MODELING COMPOUND

Abstract

The present invention relates to modeling clay comprising: a) at least one starch-containing material; b) at least one low-vapor-pressure polar solvent; and c) an aqueous component. The clays generally also contain optional ingredients such as softeners, preservatives, and / or additives. The invention further relates to filled clays comprising modeling clays incorporating an inert filler, and to methods for producing both the modeling clay and the filled clay.

Description

MODELING COMPOUND FIELD OF INVENTION The invention generally relates to flexible modeling compounds that can be used for extrusion, lamination, molding, or sculpting. In particular, the invention relates to starch-based modeling compounds. BACKGROUND OF THE INVENTION For over 50 years, starch-based modeling compounds have been well known and used (McVicker et al.). The binder in starch-based modeling compounds comes from various sources, including wheat, rye, rice, or tapioca flour. According to known methods in the art, such starch-based binders can be mixed with other components such as water, a salt, a lubricant, and / or a preservative to form a modeling compound. Modeling materials can generally be divided into starch-based masses and non-drying clays. Starch-based masses like Play-Doh (RTM) are typically bound with water and are susceptible to drying out when left uncovered. In contrast, non-drying modeling materials are typically clays that do not offer the same "feel" as masses in use. Generally, non-drying clays, such as Plasticine (RTM), are based on a liquid hydrocarbon or wax with a high level of a filler, such as a mineral filler, incorporated. Similar well-known products include polymer clays such as Fimo (RTM), Sculpey (RTM), and Cernit (RTM), which are typically based on PVC, hydrocarbons, and plasticizers. Non-drying materials, especially those incorporating hydrocarbons, tend to leave a residue on the hands after use and can be sticky, particularly under warm conditions.In addition, starch-based doughs have a more desirable "feel," especially for children. Starch is a polysaccharide produced by most green plants and is the primary source of stored energy in grains. Besides starch, flour typically contains protein, dietary fiber, and fat. Starch is a mixture of the water-soluble polysaccharides amylose and amylopectin. Amylose is comparatively low in molecular weight. It is linear, composed of α(1 → 4) 1 or —LO glucose molecules linked together, and forms helical coils in solution. Amylopectin is highly branched, has a much higher molecular weight, and, in solution, a higher viscosity. The glucose units in amylopectin are linked linearly (α(1→4) glycosidic linkages), while branching occurs with α(1→6) linkages that take place every 24 to 30 glucose units. Dissolved amylopectin starch has a lower tendency to retrogradation (gelation) during storage and cooling than amylose-rich starch. Amylose tends to retrograde even at concentrations as low as 1% in water. In starch, amylopectin is the dominant component, typically comprising around 70% of the polysaccharide content, but the amount varies depending on the source. Medium-grain rice has a higher proportion of amylopectin, and in glutinous rice, it can reach up to 100%. For example, wheat starch contains approximately 75% amylopectin, and tapioca starch contains approximately 83%. Waxy corn starch contains over 99% amylopectin. In semicrystalline starch granules, amylose and amylopectin are important components. Heating an aqueous starch solution induces gelatinization, during which the crystalline structure of the starch granules breaks down, the granules absorb water and hydrate, and the viscosity of the solution increases (Thomas & Altwell). The retrogradation process begins immediately upon cooling of a freshly made starch gel. This involves the reassociation of starch molecules through the alignment of linear amylose chains and linear regions of amylopectin molecules, and the formation of intermolecular hydrogen bonds. All these processes occur in starch-based modeling compounds and affect their characteristics. The texture can go from soft and easy to manipulate and shape to being significantly harder within a couple of days. This was addressed by Doane Jr. and Tsimberg by adding a retrogradation inhibitor in an amount of 2 to 10% to a starch-based modeling compound. Amylopectin starch, which is known to be resistant to retrogradation, was used as the retrogradation inhibitor. However, there is another drawback to all previously known starch-based modeling compounds. Because they contain large amounts of water (typically 50% or more) as a solvent, they dry out and must be stored in sealed containers between uses. X w NJ o —L o The piece left exposed to ambient air hardens over time (usually a few hours), and the play value is lost. It is often very difficult or impossible to restore the texture by adding water, as the reabsorption of the added water is problematic. This applies not only to low relative humidity but also to normal relative humidity (40-60%) and even high humidity (e.g., 60% or higher). When modeling compound residue dries in plastic molds and extruders, which are used with the dough by children, it becomes clogged, and the molds and extruders are (very) difficult to clean. It would be a considerable advantage to provide a modeling compound with improved property stability. In particular, it would be advantageous to provide a modeling compound that is less prone to drying and / or changes in properties, especially when left exposed to the environment. It would be advantageous to provide a non-drying or drying-resistant dough, which would reduce the problem of dough drying out in molds and extruders. It would also be advantageous to provide a dough that could be stored without special precautions to prevent drying. In particular, it would be advantageous if the dough did not need to be stored in sealed containers. These are obvious advantages for users, but manufacturers would also not have to package the product in airtight containers. BRIEF DESCRIPTION OF THE INVENTION The present inventors have now established that, by formulating a mass with at least one polar liquid, with a low vapor pressure, the drying of the modeling mass can be significantly reduced. In a first aspect, the present invention provides a modeling compound, comprising: a) at least one flour containing starch; b) at least one polar solvent with low vapor pressure; and c) an aqueous component. Optional, but preferred, components include one or more of the following; d) at least one softening agent; e) at least one conservative; or f) at least one additive. Generally, the weight of the aqueous component c) will be less than the weight