DE202005021514U1 - Plastically deformable mass - Google Patents

Abstract

Hardenable, plastically deformable mass with a penetration depth of 8-35 mm, measured with the needle penetrometer according to DIN 51579 at 25 ° C for modeling, molding or filling, containing
A. 20 to 90% by weight of at least one binder,
B. 10 to 60 wt .-% of water,
C. at least one filler and
D. from 0.5 to 40% by weight of at least one additive,
characterized in that the filler consists at least of a light filler having a density of less than 1.0 g / cm ³ at 20 ° C, which is either particulate, span- or sheet-like or as a mixture and the
a) having pores with an average pore diameter of less than 800 microns
b) less than 10% by volume in water at 20 ° C., based on the volume at 20 ° C. in air at equilibrium,
c) has a non-smooth, rugged surface, such as occurs when crushing porous materials by grinding,
wherein the particulate lightweight fillers grain sizes in the ...

Description

The Invention relates to a plastically deformable mass for modeling, Molding and filling based on binders, fillers and additives

such plastically deformable masses are known. In practice will be they z. B. widely used as fillers, z. B. in model making, automotive and building construction. In many cases it is not only desirable to remove bumps from surfaces compensate, but the filled area as quickly as possible continue to work without repeating, z. B. by grinding and painting. This is different u. a. the one of the two-component ones Fillers: One-component fillers are not fast dry and have a distinct fading, the two-component however, are fast and have virtually no fading; but they have a limited pot life.

State of the art

Such plastically deformable masses have also been described in the patent literature. So be in the DE 297 20 344 U1 Industrial Plasteline, which consist of minerals, binders, fillers and colorants and are characterized by lightweight fillers. As light fillers are hollow microspheres of glass and plastics with a diameter of 5 to 500 microns with an average particle size of 60 microns and a density of less than 1.2 g / cm ³ understood. The known composition can be deformed at temperatures above 50 ° C and after cooling to room temperature has a final hardness similar to that of candle wax, so that they can be further processed mechanically, for. B. by milling or manually with scraping tools. The lower the ambient temperature, the harder the mass becomes. The disadvantage is that this mass used in industry can only be deformed above 50 ° C and occupies no final state of aggregation.

In the DE 102 01 946 A1 describes a modeling, which consists of binders, fillers, colorants and optionally other additives, wherein the filler is essentially a lightweight filler made of hollow microspheres and the binder is based on wax and oil-based and characterized by their special components. This mass can be used at room temperature to model and design objects. The disadvantage, however, is that the mass remains permanently plastic under normal conditions and does not harden. Another disadvantage is that the mass can not be processed mechanically.

In the WO 91/14736 (Subsequent application to DE 40 089 80 ) describes a plastic mass for kneading, modeling, crafting and decorating of binders, plasticizers and fillers and optionally colorants and / or other additives. As binder, filler and / or further additive, it contains polyalkyl methacrylate (PAMA) according to characterization. Preferably, a plastisol-type binder of PAMA particles and plasticizer, z. B. alkyl phthalates. Water and light fillers are not mentioned. A disadvantage of such plastic compositions is that they contain organic plasticizers that can migrate. Another disadvantage is that the mass requires several weeks to cure irreversibly at room temperature. The cured at room temperature parts also give no homogeneous results. The hardening process can be accelerated by heating at a higher temperature. Because of the toughness, the brittleness and the high specific gravity of the mass, it is poorly suited both for filigree manual processing and for mechanical processing, especially for larger parts.

In the EP 0792926 A2 describes an aqueous dispersion filler dispersion based on 20 to 99 wt .-% of a polymer having the glass transition temperature below -25 ° C and from 1 to 80 wt .-% of a filler. The dispersion adhesive contains, according to the invention, at least one light filler having a specific gravity of less than 1.0 g / cm ³ . Preferably, the average diameter is 5 to 20 microns. Conveniently, the particles are round and smooth and porous. The known filling dispersion adhesive is particularly suitable for bonding floor coverings, for which purpose it is applied to the substrate with a toothed strip, for example. The effort required to apply is very low to acceptable. After curing in air, the shrinkage is about 25 to 35 vol .-%.

task

Based on this prior art, a plastically deformable mass for modeling, molding or filling should be provided, which contains as possible none of these disadvantages. In particular, a mass should be made available for use by both model makers in the car It should be good and easy to work with and irreversible hardening so that it can be worked on regardless of the environment and used indoors and out. Appropriately, the hardened surface should be very smooth and can be further processed if necessary, for example by painting and painting. In particular, the mass should have the lowest possible shrinkage and have a low specific weight after curing.

The Solution according to the invention is the claims refer to. It is essentially based on the fact that an aqueous Binder system together with special lightweight fillers used in the mass, so that despite the volatilization the water from the compositions according to the invention Volume is reduced only relatively little.

• A. 20 bis 90 Gew.-% mindestens eines Bindemittels,
• B. 10 bis 60 Gew.-% an Wasser,
• C. mindestens einen Füllstoff und
• D. 0,5 bis 40 Gew.-% mindestens eines Zusatzstoffes,

der dadurch gekennzeichnet ist, dass der Füllstoff zumindest aus einem Leichtfüllstoff mit einer Dichte von weniger als 1,0 g/cm³ bei 20°C besteht, der entweder partikelartig, span- oder blattartig oder als Mischung vorliegt und der

• a) Poren mit einem mittleren Porendurchmesser von weniger als 800 μm aufweist
• b) in Wasser von 20°C weniger als 10 Vol.-% quillt, bezogen auf das Volumen bei 20°C in Luft im Gleichgewichtszustand,
• c) eine nicht glatte zerklüftete Oberfläche hat, wie sie beim Zerkleinern von porösen Stoffen durch Mahlen entsteht,

wobei die partikelartigen Leichtfüllstoffe Korngrößen im Bereich von 2 bis 800 μm nach der Siebanalyse von Mesh (vergleiche ASTM specification E11) enthalten, die spanartigen einen Durchmesser von 2 bis 800 μm und eine Länge von 1 bis 20 mm und die blattartigen Leichtfüllstoffe eine Dicke von 2 bis 800 μm und einen mittleren Durchmesser von 1 mm bis 20 mm aufweisen können.The invention therefore provides a curable, plastically deformable mass having a penetration depth of 8-35 mm, measured by the needle penetrometer according to DIN 51579 at 25 ° C for modeling, molding or filling containing

