Permanently plastic moldable mass, method for producing same, mass according to the method, and use thereof

Abstract

Molded articles made of established permanently plastic moldable masses are disadvantageously either not stable over several weeks or can no longer be remolded after several weeks. The aim of the invention is to overcome said disadvantages. This is achieved by means of a mass based on starch-based colloid, fat, and adjusting agents and auxiliary agents, a flocculation aid being added to the mass. The flocculation aid is capable of supporting the moisture content and enclosing impurities. For the first time, it is thus possible to obtain molded articles which last for months to years and can be remolded and which can be meaningfully used and reused for long periods of time as toys, modeling compounds for pastry designs, modeling compounds for molded building blocks, or also seals and reference bodies for lines.

Description

[0001] Permanently plastic, moldable mass, methods for its production

[0002] Production, process mass and its use

[0003] GENERAL AREA

[0004] 'Modelable masses' have long been found in very different fields.

[0005] As early as 1912, US patent 1029800A disclosed a permanently plastic, resin-based compound, kept pliable with oils and containing mineral powders as fillers. Similarly, in 1917, GB patent 191515249A proposed a mixture of animal glue, petroleum, flour, resin, and water suitable as a wood filler. In this process, the flour is mixed with a portion of water, heated, combined with the glue, and finally mixed with resin, petroleum, and the remaining water.

[0006] Similarly, DE 737 682 1943 describes the mixing of lignin sulfonate with chalk and / or kaolin and glycerin to obtain a permanently plastic sealant for oil lines.

[0007] Finally, in 1965, US 3,167,440 A described recipes for durable, plastic, moldable materials, which are particularly suitable as non-toxic children's toys. For this purpose, a vegetable flour is heated with water until it gels, mixed with salt, preserved with a germicidal agent or desiccant, and adjusted to a suitable firmness with a hardener / astringent such as aluminum sulfate and hydrocarbons.

[0008] All these compounds have in common that hydrophilic and oleophilic components are prepared in a storable, malleable mixture and subsequently shaped. Further research and development will identify suitable additives for specific purposes. SCIENTIFIC BACKGROUND

[0009] The present invention relates to permanently plastic, moldable materials according to the preamble of the independent claims, a method for their production, materials produced according to the method, and their use. Numerous measures and additives are already known in this field which can impart certain properties to such a material.

[0010] US 3 634 280 A proposes mixing a borate polymer mixture with SiO2 flakes, an alkylsiloxane and transparent glass or plastic beads so that an added phosphorescent substance can make the elastic mass, which can be used as a rubber ball, glow as a whole in the dark.

[0011] US 4,076,547 A describes which additives can stabilize a base mixture of water, glycerin, cellulose derivatives and salts and, in combination with polyvinyl alcohol, allow it to solidify later.

[0012] The JP 05 001 227 A proposes a mixture of various organosiloxanes, liquid paraffin, and boron oxide or boric acid as a permanently elastic, silicone-based sealant.

[0013] WO 1993014159 A proposes a water-glycerin mixture with guar gum binder as a non-toxic, easily washable, and child-friendly modeling clay. This mixture can be adjusted to suit the target group by modifying the mixing ratio and adding buffering phosphate salts and various preservatives and disinfectants. WO 1993016132 A proposes an alternative mixture of water, sodium alginate binder, and glycerin, which contains salts and parabens. A disadvantage of such water-based modeling clay mixtures is that they dry out over time when stored openly and then lose their plasticity and moldability.

[0014] WO 1996039470 A proposes combining polymeric microsphere fillers with water, a thixotropic hydrogel, and a humectant to create a modeling compound from which shaped bodies can be produced. After drying, the shaped bodies can be machined.

[0015] US Patent 5,990,205 A proposes a rheopex formulation of a mixture of polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) with a plasticizer / humectant, crosslinker, polysaccharide elastomer, and water. This inherently malleable mass exhibits rubber-like elasticity and high play value under rapid impulse. However, the mass tends to spread when at rest, stretches across surfaces, loses liquid phase, and attracts dirt. This mixture is therefore unsuitable as a modeling compound for permanently displayed works.

