particles, the size is generally the minimum diameter (i.e., the diameter along the minimum axis). Sand fillers (and all other fillers) can be "bimodal" or "polymodal" in that there can be fillers of multiple sizes. For example, fine sand or silica fillers with an average particle size of less than 100 μm can be used in combination with coarse "sand" or gravel fillers with a particle size of 1 mm or more (e.g., 1 to 10 mm). Such a bimodal mixture of fillers can allow for a better coating of the larger particles and potentially improve the properties of the binder. Typically, in such cases, when the filler particles of the two sizes have a similar density (e.g., ±50%), the filler component c) contains at least 60% by weight, preferably at least 75% by weight, of the larger-sized filler.

[0058] A very suitable "small" filler is finely powdered calcium carbonate or silica. Such fillers do not significantly affect the texture of the material but serve to increase the bulk of the binder component. This type of finely powdered filler ("small filler") may have an average particle size of 20 μm or less (e.g., 0.5 - 20 μm), preferably 10 μm or less (e.g., 1 - 10 μm). An average particle size of 0.5 - 8 or 2 - 20 μm is very suitable for such small fillers, which may be formed of any filler material disclosed herein, particularly inorganic filler materials such as silica or calcium carbonate. Such small filler particles can form the sole filler or can be used in combination with larger filler materials. Although all ranges of filler content discussed herein are suitable, a preferred range for the small filler particles is about 10 - 50 wt% of the total components in the composition, particularly 20 - 40 wt% is a preferred range.

[0059] Silica fillers, particularly hydrophobized silica fillers, form mineral fillers that are highly preferred for use as "small fillers" that form at least part of component c) of the present invention. Such fillers may be added in an amount of about 1 - 30 wt% of the total components in the composition. When this preliminary filler composition is added to a larger amount of another filler (see below for typical filler amounts), the small filler has the effect of increasing the volume without requiring more polymer or softener and potentially also increasing the binding effect of components a) and b).

[0060] In an advantageous embodiment, the various products of the present invention may include both a "small filler" such as a hydrophobized fumed silica filler or a fine particle calcium carbonate filler and a second filler of any of the types indicated herein. This provides advantages to the elasticity and robustness of the binder, particularly when the small filler (e.g., hydrophobized fumed silica filler) is employed at a level of about 5 to 30% by weight (e.g., 10 to 25% by weight or 5 to 15% by weight) relative to the total of that filler and components a) and b). Preferred hydrophobized fumed silica fillers may include various particle sizes including aggregates of fine particles. Typical aggregated fumed silica particles may range from 1 to 100 μm in minimum dimension, preferably about 5 to 50 μm.

[0061] All fillers, particularly mineral fillers including glass, sand, silica, alumina, and other mineral fillers, may be surface-treated. There are many useful surface treatments to improve various properties such as performance and / or appearance. One preferred surface treatment is a hydrophobic surface treatment that "hydrophobizes" the surface of the filler. Thus, surface-treated (e.g., hydrophobized) glass, sand, silica and / or alumina form preferred fillers in the present invention. Surface treatments, particularly those suitable for silica-containing fillers, include treatment with 0.05 to 0.2% by weight of an alkoxysilane or silyl alkanate of the filler.

[0062] Glass fillers useful as component c) in all aspects of the present invention include ground glass fillers, glass bead fillers, hollow glass bead fillers, and mixtures thereof. The average particle size is preferably on the order of 10 μm to 2 mm, although ground glass fillers may be composed of very small particles such as 1 μm or less.

[0063] Certain mineral fillers are highly advantageous as all or part of component c) in all aspects of the present invention. Such mineral fillers include sand (as described above), silica fillers, titania fillers, alumina fillers, calcium carbonate fillers, calcium sulfate fillers, sodium sulfate fillers, silicate compounds, kaolin and other clays, calcium phosphate, talc, and mixtures thereof.