• A. 20 to 90% by weight of at least one binder,
• B. 10 to 60 wt .-% of water,
• C. at least one filler and
• D. from 0.5 to 40% by weight of at least one additive,

characterized in that the filler consists at least of a light filler having a density of less than 1.0 g / cm ³ at 20 ° C, which is either particulate, span- or sheet-like or as a mixture and the

• a) having pores with an average pore diameter of less than 800 microns
• b) less than 10% by volume in water at 20 ° C., based on the volume at 20 ° C. in air at equilibrium,
• c) has a non-smooth, rugged surface, such as occurs when crushing porous materials by grinding,

wherein the particulate light fillers contain grain sizes in the range of 2 to 800 microns after the sieve analysis of mesh (see ASTM specification E11), the span-like a diameter of 2 to 800 microns and a length of 1 to 20 mm and the sheet-like lightweight fillers have a thickness of 2 may have up to 800 microns and a mean diameter of 1 mm to 20 mm.

The preferred embodiments are dependent Claims to be taken.

Under "plastically deformable" is the property that is understood the mass is irreversibly deformed under the action of force. The irreversible deformation is more than 90% and is thus significantly higher than the visco-elastic fraction (= delayed reversibility) and even more so higher than the elastic part (= instantaneous reversibility). The composition of the invention is easy to work, especially by hand to knead. Your consistency can be through Penetrometry (needle penetration) with a penetration depth of 8 to 35 mm, in particular from 15 to 25 mm according to DIN 51579 at 25 ° C to be discribed. The desired consistency can be achieved by the variation of the different binders to each other and through their shares are discontinued. Because of her tough Consistency, the mass is therefore suitable for modeling, molding or To fill. Thus, the inventive allow Masses in the uncured state that thin Plates (best between two water-repellent films) rolled out and can be tailored. The parts thus produced can be achieved by passing or pressing on each other If necessary, connect with moistened fingers or tools. The plates can also be applied to fabrics (gauze, jute or similar) or Roll up carrier materials such as Styrofoam or with a spatula or another tool and if necessary together with processing the tissue.

The composition of the invention is "curable" by removing the water. This is usually evaporated in air, be it at room temperature or at temperatures until boiling, especially at temperatures between 70 and 90, especially between 75 and 85 ° C mass temperature. Also, a drying by use of microwave radiation is possible. The drying time depends on the amount of water, the thickness of the composition of the invention and the amount used. It is preferably 4 hours to 48 hours at a thickness of 1 cm and an area of 200 cm ² in a convection oven at 80 ° C. When selecting suitable binders and optionally additives, the curing is also irreversible, that is, the hardened mass does not return to its initial state when exposed to water, but remains insoluble and solid. Suitable compositions are on the Adhesive known, for example, in the dispersion adhesives, namely PVA-stabilized dispersions or carboxyl-containing dispersions crosslinked with Zn oxide, or chlorinated paraffins.

at The "binder" is a product containing the fillers and optionally the additives with each other and if desired also able to bind with a subsoil. They bind by withdrawal of the water, in particular by its evaporation. Suitable are all film-forming aqueous polymer dispersions, So dispersions of finely divided natural and / or synthetic polymers with a particle size from 0.05 to 5 μm. Included are all aqueous Dispersions of polymers such as natural and synthetic rubber (rubber latices) and of synthetic resins (synthetic resin dispersions) and plastics (plastic dispersions) regardless of their production. With "dispersion" should in a broader sense, all multiphase systems are referred to in where the polymer is molecularly dispersed, colloidally disperse or coarsely dispersed is in an aqueous phase.

Under "Film education" will be the transition of the liquid Form of the binder in the solid state by forming a understood homogeneous skin. An addition of "film formers" to the Polymer dispersion may be advantageous, for. As the addition of solvents or glycol derivatives such as. B. butyltriglycol.

• – Polyurethan,
• – Cellulose-Derivate, insbesondere -Ether und -Ester,
• – Stärkederivate oder
• – Vinyl-Polymere.

The film-forming polymer dispersion of the binder is based in particular on at least one of the following group members of polymers:

• - polyurethane,
• Cellulose derivatives, in particular ethers and esters,
• - starch derivatives or
• - Vinyl polymers.

Prefers are the vinyl polymers.

When Polyurethanes are called polyether, polyester urethane, PU rubber, PU copolymers (for example polysiloxane-polyethers) or PU prepolymers.

When Cellulose derivatives are called methyl, hydroxyethyl, methylhydroxypropyl cellulose, As starch derivatives may be mentioned rice starch, Potato starch, amylose, amylopectin and mixtures thereof.

The vinyl polymer is preferably a free-radically polymerized polymer of ethylenically unsaturated monomers having 1 or 2 C, C double bonds, in particular vinyl monomers. The following monomers may, for. B. to 60 to 100 wt .-%, preferably 80 to 100 wt .-%, particularly preferably 90 to 99.8 wt .-%, based on the polymer, be contained in the polymer:
The polymer may, for. B. from C ₁ -C ₂₀ alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl aromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, non-aromatic hydrocarbons having at least 2 conjugated double bonds or Be developed mixtures of these monomers. To name a few are z. B. (meth) acrylic acid alkyl ester having a C ₁ -C ₁₀ alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate. In particular, mixtures of (meth) acrylic acid alkyl esters are also suitable. Particularly preferred are (meth) acrylic acid esters and mixtures thereof.

Vinylester of carboxylic acids having 1 to 20 carbon atoms are z. Vinyl laurate, stearate. Vinyl propionate, vinyl versatate and vinyl acetate.

When vinylaromatic compounds include vinyltoluene, methylstyrene, .alpha.-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene. Examples of nitriles are acrylonitrile and methacrylonitrile.

The Vinyl halides are ethylenically substituted with chlorine, fluorine or bromine unsaturated compounds, preferably vinyl chloride and vinylidene chloride.