of the low-pressure solvent or _L O vapor pressure b). w In another aspect, the present invention provides a filled modeling compound comprising a modeling compound as described herein and at least one filler material. Typically, the filler will be present in an amount of 1 to 40% by weight of the filled compound. Such a filled compound will be formed by the described modeling compound with the addition of at least one filler material. In another aspect, the present invention provides a method for forming a modeling compound as described herein. The method comprises mixing at least one starch-containing flour, at least one low-vapor-pressure polar solvent, and an aqueous component, and heating the resulting mixture. The procedure may be followed by a drying and / or kneading step. DETAILED DESCRIPTION OF THE INVENTION In the modeling clays of the present invention, component a) is at least one starch-containing material. This will normally be a "flour" ("flour containing starch"), a term used herein to denote any particulate material having a starch content greater than 60% and an average particle diameter less than 1 mm. Generally, the "flours" referred to herein will be generated by physical techniques such as milling, but may be generated by any other suitable technique, including chemical or enzymatic digestion, heat treatment, dissolution and precipitation, or any combination thereof. Typically, at least 90% by weight of the flour will fall within the particle size range of 1 µm to 1000 µm. Many suitable starch-containing materials are known in the art, and suitable materials and combinations can be readily established.The starch-containing material particularly effective for use in the present invention includes wheat flour, rye flour, tapioca flour, corn flour, potato starch, rice flour, and mixtures thereof. Rice flour and mixtures thereof are preferred. Starch-containing materials (e.g., flour) rich in amylopectin offer advantages in dough formulations. In particular, dough formulations containing high-amylopectin flour have been found to better resist becoming too soft at high relative humidity. In an embodiment applicable to all aspects of the present invention, the or —Component a) may comprise at least one "standard flour" having 60% to 88% amylopectin and at least one "waxy" flour having at least 90% amylopectin. Suitable standard flours may be wheat flour, rye flour, tapioca flour, maize flour, potato starch, rice flour (especially medium and long grain rice flour), and mixtures thereof. The proportion of amylopectin in such flours shall generally be 60% to 88%, preferably 70% to 85%. Suitable "waxy" flours include waxy maize starch, waxy (glutinous) rice flour (especially short or round grain rice flour), waxy potato starch, and mixtures thereof. Suitable blends may have a "standard flour": "waxy flour" ratio of 95:5 to 5:95, preferably 40:60 to 90:10, more preferably 60:40 to 85:15. A highly effective combination is a mixture of rice flour (e.g., medium- or long-grain rice flour) and glutinous rice flour (e.g., short- or round-grain rice flour). Such a mixture can have a rice flour to glutinous rice flour ratio of 95:5 to 5:95, preferably 40:60 to 90:10, and more preferably 60:40 to 85:15. One advantage of rice flour is that it is substantially or completely gluten-free. Even so-called "glutinous rice" is indeed gluten-free and suitable for those with a gluten allergy or intolerance. Other gluten-free flours / starches (e.g., corn or potato starch) exist and can be used in all aspects of the present invention, but rice flour is highly suitable and readily available. Being essentially gluten-free provides the advantage that dough compositions are suitable for those with gluten allergies and / or gluten intolerance. Generally, doughs from all aspects of the invention are not for consumption, but inadvertent or mistaken consumption can be a problem, especially when the dough is used by children. Being essentially gluten-free avoids any gluten intolerance issues if the dough is swallowed.Therefore, in an embodiment applicable to all aspects of the invention, the dough may comprise less than 1% by weight of gluten (e.g., 0 to 1% by weight or 0.0001% to 1% by weight), preferably less than 0.1% by weight and more preferably less than 0.01% by weight of gluten. The total amount of starch-containing material component a) in the modeling clays according to all aspects of the present invention shall normally be in the range of 10 to 60% by weight, preferably 15 to 50% by weight, and more preferably 25 to 45% by weight. More preferably, the amount of component a) shall be 30% to 45% by weight. All percentages The quantities indicated herein are expressed as weight percentages of the final mass product comprising components a) af), unless otherwise stated. Similarly, since all percentages refer to a mass containing water, which will affect the weight percentage of other components, the quantities indicated herein may be the equilibrium level in a mass at one or more relative humidity levels within the range of 30% to 70%. In one embodiment, the weight percentages indicated shall apply at equilibrium to a relative humidity of 50%. The percentages of components indicated herein refer to a mass comprising or consisting of components a) af). Where the mass further comprises one or more inert loading components g), the weight of such loading shall generally not be taken into account in the quantities indicated herein except where explicitly stated Component b) of the modeling compositions shall be at least a low vapor pressure solvent. Generally, any such solvent shall have a vapor pressure at 25°C of less than 2 kPa, preferably less than 1 kPa, and more preferably less than 0.1 kPa (e.g., less than 0.01 kPa). Examples of suitable polar solvents include oxygen-containing organic solvents such as alcohols, glycols (such as propylene glycol), polyols (such as glycerol), ketones, esters, amides, including cyclic compounds, and mixtures thereof. In particular, glycerol has been found to provide mass formulations that do not dry out. Since the composition also contains water, the low vapor pressure solvent shall generally be at least partially miscible with water. Preferably, the solvent shall be sufficiently polar to be soluble at least 10% by weight in water and preferably completely miscible with water.Organic molecules containing oxygen, such as those considered above, will be very suitable, particularly those comprising at least 10% oxygen by molecular weight. Solvents such as animal and / or vegetable oils are not normally sufficiently polar to be useful in the present invention. In one embodiment, the low vapor pressure solvent is not a hydrocarbon solvent such as mineral oil or paraffin. In