[0064] Polymer fillers can include compatible natural, semi-synthetic or synthetic polymers in any suitable form. Synthetic polymer fillers include, for example, polyolefins (such as polystyrene, polyethylene, polypropylene), polyesters, and / or polyamide fillers (including beads, chips, polymer sawdust, cut film, or other suitable particles of such materials). Preferred filler particles are beads, and synthetic polymer fillers may include polystyrene beads, other polyolefin beads, polyester beads and / or polyamide beads. Such polymer fillers may be in the form of solid pieces or may be formed into foamed open-cell or closed-cell foams by methods well known in the art. Such "foamed" materials are excellent fillers particularly when lightweight or insulating materials are desired. Such lightweight materials include "foamed" materials including hollow spheres of any of the polymers shown herein, expanded polystyrene, expanded polyolefins, expanded polyesters, expanded polyamides, expanded PLA (polylactide), and mixtures thereof, typically in the form of expanded beads. The size of the polymer filler particles varies from about 50 μm in diameter to several mm (e.g., about 10 mm). Generally, unexpanded or unfoamed fillers usually have a smaller particle size (e.g., 50 μm to 1000 μm, preferably 100 μm to 500 μm, etc.), and expanded or foamed fillers usually have a larger particle size (e.g., 200 μm to 10 mm, preferably 300 μm to 5 mm, etc.). Similar to the other particle sizes shown herein, the sizes described typically refer to the minimum dimension, as far as the context allows.

[0065] The polymer filler may also contain or consist of natural polymers such as starches, polysaccharides including chitin and cellulose, and other natural polymers such as polyphenols (e.g., lignin) and proteins (e.g., keratin). Polysaccharides are particularly suitable and may be in the form of, for example, flour milled from natural materials such as grains (wheat, corn, rice, etc.), or in the form of powder, dust, chippings, etc. from wood, bamboo or other fibrous materials. It is also possible to heat natural materials to "foam" them to produce materials such as popcorn, puffed wheat, crispy rice, etc. Steam expansion or steam explosion can also be utilized. Such materials can be used as the filler of the present invention as natural large particles or after being crushed or cut into small particles. Natural polymers are usually very non-toxic and can be used safely, and are very useful in embodiments of the present invention that may be used by children. Sawdust, fine wood chips, wheat flour, corn flour, wood flour, and rice flour are preferred natural polymer fillers. Carbon of natural origin can form both a filler material and a black colorant in various materials of the present invention.

[0066] The total amount of the filler in the composition of the present invention can vary in the range of about 1% to 99.5% of component c) with respect to the weight of the entire composition. In fact, there are two most likely sub-ratios depending on the type of filler used and the density of the filler. In the case of non-foamed fillers (e.g., with a density greater than 0.5 g / cm 3 ), the total amount of the filler can vary from about 10% by weight to 99.5% by weight of component c) with respect to the total weight of the composition. Preferably, the ratio of components a) and b) to c) in the total of all components is such that the binder is about 2 to 30% by weight and the filler is about 70 to 98% by weight with respect to the entire composition. In the case of foamed fillers (e.g., with a density of 0.5 g / cm 3In the case of less than [specific amount], the content may typically be about 1 wt% to 90 wt% of component c), more preferably 2 wt% to 50 wt% of component c). Since there is a maximum volume of filler that can be effectively coated by a certain amount of binder, in addition to the weight ratio, it is also important to maintain an appropriate volume ratio. Therefore, the volume ratio of the filler (component c)) to the binder (components a) and b)) should be about 500:1 or less, preferably 200:1 or less, in terms of filler volume: binder volume. General ratios may be between 100:1 and 1:1, such as between 50:1 and 2:1, or between 40:1 and 5:1.

[0067] Optional component d) is applicable to all aspects of the present invention and relates to silicone fluids (silicone oils). Such silicone fluids are generally linear, branched and / or cyclic oligo- or poly-alkylsiloxanes with or without at least one hydroxyl terminus. Poly- or oligo-dimethylsiloxanes form preferred examples with or without at least one hydroxyl terminus.

[0068] Suitable silicone fluids may have a wide range of viscosities, such as from 1 to 5000 mPas at 25 °C. This is preferably about 2 to 2500 mPas at 25 °C (e.g., 2 to 150 mPas at 25 °C). The molecular weight of suitable oligo- or poly-alkylsiloxanes can vary in the range of about 100 D to about 50 kD, such as about 0.2 to about 30 kD or 0.2 to 5 kD. Polydimethylsiloxane (PDMS) is highly suitable with any end groups (including hydroxy-terminated and / or non-hydroxy-terminated PDMS).

