COMPOSITIONS FOR PREPARING SLIP-RESISTANT SURFACES

专利摘要:
The invention relates to a composition for producing slip-resistant surfaces, which comprises a) animal protein, b) vegetable polymers, c) base selected from alkali metal and alkaline earth metal hydroxides, hydrogencarbonates and carbonates and d) polymer latex; and slip resistant coatings on backings and non-slip surface articles each made using the composition.
公开号:AT511047A1
申请号:T782011
申请日:2011-01-19
公开日:2012-08-15
发明作者:
申请人:Austria Wirtschaftsservice Gmbh；Kiss Johann；
IPC主号:

专利说明:

The invention relates to compositions for the production of slip-resistant surfaces, preferably compositions of natural raw material components.
STATE OF THE ART
A variety of different, sometimes highly effective coating and binder systems are used with the aim of improving the anti-slip effect of surfaces and corresponding product mixtures. This is done either by subsequent surface finishing of existing materials or by production of material mixtures and combinations with anti-slip effect. The largest share here modern synthetic products, for example based on polyurethane, vinyl, acrylic and synthetic rubber, such. SBR, NBR etc., as well as combinations with other synthetic products. Although natural rubber systems still cover a number of areas, their significance has been replaced by modern synthetic materials or displaced and replaced for economic or / and qualitative reasons.
For anti-slip surface finish, liquid coating and binder systems are used with known manufacturing technologies, e.g. Coating, spraying, dipping, printing, painting, transfer coating, etc., applied to the surfaces to ensure the desired properties and effects. Modern "hotmelt" systems have also gained in importance, in which modified plastics are plasticized and a "molten film film" is produced via an extrusion process. solvent-free applied to the surfaces (glued on, so to speak) is. The thermal load capacity of the coated products is not always up to the requirements of the practice (for example, due to changes in the properties in the climate change and transition to stickiness up to the melting at high temperatures).
The classic and the most widely used standard product for non-slip mats or fabrics on the market is still rubber, more precisely rubber granulate products, which are preferably made of rubber waste or used tires for cost reasons. There are also other plastic granules, such as -1 - e.g. Polyurethane waste, which is rebonded in granulated form. Another important and highly expansive product group are synthetic foams, which sometimes outperform rubber and are used specifically where high frictional resistance at the interfaces is required or where discoloration must be avoided. Another group are combination products in which different material carriers are finished with non-slip surfaces. Examples include coated paper or film, coated cardboard and cardboard / PU foam laminate and coated textiles.
However, the vast majority of existing anti-slip products are disposable and are not subject to a compulsory recycling system, which makes biocontrol uncontrolled disposal and the associated global distribution problematic. Especially rubber and polyurethanes are problematic. After vulcanization with sulfur and in conjunction with the usual additives, rubber is difficult to biodegrade and is often not degradable at all. This also applies to the large group of polyurethanes. Thermal recycling and disposal of these products is therefore complicated and expensive and sometimes, at least with simple methods and systems, no longer possible.
Especially in the field of cargo securing for transport by land, water and air, non-slip finished natural products such as paper, cardboard, cork, wood, etc. barely meet the legally regulated minimum requirements for slip-resistant documents. There are products that have not sufficiently coped with the thermal requirements of the cargo, the climate change effects and the effects of moisture and water, which limits their use accordingly. Especially natural latex systems are preferably used only where lower mechanical loads and shear forces are present, e.g. as intermediate layers for the stabilization of packaging units.
Another disadvantage of polymer latex systems, including natural latex, is their moderate to poor compatibility with certain additives, in particular the "-2"
Combination with certain electrolytes, e.g. Bases that can cause breaking of the emulsions, so that processability of latexes is possible only under special conditions and often not economical.
Against this background, the object of the invention was the development of a composition for the production of slip-resistant surfaces, with which the problems mentioned in connection with workability, degradability and recyclability can be largely solved, which can be produced economically and which with regard to a use for securing cargo meets or exceeds the applicable legal requirements.
DISCLOSURE OF THE INVENTION
This object is achieved in a first aspect of the present invention by providing a composition for producing slip-resistant surfaces which comprises: a) animal protein, b) vegetable polymers, c) base selected from alkali metal and alkaline earth metal hydroxides, bicarbonates and carbonates, d) polymer latex.
In the course of extensive studies and experiments, the inventor has found that by the interaction of these four components, surfaces can be produced which have excellent anti-slip properties by providing a surface-active, i. Friction energy receiving, the respective requirements of flexible and with any carrier material (when used as a coating) firmly connected contact surface is provided. Significantly better adhesion properties are achieved with different Reibpartnem. The surfaces obtainable using the composition according to the invention are resistant to temperature fluctuations, moisture and moisture and to shearing effects. In addition, such composition is predominantly and sometimes even exclusively natural products, which is significantly improved by the degradability and environmental compatibility of the composition compared to the prior art.