[0016] The JP 2000 072 919 A ​​proposes to equip a rubber mass with a color change that can be triggered by heat or deformation by means of functionalized, filled micro-beads.

[0017] US 6,391,941 Bl proposes various germicidal agents that can be added to a physiotherapy putty mixture to reliably prevent infection or transmission of germs during therapy. Similarly, US 6,444,199 Bl proposes the use of PVA-borate mixtures of specific viscosities in wound healing.

[0018] US 8,476,343 B2 proposes specific mixing ratios for a mixture of water, PVA, elastomer, PET glitter, water and borax to obtain a flowable yet malleable, elastic mass with high play value.

[0019] WO 2010 099 438 Al proposes So j a-based molding compounds.

[0020] WO 2013 155 380 Al proposes modeling compounds in which starch-based binders, water, degelling inhibitors, and fillers in the form of spheres / microspheres are combined in a base mixture. The base mixture is specifically tailored to achieve desirable properties through the addition of flow agents, surfactants, salts, and PVP.

[0021] US 11,891,484 B2 proposes an organosiloxane-based, flowable base mass which can be processed with crosslinking agents and catalyzing metal salts to form a suitably viscous, crosslinked mass.

[0022] DESCRIPTION OF THE STATE OF THE TECHNOLOGY

[0023] Typical materials are permanently plastic and moldable. They are designed for both good, lasting formability and shape retention, as well as permanently plastic properties. A molded part should therefore retain its shape stably and be remoldable at any time. Meeting these two requirements simultaneously proves difficult.

[0024] US 6,713,624 Bl 2004 proposes that starch-based modeling compounds be equipped with a degelling inhibitor so that the compounds permanently retain their shape stability; suitable inhibitors are named as amylopectin and / or waxy starch - which is also used as a lubricant.

[0025] A disadvantage of these types of materials is their tendency to dry and / or harden destructively. After just a few weeks, molded pieces either show cracks and defects and / or harden to such an extent that reshaping or further use of the material as a modeling clay is no longer possible.

[0026] The object of the present invention was therefore to overcome the disadvantages of the prior art and to provide a permanently plastic, moldable mass which, despite the high durability of a molded part produced with it, is able to provide a permanent further usability as a modeling material.

[0027] The solution to this problem is achieved according to the features of the independent claims. Advantageous embodiments, manufacturing processes, and uses are described in the dependent claims and the following description.

[0028] SUMMARY OF THE INVENTION

[0029] According to the invention, the permanently plastic, moldable mass comprises at least 5% by weight water; 0.1 to 4% by weight flocculation aid; 5 to 40% by weight starch-based colloid; 5 to 40% by weight free-flowing polyol with a chain length in the range of 2 to 6; 0 to 5% by weight fat; up to 6% by weight at least one adjusting / auxiliary substance from the group comprising humectants, emulsifiers, mineral fillers, fillers, preservatives, disinfectants, defoamers, antibacterial additives, thickeners, gelling agents, colorants, flavorings, fragrances, emetics, and flow agents.

[0030] DESCRIPTION OF THE INVENTION AND ADVANTAGEOUS FEATURES

[0031] The inventive mass comprises aqueous components, hydrophilic components, and hydrophobic components. The inventors assume that the combination with a flocculation aid effectively couples the equilibrium of the respective moisture levels and encapsulates interfering impurities such as fine dust, dirt, and unavoidable accompanying substances before they can disrupt the moisture balance.

[0032] Flocculants are amphoteric, aqueous-dispersible macromolecules that neutralize and bind impurities and strong acids and bases. They are typically used in wastewater treatment plants as clarification aids. The preferred flocculation aids are those that are also approved for use in drinking water preparation and are physiologically safe when ingested orally.

