A model complex, its preparation method and uses

Abstract

A composition comprising: a) at least one homopolymer of vinyl acetate or a copolymer of vinyl acetate; and b) at least one softening agent.

Description

TECHNICAL FIELD

[0001] The present invention relates to polymer compositions which can be used as molding materials and / or model materials, as adhesives in sealants, packaging materials and / or filling materials. In particular, the present invention relates to compositions which remain usable under a wide range of environmental conditions. BACKGROUND OF THE INVENTION

[0002] Moldable materials can be used for a wide variety of tasks including artistic pursuits such as sculpture and model making for adults and children, molding and tooling for home and industrial use, as fillers or sealants, as protective / packaging materials, and as protectants to protect areas from surface treatments such as paints or etchants. The material composition can consist entirely of "adhesive" type materials such as polymers, softeners and other "active" materials, or can include inert "filler" materials which mainly serve as bulking agents. Filled materials can be obtained by providing an adhesive coating on at least one filler, where the filler is formed of granules or microparticles. Other proposed uses include: as educational materials, as landscape architecture aids, forming sculptures, generating prototypes, as materials for museum interiors and aquarium decorations, as materials for industrial design, as tooling or impression materials, as liquid-impermeable (sealant) layers, and / or as filler materials, insulation materials, packaging materials, shock-absorbing materials and / or flame retardants in building construction and / or maintenance. Suitable adhesives can also be used as temporary adhesives by coating at least a portion of an object surface, which can then be assembled for carving, prototyping, model making and similar activities for adults or children.

[0003] It was taught in WO9807787 and WO9841408 approximately twenty years ago that a sandy material could be produced where the filler is sand or a sandy material and the adhesive can be a material similar to beeswax or a mixture of materials. The disadvantage of using an adhesive with properties similar to beeswax is that it shows a tendency to gradually soften as the temperature increases. For example, such a temperature increase can be obtained when the material is manually processed. Under such conditions, the material may become too soft to maintain the sculpted shape that has been formed and / or it may be felt to be sticky on the hand or other surfaces. Greasiness may contaminate the surface and / or clothing.

[0004] To reduce stickiness and greasiness under normal conditions, waxes with a higher melting temperature can be used as binders. The disadvantage of having a higher melting temperature is that the wax is very hard at lower temperatures. The product is typically free-flowing and scattered because it is not cohesive under storage conditions and must be processed or treated for some time before being used and pressed together to form a body. To achieve a material composition with a moderate softness suitable for direct use and which can also harden to obtain a permanent or semi-permanent object, WO2006101440 describes a material with a binder having at least two solid phases - one harder and one softer. However, this technology still has disadvantages, such as the binder adhering to the plastic materials commonly used in molds and equipment. What is more obstructive in practice for the widespread and general use of the materials provided by this technology is that due to the low cohesion of the material, it is scattered during use and difficult to clean up. Therefore, such materials would benefit from being more cohesive. A third important disadvantage is that the material must be manufactured in a rather complex and highly specialized process. The two (polymer) phases of the binder must be mixed and applied to the surface of the filler particles at elevated and rather high temperatures. The mixture must then be cooled during a continuous kneading process. If this does not occur, the binder system will delaminate. This delamination will result in a material with a texture characterized by hard entities of various sizes rather than a material similar to wet sand. To address these disadvantages, WO2008020800 proposed a silicone-based binder system, which was later refined in WO2014177710.

[0005] An inherent property of silicone-based binder systems is that they have a low glass transition temperature (Tg) and melting temperature, which provides a binder that is quite stable with respect to temperature changes in the normal temperature range (e.g., over 5 °C to 35 °C). Silicone-based binder systems are also cohesive and stick to themselves and hardly stick to any other surface. Although there are significant improvements over previously known binder systems, silicone-based binder systems do suffer from defects.

[0006] A property that at first sight appears to be an advantage - the intrinsic tendency of silicone to repel or not adhere to almost any other surface - is a disadvantage in many technical applications. The incompatibility of the binder system with almost any surface other than the silicone surface hinders its use as a binder system, because the binder cannot adhere to the surface of the filler particles and tends to slide off the surface of the filler particles. When processing and using the material, the filler particles tend to drip out of the matrix. This is an escalating problem as the size of the filler particles increases, because it can become more difficult to maintain a completely encapsulated coating. It has been found in practice that this can also be a problem for silica-based fillers (sand) of relatively small size (less than 1 mm), especially if production involves moist sand or a production environment with high relative humidity. Without strict control of production conditions and methods, costly high rejection frequencies can occur due to separation of filler and binder.

[0007] Another serious problem of silicone-based adhesives is that the final material properties are strongly affected by the relative humidity of the surrounding environment. This greatly hinders the widespread use of materials based on this technology. Materials suitable for dry conditions cannot be used at higher relative humidity. For example, materials with the desired texture in an environmentally controlled heated and / or air-conditioned indoor climate with low relative humidity (e.g., less than 40% RH) will not be suitable under high relative humidity (e.g., greater than 90% RH). The trace amount of water absorbed by the material at higher relative humidity effectively acts as a softener for the adhesive, giving the material an overly soft and sticky texture. Usually, the material properties can be restored simply by drying the material, but in some cases, the absorption of water can also cause the delamination of the material, causing the filler to fall off from the matrix. The latter observation may be due to the adhesive sliding off the surface of the wet filler particles.

[0008] In view of the foregoing, it will be very advantageous to find an adhesive composition that can work within a certain temperature range.It will be further advantageous to find an adhesive composition that can work within the relative humidity range of the surrounding environment.If the feature of the adhesive composition is compatible with the surface of the particles from a variety of different sources, it will be a further substantial improvement.If the adhesive composition and / or the filled composition of gained are substantially non-adhesive for the surrounding surfaces such as hand and desktop, it will be a further advantage.At first glance, these advantages seem to conflict, so if two or more of these advantages can be provided in a single composition, there will be special value.The inventor is now surprised to find that by providing a composition comprising a suitable polymer, a softening agent and optional other additives, it is possible to form a composition that provides at least one, preferably two or more of the aforementioned advantages, and other advantages shown below herein. Summary of the invention

[0009] In a first aspect, the present invention provides a composition comprising:

[0010] a) at least one homopolymer of vinyl acetate or a copolymer of vinyl acetate; and

[0011] b) at least one softening agent;

[0012] Preferred compositions may additionally comprise certain optional components, such as at least one of the following:

[0013] c) at least one silicone oil and / or

[0014] d) at least one filler.

[0015] Such a composition is very useful as a model complex. Accordingly, in a second aspect, the present invention also provides a model complex comprising at least one composition as described in any corresponding embodiment herein. Other materials that may usefully comprise or consist of the composition of the present invention include filler materials, sealant materials, protective materials, packaging materials, and insulating materials. Preferably, all of these materials can be molded by hand and / or using hand tools and will have the properties described herein for the various embodiments of the present invention. These materials will each form other aspects of the present invention.

[0016] The compositions, model complexes, and other materials of the present invention will preferably be stable over a wide range of relative humidity (e.g., 0% RH to 100% RH or 10% RH to 90% RH) and / or a wide range of operating temperatures (e.g., 0°C to 100°C or 0°C to 40°C). The composition and other products are preferably also stable in contact with liquid water and other polar fluids (such as aqueous solutions).

[0017] The model complexes of all embodiments of the present invention are suitable for forming impressions of solid objects, such as for use as molds or in children's play. In another aspect, the present invention accordingly further provides a method of forming an impression of an object (having an inner surface and / or an outer surface), the method comprising pressing a model complex as described in any corresponding embodiment herein against at least a portion of the inner surface and / or the outer surface of the object.

[0018] In still further embodiments, the present invention accordingly provides the use of a composition of any of the embodiments described herein as a model complex.

[0019] A further desirable feature of the filling compositions of the present invention (comprising component d)) is that they can be prepared by cold - bonding an adhesive composition (comprising components a), b) and optionally c)) with at least one filler material (component d)). In a still further aspect, the present invention thus provides a method for forming at least one filling composition comprising an adhesive composition and at least one filler, the method comprising:

[0020] generating the adhesive composition by mixing:

[0021] a) at least one homopolymer of vinyl acetate or a copolymer of vinyl acetate;

[0022] b) at least one softening agent; and

[0023] c) optionally at least one silicone oil;

[0024] and combining the adhesive composition with at least one filler material (such as any of those described herein), wherein the combining is carried out at a temperature of from 0 °C to 50 °C. Detailed Description

[0025] The inventors have surprisingly found that a mixture based on homopolymers of polyvinyl acetate and / or copolymers of polyvinyl acetate can provide an adhesive composition that achieves two or more of the advantages in the above - mentioned wish list, preferably three or four such advantages. All or some of the compositions of the present invention also provide other advantages as described below.

[0026] The most advantageous mixtures are characterized by at least one of the following;

[0027] (i) soft enough to be shaped by hand or with simple hand tools;

[0028] (ii) adherent to the surface of the filler particles such that the matrix holds firmly together, while the material does not adhere excessively to the surrounding surfaces (hands, workbench, tabletop);

[0029] (iii) cohesive enough to prevent over - dispersion or uncontrollable material, and the material can be easily restored for re - molding and re - use.

[0030] It has also been found that a further advantage of the compositions and other aspects of the present invention is that for the polyvinyl acetate (PVAc) - based systems of the present invention, the manufacturing method is very simple. The adhesive system can be pre - prepared and cold - mixed with the filler particles at a later stage. This is in sharp contrast to the previously known techniques, which are characterized by complex manufacturing procedures, including elevated temperatures, correct mixing sequences, dry raw materials, and continuous kneading.