When non-aromatic hydrocarbons having 2 to 8 C atoms and at least two olefinic double bonds are butadiene, isoprene and chloroprene called.

Other monomers that z. B. from 0 to 40 wt .-%, preferably from 0 to 20 wt .-% and particularly preferably from 0.2 to 10 wt .-% may be contained in the polymer, in particular C ₁ -C ₁₀ hydroxyalky (meth) acrylates, (meth) acrylamide and its on the nitrogen with C ₁ -C ₄ alkyl-substituted derivatives, ethylenically unsaturated carboxylic acids, dicarboxylic acids, their half-esters and anhydrides, eg. B. (meth) acrylic acid, Maleic acid, fumaric acid, maleic anhydride, maleic acid and fumaric acid half esters and itaconic acid. Very particular preference is given to a content of from 0.2 to 5% by weight of an ethylenically unsaturated carboxylic acid.

The Glass transition temperature of the vinyl polymer is preferably below -25 ° C, especially between -25 ° C and -60 ° C, more preferably between -30 ° C and -50 ° C. She settles for usual Methods such as differential thermal analysis or differential scanning Calorimetry (see eg ASTM 3418/82, so-called "midpoint temperature") determine.

The number average molecular weight Mn of the polymer is preferably greater than 10,000, preferably greater than 20,000, more preferably greater than 30,000 and the weight average molecular weight M _w is preferably greater than 25,000 (determined by gel permeation chromatography with polystyrene as standard on a polymer solution in tetrahydrofuran according to Sedimentation of the insoluble constituents).

The Production of the polymer takes place by free-radical polymerization. Suitable polymerization methods, such as substance, solution, Suspension or emulsion polymerization are known to the person skilled in the art. The polymerization can be carried out by subsequent polymer-analogous reactions are modified, for. B. by partially Transesterification or hydrolysis.

Preferably is the copolymer by solution polymerization with subsequent dispersion in water or particularly preferred produced by emulsion polymerization, so that aqueous Copolymer dispersions arise.

The Emulsion polymerization can be batch, with or without use of seed latices, with submission of all or individual ingredients of the reaction mixture, or preferably with partial introduction and subsequent addition the or individual constituents of the Reaktonsgemisches, or after be carried out without dosing the metering process.

The Monomers may be used in the emulsion polymerization as usual in the presence of a water-soluble initiator and a Emulsifier at preferably 30 to 95 ° C are polymerized.

Suitable initiators are, for. As sodium, potassium and ammonium persulfate, tert-butyl hydroperoxides, water-soluble azo compounds or redox initiators such as H ₂ O ₂ / ascorbic acid.

When Emulsifiers serve z. B. alkali salts of long-chain Fatty acids, alkyl sulfates, alkyl sulfonates, alkylated aryl sulfonates or alkylated biphenyl ether sulfonates. Furthermore come as Emulsifiers Reaction products of alkylene oxides, in particular ethylene or propylene oxide with fatty alcohols, acids or phenol, or alkylphenols into consideration.

In the case of aqueous secondary dispersions, the copolymer is first prepared by solution polymerization in an organic solvent and then with the addition of salt formers, for. B. from ammonia to carboxylic acid group-containing copolymer dispersed in water without using an emulsifier or dispersing aid. The organic solvent can be distilled off. The preparation of aqueous secondary dispersions is known in the art and z. B. in the DE-A 37 20 860 described.

to Adjustment of the molecular weight may occur during the polymerization Regulators are used. Suitable z. B. -SH-containing compounds such as mercaptoethanol, mercaptopropanol, thiophenol. thioglycerol, Thioglycolic acid ethyl ester, thioglycolic acid methyl ester and tert-dodecylmercaptan.

The solids content of the polymer dispersions obtained is preferably 40 to 80, particularly preferably 45 to 75 wt .-%. High polymer solids can be z. B. by methods which in the German Patent Application P 43 01 683.1 or the EP 37 923 are set to be set.

The Binder may consist of one or more polymers, in particular out of two. A preferred plastic dispersion consists of combinations of polyvinyl acetates, polyvinyl alcohol and styrene / acrylate copolymers with 1 to 100, in particular 1 to 20 C-atoms in the alkyl group. As a further binder is in particular a cellulose derivative, such as methyl cellulose.

Of the Content of binder (equal to polymer content) is 20 to 90 wt .-%, preferably 20 to 30 wt .-%, based on the inventive Dimensions.

The Polymer dispersion can be as such, especially right after their Production can be readily used as a binder. Depending on Application - especially if the bond strength increases should be - but it may be appropriate be it first to a water-based adhesive, in particular to a dispersion adhesive, a glue or a Make up Kleister and then set as a binder.

Preferably are used as binders water-based adhesives, in particular Dispersion adhesives, glues and pastes. They are based in particular on cellulose ethers, starch and their derivatives, dextrin, Chasuble, glutin, as well as polyvinyl alcohol and polyvinylpyrolidone. The Dispersion adhesives are based in particular on the polymers (poly (meth) acrylates, Polyurethanes and polyvinyl acetates).

Next The polymer dispersions can thus still Supplements included. So can the dispersion adhesive on the basis of vinyl polymers nor wetting or dispersing z. B. for the fillers, thickeners and z. B. even more common additives, such as defoamers and preservatives. Wetting or dispersing agent can z. B. in amounts of 0 to 5 wt .-%, thickener in Amounts from 0 to 10% by weight, preservatives in amounts of 0 up to 1% by weight and defoamer in amounts of 0 to 5% by weight be contained in the aqueous composition. The weights refer to the sum of all components of the aqueous Mass according to the invention, with the exception of water.

The plastic mass is preferably substantially free of organic Solvents and plasticizers such. Butyl acetate, Toluene or phthalic acid ester. It therefore contains essentially no organic compounds with a boiling point below 260 ° C at atmospheric pressure (1 bar) preferably less as 0.5% by weight. The composition may be in addition to Increasing the tackiness of tackifying resins, such as rosin resins and / or esters of tackifying resins up to 20% by weight. The resins and / or rosin esters must be compatible with the one used Be plastic dispersion.

ever by mixing ratio of the binder components and the additives differ the properties of the invention Dimensions. If the proportion of adhesive is very high, so has the mass after setting a flexible consistency on. A high proportion On plastic dispersion leads to a brittle and hard consistency of the set mass.