The composition can either be applied as a coating to a carrier or used as a molding composition or binder and made into a three-dimensional object, wherein in all cases more or less large proportions of other optional components can be taken into account. These are not particularly limited and include, for example, pigments, dyes, plasticizers, flow or thickeners, mixing aids and fillers. These also include blowing agents to deliberately and selectively foam the composition, if a foamed slip-resistant surface or a viscoelastic foamed component is to be obtained. The skilled artisan will be able without excessive effort to determine the appropriate for the particular application additives for each system, with particular attention should be paid to the natural origin of these additives. However, the properties of the composition as a whole are significantly determined by the selection of the most suitable for the particular application components a) to d) and their mixing ratio in the composition according to the invention, which is why below in particular these basic components will be discussed.
Component a) - Animal protein
Without wishing to be bound by any particular theory, it is believed from the results obtained that of the four components of the composition of the invention, the animal protein is responsible for the internal cohesion of the components of the composition due to the following functions. By appropriate and appropriate selection of the animal protein, the compatibility with other auxiliaries or additives, such. Fillers, manufactured or improved. The following statements apply in part also to vegetable proteins described in more detail later: Proteins, especially animal proteins, have after the reaction, i. inter alia cross-linking, with other components of the combination according to the invention
Setting a strong dispersing or emulsifying effect, which makes it possible to include certain, previously considered incompatible components together in a stable composition. - Proteins have hydrophilic and hydrophobic functional groups that support and enhance the adhesion to different contact surfaces and friction partners in the targeted application in a slip-resistant system. Proteins, especially animal proteins, form in the composition according to the invention a natural adhesive system which supports and enhances anchoring and bonding to other contact surfaces in coating and binder systems. Natural proteins, especially animal proteins, after curing and cross-linking, increase the internal strength of coating and binder systems, which are enhanced by the particular reactants selected, i. the remaining components of the composition according to the invention, can be increased or even reduced.
The animal protein is not particularly limited, and milk proteins may be used as well as other natural protein sources or waste products containing animal protein components, e.g. Kotlagen or gelatin. Animal proteins are of 100% natural origin and are therefore fully biodegradable and, moreover, relatively inexpensive. In preferred embodiments of the composition according to the invention, animal proteins are milk proteins, more preferably milk, skimmed milk and / or one or more milk products, in particular cow's milk or products thereof, e.g. Quark, cheese or yoghurt, or also optionally defatted milk powder and whey proteins. Their composition is not subject to such strong fluctuations as those of other natural sources of protein, since casein proteins constitute as major constituents about 80% of the protein content in milk. The impurities contained in the original and naturally occurring milk protein source, e.g. Sugar and fat are not interfering with the composition of the present invention and assist / improve the compatibility of the components with each other as well as those with additional optional components, e.g. Fillers. Although fats in the alkaline formulation saponify and support the system favorably, the concentration and the amount of fat must be taken into account in view of the best possible frictional resistance of a non-slip surface and also in connection with a water-resistant formulation.
Other animal proteins than milk proteins and skin glue were tested in simple parallel experiments on their suitability and effectiveness for the production of anti-slip coating and binder compositions and compared. It was confirmed that although the reactions and results of the animal proteins are basically comparable, each protein source has its own individual product characteristics due to its composition, which must be taken into account and, if necessary, can also be used selectively.
Animal proteins usually lead to hard, stable and solid compounds with the appropriate reaction partners, whereby it must be taken into account that the protein concentration in a protein-containing starting product may vary and must be taken into account accordingly in the formulation. Individual, preferred representatives of this group and their specific effects on the properties of the compositions according to the invention will be discussed in more detail later. By contrast, plant proteins differ significantly in their properties and are described below.
Component b) - Vegetable polymers
Among the vegetable polymers, which are not exclusively understood here, but especially vegetable proteins and polysaccharides and the latter especially starch and cellulose, is due to their characteristic properties {again: without wishing to be limited to a particular theory), that they predominantly support the adhesive and adhesion promoting functions of the coating and binder systems of the invention and stabilize and enhance the internal strength of the targeted systems. In addition, they can improve viscoelastic properties of a highly elastic system and thus contribute to the control of the coatings or articles obtained from the composition.
The properties of vegetable proteins as natural polymers vary relatively widely. Apart from the already very different protein qualities in the plant natural substances, which each have different property profiles, the concentrations of the proteins and the accompanying substances such as starch, fat, sugar, pulp, etc. differ. However, compared to animal proteins, it can be concluded that lead to more flexible and elastic products and the reaction with alkaline reaction components significantly more effective and efficient " Adhesive Systems " allows. The wettability and anchoring on different materials is much more promoted by plant proteins than by animal protein systems.
The concomitants of plant proteins, which is rather disturbing in pure adhesive systems due to undesirable properties there, are deliberately used in the composition according to the invention and used as further important functional components. Thus, for example, the starch content of the vegetable polymers unfolds its optimum effect when it is disrupted in a cooking process and reacts in the decomposed state with the alkaline reaction components and cures crosslinked. The reaction product of such vegetable polymers is a hard, very stable product in which very good water resistance is combined with a high degree of crosslinking.