[0031] As used herein, "adhesive" or "adhesive system" comprises components a) and b) as described herein, and optional component c) if present. The adhesive system is responsible for the key cohesive properties of the composition and other materials of the present invention, and forms a key component of the composition. The fillers and filler materials described herein are essentially inert materials that act as carriers or fillers for the adhesive. Obviously, fillers and bulk materials will have an impact on the properties of the composition, but these have a relatively small impact on key properties such as cohesion and stability within a certain humidity range and a certain temperature range, which provides some of the key advantages of the products of the present invention.

[0032] Polyvinyl acetate has long been used for a variety of applications in different technical fields, and copolymerization of vinyl acetate with other monomers has greatly expanded this use. For example, polyvinyl acetate can be used in adhesives and is a film-forming component in many water-based (latex) coatings. In combination with vinyl alcohol, copolymers are used in white wood glue and vinyl laurate, and in improved chewing gum formulations.

[0033] Pure polyvinyl acetate has a melting point of almost 100°C (Tg of about 40°C), below which it is in solid form. For this reason, softeners are required in many applications. In chewing gum compositions, triacetin (triacetin) has historically been used as a non-toxic additive. The obvious disadvantage is that triacetin leaks out of the chewing gum composition during use and the formulation loses its texture. One way to solve this problem is to prepare copolymers with lower Tg and melting temperature. One such copolymer is vinyl acetate-vinyl laurate copolymer.

[0034] Back in 1966, Wacker had a priority application for adhesives using copolymers of vinyl acetate and vinyl laurate (US3519587A - priority 1966-10-31), used in the form of a melt. To obtain the desired properties, the copolymers were melted and mixed with a certain percentage of wax. These adhesives bonded so strongly that they could not be removed from the paper without tearing it.

[0035] The Wrigley Company describes in Patent US5173317 (priority 1991-10-29) chewing gums and chewing gum bases containing vinyl laurate / vinyl acetate copolymer as the main elastomer. This application provides a gum base with a softer texture, reduced cohesion and bubble tack, and improved bubble formation. Prior to this, polyvinyl acetate and glyceryl triacetate were commonly used, sometimes in combination with vinyl laurate / vinyl acetate copolymer, but these all had the drawback that glyceryl triacetate tended not to be fully retained in the polymer matrix. In addition, these chewing gum compositions had to be processed using heat, which could damage the elastomer.

[0036] In Patent Application US2013071515 (priority 2011-09-19), Wacker describes a chewing gum base that can be used for the preparation of non-tacky chewing gums. This gum base consists of a certain proportion of polyvinyl acetate and a copolymer of vinyl laurate-vinyl acetate plus softeners (diacetin, triacetin, acetem, glyceryl monostearate). Along the same lines, in Patent Application US2013309352 (priority 2012-05-15), Wacker describes a ready-made gum base for the preparation of pharmaceutical chewing gums. This gum base consists of polyvinyl acetate, a copolymer of vinyl laurate-vinyl acetate, wax or fat, plasticizers, and emulsifiers. In Patent Application WO2015154780 (priority 2014-04-08), chewing gums containing a pharmaceutically active ingredient are described, in which Fertin Pharma teaches a medical chewing gum consisting of polyvinyl acetate and a copolymer of vinyl laurate-vinyl acetate and a pharmaceutical ingredient (nicotine).

[0037] Wacker discussed the problem of polyvinyl acetate resin being tacky to surrounding surfaces and provided a solution in US8071669 (priority 2005-03-03), which taught how to use silica (such as talc or pyrogenic silicic acid) compounds as free-flow agents in the production of solid polyvinyl acetate resins in order to meet the surface tack of pellets due to the relatively low Tg of the polymer resin. In US7479293 (priority 2005-02-17), Wacker described that the problem with previous chewing gum bases was that they were difficult to remove from the road surface (and the like), and the previous bases were non-biodegradable and did not disappear over time. The solution in this patent was to include a photoactive filler (TiO2) in the formulation, which induces the decomposition of organic molecules when exposed to UV light. These latter two patents show that it is by no means obvious that a PVAc system can act as an adhesive and, together with fillers, produce a matrix that does not stick to surrounding surfaces. Even more surprisingly, the following examples will show that certain mixtures (without fillers) based on the PVAc system can achieve almost non-tacky but cohesive, such that they can be used as toys for indoor games. In addition, adhesives based on the PVAc system not only resist changes in relative humidity in the surrounding environment, but in some cases exposure to water can even improve the properties of the final material.

[0038] In a first aspect, the present invention provides a composition comprising:

[0039] a) at least one homopolymer and / or at least one copolymer of vinyl acetate; and

[0040] b) at least one softening agent;

[0041] Optionally, one or more other components such as the following may be included:

[0042] c) at least one silicone oil;

[0043] d) at least one filler;

[0044] e) pigments;

[0045] f) flash agents;

[0046] g) mica or coated mica;

[0047] h) fragrances;

[0048] i) preservatives;

[0049] Each optional component provides useful and valuable advantages in certain embodiments and certain applications, and can be selected independently and used alone or in any combination when technically feasible. For clarity, the various components are described separately herein, but can be used in combination to provide the desired properties for the compositions of the present invention.

[0050] The vinyl acetate homopolymer and / or vinyl acetate copolymer component a) can consist of a vinyl acetate homopolymer, can consist of vinyl acetate copolymerized with at least one other monomer, or can comprise or consist of a mixture of these homopolymers and copolymers.

[0051] The average molecular weight of the vinyl acetate homopolymer useful in all aspects of the present invention is generally from 5 kD to 1000 kD, more usually from 20 kD to 500 kD, and most preferably from about 25 kD to 200 kD or 25 kD to 100 kD. An average molecular weight of about 50 kD or about 70 kD is highly preferred.

[0052] Typical vinyl acetate copolymers useful in all aspects of the present invention are copolymers of vinyl acetate and at least one other vinyl ester. Such other vinyl ester can be any suitable vinyl ester, but examples include vinyl esters of the formula H2C=CH-O-CO-R, where R is a substituted or unsubstituted alkyl, alkenyl, alkynyl group which is straight-chain, branched and / or aromatic, preferably having 2 to 24 carbons. Preferred R groups include C2 to C18 branched or straight-chain alkyl groups, optionally substituted by moieties such as halides (F, Cl, Br, I), amines, amides, alcohols, esters or ethers. Vinyl esters of medium-chain to long-chain alkyl acids such as propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid and any isomers of acrylic acid and mixtures thereof are very suitable. The most preferred comonomer is vinyl laurate, and the vinyl acetate / vinyl laurate copolymer forms a preferred component of component a). Thus, component a) can comprise at least one vinyl acetate / vinyl laurate copolymer, consist essentially of at least one vinyl acetate / vinyl laurate copolymer or consist of at least one vinyl acetate / vinyl laurate copolymer.

[0053] Copolymers of vinyl acetate and at least one other vinyl ester as described herein generally contain from 10% to 95% vinyl acetate and from 5% to 90% of at least one other vinyl ester. Preferably, this will be from about 30% to 90% vinyl acetate and from 10% to 70% of at least one other vinyl ester.

[0054] Copolymers with a greater amount of vinyl acetate than other vinyl esters are preferred, and thus the amount thereof can be 50% to 90% vinyl acetate and 10% to 50% of at least one other vinyl ester, such as 55% to 85% vinyl acetate and 15% to 45% of at least one other vinyl ester. Such other vinyl ester can be any as indicated herein, but preferably contains or consists of vinyl laurate.

[0055] The average molecular weight of suitable copolymers of vinyl acetate and at least one other vinyl ester for use in the present invention is generally 25 kD to 2000 kD, more usually 50 kD to 1000 kD, and most preferably about 75 kD to 600 kD or 100 kD to 400 kD. An average molecular weight of about 200 kD is highly preferred.

[0056] In all aspects of the present invention, the key component is vinyl acetate homopolymer and / or vinyl acetate copolymer. In some cases, component a) can consist of one or more homopolymers of vinyl acetate, and in other cases, component a) can consist of one or more copolymers of vinyl acetate and at least one other vinyl ester (such as those described herein). In one embodiment, component a) comprises at least one vinyl acetate homopolymer ("homopolymer") and at least one copolymer of vinyl acetate and at least one other vinyl ester ("copolymer"). In one such embodiment, the copolymer can be present in an amount less than that of the homopolymer. In such an embodiment, the copolymer can be present in up to 25%, up to 22% or up to 20% (such as 1 to 25%) of component a), with the remainder being the homopolymer. In another embodiment, the copolymer can be present in an amount greater than that of the homopolymer. In such an embodiment, the homopolymer can be present, for example, in up to 25%, up to 22% or up to 20% (such as 1 to 25%) of component a), with the remainder being the copolymer.

[0057] The softening agent component b) can be any suitable softening agent for vinyl acetate homopolymer and / or vinyl acetate copolymer. Suitable examples are generally based on alcohols and / or other oxygen-based functionalities. Monohydric alcohols, diols and triols containing groups with 3 to 20 carbon atoms and the corresponding esters (such as with acids, such as acetic acid and / or the above medium-chain to long-chain acids) will be typical. Examples include glycerol, glycerol esters and medium-chain to long-chain alcohols, such as alcohols with branched or straight-chain alkyl groups of C2 to C24 (for example, monohydric alcohols, diols or triols of such chains).