a later embodiment, the low vapor pressure solvent is not an animal fat or vegetable fat (e.g., vegetable oil). The amount of low vapor pressure polar solvent will be sufficient to provide binding and flexibility to the mass product. Typically, this will be an amount of around 20% to 70% by weight of the mass, preferably around 30% to around 60% by weight (e.g., either _1 or 30% to 65% or 32% to 60%). Amounts of around 35% to 55% by weight are highly preferable and 40% to 50% even more preferable. Glycerol is a highly preferable vapor pressure solvent. It is available in many purities, from approximately 99.5% to around 86% or less. Lower purities contain corresponding amounts of water, which make up the remainder of the material. Any suitable purity level can be used, but when calculating the amount of glycerol and aqueous component present in a given mass, any significant amount of water in the glycerol material must be accounted for as a reduction in the glycerol component and a corresponding increase in the aqueous component. It has been found that a small amount of water in the heating step facilitates swelling; that is, the water acts as a solvent in the process. Since water is obviously a solvent and mixes with the dough, the water content, even in the new, undried dough, will depend on the relative humidity (RH) of the surrounding environment. Under equilibrium conditions, the water content in the dough will be higher at high RH and lower at low RH. It is important to balance the dough's properties with water absorption so that at low RH the dough is slightly stiffer, while at high RH it will be slightly softer. The dough should be flexible and usable at any normal and common RH (e.g., from 30% to 70% RH). This RH range can be evaluated by storing the dough in climate-controlled chambers at specific RH levels. Therefore, the aqueous component c) of the compositions of the present invention will vary somewhat depending on the manufacturing and storage conditions, but will generally be present at approximately 1 to 45% by weight, preferably approximately 5 to 35% by weight, and more preferably approximately 10 to 30% by weight of the total composition (e.g., 10 to 20% or 15 to 30% by weight). This amount may be reduced in environments of low relative humidity and greater at high relative humidity, and the amounts indicated herein may be the equilibrium level at one or more relative humidity levels within the range of 30% to 70%. In one embodiment, the indicated aqueous content will be applied in equilibrium at a relative humidity of 50%. The aqueous component will generally be water. As mentioned earlier, high-amylopectin flour has advantages in dough formulations. In particular, dough formulations containing high-amylopectin flour have been found to better withstand higher moisture content. The drawback oo is a (too) elastic texture at a low % RH. The elasticity can be decreased, and sometimes w completely opposite, adding an optional softening agent. Such softening agents are optional, but may be used in all aspects of the present invention including those embodiments in which at least a part of component a) is a high amylopectin flour such as glutinous rice flour, waxy corn starch (waxy corn flour) or waxy potato starch. Optional softening agents can be certain semi-organic compounds such as siloxanes (e.g., polydimethylsiloxane), certain organic compounds such as glycerides (mono-, di-, tri-, or mixtures thereof), or certain inorganic compounds such as salts (e.g., NaCl or potassium aluminum sulfate). It appears that alum (potassium aluminum sulfate) can, at low relative humidity (RH), produce a more flexible dough while simultaneously providing the dough with improved resistance to softening at high RH. The reference sample (without alum) is stiff and elastic at low RH and too soft and sticky at high RH.Blends of such optional softening agents frequently provide beneficial results. When present, the total softening agent content (component d) shall be at a level of less than 20%, such as less than 15% by weight (e.g., 1% to 20% or 1% to 15% by weight), preferably less than 10%, and more preferably less than 8% by weight. Each individual softening agent shall normally be present at less than 15% (e.g., 1% to 15%), more preferably less than 10% by weight. Typical organic compounds will be of low molecular weight, such as less than 2000 amu, preferably less than 1000 amu. Organic compounds are generally non-toxic and can be derived from natural sources. Lipids and their derivatives will be typical organic compounds used as softening agents. Generally, organic compounds will not be hydrocarbons. They will most commonly include at least one oxygen atom in their molecular structure. Halogenated organic molecules are less preferable. Glyceride softening agents constitute a preferred embodiment suitable for all aspects of the invention. Suitable glycerides include a polar "head" fraction of glycerol and one, two, or three nonpolar "tail" fractions, typically linked by an ester bond. Suitable nonpolar fractions include saturated and unsaturated fatty acids such as C8 to C24 fatty acids. Specific examples include nonpolar chains based on natural fatty acids, including caproic, caprylic, capric, lauric, and myristic acids. or —LO palmitic, titanic, palmitolic, stearic, oleic, elaidic, linoleic, linolenic, Sij arachidonic, behenic, or lignoceric. Preferred nonpolar chains are based on (esters of) palmitic, stearic, oleic, and linoleic acids, particularly oleic acid. Mixtures of glycerols are obviously convenient, and in di- or triacyl glycerols, each nonpolar group can be selected independently. Monoacylglycerols are highly preferred, such as glyceryl monooleate, glyceryl monolinoleate, glyceryl monostearate, glyceryl monopalmitate, and mixtures thereof. Glyceryl tricaprylate / caprate and related lipids, particularly those with capromic, caprylic, capric, and lauric chains, are an even more preferable example. Monoacylglycerols form a group of highly beneficial softening agents that have been found to provide remarkable advantages in all aspects of the present invention. Glycerol monooleate (GMO) and other monoacylglycerols are known to form liquid crystalline phase structures in contact with water or polar solvents (such as those used in the present invention), and these structures are typically highly bioadhesive. However, the present inventors have surprisingly observed that when glycerol monooleate (GMO) is added, one might expect the dough to become stickier to the hands (since liquid crystalline phases are generally bioadhesive). The inventors have found the opposite to be true, and the GMO acts as a "release agent" such that the dough containing GMO (typically between 0.1% and 