The Type of binder and its additives varies greatly depending after the intended use and stress of the cured Dimensions. So the stickiness is increased by, for example the amount of resin and / or rosin ester increases. The weather resistance is increased by selecting water-repellent polymers and fillers and / or additives such as chlorinated paraffins.

The Water serves as a dispersion medium in which the rest Components molecularly dispersed, kolliodaldispers or coarsely dispersed are located. The water content should be as low as possible, but it can be up to 60 wt .-% amount. Preferably, it is in Range of 10 to 50, in particular from 20 to 30 wt .-%, based on the total mass of the invention. higher Amounts of water to some extent improve processability, however, extend the curing time. With addition from a lot of water, the mass becomes porous in the hardened state and prone to weathering. As a general rule The amount of water should be set so low that on the one hand a sufficiently good processability is ensured and the required drying / curing time as possible is kept low because less water has to evaporate.

Under a "filler is understood as a substance that is mixed in, but to change the volume and / or the weight also possibly to improve the technical applicability, z. B. the hardness and machinability. Depending on the milling process the fillers have a grain size of 2 μm up to 20 mm. The mean particle diameter of flours is normally in the range of 5 to 800, that of shot and granules can reach 20 mm, when using sieve analysis with test sieves in accordance with Measuring method of mesh is determined: A set of seven different Mesh size is arranged one above the other. The grain size is determined by the mesh size of the sieve which just let the grain pass. The filler can be compact or porous.

By a "light filler" is meant a filler having a specific gravity of less than 1 g / cm ³ , in particular from 0.05 to 0.8 and especially less than 0.5 g / cm ³ .

They may be of inorganic material, for. As aluminum silicate, but preferably they are made of organic polymers, eg. Example of homo- and copolymers of styrene, acrylonitrile, methyl methacrylate (hhA) and vinylidene chloride. Usual lightweight fillers are z. B. hollow spheres of glass or plastic, perlite (glass beads, volcanic rock glass), fibers of cellulose and plastic, powder of plastic and rubber powder. Kon Crete lightweight fillers are commercially available under the names Fillite, Expancel, Scotchlite, Dualite, Sphericel, Zeeospheres, Armospheres, Cenospheres, Polyfill, Mikrosil, Pangel, Pansil, Q-Cel, Poraver (expanded glass granule).

• 1. Sie quellen in Wasser von 20°C weniger als 10 Vol.-%, insbesondere weniger als 2 Vol.-%, bezogen auf ihr Volumen bei 20°C an Luft im Gleichgewichtszustand. Gemessen wird also der Gleichgewichtswert bei 20°C in Wasser und in Luft bei einer relativen Luftfeuchtigkeit von 80%. Die Messmethoden sind beschrieben in DIN 53521.
• 2. Die erfindungsgemäßen Leichtfüllstoffe sind nicht glatt und rund, sondern zerklüftet und unregelmäßig, wie sie durch Zerkleinern von porösen Stoffen durch Mahlen entstehen. Die einzelnen Partikel können deshalb ineinander verhaken.
• 3. Die erfindungsgemäßen Leichtfüllstoffe haben Poren mit einem mittleren Porendurchmesser von weniger als 800 μm. Dieser kann durch REM-Aufnahmen statistisch bestimmt werden.
• 4. Die erfindungsgemäßen partikelartigen Leichtfüllstoffe haben eine breite Korngrößenverteilung, gemessen nach der Siebanalyse nach Mesh, wobei die Korngrößen im Bereich von 2 bis 800 μm nach der Siebanalyse von Mesh (vergleiche ASTM specification E11) liegen.
• 5. Die spanartigen einen Leichtfüllstoffe haben Durchmesser von 2 bis 800 μm und eine Länge von 1 bis 20 mm und die blattartigen Leichtfüllstoffe eine Dicke von 2 bis 800 μm und einen mittleren Durchmesser von 1 mm bis 20 mm aufweisen können.

The lightweight fillers according to the invention are characterized by the following properties:

• 1. They swell in water of 20 ° C less than 10 vol .-%, in particular less than 2 vol .-%, based on their volume at 20 ° C in air in the equilibrium state. Thus, the equilibrium value is measured at 20 ° C in water and in air at a relative humidity of 80%. The measuring methods are described in DIN 53521.
• 2. The lightweight fillers of the invention are not smooth and round, but rugged and irregular, as they arise by crushing porous materials by grinding. The individual particles can therefore get caught in each other.
• 3. The lightweight fillers according to the invention have pores with a mean pore diameter of less than 800 microns. This can be statistically determined by SEM images.
• 4. The particle-like lightweight fillers according to the invention have a broad particle size distribution, measured according to the mesh sieve analysis, the particle sizes being in the range from 2 to 800 μm after the sieve analysis of mesh (compare ASTM specification E11).
• 5. The span-type one lightweight fillers have diameters of 2 to 800 microns and a length of 1 to 20 mm and the sheet-like lightweight fillers may have a thickness of 2 to 800 microns and a mean diameter of 1 mm to 20 mm.

at the span and the sheet-like lightweight filler let the sizes z. B. using a scanning electron microscope determine. Especially with the leaf-like lightweight fillers For example, the average diameter can vary greatly from particle to particle. These sheet-like lightweight fillers z. B. as a small Cork discs may be very irregular be formed, conditioned by the fact that they are very natural porous material by cutting or tearing made contact. That means the leaf-shaped Lightweight fillers by no means a round appearance but also completely irregular may have shaped edges, wherein the middle Diameter within the o. A. Borders lies. The spanish lightweight fillers can z. B. be present as wood or cork chips.

preferred Span-type lightweight fillers have average diameter from 2 to 500 μm, preferably from 5 to 300 μm, completely more preferably 10 to 150 μm. The lengths lie between 1 and 15 mm, preferably 2 to 10 mm, especially preferably 3 to 5 mm.

preferred sheet-like lightweight fillers have thicknesses of 2 to 500 μm, preferably 5 to 300 μm, very particularly preferably 10 to 150 μm. The mean diameters are between 1 and 15 mm, preferably 2 to 10 mm, most preferably 3 to 5 mm.