[0058] In all aspects of the present invention, the softening agent component b) can comprise at least one compound of formula (i)

[0059]

[0060] Wherein R1 to R3 are each independently selected from H; branched or straight-chain acyl groups having 2 to 24 carbon atoms (substituted or unsubstituted); saturated or unsaturated fatty acyl groups having 2 to 24 carbon atoms (substituted or unsubstituted); saturated or unsaturated mono-hydroxylated fatty acyl, di-hydroxylated fatty acyl or tri-hydroxylated fatty acyl groups having 2 to 24 carbon atoms (unsubstituted or further substituted); and mixtures thereof as described above.

[0061] Fatty acids are typically described with reference to the number of carbon atoms and the degree of unsaturation in the carbon chain. Thus, CX:Z represents a hydrocarbon chain having X carbon atoms and Z degrees of unsaturation. Examples specifically include hexanoyl (C6:0) group, octanoyl (C8:0) group, decanoyl (C10:0) group, lauroyl (C12:0) group, myristoyl (C14:0) group, palmitoyl (C16:0) group, phytanoly (C16:0) group, palmitoleoyl (C16:1) group, stearoyl (C18:0) group, oleoyl (C18:1) group, elaidoyl (C18:1) group, linoleoyl (C18:2) group, linolenoyl (C18:3) group, arachidonoyl (C20:4) group, behenoyl (C22:0) group and lignoceroyl (C24:9) group.

[0062] The fatty acyl moieties that can be used as substituents R1 to R3 in formula (i) include acyls of acids ranging from acetic acid (C2:0) up to saturated and unsaturated long-chain fatty acids such as the lignoceroyl (C24:9) group. Groups having 2 to 22 carbons are typical, and usually no more than one of R1 to R3 has more than 4 carbons (C4 - butyric acid).

[0063] Suitably high acyl, fatty acyl and / or hydroxylated fatty acyl groups may be selected from acyl groups (including mixtures thereof) of at least one of the following acids: acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, caproic acid, caprylic acid, palmitic acid, phytanic acid, palmitoleic acid, sapienic acid, stearic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, linolenic acid, arachidonic acid, behenic acid, lignoceric acid, ricinoleic acid, α-linolenic acid and dihydroxystearic acid.

[0064] Mixtures of glycerides can be very suitable for use, including natural products and partially processed natural products such as castor oil, hydrogenated castor oil, monoglycerides of castor oil and acetates of these materials. The material identified in Chemical Abstracts Reference CAS 736150-63-3 is identified as "glycerides, castor oil mono-, hydrogenated, acetate" and forms a possible component of component b). Other specific preferred components include diacetylglycerol and triacetylglycerol.

[0065] Some typical compounds that can be used in softening agent component b) include: glycerol, diacetylglycerol, triacetylglycerol, monoglycerides of castor oil, monoglycerides of hydrogenated fatty acids, acetate monoglycerides, acetates of monoglycerides of hydrogenated castor oil, monoacylglycerols, diacylglycerols, triacylglycerols, fatty acids, fatty acid esters, 2-octyl-1-dodecanol, undecanol, dodecanol, C6 to C24 alkyl alcohols and mixtures thereof.

[0066] Optional component c) is applicable to all aspects of the present invention and relates to silicone fluid. Such silicone fluids are generally straight-chain, branched-chain and / or cyclic oligoalkylsiloxanes or polyalkylsiloxanes with or without at least one hydroxy end. Polydimethylsiloxane or oligo-dimethylsiloxane (with or without at least one hydroxy end) forms a preferred example.

[0067] Suitable silicone fluids can have a wide range of viscosities, for example, a viscosity of 1 mPas to 5000 mPas at 25 °C. Preferably, it is about 2 mPas to 2500 mPas at 25 °C. The molecular weight of suitable oligomeric alkylsiloxanes or polyalkylsiloxanes can vary from about 0.5 kD to about 50 kD, for example, about 1 kD to about 30 kD.

[0068] Some examples of useful silicone fluids include CDS100 (a linear polydimethylsiloxane capped with hydroxyl groups at both ends, with a molecular weight of about 4 kD and a viscosity of about 100 mPas at 20 °C), AK5 (a low molecular weight oligomeric dimethylsiloxane without hydroxyl capping, with a viscosity of about 5 mPas at 25 °C), and POLYMER C 2T (a linear polydimethylsiloxane capped with hydroxyl groups at both ends, with a molecular weight of about 25,000 and a viscosity of about 25 mPa at 25 °C).

[0069] In the compositions and all aspects of the present invention, component a) is generally present in an amount of 30% to 95% by weight of components a) and b) (and c) if present). This is generally about 40% to 95% or 50% to 90% by weight of components a) and b) (and c) if present), and most preferably about 60% to 80%.

[0070] In the compositions and all aspects of the present invention, component b) is generally present in an amount of about 5% to 70%, more typically 10% to 50%, and most preferably about 20% to 40% by weight of components a) and b) (and c) if present). In one embodiment, the softening agent component b) is present in an amount greater than 15% by weight of components a) and b) (and c) if present). This can be, for example, 16% to 50% or 16% to 40%.

[0071] In the compositions and all aspects of the present invention, component c) is generally present in an amount of about 0.1% to 20%, more typically 0.2% to 10% by weight of components a) to c). The most preferred amount of component c) is about 1% to 5% by weight of components a) to c). In one embodiment, component c) is present in an amount of at least 0.5% (e.g., 0.5 to 10%) by weight of a) to c).

[0072] Optional component d) can be present in all compatible aspects and embodiments of the present invention and consists of at least one filler material. Many suitable fillers are known, and any filler known in the art can be used in the present invention.

[0073] Typical examples of filler component d) include sand fillers, glass fillers, polymer fillers, mineral fillers or mixtures thereof. Typical sand fillers include quartz sand and / or silica sand, and in the present invention, the composition comprising components a) and b) (and optionally c)) adheres to filler particles of all sizes. Thus, such "sand" may include particles of coarse sand or gravel size, and the binder composition does not delaminate from the filler. The average particle size of typical "sand" as shown herein is from 50 μm to 5 mm (e.g., 63 μm to 5 mm), preferably from 95 μm to 3 mm, but sand may also be used including filler of gravel and pebble size with an average particle size up to about 10 mm. All dimensions are typically the minimum diameter. Sand fillers (and all other fillers) can be "bimodal" or "multimodal" since there can be more than one size of filler present. For example, fine sand or silica filler with an average particle size less than 100 μm can be used in combination with coarse "sand" or gravel filler with a particle size of 1 mm or greater (e.g., 1 mm to 10 mm). Such a bimodal mixture of fillers allows better coating of the larger particles and can improve the properties of the binder. Typically in such cases, the filler component comprises at least 60% by weight, preferably at least 75% of the larger size filler.

[0074] Glass fillers useful as component d) in all aspects of the present invention include crushed glass fillers, glass bead fillers, hollow glass bead fillers and mixtures thereof. The average particle size is preferably from about 10 μm to 2 mm, but the crushed glass filler can include very small particles, e.g., as low as 1 μm and smaller.

[0075] Certain mineral fillers are very advantageous as all or part of component d) in all aspects of the present invention. Such mineral fillers include silica fillers, titanium dioxide fillers, alumina fillers, calcium carbonate fillers, calcium sulfate fillers, sodium sulfate fillers, silicate compounds, kaolin and other clays, calcium phosphate, talc and mixtures thereof.

[0076] Silica fillers, especially hydrophobized silica fillers, form very preferred mineral fillers and are used as at least part of component d) of the present invention. These fillers can be added in an amount of about 1% to 30% by weight of components a) to c) and the silica filler. When such a pre-filled composition is subsequently added to a larger amount of another filler (see typical filler amounts below), the silica filler has the effect of increasing the binding effect of components a) to c) without the need for more polymer, softener or silicone fluid.

[0077] Polymeric fillers can include any phase-matched natural, semi-synthetic, or synthetic polymer in any suitable form. Synthetic polymer fillers include, for example, polystyrene, polyolefin, polyester, and / or polyamide fillers, including beads, flakes, sawdust, cut film, or any other suitable particulate of these materials. Preferred filler particles are beads, and synthetic polymer fillers can include polystyrene beads, polyolefin beads, polyester beads, and / or polyamide beads. These polymeric fillers can be in the form of solid sheets or can be formed into expanded open-cell or closed-cell foams by methods well known in the art. Such "expanded" materials make excellent fillers, especially in cases where lightweight or insulating materials are needed. These lightweight materials include hollow spheres of any of the polymers described herein, as well as "expanded" foam materials, typically in the form of foam beads, including expanded polystyrene, expanded polyolefin, expanded polyester, expanded polyamide, and mixtures thereof. In a particular embodiment, the filler particles are hollow polymer spheres, i.e., a single layer of polymer in a spherical or substantially spherical shape surrounding a cavity. Such hollow spheres can be, for example, hollow polystyrene spheres, hollow polyolefin spheres, hollow polyester spheres, and / or hollow polyamide spheres. Other suitable hollow polymer spheres include phenolic and amino spheres or hollow polymer spheres made of vinylidene chloride, acrylonitrile, or methyl methacrylate.

[0078] The size of the polymeric filler particles can vary from about 10 μm up to about several mm (e.g., up to about 15 mm), for example, with a diameter from 20 μm up to about 10 mm, or 50 μm up to several mm (e.g., up to about 10 mm). Generally, unexpanded or unfoamed fillers typically have a smaller particle size (e.g., 50 μm to 1000 μm, preferably 100 μm to 500 μm), and expanded or foamed fillers typically have a larger size (e.g., 200 μm to 10 mm, preferably 300 μm to 5 mm). In particular, the diameter of the hollow polymer sphere filler can be 10 μm - 5 mm, such as 20 μm - 3 mm, or 100 μm - 2 mm. Other suitable size ranges for the hollow polymer sphere filler include 10 μm - 500 μm, 15 μm to 250 μm, or 20 μm to 100 μm in diameter. A size of about 25 μm to 75 μm is highly suitable. As with the other particle sizes indicated herein, the sizes generally refer to the smallest size permitted by the context.