10% by weight) does not stick to the hands or processing equipment and adheres much less than a comparator sample without GMO.This characteristic is believed to apply to comparable monoacylglycerols (e.g., those with acyl chains as described herein) and mixtures of such monoacylglycerols with diacylglycerols (again, particularly those with acyl chains as described herein). In an embodiment applicable to all aspects of the present invention, the masses may therefore comprise at least one monoacylglycerol, preferably a monoacylglycerol having at least 80% acyl chains as described above herein. Glycerol monooleate (GMO) is a highly preferred example. When GMO is used in the masses of the present invention, it shall generally be of high purity in order to achieve the best non-sticky effect. Thus, a GMO component containing at least 70% glycerol monooleate, preferably at least 80%, is preferable. In a corresponding embodiment applicable to all aspects of the present invention, the masses may comprise at least one monoacylglycerol and at least one diacetylglycerol (e.g., in a ratio of 95:5 to 5:95 by weight, preferably 30:70 to 70:30 by weight). In the case of the monoacyl and diacyl components, these preferably have at least 80% acyl chains as described above in this document. The "mono- and diglycerides of fatty acids" are food emulsifiers designated E471. Such a mixture may be used. In a highly preferred embodiment, either a monoglyceride (e.g., GMO) or a mono / diglyceride mixture (e.g., E471) may be used. The present inventors have further established that the use of mixtures of mono- and diglycerides (such as E471) can provide an excellent texture to the modeling clay of all embodiments of the invention. In particular, the use of such a mixture, especially in combination with a monoacylglycerol (such as OGM), can provide excellent workability of the clay after standing for long periods (e.g., 3 days or more). All non-toxic salts can potentially be included in softening agents, although these will generally be water-soluble. Non-toxic or low-toxicity salts of sodium, aluminum, calcium, or potassium are preferable, including chlorides, carbonates, sulfates, phosphates, acetates, etc. Sodium chlorate, potassium chloride, aluminum sulfate, potassium aluminum sulfate, and similar salts, especially potassium aluminum sulfate, are particularly suitable. Another surprising observation made by the present inventors is that salts, as they indicated herein, and alum in particular, appear to lessen changes in dough texture with variations in relative humidity, such that the dough becomes softer at low relative humidity and at the same time retains its texture better at high relative humidity. (All compared to a reference sample without alum.) Not being limited by theory, it is believed that this is related to the high "salt precipitation" effect, according to the lyotropic (or Hofmeister) series. Thus, in one embodiment, the doughs may contain at least one salt comprising anions up to and including chloride in the lyotropic series (e.g., sulfate, phosphate, acetate, and / or chloride). Similarly, in one embodiment, the doughs may contain at least one salt comprising cations up to and including sodium in the lyotropic series (e.g., ammonium, potassium, and / or sodium).Obviously, such anions and cations can both be present. - present and preferably shall be present. Such salts may be present in up to about 15% by weight, preferably up to about 12% by weight, such as 1 to 12% or 5 to 10% by weight. or —LO Other components (additives - component f) of the present invention) may also be present in the masses of all aspects, normally in the modeling masses in quantities less than 10% (for example, from 0.01 to 10%) by weight, preferably less than 5% (for example, 0.01 to 5% or 0.1 to 4%) by weight.Such components include many that are well known in the art as appropriate for modeling compositions, including surfactants (e.g., PEG esters of stearic acid, PEG esters of lauric acid, ethoxylated alcohols, PEG sorbitan esters such as PEG sorbitan monooleate, PEG sorbitan monostearate, PEG sorbitan monolaurate)), aromas or perfumes (such as perfume oils or essential oils), colors (such as non-toxic food dyes), preservatives, salts, drying agents, hardeners, astringent agents, lubricants (e.g., mineral oil, preferably in less than 5%, more preferably in less than 2% or less than 1% or propylene glycol), fillers, etc. One advantage of including a surfactant as component f) is that it improves the compatibility between the main components and various additives, and prevents segregation and separation into different phases during storage, which would compromise the material's properties. The surfactants described herein, as well as hydrophobically modified polymers (e.g., hydrophobically modified cellulose derivatives, hydrophobically modified polyacrylates, etc.), can be used for this purpose. The additives of component f) can be used to modify the texture of the dough. Polymers are well known for their use in modifying viscosity and elasticity, and in the present invention, many polymers can be compatible with the "aqueous component" c) and the "polar low vapor pressure solvent" b). The polymers mentioned above are among those suitable for this purpose. Others include non-ionic or ionic polymers (cationic and anionic) such as cellulose derivatives (see hydroxyethylcellulose, ethylhydroxyethylcellulose, methylcellulose, carboxymethylcellulose, quaternary ammonium-modified celluloses); chitosan; various homopolymers (e.g., polyacrylic acid, various polyacrylates, polyvinyl alcohol, poly(N-isopropylacrylamide); polyacrylamide; polyethylene oxide; polyvinylpyrrolidone, poly(dimethyldialylammonium chloride), etc.).) and copolymers (for example, various polyethylene oxide polymers copolymerized with propylene oxide, ethylene-butylene, caprolactone, poly(vinyl acetate)-co-vinyl alcohol, etc.). Many suitable preservative agents (component e)) are known in the art and with Parabens will only be necessary when the preservative function is not provided by another component, such as salt or an organic molecule. Therefore, the preservative component (e) may be present or absent. When present, suitable preservatives include sodium benzoate, methylparaben (E218), ethylparaben (E214), propylparaben (E216), butylparaben, and heptylparaben (E209). Less common parabens include isobutylparaben, isopropylparaben, benzylparaben, and their sodium salts. Compositions may be resistant to fungal growth in the absence of any specific or added preservative at low to medium relative humidities. For example, compositions may be stable against fungal growth for at least 1 month, preferably at least 2 months, at relative humidities of at least 