[0069] Examples of useful silicone fluids include CDS100 (linear polydimethylsiloxane with hydroxy-terminated ends, molecular weight about 4 kD, viscosity about 100 mPas at 20 °C), AK5 (low molecular weight oligodimethylsiloxane without hydroxy-terminated ends, viscosity at 25 °C is about 5 mPas), AK10 (manufactured by Wacker, polydimethylsiloxane without hydroxy-terminated ends, MW is about 1100 D) and polymer C2T (manufactured by Wacker, linear polydimethylsiloxane with hydroxy-terminated ends, molecular weight is about 25000, viscosity at 25 °C is about 2000 mPas).

[0070] Component c), when present, is typically present in an amount of 20% by weight or less (e.g., 0.5% - 20%) based on the total weight of the composition. This is preferably 1 - 15% by weight or 3 - 12% by weight (e.g., 5 - 10%). With respect to binder components a) and b), the amount of silicone oil (when present) may be up to about 15% by weight of components a) and b) (e.g., 0.1 - 15% by weight), preferably 1 - 12% by weight such as 2 - 10% by weight.

[0071] In all aspects of the present invention, the products and compositions may optionally contain at least one of the following various optional components; e) Pigments; f) Glitter; g) Mica or coated mica; h) Perfumes; i) Preservatives; and / or j) Flame retardants.

[0072] Each optional component provides useful and valuable advantages in specific embodiments and specific applications, is independently selected, and can be used individually or in any combination if technically possible. Although described separately herein for clarity of the various components, they may be used in combination to provide the desired properties of the compositions of the present invention.

[0073] Examples of each of these additives are well known to those skilled in the art, and many of them are exemplified herein. In a preferred embodiment, these optional components may be any of those described in the Examples section of this specification, particularly in the "Table of Chemical Substances Used in Examples" preceding the Examples. The glitter as referred to herein includes plastic film-based glitter (e.g., polystyrene film glitter).

[0074] When additional components e) - j) or other additional components are present, each typically is present at 5 wt% or less of the total composition (e.g., 0.01 - 5%). This is preferably 2 wt% or less or 1 wt% or less.

[0075] The present invention further provides a method of forming a three-dimensional shape using the composition described herein. Such a method preferably requires only very mild conditions that are almost risk-free and can be carried out by people of all ages with minimal supervision. Generally, the composition of the present invention is formulated to soften at or near body temperature, such that the composition can be thermally softened without the risk of burns and handled in the softened state. Water is a very effective medium for heat transfer and can be used for this purpose. Warm water can be supplied, for example, to a low-output constant temperature heating tank and maintained at a safe temperature sufficient to soften the composition. A suitable temperature is 45°C or less, preferably 42°C or less (e.g., 35 - 42°C).

[0076] Correspondingly, the composition of the present invention has a melting point (e.g., softening point if the filler hinders easy evaluation of the melting point) of 30 to 40 °C, such as 35 to 40 °C or 36 to 39 °C. The melting point can be evaluated using the standard "hot stage" method. In all suitable embodiments, particularly when the composition is not easily evaluated for the melting point (e.g., due to the presence of solid fillers), the "melting point" as used herein can be interpreted to mean "softening point". Any suitable measurement of such softening point can be used. For example, a 100×10×3 mm bar of the composition is prepared, cooled to room temperature, and then the bar is supported 1 cm from each end at a controlled temperature, and the temperature at which the bar sags by 5 mm or more in the center under gravity is measured. Since this test is relatively independent of the bar thickness, when using large fillers, a bar with a thickness of at least two filler particle thicknesses can be used.

[0077] The composition can be repeatedly heated and molded until the final shape is created, at which point the composition can be cooled. Cooling can be done simply by leaving the three-dimensional shape in ambient air or cooled air (e.g., in a refrigerator or household freezer), or by immersing it in ambient water or cooled water. Ice water serves to essentially immediately "solidify" the composition of the present invention. Rapid solidification can also be achieved in a refrigerator or household freezer.

[0078] In one embodiment, the composition of any aspect or embodiment of the present invention remains moldable at a suitable temperature (e.g., 35 to 42 °C). The composition of the present invention preferably does not "coagulate" or "harden". That is, the composition of the present invention does not form a hard material that cannot be reformed by hand at a suitable temperature (e.g., 35 to 42 °C).