In addition to the lightweight filler according to the invention, not only other lightweight fillers but also heavy fillers having a specific gravity of more than 1 g / cm ³ may be contained, e.g. As carbonates (especially calcium carbonate), silicates (especially talc, clay, mica), sulfates (especially of barium and calcium), oxides and hydroxides (especially of iron, silicon and aluminum) and carbon black. Organic fillers are possible, for. B. plastics of all kinds.

preferred Fillers are chalk, kaolin, cellulose fibers, iron oxide and microglass hollow spheres. The preferred invention Lightweight filler is cork flour, but also ground foam plastics are useful, for. As polystyrene or polyurethane, also suitable are foam glass, Birns, tubular fibrous materials (Tubular particles analogous to the microglass hollow spheres) or diatomaceous earth (limestone skeletons of diatoms).

Of the Proportion of the marked lightweight filler in the composition of the invention 1 to 30, in particular 8 to 20 wt .-%. Of these, 0 can to 50 wt .-%, in particular 0 to 30 wt .-% by nichtkennzeichnungsgemäße Light fillers are replaced, based on the proportion the lightweight fillers in total. The proportion of heavy Fillers in the composition of the invention is up to 70 wt .-%, in particular 5 to 50 wt .-%.

Depending on the total content of fillers, the density of the composition according to the invention is up to 2.0 g / cm ^3, preferably up to 1.5 g / cm ³ ; With a high proportion of light fillers in relation to the total content of fillers, the density of the composition according to the invention is preferably between 0.1 and 0.9 g / cm ³ .

Under "Additives" means substances that are not essential to the invention, but the composition depending on the Field of application add a desired property, be it to improve the production, the processing or the End properties of the composition of the invention. Such additives may be: colorants, preservatives, Thixotropic agents, thickeners, wetting or dispersing agents, defoamers, Tackifiers, plasticizers, film formers.

One important additive is the colorant. It is about in particular pigments, whether in pure form or as Powder pigments or as aqueous pigment preparations available. As a selection of a variety of possible color pigments are Pigment Black (C.I. 77266), Pigment Blue (C.I. 74160) and preparations called from iron oxide. The content of colorants should preferably Do not exceed 10 wt .-% of the total mixture. In In this area, the consistency is not due to the addition of colorants or not significantly changed.

One another additive is the preservative with the aim of especially to suppress mold growth. It will expediently used when using organic binders, in particular of cellulose and starch derivatives. Its amount can be up to 1 wt .-%, based on the inventive Dimensions. Specific examples are: chloroacetamide, thiazolinone and Isothiazolinone derivatives.

The Wetting and dispersing agents may be used in quantities of up to 5% by weight. be contained, based on the inventive Dimensions. They become predominantly along with the binder brought in. The same applies to the defoamers in an amount up to 5 wt .-% and for the thickener in an amount up to 10% by weight.

In a likewise preferred embodiment of the invention Composition is this conveniently in Essentially free of organic solvents and plasticizers, such as As butyl acetate, toluene or phthalic acid esters. she contains in this case substantially no organic Compounds with a boiling point below 260 ° C at Normal pressure (1 bar), preferably less than 0.5% by weight

The Composition is also as free as possible of polyvinyl chloride. Depending on the field of application but can be up to 20, in particular be contained up to 10 wt .-%.

Also possible is the use of lightweight plastics in the form of PVC powder or microspheres with a shell of mixed polymer z. For example, methyl methacrylate, acrylonitrile, containing vinylidene chloride a propellant z. Isobutane, isopentane.

• – weniger als 0,5 Gew.-% an flüchtigen organischen Verbindungen,
• – weniger als 10, insbesondere weniger als 0,5 Gew.-% an Weichmachern, insbesondere auf der Basis von Phthalsäurederivaten oder Phenolen,
• – weniger als 20, vor allem 10, insbesondere weniger als 5 Gew.-% an Polyvinylchlorid.

The composition of the invention contains in particular

• Less than 0.5% by weight of volatile organic compounds,
• Less than 10, in particular less than 0.5% by weight of plasticizers, in particular those based on phthalic acid derivatives or phenols,
• - Less than 20, especially 10, in particular less than 5 wt .-% of polyvinyl chloride.

you Heavy metal content meets the requirements of EN71 (1994, Safety of Toys.

compositions this species is very well suited for use in objects, with which children come into contact, as in toys or as a building material on children's playgrounds, z. B. for caves or seating.

The inventive composition can in a simple manner be prepared by adding the aqueous polymer dispersion the fillers and optionally further additives with stirring Adds and mixes. But it is also possible, the polymers in the form of a redispersion powder with the other powdery components (ie the components A, C and D) to mix and this dry mix mix with water shortly before use. advantageously, vacuum is used.

The composition according to the invention is usually shaped as follows:
With the hands, with tools such as rollers, spatula and pressing.

After deformation, the mass is usually irreversibly hardened by drying as follows:
Allow to stand under normal ambient conditions or in a paint booth at 70 to 90 ° C or by drying in the microwave.

• – Sie zeigen wegen des kennzeichnungsgemäßen Leichtfüllstoffes einer nur sehr geringen Schwund. Er ist so gering, dass ein erneutes Aufbringen der Spachtelmasse entfällt, was sonst bei einkomponentigen Spachtelmassen nötig ist.
• – Sie können leicht bei Raumtemperatur bearbeitet werden.
• – Bereits nach einer kurzen Antrocknungszeit von 0,5 bis 1,5 Stunden bei 70 bis 90°C im Ofen erhält man 1 bis 2 cm dicke Formteile ohne Risse und Blasen, deren Oberfläche sich sehr gut glätten, schleifen und lackieren lassen.
• – Im abgebundenen Zustand lässt sich die erfindungsgemäße Masse im Prinzip wie Holz bearbeiten, im Unterschied dazu aber wesentlich filigraner, da sie flexibler als Holz ist. Nach dem vollständigen Abbinden kann die erfindungsgemäße Masse sowohl manuell mit Schleifpapier oder Säge als auch maschinell bearbeitet werden, auch mit einer Fräse.
• – Nach dem Abbinden haben die erfindungsgemäßen Massen eine niedrige Dichte von z. B. 0,1 bis 0,9 g/cm³. Sie sind also auf Wasser schwimmfähig.
• – Nach dem vollständigen Abbinden sind die erfindungsgemäßen Massen witterungsbeständig im Außenbereich gegen Frost und Hitze (mitteleuropäisches Klima).