[0079] The polymeric filler may also comprise or consist of natural polymers, such as polysaccharides including starch, 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, for example, powders ground from natural materials such as cereals (e.g., wheat, corn, rice), or in the form of powders, dusts or debris from wood, bamboo or other fibrous materials. The natural materials may also be "expanded" by heating to produce materials such as popped corn, puffed wheat or crispy rice. These materials may also be used as fillers in the present invention in their natural granules, large granules or ground or cut into smaller particles. Natural polymers are generally very non-toxic and safe to use and are very useful in embodiments of the present invention that can be used by children. Sawdust and wood chips, wheat, corn, wood and rice flour are preferred natural polymer fillers. Charcoal from natural sources may form a filler material and a black colorant in various materials of the present invention.

[0080] The total amount of filler in the composition of the present invention to the binder (components a) to c)) may be from about 1:100 to about 200:1, corresponding to component d) being from 1% to 99.5% by weight of the total composition. In fact, depending on the type of filler used and the density of that filler, two sub-ratios will most likely be used. For non-expanded fillers (e.g., those with a density greater than 0.5 g / cm 3 ), the total amount of filler may be from about 1:10 to about 200:1, corresponding to component d) being from 10% to 99.5% by weight of the total composition. Preferably, the ratio of component d) to the sum of components a) to c) (or components a) and b), if c) is absent) is from 10:1 to 50:1, corresponding to the whole composition containing from 2% to 10% by weight of binder and from 90% to 98% by weight of filler. For expanded fillers (e.g., those with a density less than 0.5 g / cm 3 ), the ratio will generally be from about 1:100 to 10:1, more preferably from 1:50 to 1:1. In addition to the weight ratio, it is also important to maintain a suitable volume ratio, since there is a maximum volume of filler that can be effectively coated by a given amount of binder. Thus, the volume ratio of filler to binder (filler volume: binder volume) should not be greater than about 500:1, preferably not greater than 200:1.

[0081] When a composition in any aspect of the present invention contains a silica filler, such as a hydrophobized fumed silica filler, as part of component d), the silica filler may be present in a ratio of 10:1 to 1:50 (ratio of binder (components a) to c)) to silica filler). When calculating the filler-to-binder ratio discussed elsewhere herein, the silica filler will be counted as part of component d). In a preferred embodiment, the various products of the present invention may include a hydrophobized fumed silica filler and any type of second filler described herein. This provides the advantages of elasticity and robustness to the binder, especially when the hydrophobized fumed silica filler is used at a level of about 5 wt% to 20 wt% relative to the total amount of filler and components a) and b) (and component c) when present). Preferred hydrophobized fumed silica fillers may comprise various particle sizes, including aggregates of small particles. The minimum size of typical aggregated fumed silica particles can be from 1 μm to 100 μm, preferably about 5 μm to 50 μm.

[0082] In all aspects of the present invention, the products and compositions may contain at least one of various optional components, such as:

[0083] e) Pigments;

[0084] f) Glitter agents;

[0085] g) Mica or coated mica;

[0086] h) Fragrances;

[0087] i) Preservatives; and / or

[0088] j) Flame retardants.

[0089] Examples of each of these additives are well known to those skilled in the art, and many have been illustrated herein. In a preferred embodiment, these optional components may be any of the components listed in the Examples section herein, particularly in the "Table of Chemicals Used in Examples" before the working examples. Glitter agents as mentioned herein include plastic film-based glitter agents (such as polystyrene film glitter agents).

[0090] In one embodiment of the present invention, the compositions and other products in all aspects of the present invention are not chewing gum products. As a result, the compositions and other materials may, for example, not contain any sugars or other sweeteners. Similarly, the composition may exclude natural and naturally derived chewing gum ingredients, such as terpene resins, gum rosin resins, wood rosin, tall oil or tall oil resins. In another embodiment, the compositions and materials in all aspects may not contain any edible oils or fats, such as triglycerides, vegetable oils, animal oils, animal fats, lecithin and / or other phospholipids. In a further embodiment, the compositions and materials in all aspects may not contain any active pharmaceutical ingredients. In addition to pharmaceutical ingredients, other ingredients with biological activity may also be excluded, such as probiotics, flavorings, herbs or spice oils or extracts (such as peppermint oil, orange oil, menthol or citronella oil), sweeteners, tobacco or tobacco powder or other natural products or extracts containing any active pharmaceutical ingredients. Similarly, buffer components may be excluded. Nicotine is particularly common in chewing gum, and in one embodiment, all nicotine and nicotine derivatives are excluded from the compositions of the present invention. In a similar embodiment, the compositions and other products in all aspects of the present invention may exclude waxes, such as paraffin wax, microcrystalline wax, polyethylene wax and natural waxes (such as beeswax).

[0091] One of the main uses of the compositions of the present invention is as a modelling composition for sculpture and / or moulding. A particular advantage of the compositions of the present invention (especially those previously using siloxane-based binders) is that the compositions and modelling compounds of the present invention are stable for a variety of different relative humidities, for a range of working temperatures, and for water and polar fluids including aqueous fluids and other materials containing a high level of water or polar solvents.

[0092] Thus, in all aspects, the compositions and modelling compounds of the present invention are preferably stable in a humidity range (relative humidity) of 1% to 100%, 10% to 90% or 20% to 80%.

[0093] In all aspects, the compositions and modelling compounds of the present invention are also preferably stable in a temperature range of 0°C to 100°C, 0°C to 50°C or 0°C to 40°C. This allows children or adults to use these materials in a warm environment (such as a bathtub or hot tub), and in certain embodiments, the material can even be heated in boiling water or a low-temperature oven to achieve special effects such as the fusion of filler materials.

[0094] In all respects, the compositions and model complexes of the present invention are also preferably stable to exposure to water, aqueous fluids or other polar fluids and solutions. This is particularly in the temperature range of 0 °C to 100 °C, 0 °C to 50 °C or 0 °C to 40 °C. Exposure to these fluids may occur when using gaming materials or model materials that include water or may allow the materials to be used in "wet" situations (including in humid, outdoor conditions or in a bathtub or hot tub) with shaping features. In construction building and maintenance, the various compositions and materials of the present invention are preferably stable to exposure to fluids and other materials with a high water content (such as wet concrete or wet plaster), and this stability also allows for molding in which materials (such as wet gypsum) will be cast. The various materials are also preferably stable to contact with other polar fluids, solutions and solvents (such as ethylene glycol (antifreeze), glycerol and their mixtures with water).

[0095] In the context of the present invention, a composition or model complex can be considered "stable" if there is no significant delamination of the filler component from the binder component (component a) to component c)) during exposure to these conditions for at least 1 hour, preferably at least 4 hours, more preferably at least 24 hours. Significant delamination can be seen as a weight loss of the filler from the composition of greater than 5% by weight.

[0096] In some cases, when applying an adhesive or adhesive mixture to a filler, it may be necessary to dilute the adhesive / adhesive mixture with a suitable medium (such as water) into a fluid with a lower viscosity to facilitate mixing with the filler particles. Similarly, dilution may be useful to facilitate covering larger objects, such as the covering of "loose materials" described below. The dilution mentioned herein can be carried out by simply diluting the adhesive emulsion / dispersion with a suitable medium (such as water or a suitable solvent, preferably water). In the case of diluting an emulsion or similar mixture, this is clearly a solvent that is miscible with the continuous phase.

[0097] In addition to producing the filler material as described above, the binder material of the present invention (optionally with up to 20% by weight of certain fillers added) can be used as a cohesive coating on a surface (such as a model article). In particular, the binder system of components a), b) and optionally c) as described herein can be applied to at least a portion of at least one surface of an article, so that the treated portion of the article is sticky, especially when in contact with other surfaces so treated. Compared with filler and polymer particles, these articles are generally macroscopic and can, for example, have a minimum size greater than 5 mm, preferably greater than 10 mm, more preferably greater than 20 mm. These articles are referred to herein as "loose materials" and can be surface-coated completely or partially as described above. When the coated surfaces of two loose materials are placed together, a temporary connection will be formed, which can facilitate games or model building, prototyping, etc. Then the coated materials can be separated and reconnected as needed, and because the cohesive coating can resist water, the coating material can be washed with water to at least partially remove dirt and restore the cohesive properties.

[0098] Suitable "loose materials" for this aspect of the present invention can be formed from any of the materials described above with respect to the fillers, including polymers (natural or synthetic), glass, minerals, ceramics, etc. Loose materials of synthetic polymers, wood or glass are very suitable and can be of any suitable shape including geometric shapes, such as spherical, cubic, cuboid, prismatic, pyramidal or combinations of these shapes. Articles such as wooden blocks, glass marbles, polymer table tennis balls and similar items are very suitable.

[0099] In this embodiment, a small amount (e.g., up to 20% by weight of components a) to d) if present) of filler can be included in the "binder" before application to the surface of the loose material. Very suitable fillers for these embodiments include (optionally hydrophobized) silica fillers having a small particle size of 1 μm to 100 μm, preferably 5 μm to 50 μm.

[0100] Accordingly, the present invention provides a method for coating at least a portion of the surface of a loose material article (as described herein), the method comprising forming a binder by mixing:

[0101] a) at least one homopolymer of vinyl acetate or a copolymer of vinyl acetate;

[0102] b) at least one softener;

[0103] c) optionally at least one silicone oil, and

[0104] d) optionally up to 20% by weight of small particle fillers.