[0079] As used herein, the terms "about," "approximately," "substantially," or "around" in connection with a numerical value or numerical range generally mean that the specified numerical value or range is preferred, but such a numerical value can vary within a range without materially affecting the properties of the relevant material, composition, or similar product. A person skilled in the art can typically readily determine to what extent such a numerical value can be varied without impairing the important advantages of the present invention. As a general guideline, such a numerical value or the two ends of such a range may be varied by ±10%, preferably ±5%, more preferably ±1%. A corresponding meaning may be attributed to a composition "consisting essentially of" a particular component, which composition may contain other components up to 10%, preferably up to 5%, most preferably up to 1% in addition to the specified component. When it is described herein that a chemical group, chain, or other moiety is optionally substituted, such substitution may be absent, or one or more atoms (typically one or more hydrogens and / or carbons) of that moiety may be substituted with a halide (e.g., F, Cl, Br, I) group, an oxygen-based moiety such as an ether, alcohol, ester carboxylic acid, or epoxide, a nitrogen-based group such as an amine, amide, nitrile, or nitro group, or a sulfur-based group such as a thiol, disulfide, or thioester. Such substitution may be carried out up to about 10 if possible in the context, but typically, three or a few substitutions such as 1, 2, or 3 substitutions by independently selected substituents will be typical.

[0080] Examples The examples demonstrate that standard grade polycaprolactone polymers and copolymers can be effectively used in the present invention. By combining the polymer with a softening agent, a robust, reproducible, and composition with controlled properties was obtained. The addition of the softening agent can be used to control and adjust the properties in a reproducible manner.

[0081] Materials and Properties

[0082] [Table 1]

[0083] [Table 2]

[0084] [Table 3]

[0085] [Example 1 Polyester Homopolymers and Copolymers] The melt temperature as a function of lactide content (Table 4) was investigated and the temperature of the polymer samples was controlled using a hot stage. Visual observation was used to measure the melt temperature, and the temperature at which the polymer matrix changed from opaque / white to transparent / semi-transparent and from solid to soluble was taken as the melt temperature.

[0086] The first observation is that the melt temperature decreases when the molecular weight of the (homo)polymer is low.

[0087] The lactide content in the copolymers was extended to non-commercial samples and the melt temperature over a wider range of lactide contents was investigated. There was a large variation between batches, the data was scattered, and the melting point temperature varied between different production batches even at the same lactide content. As a rough general observation, the melt temperature of poly(caprolactone-co-lactide) polymers tended to decrease by about 1 °C per 1% of lactide in the copolymer. The decrease in melt temperature with increasing lactide content stopped immediately, and the lowest melt temperature observed was in the range of 40 °C to 45 °C. The melt temperature of the caprolactone homopolymer is about 60 °C and that of the polylactide homopolymer is about 170 °C. Thus, the melt temperature of the copolymer as a function of lactide content passes through a minimum.

[0088] [Table 4]

[0089] [Example 2 Plasticizer] Thirteen types of plasticizers were tested to evaluate the melting temperature and material properties of PCL homopolymer-based mixtures (Table 5).

[0090] Judging from the combination of melting point depression and mechanical properties, it is considered that the best plasticizers at an addition of 40 wt% are Benzoflex 988 and Benzoflex 2088. Benzoflex 988 or Benzoflex 2088 were evaluated at higher addition levels (50% and 60%). In fact, the melting temperature further decreased (41 °C and 37 °C). Despite the high addition levels, the mechanical properties in the solid state are within the acceptable range for PCL (high Mw), while the samples prepared with PCL (low Mw) show more clearly negative effects such as a softer and more brittle matrix in the solid state and more sticky properties in the molten state.

[0091] Based on the results in Table 5, as a possible alternative, a mixture of 50% CAPA 6500D (high molecular weight polycaprolactone), 40% Benzoflex 988, and 10% Edenol 1200 was evaluated. As a result, the melting temperature was about 44 °C and the material properties were not optimal. Therefore, in this case, pure Benzoflex 988 seems to be a better choice than combining the other two promising plasticizers.