The compositions according to the invention show the following advantages after deformation and hardening:

• - They show because of the characteristic lightweight filler a very low shrinkage. It is so low that it eliminates the need for re-application of filler, which is otherwise necessary with one-component fillers.
• - They can be easily edited at room temperature.
• - Already after a short drying time of 0.5 to 1.5 hours at 70 to 90 ° C in the oven to obtain 1 to 2 cm thick moldings without cracks and bubbles, the surface can be smoothed very well, grind and paint.
• - In the hardened state, the composition of the invention can be treated in principle as wood, but in contrast much filigree, since it is more flexible than wood. After complete setting the composition of the invention can be processed both manually with sandpaper or saw as well as by machine, even with a milling cutter.
• - After setting the compositions of the invention have a low density of z. B. 0.1 to 0.9 g / cm ³ . So you are buoyant on water.
• - After complete setting the compositions of the invention are weather-resistant in the outdoor area against frost and heat (Central European climate).

Especially surprising was the small fading of max. 10, preferably 5 vol .-% measured according to DIN 52451, although the water content in wt .-% equal or even greater is. But it is also surprising that the mass is irreversible cures.

by virtue of These properties are the inventive Mass for use as modeling, as an impression and as Fillers, fillers and sealants or as putty for filling. In all these cases, the informal invention Mass first deformed and then cured by drying irreversible become.

Under "Deforming" is the processing of the unformed or preformed plastic mass by pressure within a temperature range from 10 to 80, especially from 20 to 30 ° C, optionally with wet hands or tools, in the desired To understand form.

The Composition according to the invention can be used as a modeling mass especially by hobbyists and do-it-yourselfers for the production of Items are used indoors or outdoors Find application. Concrete examples and applications are: Construction of Nesting boxes and birdhouses for durability against the weather. Production of floor and wall tiles because of the rugged strength, crafting accessories for Pets or model train.

The Composition according to the invention is also suitable as an impression material (Casting compound, casting material) to be used for reproduction of objects, for the development of models and parts thereof, in particular in the automotive industry and in the construction industry. Because of Their low density and excellent machinability hardened, hardened state is the inventive Mass awarded for making objects in watery and humid environment. As concrete replicas may be mentioned: impression of objects that do not undercuts exhibit. They are made by talculating the object, formed with mass, allowed to dry, with the help of a knife demolded (eg two halves) and, if necessary, the parts bonded.

The Composition according to the invention is also suitable as a Filler, filler, sealant or filler for filling, in particular for the sealing filling of cavities, such as pores, cracks, cracks and joints, as well as to compensate for unevenness of substrates. So she can z. In the automotive industry be used as a body, metal or repair filler and in the construction industry as a wall, facade or wooden spatula. Depending on the application method, the viscosity is different adjust. So should z. For example, when coating the viscosity at 23 ° C to about 350,000 mPas (Brookfield). The Compositions according to the invention are kneadable until viscous masses can also be used as putty, and Although both as an adhesive putty as well as filling putty.

in the Building construction can be the invention Masses are used as fillers and fillers, z. B. in the area of cleaning and crack bridging. Here is the low shrinkage and the good recoatability particularly important. The desired, plaster-like Structure of the surface may vary with different cork flour grains be achieved.

The Invention will now be explained in detail:

embodiment

Examples

I. Starting materials:

• 1. Methylcellulose with the trade name Culminal (BM3)
• 2. Plastic dispersion with the trade name Wormalit based on polyvinyl acetate / polyvinyl alcohol or Roximat of Rhodia based on styrene acrylate (BM1)
• 3. Adhesive based on a styrene-acrylate copolymer (BM2)
• 4. Kaolin with the trade name Kaolin K1 (FS)
• 5. Cellulose fibers with the trade name Arbocell and with a viscosity of 300-500 mPas (2% solution; dynamic at 20 ° C) (FS)
• 6. Cork powder with the trade designation MF5 and with a specific gravity of 0.05 to 0.25 g / cm ³ and with a particle size distribution of 0.2 to 0.6 mm and a swelling of 2% by volume at 20 ° C (LFS).
• 7. microglass hollow spheres with the trade name "Scotchlite Glas Bubbles K25" from the company. 3M with the following characteristics: density of 0.13 to 0.27 g / cm ³ , swelling 0 vol .-%, round shape and smooth surface due to the production Particle size distribution: 25 to 100 μm; (largest diameter 105 μm). (LFS)
• 8. iron oxide with the trade name G2861 from Jäckle (FM)
• 9. Water
• 10. Preservative Acticide MBS (ZS)
• 11. Sticky binder based on a rosin ester and / or a resin (BM4) z. B. resin ester with the trade name Sylvatac RE 12 from Arizona Chem.
• 12. Perlite (LFS) with the trade name Superlitel of knob

II. Production of the Inventive Dimensions

Out The above starting materials were the inventive Made by weight in the proportions by weight given below be mixed at room temperature until they are for the eye appear homogeneous. In detail, the liquid and pasty components (BM1, BM2, BM4 water, ZS) submitted, then the solid ingredients (BM3, LFS, FS, FM) added. Mixed was at room temperature for 15 to 40 minutes in the Z-kneader.