In the present invention, vegetable proteins are an important ingredient to enhance the binding and adhesive power to a carrier medium or to any fillers, to improve the adhesive surface properties, to increase the internal strength without unduly reducing the elasticity of the viscoelastic system, as well as to optimize the cross-linking and water resistance of the latex system. ·· I »♦ · · I» * * * »··· · Μ • · · * * · ** 4 9 · · #» ·
Divided into main groups, the following vegetable protein sources are particularly suitable. - cereal products containing gluten (gluten), e.g. Barley, wheat - high protein content plant and vegetable fruits, e.g. Soya - Protein waste products from the production of starch, oil or alcohol - Protein-containing products which are not digested and crosslinked during the second stage of the anti-slip finishing or binding of a vegetable material, as described in more detail below, e.g. Grasses, bark granules, vegetable fibers
The selection of the vegetable polymers is determined by the composition of the respective source, where specific property profiles are used and used depending on the protein content and concentration of the accompanying substances.
Vegetable protein sources containing gluten include the preferred form of vegetable protein sources in accordance with the present invention. Glues in particular assist and improve the adhesion and adhesion of latex-based compositions, maintain elasticity through their flexibility while increasing the internal strength of elastic blends.
Other preferred vegetable protein sources, in addition to their emulsifying, wetting, and more or less strongly adhesive and elastic action, contain water-binding pentosans or slime-forming hemicelluloses, i. Substances that provide sufficient surface wettability in wet or wet conditions in highly crosslinked (water resistant) mixtures and avoid water repellency (" Silicone Effect ", see below).
Of the plant polysaccharides, above all the starch component on thermal digestion forms a more or less strong " starch paste " which has different strength and toughness depending on the origin of the starch and promotes the wettability and adhesion of a coating system of the invention. In the presence of digested proteinaceous substances -8- ············································································································ starch components can be uniformly crosslinked with alkaline earth metal hydroxides and with CO2 to water resistant very stable and solid products "carbonates".
Specific herbal polymers and their effects on the properties of the compositions of the invention will be described in more detail later. Generally, however, the vegetable polymers are not particularly limited. Preferably, more or less finely minced or ground plants or plant constituents are used as the source of the vegetable polymers, e.g. Plant meal or meal, natural fibers, cotton, sawdust, pulp, etc., as these are readily available and inexpensive. In the composition according to the invention, the source of the vegetable polymers is particularly preferably cereal flour, more preferably wheat flour or rice flour, in particular wheat flour, since, when readily available, it contains relatively high levels of vegetable polymers, i. 70% starch, about 12% protein, about 2% fat, rice: about 75% starch, about 7.5% protein, about 5% protein and starch components, with a relatively low fat content. 2% fat, oats: about 63% starch, about 12% protein, about 7% fat).
Component c) - Base
The reaction components selected from alkali metal and alkaline earth metal hydroxides, bicarbonates and carbonates, including, for the purposes of the present invention, also, in accordance with the accepted definition of " alkalis " ammonia and its carbonate and bicarbonate, e.g. in the form of deer horn salt, are used ostensibly for the digestion and conversion of the natural substances contained to corresponding reaction products. In addition, strong cross-linking effects and the " carbonation " the composition, which has a protective function against external influences, such. Wetness and heat, causes. In addition, the base provides an alkaline pH of the composition as a whole and thus the best possible wettability of various materials to be coated therewith as well as resistance to mold and other undesirable (because premature) rotting influences. At the same time, it is certain that it is safe to take care of it. -9- ····················································································. ··
provided by the in an acidic environment, such as. in the soil or soil, neutralization takes place so that the natural components of the composition can be microbiologically digested, allowing a slow natural rotting of the coatings or articles made from the composition of the invention after their disposal. In addition, light metals react with alkaline systems, so that the composition according to the invention can be used for slip-resistant finishing of light metal surfaces or at the same time as a binder or adhesive for further combinations with light metals. It should also be noted again that alkaline systems saponify fats and thus neutralize fat deposits in the formulation as well as traces of grease or slight grease contamination on coating surfaces, which represents a significant advantage for a coating system and forms the prerequisite for effectively using natural by-products can.
For reasons of cost, availability and toxicity, the base preferably used in the composition according to the invention is Ca (OH) 2, NaOH or KOH or a mixture thereof, more preferably Ca (OH) 2 in the form of lime, particularly preferably a mixture of lime and at least one alkali metal hydroxide, in particular a mixture of lime and NaOH. When using such a mixture, the alkali metal hydroxide (or at least one of them, if any), which is preferably NaOH for reasons of cost, should be premixed with the animal and vegetable components and optionally heated to cause at least partial digestion of these components before release Polymer latex and then the slaked lime is added, as explained in more detail below. If the base comprises a carbonate or bicarbonate, by means of which the water resistance can be increased, this is preferably also added only in the last mixing step in order to prevent any foaming of the mixture, if this is not explicitly desired.