[0092] [Table 5]

[0093] [Example 3 Polymer / Plasticizer Optimization] Based on the results of Examples 1 and 2, the change in the melting temperature of PCL(90)-co-PLA(10) due to the addition of Benzoflex 988 was investigated and optimized. Samples were prepared by melt mixing the polymer and the plasticizer. The change from opaque / white to transparent / translucent of the solid samples, and the change from solid to malleability (by which the melting temperature was determined) were determined using a hot stage. Figure 1 shows that the melting temperature of the mixture decreases strongly up to about 40 wt% of Benzoflex 988 and then levels off at about 35 °C.

[0094] Similar behavior was also observed for the PCL (high Mw) homopolymer, and for the arrays of 0 wt%, 40 wt%, 50 wt%, 60 wt%, and 64 wt% benzoflex 988, the melting temperatures were 60 °C, 45 °C, 41 °C, 37 °C, and 37 °C, respectively.

[0095] The addition of benzoflex 988 appears to be a convenient and reproducible way to provide mixtures with an optimum melting temperature of about 35 °C to 37 °C. In this way, even when a melting temperature near body temperature is desired, "simpler" homopolymers can be used instead of more complex copolymers.

[0096] [Example 4 Filled Composition] Four types of modeling compounds were prepared using the polymer PCL(88)-co-PLA(12) (Table 6). The melting temperature was controlled by reducing it to about 39 °C by a well-balanced addition of a softening agent (Blend 1).

[0097] To properly disperse the micronylene, a temperature of about 85 °C is required. To prepare Blend 2, first mix PCL(88)-co-PLA(12) and micronylene (blue) at about 85 °C. Add benzoflex 988 and, once properly mixed, add Locrit A and then AK5.

[0098] To prepare Blend 3, a lower temperature can be used. The mixing can be carried out at a temperature slightly higher than the melting temperature of the polymer. PCL(88)-co-PLA(12), Lysopure (red), and benzoflex 2088 were mixed at a temperature of about 50 °C. Next, Locrit A was added, followed by Geoglit silver and AK5.

[0099] Blend 4 contains substantially more filler, and the mixing follows the same preparation sequence as Blend 3.

[0100] The obtained modeling compound can be hand-molded and carved at working temperatures above a melting temperature of about 39 °C. The material settles and solidifies under normal room temperature conditions. Blend 4 contains a large amount of inexpensive filler, so it has an inexpensive formulation. The higher the filler content, the more brittle and less flexible the solidified compound becomes.

[0101]

Table 6

[0102] [Example 5 Use of Various Grades of Sand Filler] As shown in Table 7, modeling compounds can be obtained using sands of various sizes. The ratio of PCL (high Mw) to Benzoflex 988 was optimized to achieve a balance between physical properties (strength of the compound in the solid state) and melting temperature (37 °C). All of Blend 5, Blend 6, Blend 7, and Blend 8 have a melting temperature of about 37 °C or higher, which is convenient for hand-molding. Below that temperature, the material settles and solidifies. By repeating the temperature cycle, the material can be shaped into a new solid. Due to the different sizes of the sand grains, the texture of the material varies from "soft and smooth" to "coarse and granular".

[0103] Commercially available sand raw materials first required surface treatment suitable for use in combination with a binder. First, an aqueous dispersion containing two types of silanes was prepared: a mixed silane of Wacker Geniosil XL10 (4.5 g) and Wacker Silres 1701 (0.5 g) was added to an aqueous solution of 94.5 g of water and 0.5 g of HAc (24%) with vigorous stirring to prepare a coarse dispersion. Stirring (vigorously) was continued for about 30 - 60 minutes. During that time, sand GA39, M32, or B55 was heated to 55 - 60 °C in a stainless steel pot. The aqueous silane dispersion (100 g) was added to the hot sand with continuous stirring. Mixing was continued until the water evaporated and the sand dried. This process yielded surface-treated sand samples GA39(ST), M32(ST), or B55(ST), which were used as fillers.

[0104]

Table 7

[0105] [Example 6 Composition Using Foamed Polymer Filler] (Using (foamed) polymer fillers of various sizes, the filled modeling compounds in Table 8 can be obtained. The ratio of PCL (high Mw) to Benzoflex 988 is the same as in Example 5, and the melting temperature is about 37 °C. Above this temperature, the modeling compounds in Table 8 can be easily molded by hand. Below this temperature, the material will settle and solidify. By repeating the temperature cycle, the material can be reformed into a new solid. Due to the different sizes of the fillers, the texture of the material is different. Since the fillers have voids or are hollow, Blend 9 and Blend 10 have a soft and elastic texture. Blend 11 has a high ratio of binder to filler, and the texture of the solid-state material resembles that of a plastic material.)