50%, preferably at least 60%, and preferably up to 70% RH.The preferred ranges of specific softening agents found to be particularly useful in the methods of the present invention include 0.2 to 3%, preferably 0.5 to 2% of GMO, 1 to 5%, preferably 2 to 4% of PDMS, 0.5 to 10%, preferably 1 to 3.5% of alum, and / or 0.5 to 5%, preferably 1 to 3% of E471. These agents in the ranges indicated may be used individually or in any combination and may be used in the same modeling compound product. The preservative component (e), when present, shall be at a level adequate to inhibit microbial growth. Such amounts shall normally be less than 3% by weight (e.g., 0.01 to 3% by weight), preferably less than 2% or less than 1% by weight (e.g., 0.01 to 1% by weight). The filled masses described herein comprise modeling masses with the addition of component g) – at least one filler. Such filler material can be used to reduce sagging, improve texture and embossing properties, and / or to provide a non-glossy (matte) appearance. Fillers are also useful for reducing the production cost by weight of the material without sacrificing usability. Filled masses tend to be slightly drier and more crumbly than the modeling masses of the invention, but this does not normally hinder their use and may be an advantage in some mixtures. Suitable fillers shall be selected as invertible and non-toxic in use and may include at least one filler selected from titanium dioxide, mianite, calcium carbonate, pyrogenic silica, precipitated silica, silicates, silicates of or —L EITHER aluminum, alumina, dolomite, calcium magnesium silicate, talc, calcium magnesium carbonate and with similar well-known fillers. Talc is a preferred filler. Another particle / filler that can add large volume with a low weight addition is plastic-encapsulated gas filler, such as plastic microspheres containing gas. A typical example is Expancell (see https: / / www.akzonobel.com / expancel / This filler can provide anti-sagging properties to detailed molded structures and also reduce the density of the mass. The filled mass of the present invention shall comprise from 60 to 99% of a modeling mass as described in any embodiment of the present invention (preferably any preferred embodiment as described herein) and from 1 to 40% by weight of filler (such as those indicated above). The filled mass shall preferably comprise from 5% to 30% filler, more preferably from 10% to 25% by weight of filler. In the methods of the present invention, the mixing step can be carried out by any suitable mechanical mixing means, such as a commercial dough mixer. The heating step can also be carried out using established means such as combustion heating, electric heating, or heating with a medium such as steam. The heating will generally be to at least 70°C (e.g., from 70 to 120°C, preferably from 70 to 99°C), preferably to at least 80°C, and more preferably from 85 to 99°C. A more preferred temperature range is from 90 to 99°C. The heating period will generally be from about 5 minutes to about 4 hours, preferably from about 10 minutes to about 60 minutes. The method of the present invention is based on heating a mixture of the starch-containing material (e.g., component a) as described in any embodiment of the present invention) and the low vapor pressure liquid (e.g., component b) as described in any embodiment of the present invention). An aqueous component (e.g., c) as described herein) may optionally be present during the heating stage. Typically, the amount of aqueous component will be greater during the manufacturing process than that required in the final modeling clay product. This additional water aids in the swelling of the starch-containing material, particularly at lower temperatures. Therefore, although the components added in the methods of the present invention will generally be in the quantities indicated for the final product, they may be reduced somewhat in percentage terms. or _L O by adding up to 20% additional water by weight. Thus, the amounts in The weight percentage of any other component indicated herein may be reduced to 20% using the methods of the invention. This allows for the correct proportion of each component after evaporation of up to 20% by weight of excess water. Heating to higher temperatures (e.g., above 100°C) allows for the inclusion of smaller quantities of water in the formulation for heating. However, formulations typically gain or lose water once they are allowed to equilibrate at room temperature and humidity. Unlike conventional modeling clays, the modeling clays of the present invention are flexible and retain good modeling properties when the water content has equilibrated at room temperature and humidity (e.g., at 25°C and 30% to 70% relative humidity). When the method of the invention involves heating to more than 99°C, this will generally be carried out in sealed and / or pressurized heating vessels to reduce water loss during heating. In one embodiment, one or more of the starch-containing material, the low-vapor-pressure solvent, and / or the aqueous component (and optionally the additive) (e.g., components a) ac) (oa) ad) where d) is present) may be preheated to a temperature lower than that required for starch gelatinization (e.g., between 40 and 68°C, preferably between 50 and 65°C). When such a preheating step is carried out, heating to at least 70°C (as above) may be performed for approximately 5 to 60 minutes, preferably 5 to 30 minutes. EXAMPLES The invention will now be illustrated with reference to the following non-limiting examples: Materials: When. of Material Type Source 1. G1icerol Glycerol 99.5 CP, AarhusKarlshamn Sweden AB 5. GMO Danisco Dimodan MO 90 / D 6. PDMS Fluid Wacker of silicone in the AK series (for example, AK5, AK35, or AK100 - the numbers correspond to the viscosity in cP) w 7 . 