[0105] And the adhesive is applied to at least a portion of the at least one surface. The coating method can be, for example, by melting the adhesive material and applying it at an elevated temperature (e.g., 40°C to 80°C); or by dissolving the adhesive material in a suitable solvent (e.g., an alcohol such as ethanol, or an ester solvent such as ethyl acetate), applying the resulting solution to the at least partial surface and evaporating the solvent.

[0106] In addition to being used for molding and as play items for children (and even adults), the compositions of the present invention can also be used in a variety of other fields, and thus these various other uses will form other aspects of the present invention.

[0107] Another advantage of the compositions of the present invention is that they can be formulated by simple mixing at low temperatures. In particular, the compositions of the present invention can be formed by mixing the following:

[0108] a) at least one homopolymer of vinyl acetate or a copolymer of vinyl acetate;

[0109] b) at least one softening agent; and

[0110] c) optionally at least one silicone oil, and combining the adhesive composition with at least one filler, wherein the combining is carried out at a temperature of 0°C to 50°C. Usually, this combining is at ambient temperature, e.g., 15°C to 28°C. Usually, this combining will last for 10 minutes to 12 hours, preferably 30 minutes to 4 hours.

[0111] In a further aspect, the present invention provides the use of the various compositions described herein as a sand replacement material, for example, in the holes of a golf course. The materials of the present invention are cohesive and thus are less likely to be moved by wind and rain than natural sand, and thus provide a more permanent alternative to regularly replacing natural sand in golf hazards. In addition, the consistency of the material is little affected by weather conditions and thus provides a consistent playing experience regardless of the weather. Similar uses as a sand replacement will apply to children's play pits and playgrounds, where the materials of the present invention are less likely to be removed by weather and other natural processes and are less likely to be contaminated by animal waste compared to natural sand.

[0112] Accordingly, the present invention also provides a method for preventing or reducing the weather erosion of sand in outdoor sandy areas having natural sand (e.g., in golf course bunkers, sand-pits, or outdoor children's play areas), the method comprising replacing at least a portion of the natural sand at the outdoor sand site with a composition as described herein.

[0113] When aspects of the present invention relate to the use and method of replacing natural sand, preferably component d) comprises at least one sand filler (such as described herein). Further, in these aspects, preferably the sand filler is present in a ratio of at least 10:1 of sand:total amount of components a) to c).

[0114] In yet a further aspect, the present invention provides the use of the various compositions described herein as cleaning products for removing dirt from surfaces (such as painted surfaces). In particular, the present invention provides the use for removing hydrophobic materials (such as oil, grease, tar, asphalt and / or bitumen) from at least one painted surface (e.g., a painted vehicle surface). Such removal is typically carried out by rubbing the dirty surface with the material of the present invention, optionally after applying a surfactant to the surface.

[0115] In a corresponding aspect, the present invention provides a method for cleaning at least one hydrophobic material from a surface (such as a painted surface), the method comprising optionally applying at least one surfactant (especially an aqueous surfactant solution) or a lubricant to at least a part of the surface to be cleaned, and then rubbing the surface to be cleaned with the composition described herein. Such rubbing can be carried out manually or mechanically, for example by hand in a lump or on a cloth or sponge, or using a rotary or orbital device (such as a polishing machine). Typical hydrophobic materials are for example oil, grease, tar, asphalt.

[0116] When aspects of the present invention relate to the use and method of cleaning hydrophobic materials from a surface, the compositions of the present invention for such use and method generally do not contain large particles of high hardness fillers, such as sand, glass or mineral fillers. In the presence of a filler, it is preferably a polymer filler (such as those described herein) and / or a filler with an average particle size not greater than 100 μm. Small particles of hydrophobized calcined silica are very suitable (e.g., with an average particle size of 10 μm to 100 μm). In these aspects, the amount of the filler is generally less than 50% by weight of the total composition, preferably less than 40%.

[0117] In a still further aspect, the present invention provides the use of the compositions of the present invention for filling gaps or voids, such as in the construction and / or maintenance of buildings. In many cases, voids must be filled to improve thermal insulation or sound insulation or to prevent the passage of flames. In such cases, the compositions of the present invention can be used as an alternative to an expanding foam to fill these voids. By appropriately selecting the filler and / or additive, the compositions of the present invention can be made lightweight and highly insulating and can contain flame retardant additives.

[0118] In a corresponding aspect, the present invention provides a method for filling voids in the construction or maintenance of a building, the method comprising adding a composition as described herein to the voids. This can also be a method of filling voids to improve the thermal insulation and / or sound insulation of the building and / or delay the passage of flames in the building.

[0119] When an insulating effect is desired in the methods and uses of the compositions of the present invention, component d) preferably comprises a lightweight filler, such as hollow glass or polymer spheres or expanded polymer materials. These lightweight materials contain a large amount of gas (such as air) and are thus highly insulating.

[0120] In a further aspect, the present invention provides the use of a composition as described herein in a protective and / or shielding area to prevent the application of paint or surface treatment to the area. In a corresponding aspect, the present invention provides a method of preventing paint or other surface treatment from contacting at least a portion of a surface, the method comprising applying a composition of the present invention to the surface portion before applying the paint or other surface treatment.

[0121] As used herein, the terms "about, around, approximately" and "substantially" in relation to a number or a range of numbers generally mean that the specified number or range is preferred, but such a number can vary to some extent without materially affecting the properties of the relevant material, ingredient or similar product. Without prejudice to the key advantages of the present invention, the person skilled in the art will generally be able to readily determine the extent of such variation of the numbers. As a general guide, the ends of these numbers or these ranges can vary by ±10%, preferably ±5%, and more preferably ±1%. A corresponding meaning can be attributed to a composition "substantially consisting of certain components", which can include up to 10%, preferably up to 5%, and most preferably up to 1% of other components in addition to those specified. When a chemical group, chain or other moiety is described herein as being optionally substituted, such substitution may be absent, or one or more atoms (usually one or more hydrogens and / or carbons) in the moiety may be substituted by the following groups: halide (e.g. F, Cl, Br, I) groups, oxy moieties (such as ethers, alcohols, esters, carboxylic acids or epoxides), amino groups (such as amines, amides, nitriles or nitro groups) or thio groups (such as thiols, disulphides, thioesters), etc. Up to about 10 such substitutions may be made where the context permits, but usually 3 or fewer substitutions, e.g. 1, 2 or 3 substitutions with independently selected substituents will be typical.

[0122] Table of chemicals used in the examples

[0123]

[0124]

[0125] Each of the materials listed in the above table forms a preferred example of the corresponding component of the composition of the present invention and can be used together with any other materials in any aspect of the present invention or used independently.

[0126] The present invention is further illustrated by the following non-limiting examples:

[0127] Example 1

[0128] Polyvinyl acetate (PVAc) is a thermoplastic synthetic polymer resin. At room temperature it is solid and has no cold flow. Without the addition of a softening agent, PVAc is too hard and too stiff to be used as an adhesive in materials for hand molding and shaping. Vinnapas B 30S has a glass transition temperature of about 40 °C and a softening point of 90 °C. 30 g of Vinnapas B 30S was melted and mixed with increasing amounts of triacetin (4.5 g; 9.1 g; 13.5 g; 18.5 g). At the highest addition level, corresponding to 38% triacetin and 62% PVAc, the mixture was found to be soft at room temperature. 4 g of PVAc / triacetin was carefully mixed with 48.5 g of Sibelco Baskarps 1-3 and kneaded into a homogeneous material containing 7.6% PVAc / triacetin and 92.4% sand. Using the same PVAc / triacetin mixture, 4 g of the binder was mixed with 68.5 g of sand M32 by the cold mixing method and kneaded into a homogeneous material containing 5.5% binder and 94.5% sand to prepare additional materials. PVAc / triacetin was found to be usable as an adhesive for sand, and the resulting materials all had textures that allowed for convenient use in molding and hand shaping. These materials had sufficient cohesiveness, were easy to clean, and did not stick excessively to the hands or the workbench.

[0129] Example 2

[0130] Various additives were evaluated as softening agents for polyvinyl acetate and poly(vinyl laurate-vinyl acetate) copolymer.

[0131] 40 wt% of the experimental softening agent was added to the molten polymer and mixed during the cooling process.

[0132]

[0133] m: miscible; sm: slightly miscible, with some liquid in equilibrium in the mixture; um: immiscible, the softening effect is graded on an arbitrary scale from 0 to 5, where 5 is the strongest softening effect

[0134] Different plasticizers are characterized by a change in softening effectiveness and a change in the perceived viscosity of the material. Vinnapas B 500 / 40VL with a high vinyl laurate content is already viscous by itself at room temperature. A common result of adding plasticizers is an increase in viscosity. It can be noted that for some plasticizers, although they exert a softening effect, the adhesiveness is acceptable. It has been found that copolymers of PVAc are compatible with a wider range of additives compared to homopolymers. This provides an opportunity to customize adhesives in more ways than polyvinyl acetate homopolymers. For the plasticizers evaluated, PVAc homopolymers can only be mixed with the acetate of glycerol.

[0135] Example 3

[0136] Three compounds, Dimodan MO90 / D (glyceryl monooleate), MCT60 (tricaprylin-caprate), and Isofol 20, were each mixed with molten Vinnapas B500 / 40VL in a 1:1 weight ratio to form a homogeneous mixture. MCT60 seems to be the most effective plasticizer, but the mixture is very viscous. Isofol 20 has the weakest softening effect, and the mixture is hardly viscous, while Dimodan MO90 / D gives Vinnapas B500 / 40VL medium softness.