[0106]

Table 8

[0107] [Example 7 Composition with Polymer Filler and in-situ Expansion] When Expancel 461DU is heated to about 100 °C, the filler polymer shell softens. It expands due to the incorporated blowing agent, and particles similar to Expancel 461DE are obtained.)

[0108] A mixture of 63 wt% PCL (low Mw), 27 wt% Benzoflex 988, and 10 wt% Expancel 461DU was prepared by first mixing PCL (low Mw) and Benzoflex 988 at about 65 °C and then mixing in Expancel 461DU. The PCL-based binder of this material melts at a temperature of about 50 °C, and the material becomes malleable.)

[0109] When a small piece of solid material containing Expancel 461DU is brought into contact with boiling water, first the PCL (low Mw) - based binder melts, and then, after its polymer shell softens due to the high temperature, the blowing agent in situ expands the filler particles. The final material is a lightweight material with properties similar to those of a similar material prepared with pre - foamed Expancel 461DE. Initially, a low Mw PCL polymer was chosen because a high melt flow index (MFI) facilitates the in - situ expansion of Expancel. The drawback of low Mw is that the material adheres easily to hands and surroundings when in a molten state.

[0110] A similar preparation was also carried out with PCL (high Mw): 63 wt% PCL (low Mw), 27 wt% Benzoflex 988, 10 wt% Expancel 461DU. Similar to the mixture based on the low - molecular - weight polymer, this preparation also expands in hot water despite having a low MFI. Both formed effective compositions.

[0111] [Example 8 Use of Two Kinds of Fillers] Even when incorporating small - sized fillers into the binder system, the influence on the final material properties is limited (essentially negligible). In Blend 13, HDK H2000 was used to reduce the amounts of PCL (high Mw) and Benzoflex 988 by 25 wt% (from 6 wt% to 4.5 wt%, from 9 wt% to 6.7 wt%). This is an effective way to reduce the content of expensive polymers without significantly affecting the material properties.

[0112] [Table 9]

[0113] [Example 9 Use of Carbonate as a Softening Agent] DMC can be easily mixed with PCL (high Mw) when melted at any evaluation ratio (up to 50%), so it seems to be a suitable softening agent. However, due to its low boiling point and the accompanying high vapor pressure, its compatibility is hindered. Therefore, especially when heated, DMC is rapidly lost. However, since PC has a much higher boiling point than DMC, it becomes a more attractive option. After mixing the PC softening agent and PCL (high Mw) in the molten phase, the mixture was cooled rapidly to solidify it, or cooled slowly so that solidification occurred over a longer period of time. The melting temperatures of various mixtures were evaluated using a hot stage and an infrared thermometer.

[0114]

Table 10

[0115] Slow cooling seems to induce partial separation of only a small part of the solvent at a high ratio, which is reflected as sweating or a granular texture, and also by the fact that the melting temperature of the "33 / 67" sample is higher compared to the case of rapid cooling.

[0116] [Example 10 Softening Agent Mixture for PCL Polymer in a Mouldable Composition] Furthermore, it is also possible to blend different softening agents in the mouldable composition. Table 11 reports a composition containing both PC and Benzoflex 988, where the two softening agents were melt-mixed to form a homogeneous mixture. Expancel 461DE, Rocalit A and AK5 were added to the mixture and mixed into a homogeneous mouldable composition.

[0117]

Table 11

[0118] All three compositions were evaluated by melting them in a water bath at 39 °C and then cooling them to room temperature for solidification. This process was repeated approximately 10 times. The "5% sample" and "10% sample" showed stable properties, while the "50% sample" showed changes with the number of cycles and ultimately did not melt at 39 °C. This may reflect a compositional change due to the loss of PC, based on the fairly high solubility of this plasticizer in water.

[0119] [Example 11 Loss of plasticizer in a mixture with PCL polymer] A PCL(high Mw) / PC mixture (33% / 67%) was prepared by melt mixing and formed into cubes (0.88 g), and the temperature was lowered for solidification. This "33 / 67" material has a variation in the perceived melting temperature depending on whether the cooling is fast or slow, but it is low, approximately 30 °C (Example 9).