7 . Glyceryl tricaprylate-caprate Grindsted MCT éO X Ó . Alum Alun, APL Pharma Specials 9. Mono-diglyceride (E471) GRINDSTED® MONO-DI MO 40-M KOSHER or Grindstedt mono-di R50 12. Talc Finntalc M15, Ornya AB, Sweden 13 Sodium benzoate Probenz, Eastman Chemicals 14 Ethyl paraben Solbrol A, 12. . Lanxess Distribution GmbH 15 Methyl paraben Solbrol A, Lanxess Distribution GmbH and Ethyl hydroxyethyl cellulose BERMOCOLL E 230 X, Akzo Nobel 17 Polyvinylpyrrolidone Luvitec K30, BASF Example 1: 1. Glycerol 120g 2. Water 60g 3. Rice flour 75g 4. Glutinous rice flour 25g 5. Glycerol monoleate 3.7g 6. Short-chain PDMS (in the approximate viscosity range of 5-100 cP) 3.7 g Glycerol (1) and water (2) were mixed, and rice flour (3 and 4) was dispersed in the liquid. The dispersion was enclosed in an airtight plastic bag and heated to approximately 92°C until the flour thickened the liquid. The plastic bag was opened, and the excess process water was evaporated while glycerol monooleate (5) and short-chain PDMS (6) (polydimethylsiloxane) were added, and the mixture was kneaded to a final product. Before adding glycerol monooleate (5) and short-chain PDMS (6), the dough was too elastic and sticky, whereas after the addition at 40% RH it was less elastic and less sticky and had good dough properties. At 70% relative humidity it was softer and stickier than desired. Long-term storage for several months in an indoor climate did not alter the formulation and it did not dry out. A commercial modeling compound (Play-Doh (RTM)) stored in the same manner for the same amount of time was found to have dried out, become hard, and be unusable for modeling purposes. Example 2: w 1. Glycerol 2. Water 3. Rice flour 4. Glutinous rice flour 5. Glycerol monoleate 7. Glyceryl tricaprylate-caprate 130g 60g 75g 25g 7.3g 15g Glycerol (1) and water (2) were mixed, and rice flour (3 and 4) was dispersed in the liquid. The dispersion was enclosed in an airtight plastic bag and heated to about 92 degrees C until The flour thickened the liquid. The plastic bag opened and the excess processing water evaporated. while glycerol monooleate (5) and glyceryl tricaprylate caprate (7) were added and the mass was kneaded until a final product was formed. Before adding glycerol monooleate (5) and glyceryl tricaprylate caprate (7), the mass was too elastic and too adherent and sticky, whereas after the addition to 40% HR was less elastic and less sticky / sticky and had good dough properties. 70% relative humidity made it softer and stickier than desired. Long-term storage for several months in the indoor climate did not change the formulation and did not dry. A commercial modeling compound (Play-Doh (RTM)) stored in the same way for the same amount of time was found to have dried out, hardened, and could not be used for modeling purposes. Example 3: 1. Glycerol 130g 2. Water 60g 3. Rice flour 75g 4. Glutinous rice flour 25g 5. Glycerol monoleate 3.7g 7. Glyceryl tricaprylate-caprate 3.7g 8. Alum 3.7 g Glycerol (1) and water (2) were mixed, and rice flour (3 and 4) was dispersed in the liquid. The dispersion was enclosed in an airtight plastic bag and heated to approximately 92°C until the flour thickened the liquid. The plastic bag was opened, and the excess process water evaporated while glycerol monooleate (5) and glyceryl tricaprylate caprate (7) were added, and the mixture was The alum dissolved in a small amount of water was added and the dough was kneaded until a final product was formed. The dough had good properties and was not too elastic at 40% RH. Furthermore, at 70% HR also had good properties and was not too soft or too sticky. Long-term storage for several months in an indoor climate did not alter the formulation and it did not dry out. A commercial modeling compound (Play-Doh (RTM)) stored in the same manner for the same amount of time was found to have dried out, become hard, and be unusable for modeling purposes. Example 4: Very high quantities of alum can be used, and mono- and diglycerides can be used to control the texture. Pigment and fragrance can be added to obtain more consumer-oriented products. 1. Glycerol 130g 2. Water 65g 3. Rice flour 70g 4. Glutinous rice flour 30g 5. Glycerol monoleate 2.5g 6. Short chain PDMS (in the approximate viscosity range of 5-100 cP) 15g 8. Alum 45g 9. Mono-diglyceride (E471) 4.5 10. Fluorescent Pigment (Radiant GWT Series Green) 2.5g 11. Vanilla Aroma 0.4g Glycerol (1) and water (2) were mixed, and rice flour (3 and 4) was dispersed in the liquid. The dispersion was sealed in an airtight plastic bag and heated to approximately 92°C until the flour thickened the liquid. The plastic bag was opened, and the excess process water evaporated while glycerol monooleate (5) and short-chain PDMS (6) were added, and the mixture was kneaded to a final product. Solid alum (8) and mono-diglyceride (9) were added, and the mixture was kneaded again. Pigment (10) and fragrance (11) were added to obtain a colored final product with a pleasant odor. Although the dough was a little short and brittle, it had good properties and wasn't too elastic at 40% RH. Furthermore, at 70% RH it also had good properties and wasn't too soft or too sticky. A slightly grainy texture may indicate that not all the alum dissolved. oo Long-term storage for several days in an indoor climate did not change the formulation w and it didn't dry out. Example 5: A higher preparation temperature allows for the use of less flour. 1. Glycerol 130g 2. Water 65g 3. Rice flour 50g 4. Glutinous rice flour 25g 5. Glycerol monoleate 2.5g 6. Short-chain PDMS (in the approximate viscosity range of 5-100 cP) 10g 10. Fluorescent Pigment (Radiant GWT Series Green) 1.5g Glycerol (1) and water (2) were mixed, and rice flour (3 and 4) was dispersed in the liquid. The dispersion was sealed in an airtight plastic bag and heated to approximately 111°C until the flour thickened the liquid. The plastic bag was opened, and the excess process water evaporated while glycerol monooleate (5) and short-chain PDMS (6) were added, and the mixture was kneaded to a final product. Pigment (10) was added to obtain a colored final product. The dough had good properties and was not too elastic at 40% RH. At 70% RH the texture was not optimal, being somewhat too soft and too sticky. Long-term storage for several days in the indoor climate did not change the formulation and it did not dry out. Example 6: GMO is important for giving non-stick properties, a property that cannot be fully obtained by replacing GMO with mono-diglyceride. 1. Glycerol 130g 2. Water 65g 3. Rice flour 70g 4. Glutinous rice flour 30g 8. Alum 4.5g 9. Mono-diglyceride (E471) 4.5 10. Fluorescent Pigment (Radiant GWT Series Green) 2.5g 11. Vanilla Aroma 0.4g XM MO _Yo or _L or Glycerol (1) and water (2) were mixed, and rice flour (3 and 4) was dispersed in the liquid. w The dispersion was enclosed in an airtight plastic bag and heated to about 92 degrees C until The flour thickened the liquid. The plastic bag opened and the excess processing water evaporated. while glycerol monooleate (5) was added and the dough was kneaded to a final product. Add the alum (8) dissolved in water and knead the dough. Pigment (10) and aroma (11) were added to obtain a colorful final product with a pleasant smell. The dough had a pleasant texture and was not too elastic at 40% RH, while it was sticky to hands and processing equipment. The addition of 4.5 g of GMO at a later stage did not repair the properties, at least not immediately. Long-term storage for several days in an indoor climate did not change the formulation and it didn't dry out. Example 7: Large quantities of GMOs can be added without losing their anti- adherents. 