[0137] Example 4

[0138] The glass transition temperature of pure B 500 / 40VL is about 0 °C, and the softening point is 85 °C, lower than the corresponding values of 40 °C and 90 °C for PVAc. Although cold-flow B 500 / 40VL is rigid and very viscous at room temperature. Based on the results in Example 2, adhesives were prepared by melting B 500 / 40VL and during the melting stage of mixing with other components:

[0139]

[0140]

[0141] This mixture constitutes 71% of the B500 / 40VL polymer and has a lower melting temperature and a softer texture than the pure polymer.

[0142] Example 5

[0143] The adhesive from Example 4 was mixed with silica sand M32. When the adhesive was added at a concentration of 2% or 4%, the resulting materials were sand materials that were loosely held together or better held together, respectively. The sample with the highest adhesive concentration can be used to manufacture molds and sand structures. In both materials, the adhesiveness of the adhesive to the surface (tabletop) and the hand is low, but still higher than the best.

[0144] Example 6

[0145] The same binder system as in Examples 4 and 5 is used with hollow glass spheres and calcined sand with coarser sand grains at a higher concentration (29.3%).

[0146]

[0147] This gives the material a granular, flexible and elastic nature. The density of the material is less than 1 (i.e., the material floats on water). In particular, the material does not degrade when in contact with water. Despite contact with water, the material maintains its cohesiveness and a completely non-sticky texture.

[0148] Example 7

[0149] A binder system is prepared with approximately 57% polymer and 43% other components (plasticizer, anti-sticking agent, etc.). The binder (2.8%) is mixed with 97.2% of M32 sand. Due to the lower polymer content, the binder is softer than in the previous examples.

[0150]

[0151]

[0152] The mixture is cohesive and works well as sand for molding or children's indoor games, although it is a bit sticky to hands and the table. By adding 0.10% equivalent of Wacker AK5 silicone oil, the stickiness is reduced and almost disappears.

[0153] Example 8

[0154] The pure polymer is a matrix that is too hard and rigid to be used as a binder or as a moldable material alone. Many of the products in the above examples stick to the surrounding surfaces. Therefore, six samples were studied in which the polymer Vinnapas 500 / 40VL was mixed with different plasticizers / anti-sticking agents. Vinnapas 500 / 40VL showed compatibility with many plasticizers in Example 2 above. It was found here that glycerol was useless, while the tested glycerol esters (Dimodan MO90 / D and MCT60) worked well, as did Isofol 20.

[0155]

[0156] Example 9

[0157] In the above embodiments, it was found that MCT60 is a strong softener for Vinnapas B 500 / 40VL, while it brings sticky and tacky properties. Isofol 20 has a slightly worse softening effect, but brings lower stickiness and tackiness properties, and silicone oil (such as AK5) has almost no softening performance but acts as a strong anti-sticking agent. Based on this, the following mixtures are prepared by melting and mixing the following components:

[0158]

[0159] This gives the matrix itself a soft and elastic texture without sticking to the hand or the tabletop. It can itself be used as a molding material, filler or movable toy.

[0160] Example 10

[0161] The materials in Example 9 can be mixed with various (effect) pigments and colorants to obtain various colors and optical effects of the materials.

[0162] 0.5 wt% of various Radglo GWT fluorescent pigments can be simply kneaded into the material to obtain strongly colored materials. The tested colors include yellowish green (type GWT-10), green (type GWT-11), orange (type GWT-13), red (type GWT-15), pink (type GWT-17), blue (type GWT-19) and purple (type GWT-88).

[0163] 0.1% of various BASF Microlene pigments can be melted (at about 70 - 80 °C) and mixed into the matrix in a molten state. The tested colors include black (type 0062MC), blue (type 6916MC), green (type 8730MC), orange (type 2910MC), pink (type 4430MC), red (type 3840MC), violet (type 5700MC) and yellow (type 1500MC).

[0164] 0.3% of various effect pigments can be cold mixed with the matrix. The tested effect pigments include; mica-coated flakes, Sparkle Brass S 9222J from BASF; Geoshine Red (004*004*001) or Geoglit Iris R / G from Geotech International B.V.; KuncaiPearl KC9825C from Kuncai Europe B.V. Sparkle Brass S 9222J; Geoshine Red (004*004*001) or Geoglit Iris R / G from Geotech International B.V.; KuncaiPearl KC9825C from Kuncai Europe B.V.

[0165] Example 11

[0166] The material in Example 9 was colored as in Example 10, but the pigment content was increased 15-fold to obtain a strongly colored binder system. 5 wt% of the resulting binder was mixed with 95% silica sand Mam 1S to obtain a material that can be used as a cohesive alternative to natural sand or children's play sand. The resulting material is cohesive such that it does not scatter too much and is suitable for indoor play, having properties similar to wet sand. Since the silica sand Mam 1S is rather light in color (white), the various colorings of the binder system result in a wide variety of colored sand materials.

[0167] Example 12

[0168] The material prepared in Example 11 was kept at low (30% RH) and high (90% RH) relative humidities. Evaluation of the material after two days showed that the material properties were not affected by the change in relative humidity.

[0169] Example 13

[0170] 15 wt% of the binder in Example 9 was mixed with 85 wt% glass granules ST-180 to form a flexible and stretchable material. This material can not only resist high humidity (90% RH), but can also be used to make molds or seal gaps under wet conditions and can be used underwater. Surprisingly, when the substrate gets wet, the cohesive properties of the material increase. The same observation was made when the material was exposed to glycerol instead of water. When the material was kneaded in excess glycerol, the cohesive properties increased.

[0171] Example 14

[0172] The binder in Example 9 was mixed with expanded PSI standard colored EPS to form a flexible and stretchable material. Two materials were prepared with slightly different binder contents of 70 wt% and 96 wt% respectively. These two materials can not only resist high humidity (90% RH), but can also be used and played with in wet environments including underwater. Surprisingly, when the substrate gets wet, the cohesive properties of the material increase. Cold water and warm water can be used.

[0173] Two methods have been used to change the color of the material. EPS beads of different colors can be used, or uncolored beads can be used and the binder can be colored by the method described in Example 10.

[0174] Example 15

[0175] 10 wt% of the binder in Example 9 was mixed with 90 wt% unexpanded PSI standard colored EPS to form a flexible and stretchable material. This material can not only resist high humidity (90% RH), but can also be used and played with in wet environments including underwater. Surprisingly, when the substrate gets wet, the cohesive properties of the material increase. Cold water and warm water can be used.

[0176] Two methods have been used to change the color of the material. EPS beads of different colors can be used, or uncolored beads can be used and the binder can be colored by the method described in Example 10.

[0177] Example 16

[0178] A sand-based material was prepared by first preparing the binder by fusing it together:

[0179]

[0180] Then the binder was cold mixed with 17100 g of quartz sand Mios BB1 / 2,5 to obtain a cohesive sand-based material that is non-sticky and non-adhesive to hands and the tabletop. Unexpectedly, this example shows that this binder system can be used for large filler particles and the filler particles do not leak out of the material. At the same time, the material is non-adhesive to other surfaces.

[0181] Example 17

[0182] A lightweight material was prepared by mixing 83% of the binder in Example 9 with 17% of Expancel 461DET 40d25. The material has a very low density, is cohesive but has no adhesiveness to hands and the workbench.

[0183] Example 18

[0184] 0.8% wt of HDK2000 was added to the material of Example 16 and it was mixed with the matrix by cold kneading. This corresponds to 15% wt of HDK2000 in the binder. The resulting material becomes more stretchable, and long thin lines are formed between the sand grains when the material is stretched. The lines are very strong and long-lived, such that in the pulled-apart matrix, the thin lines last for several seconds to several minutes without breaking.

[0185] Example 19

[0186] By examining the threads formed in Example 18, they appear slightly cloudy and opaque. This may be the result of larger aggregates of HDK2000, which can scatter the light passing through the binder. Although the mechanical properties are attractive by adding HDK2000, there are challenges with the optical properties. This is even more prominent when using effect pigments in the matrix, as in Example 10 for instance. HDK2000 produces a shaded color and loses color and gloss. The negative impact on the optical effect can be balanced by adding less HDK2000. Thus, when adding 2.5% wt HDK2000 to the binder system, adding 0.3 wt% effect pigment makes the matrix produce a vivid color. However, although still present, the positive mechanical effect of HDK2000 is not as strong as in Example 18.

[0187] Example 20

[0188] 10% wt HDK2000 was added to the material of Example 9. This addition led to an improvement in the stretchable mechanical properties of the matrix. The material containing HDK2000 can be stretched to be very thin (much thinner than a human hair) and can be stretched into long self-supporting threads. A further addition corresponding to 35% wt HDK2000 can be easily kneaded by hand and cold into the matrix. The latter addition gives the matrix a slightly harder texture. This can be offset by adding an additional 15% wt of Isofol 20. This example shows that the system of Example 9 containing almost pure binder (without fillers) and 53% of Vinnapas B 500 / 40VL can be "diluted" with HDK2000 and more softener (Isofol 20) to a Vinnapas B 500 / 40VL concentration of about 29% with little impact on the mechanical properties.

[0189] Example 21

[0190] 1.85 kg of Vinnapas B 30S was melted and mixed with 1.15 kg of triacetin, corresponding to 38% of triacetin and 62% of PVAc. The resulting binder is also soft at ambient temperature. 100 kg of sand from an outdoor sandpit was filled in a concrete mixer and 3 kg of binder was added. After mixing for about 10 minutes, the material was emptied from the mixer. The material is similar to wet sand and can be used to fill children's outdoor sandboxes, or as a top layer for golf sandpits to prevent sand erosion due to weather and wind.