Polymer latices sometimes react violently and incompatible with strong bases, and these can lead to breakage of the dispersion or emulsion. This effect -10- ······················································································. φφφ φ φ φ i φΦ Μ can be inhibited or prevented by the components a) and b), in particular when a mixture of lime lime and at least one alkali metal hydroxide such as NaOH is used as base, of which NaOH as digestion and reaction component with the components a) and b) is premixed before the polymer latex and - at the same time or only then - the lime lime are added. Under lime, herein is a slurry, i. Suspension, of Ca (OH) 2 in water. The use of lime lime has over the advantage of slaked lime the advantage that limestone lime no longer contains undelayed lime content, which could have a negative effect when mixing the components of the composition according to the invention. Therefore, it is particularly preferred to use a lime that has been left to rest for at least three months (i.e., react with water) to fully convert the calptum oxide to Ca (OH> 2.
By choosing the base components and their proportions in the composition according to the invention, both the extent of digestion of the animal and vegetable constituents and the degree of crosslinking of the polymers contained can be controlled. For example, larger amounts of NaOH preheated with components a) and b) before latex and slaked lime are added cause the properties of the animal proteins and the vegetable polymers to be more pronounced. On the other hand, the degree of crosslinking and thus the stability and stiffness as well as the swelling capacity and thus the water resistance of the cured composition can be controlled specifically based on the amount of Ca (OH) 2, as will be explained in more detail in the later examples.
Component d) - Polymeriatex
In principle, all available aqueous dispersions or emulsions of polymers, in particular elastomers and in particular rubbers, are suitable as polymer latex of component d). Since the polymer dispersed in the latex significantly affects the properties of slip-resistant surfaces and articles made from the composition of the present invention, and relatively soft, elastic surfaces are generally preferred as anti-slip surfaces, rubber latices such as e.g. of natural rubber (NR), styrene-butadiene chewing -11 - • »» • · · »· · •» * # 4 · # ** · • · t ························································ * * * · · Sch sch SB SB SB (SBR), isoprene rubber (IR), polybutadiene (BR), acrylonitrile butadiene rubber (NBR), ethylene Propylene (diene) rubber (EPM or EPDM), etc., according to the present invention preferably to further additives, such as Softener to avoid, whereby by the choice of the latex the characteristics of the slip-resistant surface in turn can be varied. Because of its natural origin, its degradability, and the softness and rubber or viscoelasticity of the polyisoprene dispersed therein, and the good adhesion to other surfaces obtainable thereby, natural latex is particularly preferably included as a polymer latex in the composition of the invention.
Although this is not known as such without crosslinking component moisture, water and heat resistant, has a much too high elasticity on surface coatings, is not easy to process by rapid, often uncontrolled film formation or foaming, responds strongly to environmental influences and anchored despite excellent Wettability only very weak on other materials and materials. However, these disadvantages over other polymer latices of interest can be compensated for by the appropriate choice of other formulation components.
Thus, a composition according to the invention for the production of slip-resistant surfaces in preferred embodiments comprises exclusively natural and naturally biodegradable components, which are also inexpensive and also readily recyclable. As stated above several times, the properties such as e.g. Flexibility, softness, elasticity, adhesion and swelling power, the cured composition by the appropriate choice of the type and amounts of all components a) to d) in relatively wide ranges adjustable.
With regard to the amounts of the components, the composition of the invention comprises in preferred embodiments: a) 1 to 25% by weight of animal protein (calculated as pure protein content), -12- (b) 1 to 40% by weight of vegetable polymers (cf. c) from 0.5 to 50% by weight of base (where the lower limit refers to a solid powder and the upper limit to aqueous silty lime); d) the lower limit refers to the one polymer portion and the upper limit to the amount of a vegetable polymer source; ) 5 to 75 wt .-% polymer latex (calculated as dispersion with 50% solids), which together give 100%.
As the examples below show, within these preferred limits, the properties of the coatings or articles obtained from the compositions of the present invention are highly variable and thus adaptable to the particular requirements of the slip-resistant product. However, this variability is also absolutely necessary in view of the practical suitability of the slip-resistant products produced from the composition according to the invention. For example, the best anti-slip coating can not work if it is not matched to the wearer.
The anti-slip coating only has the task of ensuring the best possible contact surface and adhesion to the friction partner. However, the released energies which occur during a movement of the friction partner, however, must be absorbed via the contact surface and transferred to the carrier material itself. It is advantageous if the non-slip surface is designed to be elastic, to ensure the wetting and the compensation of unevenness of the different friction partners. At the same time, however, care must be taken to ensure that the contact surfaces do not build up too high adhesive forces in order to avoid undesired sticking, but at the same time they do not become too stiff and inelastic in order to prevent slipping on the contact surface. With soft, flexible surface finishes, in turn, the slip-resistant effect occurs even at low contact pressure and does not require, as with harder surfaces, a minimum pressure to build up the necessary adhesion. However, soft-elastic coatings rapidly reach the limits of their mechanical load capacity at high shear forces and become ineffective or delaminate due to destruction, and in the worst case even come off the carrier material. On the other hand, foams or foamed surfaces have the advantage of a soft-flexible as well as the largest possible active surface, however, a sufficiently high internal strength of the cell structures must be ensured in order to withstand even stronger forces without undue damage and to absorb and distribute the forces acting on them. It is therefore crucial that a surface-active, the requirements of flexible and firmly anchored to the substrate contact surface is ensured.