1. Glycerol 130g 2. Water 65g 3. Rice flour 70g 4. Glutinous rice flour 30g 5. Glycerol monooleate 25g to 65g Glycerol (1) and water (2) were mixed, and rice flour (3 and 4) was dispersed in the liquid. The dispersion was sealed in an airtight plastic bag and heated to approximately 92°C until the flour thickened the liquid. The plastic bag was then opened, and the excess process water evaporated while GMO (5) was added and the mixture was kneaded. The high GMO content changed the texture of the dough to a clay-like consistency, with a pleasant, completely non-elastic texture and a "dead" feel. The more GMO was added, the more pronounced the clay-like properties became. Quite unexpectedly, the formulation was not sticky to the hands or processing equipment, even at the maximum GMO level. Long-term storage for several days in the indoor climate did not change the formulation and it did not dry out. Example 8: Mono-diglyceride is an effective softener and texture provider. Basic recipe: 1. Glycerol 2. Water 3. Rice flour 130g 65g 70g 4. Glutinous rice flour 30g 5. Glycerol monoleate 4.5g Glycerol (1) and water (2) were mixed, and rice flour (3 and 4) was dispersed in the liquid. The dispersion was sealed in an airtight plastic bag and heated to approximately 92°C until the flour thickened the liquid. The plastic bag was opened, and the excess process water evaporated while GMO (5) was added and the dough was kneaded. The formulation was non-sticky to the hands and processing equipment, but somewhat too elastic and had a stiff texture. Addition of 2.25 g Mono-diglyceride (E471) to half the amount of dough (basic recipe) and this kneading on the day of formulation a dough with good properties that was not too elastic at 40% relative humidity. Adding an extra 2.25 g of glycerol (1) to the other half of the dough (basic recipe), and kneading it into the formulation did not give the improved properties that were observed by adding mono-diglyceride. A common observation after storage for several weeks was that the dough had to be kneaded and worked for about a minute before the texture would return to optimal, and the formulation was often slightly too stiff from the start. With mono-diglyceride in the formula, this is the opposite, and the dough has the appropriate properties practically from the beginning. This shows that mono-diglyceride provides texture to the dough in a different way than the solvent glycerol. Example 9. 1. Glycerol 2. Water 3. Rice flour 4. Glutinous rice flour 5. Glycerol monoleate 6. Short-chain PDMS (in the approximate viscosity range of 5-100 cP) 8. Alum 130g 65g 70g 30g 2.5g 8.0g 4.5g 9. Mono-diglyceride (E471) 4.5 Glycerol (1) and water (2) were mixed, and rice flour (3 and 4) was dispersed in the liquid. The dispersion was sealed in an airtight plastic bag and heated to approximately 98°C until the flour thickened the liquid. The plastic bag was opened, and the excess process water evaporated while glycerol monooleate (5) was added, and the dough was kneaded. The GMO provided a dough that did not stick to the hands or processing equipment. Short-chain PDMS (6) was added to provide anti-stick properties, alum (8) was added to retain desirable dough properties across an extended relative humidity range, and monoglyceride (9) was added to provide X / a / 2017 / 010373 softness and a texture appropriate to the dough. Example 10 1. Glycerol 130g 2. Water 65g 3. Rice flour 70g 4. Glutinous rice flour 30g 5. Glycerol monoleate 2.5g 6. Short-chain PDMS (in the approximate viscosity range of 5-100 cP) 8.0g 8. Alum 4.5g 9. Mono-diglyceride (E471) 4.5 12. Talc 50.0g Glycerol (1) and water (2) were mixed, and rice flour (3 and 4) was dispersed in the liquid. The dispersion was sealed in an airtight plastic bag and heated to approximately 98°C until the flour thickened the liquid. The plastic bag was opened, and the excess process water evaporated while glycerol monooleate (5) was added, and the dough was kneaded. The GMO provided a dough that did not stick to the hands or processing equipment. Short-chain PDMS (6) was added to provide anti-stick properties, alum (8) was added to retain desirable dough properties over an extended relative humidity range, and monoglyceride (9) was added to provide smoothness and an appropriate texture to the dough. Finally, talc (12) was added to provide a visual matte effect and improved print collection detail. The dough was observed to incorporate substantial amounts of filler while maintaining good modeling properties.The more filling was added, the shorter the dough became. The result was still a dough that didn't dry out and behaved well. Example 11 1. Glycerol 2. Water 3. Rice flour 4. Glutinous rice flour 5. Glycerol monoleate 6. Short-chain PDMS (in the approximate viscosity range of 5-100 cP) 120g 60g 75g 25g 3.7g 3.7 g First, a mass was prepared with components one through six following the method in Example 1. One-third of the sample was kept unchanged. To one-third, the following was added and dissolved in the matrix by kneading: 13. 0.5 g of sodium benzoate as a preservative, which corresponds to approximately 0.5% of the final material. 17. Ig of polyvinylpyrrolidone polymer, which corresponds to approximately 1% of the final material The last third of the sample was added and dissolved in the matrix by kneading: 14. 0.15 g of ethylparaben as a preservative, corresponding to approximately 0.15% of the final material. 15. 0.15g of methylparaben as a preservative, corresponding to approximately 0.15% of the final material 16. 0.15 g of ethylhydroxyethyl cellulose, corresponding to approximately 0.15% of the final material The three samples were stored at room temperature and high relative humidity (nearly 100% RH) in a bucket. After two months, the preservative-free sample was completely covered with a biofilm of growing material (bacteria, mold, or fungi), while the sample with sodium benzoate showed less growth, and the sample with methylparaben and ethylparaben appeared growth-free. This example demonstrates that the polymer and preservatives are compatible with the matrix and that the addition of preservatives may be necessary when the material is exposed to very high relative humidity. Note that a complementary experiment has shown that with a sample containing no added preservative, there is no growth of bacteria, mold, or fungi at lower relative humidity (<70% RH): A piece of the dough (components 1 to 5) without preservatives X ai The sample was stored at 70% relative humidity in a climate chamber. No changes were observed. no growth after storage for two months. REFERENCES 5 McVicker et al., U.S. Patent No. 3,167,440 David J. Thomas and William Altwell, Starches (1999) LE Doane Jr. and L. Tsimberg, U.S. Patent No. 6,713,624, B1