[0033] The binding capacity of the added flocculation aid can convincingly demonstrate that a mass with certain basic components and a flocculation aid exhibits a basic moisture content that adapts to the external humidity, permanent formability, and dimensional stability over months. Careful series of tests and trials led to the basic formulation claimed here.According to the invention, the permanently plastic, moldable mass comprises at least 5% by weight water; 0.1 to 4% by weight flocculation aid; 5 to 40% by weight starch-based colloid; 5 to 40% by weight free-flowing polyol with a chain length in the range of 2 to 6; 0 to 5% by weight fat; up to 6% by weight of at least one adjusting / auxiliary substance from the group comprising humectants, emulsifiers, mineral fillers, fillers, preservatives, disinfectants, defoamers, antibacterial additives, thickeners, gelling agents, colorants, flavorings, fragrances, emetics, and flow agents.

[0034] Starch-based colloids, in the sense of pretreated, aqueous starch products capable of forming aqueous mixtures of increased viscosity, have long been known. For illustrative purposes, reference is made to documents US 579,827 A, US 1,947,295 A, US 2,283,044 A, US 2,386,509 A, US 3,525,672 A, DE 25,12810 B, and US 4,116,770 A.

[0035] Preferably, the flocculation aid comprises at least one water-soluble flocculation aid based on a polyelectrolyte, selected from the group consisting of proteins, polyamines, polyamides, and polyacrylamides. Polyelectrolytes comprise acidic and basic dissociable groups, which, through their interaction, determine the three-dimensional arrangement of the macromolecule in space; it is essential that polyelectrolytes can exhibit an increase in viscosity upon aqueous dilution; the inventors assume that these preferred polyelectrolytes further support and improve the shape stability at elevated humidity levels.

[0036] Preferably, the fat consists of at least one triglyceride. Medium- to long-chain triglycerides are similar to the skin's natural fats and increase customer satisfaction: Slightly emollient mixtures that do not dry out the skin are perceived as pleasant and smooth to the touch. Saturated, medium- to long-chain triglycerides are preferred; the absence of CC multiple bonds makes such triglycerides more resistant to oxygen and oxidative degradation, thus improving their aging properties.

[0037] Preferably, an added fat as a stabilizer includes a buffer which adjusts the pH of the mass to a skin-neutral value of around 5.5.

[0038] Preferably, the starch-based colloid is a rice starch-based colloid, and the flocculation aid comprises at least one non-ionic polyacrylamide. Rice starch influences the formation of calcium and mineral crystals in aqueous solution; the fine and particularly durable mortar crystal structures in the mortar of the Great Wall of China are attributed to the presence of rice starch in this mortar. Combined with a non-ionic polyacrylamide, which can bind particles in a loose structure, it is particularly effective in counteracting the formation of crystals and particulate impurities based on salts – e.g., from the absorption of sweat or the corresponding salts.

[0039] Preferably, the mass contains at least 0.1% by weight chitosan as a preservative. Chitosan can be obtained inexpensively from the shells of marine animals or directly from fungi. Therefore, both inexpensive and vegan chitosan variants are available. It acts as both a preservative and a moisture regulator; in macromolecular form, it also contributes to the effect of the flocculant. For possible applications, please refer to documents JP 55081705 A, JP 56112937 A, JP 02105801 A, JP 02041473 A, and JP 05184378 A. Extracted chitosan, such as that used in bandages, is particularly preferred. Studies of the allergenic potential of this chitosan in fish allergy sufferers showed hypoallergenic properties and very good tolerability (according to ' Mil . Med . 2011 Oct , 176 ( 10 ) : 1153-6 ; ' Safety in chitosan bandages in shellfish allergic patients ' ).Preferably, the mixture contains at least 0.1% by weight of xanthan gum as a gelling agent. Xanthan gum is considered hypoallergenic; no dangerous allergies or hypersensitivities are known, and it can be preferably used as a gelling agent in hypoallergenic formulations.