The anti-slip effect of coatings is therefore the stronger, the better the carrier material can absorb and distribute the internal friction and thus the energy. For this purpose, flexible carriers require a sufficiently high internal strength in order to ensure their own dimensional stability even at high energy input. Highly elastic products with low internal friction tend to overstretch under tensile load and rapidly form a roller that suddenly leads to failure of the product. Viscoelastic products have proven to be the best and most effective media for this purpose. However, inflexible, rigid carriers require significantly more effective slip resistant coatings to enhance adhesion, or must be capable of uniformly transferring and distributing the energies into and out of the rigid carrier over a sufficient amount of the coating (or through elastic surface assemblies).
In addition, a slip-resistant surface should indeed be water resistant, but not water repellent, otherwise formed between the surface and the friction partner, a water-lubricating film, which favors the slipping, which in the art "silicone effect". is called.
However, embodiments of the composition according to the invention, besides imparting anti-slip properties, are also quite suitable for imparting water-resistance and, if desired, also water-repellent properties to coated surfaces or objects made therefrom. For this purpose, it is necessary to reduce the cross-linking and carbonation
tion, in particular with Ca (OH) 2, which further reduces the elasticity and the anti-slip effect, but at the same time increasingly increases the mechanical strength and the water-resistant effect. From a Ca (OH) 2 content of about 15% by weight, effective over hours, and even from about 20% by weight, a permanent water resistance is achieved.
Such formulation and quality optimisations of the equipment of paper and paper products have proven to be particularly advantageous, where the pulp and the starch components are dissolved in the paper and co-crosslinked in the curing process, whereby - in addition to a higher stability stabilization - the resistance to water, moisture and also be optimized against the rapid onset of rotting of paper. For paper packaging products, where the slip resistance due to other disability during handling must not be too high, as good protection against moisture and moisture but of course still desirable, can be with inventive slip-resistant coating and binder compositions in a relatively simple way, improvements and solutions to this problem achieve.
Even strongly cross-linked products retain their biological properties, depending on the circumstances, sometimes extending the time required for the biodegradation processes.
The present invention, because of the wide range of settable properties of the cured compositions, will enable one skilled in the art to develop the most suitable anti-slip coating for any support material without undue experimentation, following the teachings disclosed herein of the various (preferred) embodiments of the invention.
In a second aspect, the invention relates to a method for producing a composition according to the first aspect, as described above, by mixing the components a) to d), wherein in a first mixing step, first the -15-
Components a) and b) are mixed with at least part of component c) before component d) is added in a second mixing step. The optionally present remainder of component c) is blended either simultaneously with component d) in the second mixing step or only then in a third mixing step. When mixing the components a) to c) in the first mixing step, component a) is preferably first mixed with component c) (or a part thereof) and then component b) is mixed in first.
As already mentioned, this sequence of mixing the components effectively prevents incompatibilities between the individual components, in particular between the polymer latex and the base component or parts thereof.
When mixing some or all of the base component c), e.g. of NaOH, with the animal and vegetable components a) and b), these are partly digested and pre-crosslinked, whereby they can subsequently effectively prevent components of the polymer latex from settling in the subsequent third mixing step from the remainder of the mixture. Characterized in that in the first mixing step, first component a) with component c) or a part thereof is mixed before component b) is added, causing the coagulation / flocculation of the proteins is avoided in the course of thermal digestion of the starch components under the influence of temperature.
Especially when component c) both Ca (OH) 2 and at least one alkali metal hydroxide, such. NaOH, it is advantageous to mix the at least one alkali metal hydroxide in the first mixing step with the components a) and b) and to mix the Ca (OH) 2 only in the second or, even better, only in the third mixing step in order to avoid unwanted reactions between Ca (OH) 2 and the latex to prevent. If the base component c) comprises hydrogencarbonates or carbonates of alkaline earth metals or alkali metals, of which alkali metal bicarbonates are preferred, they are preferably also mixed in the second or third mixing step in order, as mentioned, to prevent foaming of the mixture, if this is not intentionally desired becomes. For water-resistant slip-resistant surfaces, the addition of (additional) Ca (OH) 2 or carbonates is regularly carried out in the last mixing step, whereby lump-free dispersion with suitable agitators should be ensured.
The at least partial digestion and the precrosslinking of components a) and b) by the base can be significantly enhanced by heating the mixture of components a), b) and at least part of c) to boiling temperature between the first and the second mixing step after which the third mixing step, ie mixing the latex is followed, optionally followed by a fourth mixing step, i. the incorporation of Ca (OH) 2 or carbonates. This also causes a significantly prolonged shelf life of the composition according to the invention, which remains stable for months, while a blended without the intermediate step of heating composition rapidly, i. preferably within 1 to 2 days, otherwise phase separation phenomena may occur which force further stabilization measures and additional input of matter.