The Recipes are in detail:

Table 1: Frame Example 1: total mixture the crowd

• 20-90% by weight of binder (BM)
• 1-70, in particular 5-20 wt .-% Leichfüllstoff (LFS)
• 0-50% by weight heavy fillers (FS)
• 0-10% by weight of colorant (FM)
• 0-30% by weight of other additives (ZS)
• 0-50% by weight of water

Frame Example 2: Mixture of binder components (BM)

• 20-70% by weight of plastic dispersion (BM1)
• 0-90 wt% adhesive (BM2)
• 0-5 wt% methyl cellulose (BM3)
• 0-15% by weight of rosin ester (BM4)

Formulation example 1 Kaolin (FS) 16.0% by weight Cellulose fibers (FS) 7.0% by weight Methylcellulose (BM3) 1.0% by weight Preservative (ZS) 0.4% by weight Resin ester (BM4) 8.0% by weight Plastic dispersion (BM1) 34.0% by weight Iron oxide (FM) 4.0% by weight Cork flour (LFS) 8.0% by weight Water (ZS) ad 100% by weight Formulation example 2 Kaolin (FS) 20.7% by weight Cellulose fibers (FS) 9.1% by weight Methylcellulose (BM3) 1.6% by weight Cork flour (LFS) 10.5% by weight Preservative (ZS) 0.4% by weight Plastic dispersion (BM1) 46.5% by weight Water (ZS) ad 100% by weight Formulation example 3 Kaolin (FS) 16.5% by weight Cellulose fibers (FS) 7.2% by weight Methylcellulose (BM3) 1.3% by weight Cork flour (LFS) 5.6% by weight Preservative (ZS) 0.4% by weight Plastic dispersion (BM1) 42.0% by weight Resin ester (BM4) 10.0% by weight Adhesive (BM2) 10.5% by weight Water (ZS) ad 100% by weight Formulation example 4 Kaolin (FS) 18.2% by weight Cellulose fibers (FS) 8.0% by weight Methylcellulose (BM3) 1.5% by weight Cork flour (LFS) 8.0% by weight Preservative (ZS) 0.4% by weight Plastic dispersion (BM1) 49.4% by weight Water (ZS) ad 100% by weight Formulation example 5 Kaolin (FS) 16.5% by weight Cellulose fibers (FS) 7.2% by weight Methylcellulose (BM3) 1.3% by weight Cork flour (LFS) 5.6% by weight Preservative (ZS) 0.4% by weight Plastic dispersion (BM1) 34.3% by weight Adhesive (BM2) 34.7% by weight Formulation example 6 Cellulose fibers (FS) 11.7% by weight Cork flour (LFS) 6.2% by weight Adhesive (BM2) 81.7% by weight Preservative (ZS) 0.4% by weight Formulation example 7 Cellulose fibers (FS) 11.7% by weight Cork flour (LFS) 3.8% by weight Microglass hollow spheres (LFS) 2.4% by weight Adhesive (BM2) 81.7% by weight Preservative (ZS) 0.4% by weight Formulation example 8 Kaolin (FS) 21.7% by weight Cellulose fibers (FS) 7.2% by weight Microglass hollow spheres (LFS) 4.3% by weight Cork flour (LFS) 7.2% by weight Resin ester (BM4) 8.4% by weight Plastic dispersion (BM1) 36.4% by weight Preservative (ZS) 0.36% by weight Water (ZS) ad 100% by weight Formulation Example 9 Kaolin (FS) 21.7% by weight Cellulose fibers (FS) 7.2% by weight Perlite (LFS) 4.3% by weight Cork flour (LFS) 7.2% by weight Resin ester (BM4) 8.0% by weight Plastic dispersion (BM1) 39.6% by weight Preservative (ZS) 0.3% by weight Water (ZS) ad 100% by weight Formulation example 10 Kaolin (FS) 28.1% by weight Cellulose fibers (FS) 2.6% by weight Microglass hollow spheres (LFS) 3.9% by weight Cork flour (LFS) 7.2% by weight Resin ester (BM4) 8.2% by weight Plastic dispersion (BM1) 39.4% by weight Preservative (ZS) 0.3% by weight Water (ZS) ad 100% by weight Formulation example 11 Kaolin (FS) 18.4% by weight Perlite (LFS) 1.3% by weight Cellulose fibers (FS) 5.3% by weight Microglass hollow spheres (LFS) 5.3% by weight Cork flour (LFS) 7.3% by weight Resin ester (BM4) 9.0% by weight Plastic dispersion (BM1) 26.5% by weight Preservative (ZS) 0.4% by weight Water (ZS) ad 100% by weight

In this composition, particularly good properties in the form of relatively fast dressing, easy to work with the hands, ie almost does not stick to the hands and any residues can be washed off well, also combines the mass very well with the surface. Bound mass not brittle. Low shrinkage of about 2%. Formulation example 12: Technocel 165 (FS) 7.8% by weight Culminal 500 (BM3) 1.6% by weight Kaolin TEC (FS) 6.5% by weight White oil (ZS) 1.6% by weight Cork flour MF5 (LFS) 6.3% by weight Microspheres K20 (LFS) 7.2% by weight Sylvatac RE12 (rosin ester) 6.3% by weight Acticide MBS (ZS) 0.3% by weight Rhoximat DS910 (BM1) 46.8% by weight water ad 100% by weight

This composition is flexible and compliant after drying and can be used for mending and filling, e.g. B. as a thick paste or for the production of thin plates. Formulation example 13: Technocel 165 8.3% by weight Culminal 500 1.7% by weight Kaolin TEC 6.8% by weight White oil 1.6% by weight Cork flour MF5 6.7% by weight Microspheres K20 7.8% by weight Sylvatac RE12 7.2% by weight Acticide MBS 0.3% by weight Rhoximat DS910 25.7% by weight water ad 100% by weight

This composition can be well modeled with moistened hands and becomes rigid and inflexible after drying, stable and resilient and has a very low shrinkage Formulation example 14: Technocel 165 8.8% by weight Culminal 500 1.1% by weight Kaolin TEC 13.3% by weight White oil 1.1% by weight Cork flour MF5 5.6% by weight Microspheres K20 3.3% by weight Sylvatac RE12 8% by weight Acticide MBS 0.3% by weight Rhoximat DS910 28.7% by weight water ad 100% by weight

Very hard and somewhat brittle version; is well suited for post-processing by milling. Formulation Example 15 Technocel 165 8.2% by weight Culminal 500 1% by weight Kaolin TEC 12.6% by weight White oil 1.1% by weight Cork flour MF5 5.3% by weight Microspheres K20 3.3% by weight Sylvatac RE12 7.6% by weight Acticide MBS 0.3% by weight Rhoximat DS910 21.6% by weight Ovalite S (BM2) 15.2% by weight water ad 100% by weight

This mass can be formed well. Surface dry and workable after a few hours Formulation example 16: Technocel 165 7.1% by weight Culminal 500 1.4% by weight Kaolin TEC 14% by weight White oil 1.2% by weight Cork flour MF5 7% by weight Microspheres K20 3.5% by weight Sylvatac RE12 7.8% by weight Acticide MBS 0.3% by weight Rhoximat DS910 11.6% by weight D3 Wormalite 25.3% by weight water ad 100% by weight

These Mass is very easy to process and shows after curing good mechanical properties.