[0040] In a preferred method for producing a mass according to the invention, at least the following process steps are provided: a) Dissolving the flocculation aid e in a portion of the water to obtain a solution 1; b) Mixing rice-starch-based colloid, free-flowing polyol, preservative, and gelling agent to obtain a homogeneous mixture 1; c) Adding solution 1 to mixture 1 and bringing to a boil while stirring continuously; d) Reducing the heat input to a mixing temperature 10 °C lower and adding all heat-stable adjusting / auxiliary substances while stirring continuously; e) Adding the remaining water while rapidly lowering the temperature to a temperature of 20 °C to 40 °C; f) Adding the remaining adjusting and auxiliary substances and finally homogenizing.

[0041] Dissolving the flocculation aid in step a) beforehand results in a more uniform dispersion or solution; combining it with other liquid components yields homogeneous and stable mixtures with a matte sheen. The final product thus acquires a dough-like to clay-like, silky-matte appearance.

[0042] The preliminary mixing of polyol, gelling agent, and rice starch colloid brings these components into direct interaction; when subsequently combined with water, this mixture exhibits a more pronounced tendency to adjust its moisture content with minimal change in viscosity depending on the humidity. Boiling in step c) inactivates any enzymes present or introduced, such as amylases, and ensures degassing of the water; mixtures prepared in this way exhibit more controllable properties and superior stability of the masses produced with them.

[0043] The rapid reduction of temperature in step e) prevents the slow maturation of large salt crystals; in combination with rice-starch-based colloid, fine crystals are ensured which can be effectively coated by the homogeneously distributed flocculation aid e.

[0044] After final homogenization, the advantageous process yields a moldable mass with precisely predictable properties and advantageously improved durability and moldability.

[0045] Preferably, a permanently plastic, moldable sealant according to the invention consists of bio-based – preferably vegan – human-physiologically acceptable food-grade substances, as well as food-grade additives and food-grade additives; advantageously, this can be used directly as a reference test specimen and long-term stable pipe sealant in food processing machinery. In machines where seals do not exhibit sufficient resistance due to fluctuating temperature and humidity, the sealant can be applied in the connection area, and a molded specimen can be placed in a more visible area to serve as a test specimen; thus, a clearly visible molded specimen directly indicates the condition of the sealant formed from the sealant in the less accessible area.

[0046] Further advantages arise from the exemplary embodiments. The features and advantages described above and the following exemplary embodiments are not to be understood as limiting combinations of features unless explicitly described as such. Additional advantageous features and additional combinations of features, as explained in the description and in the documents cited herein, can be implemented in the claimed subject matter, both individually and in different combinations, within the scope of the independent claims, without departing from the scope of the invention.

[0047] DETAILED EXPLANATION OF THE INVENTION USING EXAMPLES OF EXECUTION

[0048] In the first, advantageous embodiment, a permanently plastic, moldable mass is formed from the weight quantities and components.

[0049] 10 parts by weight water; 0.1 to 0.2 parts by weight non-ionic polyacrylamide as a flocculation aid; 35 to 45 parts by weight rice starch-based colloid; 35 to 45 parts by weight glycerin as a free-flowing polyol; 0.3 to 0.9 parts by weight xanthan gum as a gelling agent; 0.2 to 0.3 parts by weight chitosan as a preservative; as heat-stable stabilizers and additives: 4 to 6 parts by weight triglycerides as fat; 2.2 to 3.2 parts by weight monoglycerides and polysorbate as emulsifiers; 1 to 2 parts by weight inorganic white pigment as a colorant; 0.5 to 1.5 parts by weight PDMS silicone oil as an antifoaming agent; 10 to 20 parts by weight remaining water; Up to 10 parts by weight of additional, optional adjusting / auxiliary materials were produced.In this process, in step a) the flocculation aid is dissolved in the portion of water to obtain solution 1; in step b) rice-starch-based colloid, free-flowing polyol, preservative, and gelling agent are thoroughly mixed to obtain a homogeneous mixture 1; in step c) solution 1 is added to mixture 1 and brought to a boil while stirring continuously; in step d) the heat is reduced to a mixing temperature 10°C lower, and all heat-stable additives are added while stirring continuously; in step e) the remaining cooled water is added while rapidly lowering the temperature to between 20°C and 40°C; in step f) the remaining additives are added, and the mixture is finally homogenized. A stable, easily moldable mass with a clay-like consistency was obtained. The mass, which can be molded with good pressure, reliably reproduces even fine structures in the test using a negative mold.The molded structures are permanently stable and do not deform even under sunlight or temperature changes.