If there is no intentional heating of the mixture between the first and the second mixing step, the latex is added as component d) directly into the mixture of components a), b) and c) and then optionally the remainder of component c), The composition thus obtained should be heated to boiling temperature or higher upon subsequent manufacture of a non-slip surface on a non-slip surface or article to complete the digestion and crosslinking and solidify the composition into a solid, dry film or article ,
However, if the mixture is already fully digested, precrosslinked and composed of all desired components and formulation components, it is possible to dry the composition as a coating composition or binder at room temperature (ie from 20 ° C) up to high temperatures of 200 ° C and harden. This wide temperature range allows the existing equipment to be used effectively even without further technical equipment and without unwieldy technology. Thus, such a coating and binder composition is especially suitable for use also in temperature-sensitive materials, e.g. EPS or XPS, slip-resistant. The temperature should preferably not exceed 70 ° C, more preferably not more than 65 ° C for EPS and XPS foams in the presence of ambient or contact heat so as not to cause undesirable decomposition or unwanted shrinking processes. For other carrier materials or composition components, the thermal drying and curing process may be adapted to their respective properties, with temperatures preferably not exceeding 200 ° C, more preferably not exceeding 160 ° C being selected to avoid premature and undesirable thermal degradation or degradation Decomposition of any of the components.
In a third aspect, the present invention thus relates to the use of a composition according to the first aspect as a coating composition for the production of slip-resistant surfaces on carriers or as a molding composition for the production of objects with anti-slip surface or as a binder for the production of articles with anti-slip surface.
The first case refers to a composition which can be applied to a support, e.g. Paper, cardboard, metal (especially light metal), wood or plastic, applied and cured to provide this carrier slip resistant, the nature of the application is not particularly limited. Thus, for example, conventional methods of knife, spray, dip, print, brush or transfer coating may be used, as long as the particular viscosity of the composition of the invention permits.
The other two cases relate to the production of three-dimensional bodies from the composition according to the invention, e.g. by molding, only varying the extent to which other components are added. When used as a molding composition, the body thus formed consists mainly or even substantially of the composition of the present invention, although of course conventional additives such as dyes, plasticizers, thickeners, blends, etc. may be included to a relatively small extent. When used as a binder, the composition according to the invention contains further agents, e.g. Fillers added to a greater extent. It will be understood, however, that the transition between use as a molding compound and that as a binder is fluid. Cork granules, recycled or newly manufactured polystyrene in the form of EPS (expanded polystyrene, eg Styrofoam®) and prepared polyurethane foams may be mentioned herein as special fillers, which may be incorporated in a composition according to the invention as a binder and optionally after a preliminary and coarse comminution lightweight and slip-resistant product can be cured.
When using the natural product cork, which is one of the most preferred embodiments of the present invention, the viscoelastic properties of the binder are to be matched to the natural filler to ensure a durable use (e.g., in multiple applications) of a non-slip surface thereof. The mixture of binder according to the invention and cork granules can both be thermally digested and pre-crosslinked as well as prepared without this pretreatment by simply mixing together in the described and shown order. In pre-crosslinked approaches, a thermal processing process, as mentioned above, is not mandatory. For economic and capacity reasons in a continuous production, the thermal support for rapid curing and drying can be freely designed and adapted to the conditions. Non-precrosslinked and digested approaches should be subjected to a thermal process above 100 ° C during the manufacturing process, in order to ensure the unfinished reactions of the individual substances and the development of important constituents during the molding process. This open system offers the advantage of being transferable into existing thermal processing processes - without further additional steps - and of using very economical binder systems with the corresponding properties with the least possible effort. It should again be noted that undigested and non-crosslinked approaches only have limited shelf life and stability and should be processed promptly, preferably within a few days.
The mixing ratio between cork granulate and binder is determined by who factors: 1. Granule size: The smaller the granule size, the more binding agent is required. 2. Degree of compaction: The higher the compaction in the end product, the lower the binder requirement. 3. Effect: The higher the binder concentration, the stronger the slip-resistant effect on the surfaces and the higher the internal strength can be achieved. 4. Material thickness and size of the final product: The thicker and larger the final product, the lower the binder requirement, since the acting forces are distributed over larger areas and volumes.
As will be described in more detail in the later examples, 70% by weight of cork granules having a particle size of 2-3 mm can be mixed with 30% by weight of binder to produce a 3 mm thick, non-slip and permanently stable cork granulate plate. The resulting mixture is compacted, for example, in a platen tool to remove most of the water, e.g. in a ratio between 2: 1 and 5: 1, and then heated by the contact heating of the tool for the required period of time to the desired drying temperature. The following combinations have proven useful: 80 ° C for 7 minutes, 100 ° C for 5 minutes and 130 ° C for 3 minutes. The exact selection of the drying conditions depends, inter alia, on the heat sensitivity of the binder components, the water content of the composition and the tool design in the production of the plates or other molded parts.
Cork is a "sucking product", so that when mixed with the binder some of the water is absorbed by the cork itself. Therefore, it is crucial to adjust the elasticity of the binder to the cork properties. With further optimization of production technology, significantly shorter production times and -20- further economic potential can be realized. The product is recyclable after its application by granulation again, after which new parts can be made from it with the same or an optimized binder. Each recycling cycle becomes more advantageous because the cork granules are already encapsulated with the active ingredients, i. is coated, and so the amount of binder needed in the recycling can be significantly reduced, e.g. by up to 70% or more.