[0191] Example 22

[0192] The paint shop uses various deformed caps and plugs of various shapes to protect the areas that should not be covered with paint during the painting operation. The flexible and stretchable material with 70 wt% binder content and 30 wt% expanded PSI standard colored EPS in Example 14 is filled into three drilled holes in the metal plate. When spraying the metal plate, these holes should not be filled with paint or exposed to paint. The metal plate also has four stud bolts, and the paint is protected from the paint by wrapping them in a matrix prepared by melting and mixing the components:

[0193] Vinnapas B 500 / 40VL 60g

[0194] Isofol 20 40g

[0195]

[0196] After spraying the metal plate, the EPS filling material is removed from the three drilled threaded holes, and the HDK2000 filling material is removed from the four stud bolts. When the material is removed, the unpainted lower surface is exposed.

[0197] Example 23

[0198] The flexible and stretchable material with 70 wt% binder content and 30 wt% expanded PSI standard colored EPS in Example 14 is filled to half the volume of a cardboard box with a polyethylene liner. Two 500 mL laboratory Erlenmeyer flasks are pressed into the material adjacent to each other. The molding and holding properties of the material provide two perfectly shaped voids for the two flasks. The upper layer of the material is added on top of the flasks to completely enclose them, and the lid of the cardboard box is closed. The cardboard box is dropped from a height of 150 cm onto the floor 10 times. The box is opened and the Erlenmeyer flasks are found to be intact. Using the same flexible and stretchable material, two 500 mL laboratory round-bottom flasks are packed in the cardboard box and the process is repeated. At this time, the two flasks are found to be intact. This example shows that the material is an excellent reusable packaging material and can be used to replace molded polystyrene foam blocks.

[0199] Example 24

[0200] A very basic formulation can be prepared by melting 100 g of Vinnapas B 500 / 40VL together with 100 g of Isofol 20, while providing a lightweight material with excellent stretchability, cohesiveness, and non-stickiness. Then the liquid binder is mixed with 10 g of expanded PSI standard colored EPS.

[0201] Example 25

[0202] The matrix is prepared by melting and mixing the following components:

[0203]

[0204] By first spraying an aqueous surfactant solution on the asphalt stain and then rubbing with a clay-like material, the clay-like material is used to effectively remove difficult-to-remove dirt, such as asphalt, from the paint on the vehicle body. During this process, the asphalt dissolves in the clay-like material.

[0205] Example 26

[0206] When new windows are installed in a building, there is usually a void space between the wall structure and the window frame. Usually, this void is filled with polyurethane foam. Nowadays, polyurethane foam is sometimes questioned. The flexible and stretchable material with 70 wt% binder content and 30 wt% expanded PSI standard colored EPS in Example 14 is extruded into the void. Due to its molding properties and retention properties, it completely fills the void and provides an insulating filler.

[0207] Example 27

[0208] A wooden block measuring approximately 21×2×0.5 cm is coated with a thin layer of the following mixture:

[0209] Vinnapas B 500 / 40VL 60 g

[0210] Isofol 20 40 g

[0211] MCT60 4 g

[0212] Mixing and coating are carried out at an elevated temperature, and the thin layer is applied with a trowel. The coating provides adhesion between the wooden blocks, making it convenient to build a building with them. These structures become semi-permanent because the wooden blocks can be separated from each other and reused repeatedly. Since the polymer mixture is not sensitive to water, the wooden blocks can be rinsed with water to remove dust and dirt to some extent, if necessary, to regenerate the original adhesiveness of the surface.

[0213] Example 28

[0214] An adhesive system is prepared by melting and mixing Vinnapas B 500 / 40VL and Isofol 20 in the following proportions

[0215]

[0216] When the mixture is homogeneous and allowed to cool, PSI standard colored EPS is kneaded into the binder. The binder adheres excellently to the EPS particles. As an additional softener, a specified amount of triacetin is kneaded into the matrix. The resulting matrix is soft, cohesive and easy to sculpt objects, but non-sticky to hands and the tabletop.

[0217] Example 29

[0218] A binder system is prepared by melting and mixing Vinnapas B 500 / 40VL and Isofol 20 in the following proportions

[0219]

[0220] When the mixture is homogeneous and allowed to cool, unexpanded PSI standard colored EPS is kneaded into the binder. The binder adheres very well to the EPS particles. As an additional softener, a specified amount of triacetin is kneaded into the matrix. The resulting matrix is soft, cohesive and easy to sculpt objects, but non-sticky to hands and the tabletop. Part of the material (about 10 mL) is filled into a mold that can be closed with a lid. The mold is filled with the material to about 80% of its volume. The mold is boiled in water for 10 minutes, then cooled to room temperature, and then the mold lid is opened. It is found that the EPS particles have expanded, filled the mold, and sintered together into a single body having the shape of the inner surface of the mold.

[0221] Example 30

[0222] A table tennis ball is coated with a small amount of the following mixture:

[0223] Vinnapas B 500 / 40VL 60 g

[0224] Isofol 20 40 g

[0225] MCT60 4 g

[0226] Mixing is carried out at an elevated temperature. The thin layer mixture can be applied to the table tennis ball by dissolving the mixture 1:1 in ethanol and impregnating / contacting it with the resulting liquid. The ethanol is allowed to evaporate, leaving a coating that provides adhesion between the table tennis balls, making it convenient to use them for building structures. This structure becomes semi-permanent in this way because the table tennis balls can be separated from each other and reused repeatedly. Since the polymer mixture is not sensitive to water, the table tennis balls can be rinsed with water, and if necessary, dust and dirt can be removed to some extent to regenerate the original cohesion of the surface.

[0227] Example 31

[0228] First, 60 g of Vinnapas B 500 / 40VL, 40 g of Isofol 20, and 4 g of MCT 60 are mixed at an elevated temperature (80 - 100 °C). Then, 7.5 g of Vinnapas B 60SP and 4 g of triacetin are mixed at 130 °C. After cooling to room temperature, the two solutions are mixed to obtain a polymer composition that can be used as a molding and / or modeling material similar to "slime". The texture after mixing is granular, but after some additional mixing and manual kneading, a homogeneous polymer solution is obtained. The resulting mixture flows but has a high viscosity. It has an elastic and easy-to-use texture, but is non-sticky to hands and surfaces (such as a tabletop). The B 60SP polymer gives the solution a slight elasticity, which may be a preferred way to reduce stickiness to the user's hands if the greasiness of other non-sticky reagents is not desired.

[0229] Example 32

[0230] First, 60 g of Vinnapas B 500 / 40VL, 40 g of Isofol 20, 4 g of MCT 60, and 16 g of Luvotix HT are mixed at an elevated temperature (80 - 100 °C). After cooling, the resulting polymer composition can be used as a molding and / or modeling material and can be stretched into very thin and long self-supporting threads.

[0231] Example 33

[0232] Using 5 g of the material from Example 32 as an adhesive shows excellent adhesion to 20 g of PSI standard colored EPS polymer beads (10 mm in diameter). After thorough mixing, a non-dripping "mounting" material is obtained, where individual polymer beads can be removed and repositioned. This behavior helps in using them to construct buildings. The structure becomes semi-permanent in this way because the EPS polymer beads can be separated from each other and reused repeatedly.

[0233] Example 34

[0234] Although perfect for "mounting", due to the fairly high firmness of the adhesive and the fairly low adhesive content, the material in Example 33 has suboptimal molding properties. A softer but non-sticky adhesive texture is obtained by adding 1 g of Wacker AK5 silicone fluid to 9 g of the material from Example 32. AK5 produces softness while reducing the viscosity. After mixing this adhesive system with PSI standard colored EPS polymer beads (3 mm in diameter) in a 1:1 ratio, a moldable and non-sticky creative material is obtained.

[0235] Example 35

[0236] First, 60 g of Vinnapas B 500 / 40VL, 40 g of Isofol 20, and 4 g of MCT60 are mixed at an elevated temperature. Then, at an elevated temperature, 30 g of Vinnapas C 305 is mixed with 16 g of glyceryl triacetate. After cooling to approximately 45 °C, the C305 / triacetin is brought into contact with 6 g of water containing one drop of ammonia solution (5%). The ammonia helps to fill the polymer and forms an adhesive polymer mixture when it absorbs water. The first polymer solution and the second polymer solution are mixed and then soaked with additional water. The final water content in the mixture is approximately 15%. This example shows that a mixture containing bipolar regions and unipolar regions can be produced. The water content provides non-stickiness and a "wet and cold" feeling. The final material is similar in behavior to "mucus".

[0237] Example 36

[0238] First, 60 g of Vinnapas B 500 / 40VL, 40 g of Isofol 20, and 4 g of MCT60 are mixed at an elevated temperature. Then, at an elevated temperature, 30 g of Vinnapas C 305 is mixed with 16 g of glyceryl triacetate. After cooling to approximately 45 °C, the C305 / triacetin is brought into contact with 6 g of water containing one drop of ammonia solution (5%). The ammonia helps to fill the polymer and forms an adhesive polymer mixture when it absorbs water. The first polymer solution and the second polymer solution are mixed and then soaked with Probenz aqueous solution (30%). The final water content in the mixture is approximately 15%. This example shows that the polar domains provide a convenient way to load the matrix with a water-soluble compound (in this case, a preservative). The water content provides non-stickiness and a "wet and cold" feeling. The final material is similar in behavior to "mucus".

[0239] Example 37

[0240] To reduce the viscosity of the dispersion, 8 g of Vinnapas EAF 67 from Wacker is diluted with 4.5 g of water to a dry matter content of approximately 40%. The resulting 12.5 g of dispersion is added to 20 g of PSI standard colored EPS polymer beads, 10 mm in diameter, and carefully mixed. After drying, a "mounting" material is obtained. The vinyl acetate, ethylene, and acrylate copolymer forms a viscous film on the bead surface. Once formed, the surface film is not affected by water, and if needed, the beads can be cleaned to at least partially remove dirt and restore the cohesive properties.