[0050] In a second, advantageous embodiment, a permanently plastic, moldable mass is produced according to the method of the first embodiment from the following quantities and components: 10 parts by weight of water; 0.1 to 0.2 parts by weight of non-ionic polyacrylamide as a flocculation aid; 35 to 45 parts by weight of rice-starch-based colloid; 35 to 45 parts by weight of glycerin as a free-flowing polyol; 0.2 to 0.8 parts by weight of xanthan gum as a gelling agent; 0.2 to 0.3 parts by weight of chitosan as a preservative; and 4 to 6 parts by weight of triglycerides as fat, as heat-stable stabilizers and additives.

[0051] 2.2 to 3.2 parts by weight of monoglycerides and polysorbate as emulsifiers; 1 to 2 parts by weight of inorganic white pigment as a colorant; 0.6 to 1.6 parts by weight of PDMS silicone oil as a defoamer; 15 to 25 parts by weight of remaining water; 1 to 3 parts by weight of flow agent and fillers with a hydrophilic surface, and up to 10 parts by weight of other optional additives / auxiliary substances. A higher water content is compensated for by the addition of hydrophilic fillers, so that the overall softer mass maintains a constant moisture content and virtually non-fluctuating viscosity. A mass with a consistency similar to pastry can thus be obtained. The mass is malleable with gentle pressure and, like pastry, can also be shaped and formed by scraping with a spatula or similar shaping tools.The shaped pieces, manufactured analogously to structured and shaped baked goods and chocolates, are stable over a long period and do not deform even under sunlight or during temperature changes.

[0052] In an advantageous application, several masses were produced according to the second embodiment using various inorganic color pigments. Design examples for toy and decorative porcelain objects were created in both monochrome and polychrome versions, combining different colored mass segments. The objects remained dimensionally stable and remoldable for weeks. Continuous exposure to sunlight was simulated in a climate chamber, combined with typical indoor humidity and temperature fluctuations. The inorganic color pigments remained securely dispersed within the mass segments without migrating. Furthermore, the objects exhibited dimensional stability without any tendency to melt, crack, or disintegrate. After several simulated years, the optical appearance remained unchanged, and the mass remained remoldable and usable.For the first time, a mass can be provided which, as a storable design example or permanent keepsake, preserves a visual impression for years and yet remains malleable / playable.

[0053] INDUSTRIAL APPLICABILITY

[0054] Molded parts made from established, permanently plastic, moldable materials have the disadvantage of either not remaining stable for several weeks or becoming unremodelable after several weeks. The challenge is to overcome these disadvantages. The solution is achieved with a mass based on starch-based colloid, fat, and additives, to which a flocculation aid is added. This flocculation aid supports moisture balance and encapsulates impurities. For the first time, molded parts that are durable and remodelable for months to years can be obtained. These parts are suitable for use as toys, sample materials for pastry design, sample materials for building block molds, or even as seals and reference bodies for pipes, and can be reused long-term.

Claims

REQUIREMENTS 1. Permanently plastic, moldable mass comprising at least 5% water by weight; 0.1 to 4 percent by weight of flocculation aid e ; 5 to 40 percent by weight starch-based colloid; 5 to 40 percent by weight of free-flowing polyol with a chain length in the range of 2 to 6; 0 to 5% fat by weight; up to 6% by weight containing at least one additive / auxiliary substance from the group comprising humectants, emulsifiers, mineral fillers, bulking agents, preservatives, disinfectants, defoamers, antibacterial additives, thickeners, gelling agents, colorants, flavorings, fragrances, emetics, and flow agents.