III. Properties of the invention Masses and articles made therefrom:

• 1. Specific weight: The specific one Weight of the starting materials and the cured molding compounds is with a metal pygnometer type 290 / l according to DIN 53217 at 20 ° C determined.
• 2. The hardness / consistency was according to DIN 51579 at 25 ° C. determined as follows: Measurement with needle penetrometer at a constant force of 100 g, determination of the penetration depth.
• 3. The shrinkage was determined according to DIN 52451, wherein a defined amount of the composition of the invention applied to a support plate made of aluminum and the Buoyancy in iso-octane was determined. Then the samples became 7 Days dried at 70 ° C and weighed again and then the buoyancy determined. Overall, the following weighings carried out: a) carrier plate in air, b) Carrier plate in iso-octane, c) carrier plate with adhesive according to the invention in air, d) Support plate with adhesive according to the invention in iso-octane, e) Carrier plate with adhesive in air after drying and f) carrier plate with adhesive in Iso-octane after drying. From these data results the Mass loss and over the buoyancy and the loss after Drying of the composition of the invention.
• 4. The composition of the invention was with the Hand deformed and cured by drying in air at room temperature.

IV. Results.

• – Das spezifische Gewicht nimmt mit dem Zusatz der leichten Stoffe erwartungsgemäß ab, und zwar auf unter 1 g/m³.
• – Die erfindungsgemäßen Massen härten schwundarm und irreversibel aus, und zwar mit einem Schwund von weniger als 10 Vol.-%.
• – Die erfindungsgemäßen Massen schwimmen länger als 4 Wochen im Wasser bei Zimmertemperatur, ohne Schäden aufzuweisen.

The examples show:

• - The specific weight decreases with the addition of light substances as expected, to less than 1 g / m ³ .
• - The compositions of the invention cure shrinkage poor and irreversible, with a shrinkage of less than 10 vol .-%.
• - The compositions of the invention swim for longer than 4 weeks in water at room temperature, without showing any damage.

V. Comparative Example

A comparative composition was prepared which, as known from the prior art, contains only hollow microballoons. The composition was prepared as described above from: Microglass hollow spheres (LFS) 36.8% by weight Resin ester (BM4) 8.9% by weight Plastic dispersion (BM1) 38.3% by weight Water (ZS) ad 100% by weight

The Although mass dries quickly and has little loss, leaves However, they do not work well as they are on the hands sticks and forms no bond with the substrate.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 29720344 U1 [0003]
• DE 10201946 A1 [0004]
• WO 91/14736 [0005]
• - DE 4008980 [0005]
• - EP 0792926 A2 [0006]
• - DE 3720860 A [0033]
• - DE 4301683 [0035]
• - EP 37923 [0035]

Claims (10)

Hardenable, plastically deformable mass with a penetration depth of 8-35 mm, measured with the needle penetrometer according to DIN 51579 at 25 ° C. for modeling, molding or filling, containing A. 20 to 90% by weight of at least one binder, B. From 10 to 60% by weight of water, C. at least one filler and D. from 0.5 to 40% by weight of at least one additive, characterized in that the filler comprises at least one light filler having a density of less than 1.0 g / cm ³ at 20 ° C, which is either particulate, span- or sheet-like or as a mixture and a) has pores with a mean pore diameter of less than 800 microns b) in water of 20 ° C less than 10 vol. -% swells, based on the volume at 20 ° C in air in the equilibrium state, c) has a non-smooth fissured surface, as it results from the comminution of porous materials by grinding, the particulate light fillers grain sizes in the range of 2 to 800 microns nac h mesh sieve analysis (see ASTM specification E11), the span-type has a diameter of 2 to 800 μm and a length of 1 to 20 mm, and the sheet-like lightweight fillers have a thickness of 2 to 800 μm and a mean diameter of 1 mm to 20 mm may have. Mass according to claim 1, characterized in that the lightweight filler pores with a mean pore diameter of less than 200 microns, especially less than 50 microns having. A composition according to claim 1 or 2, characterized in that the light filler has a density of less than 0.5 g / cm ³ . Composition according to one of the preceding claims, characterized in that the light filler cork flour, Cork meal and / or cork granules is. Composition according to one of the preceding claims, characterized in that the filler is selected is from a group comprising hollow glass microspheres, cellulose fibers, Lightweight plastics, perlite and kaolin or a mixture of two or more of them. Composition according to one of the preceding claims, characterized in that the binder is on a film-forming Polymer dispersion based, in particular, at least one of contains the following group members of polymers: polyurethane, Cellulose derivatives, starch derivatives or vinyl polymers. A composition according to any one of claims 1 to 6, characterized in that the binder is a water-based Adhesive is, in particular a dispersion adhesive, a glue or a paste. Composition according to one of the preceding claims, characterized in that it contains 1 to 30% by weight of the label Light fillers and 0 to 50 wt .-% of heavy fillers contains. Mass according to claim 1, characterized in that it contains 0 to 10 wt .-% of colorants. Mass according to claim 1, characterized in that she Less than 0.5% by weight of volatile organic compounds, Less than 10% by weight on plasticizers, in particular derivatives of phthalic acid or of the phenol - Less than 20 wt .-% of polyvinyl chloride contains and / or - a content of heavy metals, complies with the requirements of EN 71 (1994, Safety of Toys).