Cork products made with a new binder are upgraded by additional new properties. In addition to the non-slip equipment, which is an important and crucial issue in the packaging sector and in the securing of cargo, every cork granulate is enveloped and encapsulated with the binder, with the result that the typical cork odor is greatly reduced. In addition, the coating and binder mass trimmed for optimum wettability with other materials already in the manufacturing process (i.e., in a "one-step process") results in further upgraded products.
Another particularly preferred embodiment of the invention is the use of the composition of the invention as a binder for polystyrene foam granules as a filler, which is preferably recycled polystyrene foam. For this application, the proportions of elasticity-reducing components, such as e.g. starch and / or crosslinking reaction components such as CaOH2, to adapt the properties of the binder to the viscoelastic product polystyrene foam while ensuring sufficient internal strength of the bond and the overall system. On the product characteristics of polystyrene foam, e.g. the low thermal load capacity and the non-absorbency, is to take into account in the form of a lower viscosity and the highest possible wettability of the binder, which can best be done by optimizing the concentrations of milk protein and latex.
In the binder, all components should be completely thermally digested and precrosslinked. The thermal processing of polystyrene foam should be limited to about 65 ° C, for a short time to a maximum of 70 ° C, to prevent decay or shrinkage.
To avoid processes of polystyrene foam. When using recycled polystyrene foam, the advantages of the invention are particularly well recognizable, as here by the use of a composition according to the invention as a binder, an economical and meaningful recycling of a waste product and the creation of new polystyrene foam qualities are made possible. The finished products have very high internal strength, sufficient elasticity and, depending on the concentration of the binder in the manufacturing a hand width of weak to very strong slip-resistant effect on the outer surfaces of plates made therefrom.
To produce a 3 mm thick, non-slip and stable polystyrene foam board, for example, 50 wt .-% polystyrene foam granules mixed with 2-3 mm grain size with 50 wt .-% binder, which corresponds to a volume ratio of about 95% filler and 5% binder), wherein However, the ratio can vary greatly depending on the desired product properties and grain size used. Similar to the production of cork granules, the resulting mixtures of binder and granules are compacted in a platen tool, again e.g. to values between 2: 1 and 5: 1, and then dried.
As mentioned above, the drying temperature is limited by the properties of the polystyrene foam, which is why after a short time heating or heating the residual moisture usually has to be removed by drying at room temperature by means of ambient air or in a recirculating drying channel or a convection oven (with or without heating).
For this purpose, the following procedures have proved suitable: a) drying at 25-30 ° G for 5 minutes in the mold under pressure; Ventilation of the residual moisture at room temperature for about 30-45 minutes. b) drying at 65 ° C for 5 minutes in the heated mold; Vent the residual moisture at room temperature for 15-20 minutes. C) drying at 70 ° C for 3 minutes in the heated mold; Ventilation of the residual moisture at approx. 50 ° C for 3-4 minutes.
As mentioned above for cork granulate, further optimization of production technology can realize significantly shorter production cycles and further economic potential. Polystyrene foam boards according to the invention are also recyclable after (preferably repeated) use in a manner similar to cork granules by re-granulation and binding. Again, by previously coating a polystyrene granule repeatedly granulated with binder components, the amount of binder needed for the rebond can be significantly reduced, e.g. by up to 50% or more.
Even in these cases, new product properties and qualities can be achieved in recycling. By enveloping each polystyrene foam combo with the binder, volatile constituents contained therein, e.g. Residual monomers, sealed, which makes the polystyrene foam largely emission-free. In addition, an " encapsulation " the polystyrene foam stabilizes the foam against external influences, as a result of which it can be bonded, for example, with virtually any desired adhesives, which by no means applies to conventional foamed polystyrene. In addition to this, there are new possibilities to combine polystyrene foam mixtures with other materials and / or also to realize multilayer systems in the manufacturing process (ie again in a "one-step process"). with interlayers reinforced multi-layered polystyrene foam sheets.
In further application examples, for example, non-pre-crosslinked and thermally digested compositions may contain bread crumbs, which are already thermally digested, instead of (therefore also not digested) cereal flour. This is especially the case with sodium bicarbonate formulations NaHCO 3 or " staghorn salt ", i. Ammonium carbonate (ΝΗ4) 2θ03 or -hydro-gencarbonat NH4HC03, as a base advantageous because here by thermal influences of the decay and gas evolution (CO2), especially in bicarbonates, started -23-. The concomitant foaming during the coating and binder production is either entirely undesirable or, if a foamed product is sought, is at least prematurely triggered, which is why in compositions containing such base components, no thermal decomposition can be done before addition of the latex. The use of breadcrumbs, an already digested cereal product, solves this problem. In the final product, the effect of Paniennehl is comparable to that of thermally processed cereal flour.