2. Mass according to the preceding claim, characterized in that the flocculation aid comprises at least one water-soluble flocculation aid based on poly-electrolytes which is selected from the group consisting of proteins, polyamines, polyamides, polyacrylamides.

3. Mass according to one of the preceding claims, characterized in that the fat consists of at least one triglyceride.

4. Mass according to one of the preceding claims, characterized in that the starch-based colloid is a rice starch-based colloid and that the flocculation aid comprises at least 0.1 wt% non-ionic polyacrylamide.

5. Mass according to one of the preceding claims, characterized in that the mass comprises at least 0.1 percent by weight of chitosan as a preservative.

6. Mass according to one of the preceding claims, characterized in that the mass comprises at least 0.1 percent by weight of xanthan gum as a gelling agent.

7. A method for producing a mass according to one of the preceding claims, characterized in that the method comprises the following process steps: a) Dissolving the flocculation aid in a portion of the water to obtain a solution 1; b) Mixing rice-starch-based colloid, free-flowing polyol, preservative, and gelling agent to obtain a homogeneous mixture 1; c) Adding solution 1 to mixture 1 and bringing to a boil while stirring continuously; d) Reducing the heat input to a mixing temperature 10 °C lower and adding all heat-stable adjusting / auxiliary substances while stirring continuously; e) Adding the remaining water while rapidly lowering the temperature to a temperature of 20 °C to 40 °C; f) Adding the remaining adjusting and auxiliary substances and finally homogenizing.

8. Permanently plastic, moldable mass, produced according to the preceding claim from the quantities and components thereof. - 10 parts by weight of water and - 0.1 to 0.2 parts by weight of non-ionic polyacrylamide as a flocculation aid; - 35 to 45 parts by weight of rice starch-based colloid - 35 to 45 parts by weight of glycerin as a free-flowing polyol - 0.3 to 0.9 parts by weight of xanthan gum as a gelling agent - 0.2 to 0.3 parts by weight of chitosan as a preservative; as heat-stable stabilizers and additives - 4 to 6 parts by weight triglycerides as fat - 2.2 to 3.2 parts by weight monoglycerides and polysorbate as emulsifiers - 1 to 2 parts by weight of inorganic white pigment as a colorant - 0.5 to 1.5 parts by weight of PDMS silicone oil as a defoamer - 10 to 20 parts by weight of remaining water; - up to 10 parts by weight of additional, optional adjusting / auxiliary materials.

9. Permanently plastic, moldable mass, produced according to claim 7 from the quantities and components by weight - 10 parts by weight of water and - 0.1 to 0.2 parts by weight of non-ionic polyacrylamide as a flocculating aid; - 35 to 45 parts by weight of rice-starch-based colloid - 35 to 45 parts by weight of glycerin as a free-flowing polyol - 0.2 to 0.8 parts by weight of xanthan gum as a gelling agent - 0.2 to 0.3 parts by weight of chitosan as a preservative; as heat-stable thickeners and additives - 4 to 6 parts by weight triglycerides as fat - 2.2 to 3.2 parts by weight monoglycerides and polysorbate as emulsifiers - 1 to 2 parts by weight of inorganic white pigment as a colorant - 0.6 to 1.6 parts by weight of PDMS silicone oil as a defoamer - 15 to 25 parts by weight of remaining water; - 1 to 3 parts by weight of flow agent and filler material with a hydrophilic surface and - up to 10 parts by weight of additional, optional adjusting / auxiliary materials.

10. Use of a permanently plastic, moldable sealant according to one of the preceding claims, wherein the sealant consists of human-physiologically acceptable food substances as well as food additives and food excipients, as a reference test specimen and long-term stable conductor sealant. Sealing compound in food processing machinery.