[0120] This solid cube was contacted with excess water (25 °C) for 6 days and then left standing in air for 7 days. After this treatment, the melting temperature of the material increased to approximately 60 °C, which was almost the same as the melting temperature of pure PCL(high Mw) (i.e., the "100 / 0" material).

[0121] This example shows that the loss of a water-soluble plasticizer can be utilized to increase the melting temperature and act as a solidification / curing mechanism for the molded body. Since PC has a slightly high boiling point and a low vapor pressure, the loss of the plasticizer due to evaporation is not much. The PCL / PC mixture can be expected to have storage stability before contacting with water. The PCL(high Mw) / DMC mixture has a lower boiling point (higher vapor pressure) compared to PC, so it will "age" when exposed to air, and for this reason, it is less preferable.

[0122] [Example 12 Surface treatment of sand filler] Very suitable surface-modified sand can be formed by treating sand or other silica-containing fillers with 0.05 - 0.2 wt% of alkoxysilane or silyl alkanoate of the filler.

[0123]

Table 12

[0124] The processing time at production scale depends greatly on the time required to evaporate the water generated from the added silane solution / dispersion. Therefore, it is advantageous to minimize the necessary water without compromising the results of surface treatment by increasing the silane concentration in the aqueous solution / dispersion.

[0125] Mam1s sand was heated to 55 - 60 °C in a steam - heated mixer with a jacket. The batch size was 400 kg at production scale.

[0126] The crude aqueous silane dispersion was prepared by vigorously mixing for 30 - 60 minutes. The pH value was adjusted to approximately 4, at which the silane reaction is minimized, using acetic acid. This results in a dispersion in which the silane does not react before encountering the silanol groups on the sand grain surface and the aqueous phase evaporates.

[0127] Subsequently, the dispersion was added to the pre - heated sand and mixing was continued until the water evaporated. It was assumed that the treatment was completed when the sand was dry. The processing time in large - scale production is about 5 - 30 minutes (varying depending on the amount of water used in the dispersion).

[0128] Table 13 shows the composition of the silane dispersions for the 400 kg test. These two types of silane dispersions were 5% by weight and 11% by weight respectively, and the sand properties evaluated by the method described below gave good results. Version B has less content of silane (XL10 and BS1701) and water, and requires a shorter processing time, so it is recommended for large - scale production. The moisture content decreased by 74% compared to Version A, and the modification degree decreased from 17 mg / m2 to 9 mg / m2.

[0129]

Table 13A

[0130]

Table 13B

[0131] The characteristics of the treated sand were determined by contacting the sand with pure water. Modification was confirmed by an increase in the hydrophobicity of the particles. This was evaluated by contacting the sand with water and subjectively judging the wettability and contact angle. There is also a method of spreading the sand on a flat surface and placing a drop of water on the sand. If the water remains as a water droplet / lens on the sand without wetting the sand, it is judged that the surface modification has been successful. As another method, there is a method of immersing the modified / treated sand in a large amount of water. If the immersed sand forms lumps and does not get wet in water, or if the sand grains are small (less than about 100 micrometers) and seem to float on the water surface, the treatment is judged to be successful. The characteristics of a suboptimal treatment are that the sand gets wet in water, does not form lumps, and small sand grains sink.

Claims

1. a) at least one polyester homopolymer or copolymer having a melting point of 40 to 70 °C; and b) at least one softening agent having a molecular weight of 50 to 500 amu; A composition comprising: The composition exhibits a melting point or softening point within the range of 30 to 45 °C, Component a) is present in 25 to 95% by weight of components a) and b); Component b) is present in 5 to 75% by weight of components a) and b).

2. c) The composition according to claim 1, further comprising at least one filler.

3. The composition according to claim 1 or 2, wherein the at least one polyester homopolymer or copolymer comprises at least one homopolymer or copolymer of caprolactone.

4. The composition according to any one of the preceding claims, wherein the at least one polyester homopolymer or copolymer comprises at least one copolymer of caprolactone and lactide.

5. The composition according to any one of the preceding claims, wherein the at least one polyester homopolymer or copolymer comprises at least one homopolymer or copolymer of caprolactone having an average molecular weight of 10,000 to 120,000, preferably 20,000 to 100,000.