Claims

or _L or CLAIMS w 1. A modeling compound comprising; a) at least one starch-containing material; b) at least in a polar solvent with low vapor pressure; and c) an aqueous component.

2. The modeling compound according to claim 1, further including at least one of the following; d) at least one softening agent; e) at least one conservative; f) at least one additive.

3. The modeling mass in accordance with any of the preceding claims, in where component a) is at least one flour containing starch.

4. The modeling mass in accordance with any of the preceding claims, in where the weight of the aqueous component c) will be less than the weight of the low-pressure solvent of steam b).

5. The modeling mass in accordance with any of the preceding claims, in where component a) comprises at least one "standard flour" with 60% to 88% amylopectin and at least one "waxy flour" with at least 90% and amylopectin.

6. The modeling dough according to claim 5, wherein the standard flour is select from wheat flour, rye flour, tapioca flour, corn flour, potato starch, rice flour (long and medium grain rice flour) and mixtures thereof.

7. The modeling compound according to claim 5 or claim 6, wherein Waxy flour is selected from waxy corn starch, waxy (glutinous) rice flour or _L or (especially rice flour from short-grain or round-grain rice), waxy potato starch and and mixtures thereof.

8. The modeling compound in accordance with any of the preceding claims, that has a "standard" flour: "waxy flour" ratio of 95:5 to 5:

95.

9. The modeling mass in accordance with any of the preceding claims in where component a) comprises a mixture of rice flour (for example, rice flour of medium grain or long grain) and glutinous rice flour (e.g., medium grain rice flour round or short grain).

10. The modeling mass in accordance with any of the preceding claims in where component a) is present at 10 to 60% by weight.

11. The modeling mass in accordance with any of the preceding claims in where component b) is selected from alcohols, glycols (such as propylene glycol), polys (such such as glycerol), ketones, esters, amides, including cyclic compounds and mixtures thereof.

12. The modeling mass in accordance with any of the preceding claims in where component b) is glycerol.

13. The modeling mass in accordance with any of the preceding claims in where component b) is present in 20% to 70% by weight.

14. The modeling mass in accordance with any of the preceding claims in where component b) is present at 32% to 65% by weight.

15. The modeling mass in accordance with any of the preceding claims in where component c) is present at 5 to 45% by weight. or _L O 16. The modeling mass in accordance with any of the preceding claims in w where component d) is present and is selected from at least one siloxane, at least one salt, at least one lipid, or mixtures thereof.

17. The modeling compound according to any of the preceding claims wherein component d) is present and comprises polydimethylsiloxane, GMO and / or potassium aluminum sulfate.

18. The modeling mass in accordance with any of the preceding claims wherein component d) is present in an amount of 1% to 15% by weight.

19. The modeling compound according to any of the preceding claims wherein component f) is present at a level of 0.01% to 10% by weight and comprises a surfactant, a fragrance, a perfume, a color, a preservative, a salt, a drying agent, a hardener, an astringent, a lubricant, a texture modifier or mixtures thereof.

20. The modeling compound according to any of the preceding claims wherein component f) is present at a level of 0.01% to 10% by weight and comprises at least one polymer.

21. The modeling compound according to any of the preceding claims wherein component f) comprises at least one polymer selected from cellulose derivatives, hydrophobically modified cellulose derivatives, hydrophobically modified polyacrylates, polyacrylic acid, chitosan, polyvinyl alcohol, poly(N-isopropylacrylamide), polyacrylamide, polyethylene oxide, polyvinylpyrrolidone, polyethylene oxide polymers copolymerized with propylene oxide copolymers, poly(vinyl acetate)-co-vinyl alcohol and mixtures thereof.

22. A filled mass comprising a modeling mass of any of the preceding claims and from 1 to 40% of at least one filler material. or _L or 23. A method for forming a modeling mass in accordance with any of w claims 1 to 21 comprising: i) comprises mixing at least one starch-containing component and at least one low vapor pressure polar solvent; ii) heat the resulting mixture.

24. The method according to claim 23, wherein step i) comprises mixing by at least one starch-containing material, at least one low vapor pressure solvent, and a aqueous component; 25. The method according to claim 23 or claim 24, which further It includes: iii) knead the heated mixture; and iv) optionally dry the hot mixture.

26. The method in accordance with any of claims 23 to 50, wherein I step ii) is carried out at 70 to 99°C for between 5 minutes and 4 hours.

27. The method in accordance with any of claims 23 to 26, comprising Additionally, allow the aqueous component to evaporate at a relative humidity of 30 to 70%.

28. The method in accordance with any of claims 23 to 27, comprising Additionally, mix in a softening agent such as GMO, E471, alum and / or PDMS.

29. A method for forming a filled dough, said method comprising forming a modeling compound according to any of claims 23 to 28 followed by the incorporation of 1 to 40% of at least one filler.