[0241] Example 38

[0242] To reduce the viscosity of the dispersion, 80 g of Vinnapas EAF 67 from Wacker was diluted with 20 g of water. A wooden block of approximately 2×12×0.5 cm was immersed in the dispersion twice, and dried for 60 minutes after each impregnation. The vinyl acetate, ethylene and acrylate copolymer formed a viscous film on the surface of the wooden block. This film provided adhesion between the wooden blocks, making it beneficial for their construction of buildings. These structures became semi-permanent in this way because the wooden blocks could be separated from each other and reused repeatedly. Since the polymer mixture is not sensitive to water, if necessary, the wooden blocks can be rinsed with water to remove dust and dirt to some extent to regenerate the original adhesiveness of the surface.

[0243] Example 39

[0244] First, 60 g of Vinnapas B 500 / 40VL, 40 g of Isofol 20 and 4 g of MCT60 were mixed at a temperature of about 80 - 100 °C. Then, at a temperature of about 80 - 100 °C, 30 g of Vinnapas C 305 was mixed with 16 g of triacetin. After cooling to about 45 °C, the C305 / triacetin was brought into contact with 6 g of water containing three drops of ammonia solution (5%). Ammonia helps polymer filling and forms an adhesive polymer mixture when absorbing water. The first polymer solution and the second polymer solution were mixed, and then soaked with water until the water content was about 15%. The polymer solution was used as an adhesive (90 wt%) and mixed with Expancel 461DET 40d25 from Akzo Nobel (10 wt%). The water content caused the innovative material to have a "wet and cold" feeling to the hand, which disappeared when the water evaporated. This example shows that adding water to the adhesive can provide a material whose properties change upon drying.

[0245] References

[0246] WO9807787 1996-08-23

[0247] WO9841408 1997-03-17

[0248] WO2006101440 2005-03-23

[0249] WO2008020800 2006-08-17

[0250] WO2014177710 2013-05-03

[0251] US3519587A 1966-10-31

[0252] US5173317 1991-10-29

[0253] US2013071515, filed on September 19, 2011

[0254] US2013309352, priority date: May 15, 2012

[0255] WO2015154780, priority date: April 8, 2014

[0256] US8071669, priority date: March 3, 2005

[0257] US7479293, priority date: February 17, 2005

Claims

1. A model composite, which comprises at least one composition, wherein the composition comprises: a) A copolymer of one or more vinyl acetates and at least one other vinyl ester, or At least one homopolymer of vinyl acetate and at least one copolymer of vinyl acetate and at least one other vinyl ester; b) At least one softening agent; and d) At least one filler; wherein component b) at least one softening agent comprises a C6 to C 24 alkyl alcohol, fatty acid, fatty acid ester or at least one glyceride of formula (i) Wherein R1 to R3 are each independently selected from branched or straight-chain acyl groups having 2 to 24 carbon atoms; saturated or unsaturated fatty acyl groups having 2 to 24 carbon atoms; saturated or unsaturated mono-hydroxylated, di-hydroxylated or tri-hydroxylated fatty acyl groups having 2 to 24 carbon atoms; Wherein component d) at least one filler is selected from the group consisting of sand filler, glass filler and / or polymer filler, wherein the polymer filler is polyolefin filler, polyester filler and / or polyamide filler; and Wherein component a) is present in an amount of 30% to 95% of components a) and b) by weight, and Component b) is present in an amount of 15% to 70% of components a) and b) by weight.

2. The model composite according to claim 1, which further comprises: c) At least one silicone oil.

3. The model composite according to claim 1, wherein component a) is a copolymer of vinyl acetate and at least one other vinyl ester.

4. The model composite according to claim 1, wherein the other vinyl ester is of the formula H2C=CH-O-CO-R, where R is a branched or straight-chain alkyl group having 2 to 18 carbon atoms.

5. The model composite according to claim 1, wherein the other vinyl ester is a vinyl ester of at least one acid selected from propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid and myristic acid.

6. The model composite according to claim 1, wherein the copolymer is a copolymer of vinyl acetate and vinyl laurate.

7. The model composite according to claim 1, wherein the softening agent comprises at least one glyceride of formula (i) as claimed in claim 1.

8. The model composite according to claim 1, wherein the softening agent comprises at least one glyceride of formula (i) Wherein R1 to R3 are each independently selected from branched or straight-chain acyl groups having 2 to 22 carbon atoms; saturated or unsaturated fatty acyl groups having 2 to 22 carbon atoms; saturated or unsaturated mono-hydroxylated, di-hydroxylated or tri-hydroxylated fatty acyl groups having 2 to 22 carbon atoms.

9. The model composite according to claim 8, wherein the acyl group, fatty acyl group and / or hydroxylated fatty acyl group are selected from acyl groups of at least one of the following acids: acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, phytanic acid, palmitoleic acid, sapienic acid, stearic acid, oleic acid, trans-oleic acid, isooleic acid, linoleic acid, trans-linoleic acid, linolenic acid, arachidonic acid, behenic acid, lignoceric acid, ricinoleic acid, α-linolenic acid and dihydroxystearic acid.

10. The model complex according to claim 1, wherein component b) is selected from at least one of the following: diacylglycerol, triacylglycerol, ricinoleic acid monoglyceride, hydrogenated fatty acid monoglyceride, monoglyceride acetate, acetate of hydrogenated ricinoleic acid monoglyceride, monoacylglycerol, diacylglycerol, triacylglycerol, fatty acid, fatty acid ester, and C6 to C24 alkyl alcohol.

11. The model complex according to claim 1, which contains component a) in an amount of 50% to 90% by weight of component a), component b), and optionally at least one silicone oil as component c).

12. The model complex according to claim 1, which contains component b) in an amount of 16% to 50% by weight of component a), component b), and optionally at least one silicone oil as component c).

13. The model complex according to claim 2, which contains component c) in an amount of 0.2% to 10% by weight of components a) to c).

14. The model complex according to claim 13, wherein component c) is a silicone fluid or a hydroxy-terminated silicone fluid having a viscosity of 1 mPas to 5000 mPas at 25 °C.

15. The model complex according to claim 1, wherein the sand filler is quartz sand and / or silica sand having an average particle diameter of 100 μm to 5 mm.

16. The model complex according to claim 15, wherein the sand filler is silica sand having an average particle diameter of 200 μm to 3 mm.

17. The model complex according to claim 1, wherein the glass filler is at least one of a crushed glass filler or a glass bead filler.

18. The model complex according to claim 17, wherein the glass filler has an average particle diameter of 100 μm to 2 mm.

19. The model complex according to claim 17, wherein the glass filler is a hollow glass bead filler.

20. The model complex according to claim 1, wherein the polymer filler includes at least one of polyolefin beads, polyester beads, or polyamide beads.

21. The model complex according to claim 1, wherein the polymer filler includes at least one of foamed polyolefin beads, foamed polyester beads, foamed polyamide beads, or hollow polymer balls.

22. The model complex according to claim 20, wherein the polyolefin beads are polystyrene beads.

23. The model complex according to claim 21, wherein the foamed polyolefin beads are foamed polystyrene beads.

24. The model complex according to claim 1, wherein the polymer filler contains hollow polymer balls having an average particle diameter of 10 μm to 5 mm.

25. The model complex according to claim 1, wherein the polymer filler contains hollow polymer balls having an average particle diameter of 20 μm to 100 μm.

26. The model complex according to claim 1, which further contains at least one component selected from the following: e) Pigment; f) Flash agent; g) Mica or coated mica; h) Perfume; i) Preservative.

27. The model complex according to claim 1, wherein the complex is stable in a humidity range of 10% to 90% relative humidity.

28. The model complex according to claim 1, wherein the complex is stable upon exposure to water.

29. The model complex according to claim 1, which is not a chewing gum product.

30. A filling material, a sealing material, a protective material, a packaging material, and / or an insulating material comprising at least one model complex according to claim 1 or consisting of at least one model complex according to claim 1.

31. A method of forming an object impression, the method comprising pressing the model complex according to claim 1 against at least a portion of the inner surface and / or the outer surface of the object.

32. Use of the model complex of claim 1 as a filling material, a sealing material, a protective material, a packaging material, and / or an insulating material.

33. A method of forming at least one filling composition comprising an adhesive composition and at least one filler, the method comprising: producing the adhesive composition by mixing: a) a copolymer of one or more vinyl acetates and at least one other vinyl ester, or at least one vinyl acetate homopolymer and at least one copolymer of vinyl acetate and at least one other vinyl ester; b) at least one softening agent; and c) optionally at least one silicone oil, and combining the adhesive composition with at least one filler material, wherein the combining is carried out at a temperature of from 0 °C to 50 °C; wherein component a) is present in an amount of 30% to 95% by weight of components a), b), and c), component b) is present in an amount of 10% to 70% by weight of components a), b), and c), and wherein component b) at least one softening agent comprises C6 to C 24 alkyl alcohols, fatty acids, fatty acid esters or at least one glyceride of formula (i) wherein R1 to R3 are each independently selected from branched or straight-chain acyl groups having 2 to 24 carbon atoms; saturated or unsaturated fatty acyl groups having 2 to 24 carbon atoms; saturated or unsaturated monohydroxylated fatty acyl, dihydroxylated fatty acyl, or trihydroxylated fatty acyl groups having 2 to 24 carbon atoms.

34. The method according to claim 33, which is used to form the model complex according to claim 1.

Images