6. The composition according to any one of the preceding claims, wherein the softening agent comprises at least one alcohol, at least one carbonyl; at least one ether; at least one organic acid, at least one halogen, at least one nitro and / or at least one aromatic moiety.

7. The composition according to any one of the preceding claims, wherein the softening agent comprises at least one benzyl alcohol, benzyl ester, benzyl ether and / or benzoyl moiety optionally substituted with at least one alcohol, at least one carbonyl, at least one ether, at least one organic acid, at least one halogen and / or at least one nitro moiety.

8. The composition according to any one of the preceding claims, wherein the softening agent comprises at least one compound of formula (i). 【Chemical 3】 [Wherein, R 1 and R 2 each independently is selected from H; Cl; F; Br; NO 2 ; CH 3 ; C 2 to C 8 a branched or linear alkyl or alkenyl group selected from; R 3 and R 4 each independently is selected from H; Cl; F; Br; CH 3 ; C 2 to C 8 branched or linear alkyl or alkenyl groups; m is an integer from 1 to 10; n is an integer from 1 to 10.]

9. R 1 and R 2 each independently is H; CH 3 ; C 2 ~C 4 a branched or linear alkyl or alkenyl group; and a mixture thereof; and is selected from; R 3 and R 4 each is H; m is an integer from 2 to 3; n is an integer from 2 to 3, The composition according to claim 8.

10. The composition according to claim 6, wherein the carbonyl moiety is a carbonic acid ester.

11. The softening agent is a C2-C12 cyclic carbonate; Formula R 5 -O-CO-O-R 6 linear alkyl carbonate [wherein, R 5 and R 6 are each independently a linear or branched alkyl group having 1 to 12 carbon atoms]; Formula R 7 -O-CO-O-R 8 aryl carbonate of [wherein, R 7 and R 8 are, independently, an aryl group or a heteroaryl group having 5 to 10 carbon atoms]; and a C2-C12 dialkyl dicarbonate and contains at least one carbonic acid ester compound selected from the composition according to any one of the preceding claims.

12. The composition according to any one of claims 2 to 11, wherein component c) comprises a sand filler, a glass filler, a polymer filler, a mineral filler or a mixture thereof.

13. The composition according to any one of claims 2 to 12, wherein component c) comprises at least one surface-treated filler.

14. The composition according to claim 13, wherein the surface treatment is a hydrophobic surface treatment.

15. The composition according to claim 13 or 14, wherein the surface treatment is treatment with at least one alkoxysilane and / or at least one silyl alkanate.

16. The composition according to any one of claims 10 to 15, wherein the polymer filler comprises polystyrene beads, polyolefin beads, polyester beads, polyamide beads, expanded polystyrene beads and mixtures thereof.

17. The composition according to any one of claims 2 to 15, comprising component c) in an amount of 10 to 95% by weight of components a), b) and c).

18. The composition according to any one of the preceding claims, further comprising d) at least one silicone oil.

19. e) a pigment; f) glitter; g) mica or coated mica; h) a fragrance; i) a preservative and further comprises at least one component selected from

20. A modeling compound comprising at least one composition according to any one of the preceding claims.

21. A method for forming a composition according to any one of claims 1 to 19, comprising: I) heating component a) to a temperature of 30 to 70 °C; II) mixing into component b); III) optionally, mixing into component c) and / or components d) to h) if present; and IV) cooling the resulting mixture to ambient temperature; comprising Steps I), II) and III) may be carried out sequentially or simultaneously. Method.

22. Component a) and b) are heated and mixed together at a temperature higher than the melting temperature of component a), and then The method according to claim 21, comprising the step of mixing in component c) and / or components d) to h) if present and cooling to ambient temperature.

23. The method according to claim 22, wherein component c) is present, comprising the step of mixing component c) with component b) and then heating and mixing in component a) (for example, at 30 to 70 °C) and cooling to ambient temperature.

24. i) a step of warming the composition according to any one of claims 1 to 16 in water, wherein the water is at a temperature of 42 °C or lower; ii) a step of shaping the composition into a desired shape (for example, by pouring into a mold, press extrusion, rolling or freehand shaping); and iii) a step of cooling the composition (for example, in ambient air, water at ambient temperature, cooled air or cooled water) A method for forming a three-dimensional shape, comprising.

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