Alternative animal and vegetable proteins and polymers or sources thereof, including e.g. Gelatin, soy, rice, potato, corn, peas, beans, eggs, as well as animal and vegetable waste products and residues have been tested in numerous formulation experiments and have confirmed the operation of the present invention without exception. It is thus easily possible to exchange the components a) and b) used in the following formulation examples with alternative animal and vegetable proteins and polymers, preferably pure natural products. On the basis of the disclosure and teaching contained herein, the person skilled in the art can determine the respective effects of alternative natural substances on the property profiles of compositions according to the invention by appropriate experiments in a simple manner and without undue experimentation and correspondingly optimize the mixing ratios of the four components.
By way of example, water-soluble animal protein sources such as gelatine, egg white and pure casein have been used instead of the representatives cited in the exemplary embodiments (ie, milk products) which have comparable dispersing properties after digestion with base and in combination with the vegetable polymers Binder compositions can be compounded with anti-slip effects. The mode of action of these other animal proteins is largely comparable with milk protein, in all cases superficially and deliberately the dispersing effect in otherwise incompatible component mixtures, the improvement of the wettability by the hydrophilic-hydrophobic molecular structure of the proteins and the more or less strong. ♦ · t «···· ·· | # • · * ·· I ♦« · · * • · · · · # # # # # # # # # · · · ································. While it is hardly possible to have a particular animal protein, e.g. Milk protein to replace in an existing formulation without any other adjustment of the formula 1: 1 by another. However, the different properties of the animal proteins can be taken into account by the choice of the other composition components, by the addition of further, complementary proteins and / or by changes in the protein concentration in the formulation. The differences in quality of the animal proteins can also be used deliberately to further optimize the desired end product or to change it in desired directions or to impart other properties in addition to the slip resistance.
To illustrate the differentiation and effect of other animal proteins and to provide those skilled in the art with guidelines for their use in recipes according to the invention, the following exemplary representatives are given and compared with the formulations of the later embodiments containing milk, quark and skin as an animal protein source.
Gelatine: Gelatine is a partially hydrolysed collagen of animal connective tissue protein and is widely used in technical applications as protein glue and thickener. Even in small amounts (from approx. 1%), gelatine is strongly thickening / gelling in water and loses its viscosity at temperatures above approx. 50 ° C (reversible). Their amphoteric properties allow reactions in acidic as well as in alkaline medium and thus, in particular, support the pronounced high wettability of different materials and materials with a composition according to the invention. Gelatin digested with alkali metal hydroxides and crosslinked loses its gelling effect at room temperature and can easily be processed analogously to digested milk protein. The dispersing effect in the material mixture is comparable to that of other animal proteins. The stickiness is markedly lower than that of milk proteins or other protein saccharides (such as skin glue, bone glue). Digested, cross-linked and compositionally hardened gelatin results in very hard and brittle products which, considering a preferably deliberately elastic formulation, make the use of gelatin meaningful only when the gelatin content is compared to that of Milk protein is reduced and / or other composition components, such as the proteins and / or polysaccharides from plant sources, be adapted.
A coating and binder composition prepared in accordance with Example 2 later, in which the milk protein is replaced by equivalent amounts of gelatin as protein, results in cured coatings or articles having less elasticity and developing lower adhesive forces.
Skin glue (Glutin-Warmleim): Skin glue and bone glue are highly effective, elastic and resistant to aging processes Koliagen products. Due to their high Schutzkoltoidwirkung they are specifically used as a dispersing aid industrial. Glutin glues are a highly effective and efficient alternative to milk proteins in the production of non-slip mixtures and gumming. Adhesive strength, wettability and internal strength are markedly enhanced, and the rubber-elastic behavior can be improved by the addition of polyhydric alcohols, e.g. Glycerin, and / or sugar can be further optimized. When such glues are used, the proportion of vegetable polymers can be significantly reduced if desired, and because of their water resistance and resistance when crosslinked with other or additional tanning agents (such as tannin), non-slip surfaces can be waterproofed.
A coating and binder composition prepared according to Example 2 later on, in which the milk protein is replaced by equivalent amounts of skin glue as protein, gives comparable coating and binder masses which, in the cured state, tend to develop even better adhesion and adhesion to contact surfaces. More complicated than milk protein, however, are processability, i. the swelling, dissolution / melting of the glue under the influence of temperature, the waterproof crosslinking in the latex system as well as the changes in the properties in the event of a strong climate change. In any case, skin glue, as shown in Examples 4 and 5, has been well established as a source of animal protein. ······ ··· * ·· * · t «··· ·· φ + 9
Casein: Casein, when used in analogous dilution to milk and milk products, exhibits the most similar properties and test results as the formulations given in the examples. Only the dispersing effect is slightly weaker, which is attributed to the saponificated fats and accompanying ingredients contained in the milk formulas, which are naturally absent in casein. The advantages of the well-defined and uniform quality of casein, the freely adjustable protein concentration in processing and also the shelf life of the protein source are offset by economic disadvantages due to the higher processing costs and higher raw material costs for the purified and concentrated milk protein. From a qualitative point of view, only a few formulations are needed to replace dairy products with concentrated casein. In sum, for economic reasons and because of the simple uncomplicated availability and processing, the decisive advantages are the use of dairy products as a source of protein.
Egg white: A high-quality protein source that is largely fat-free and composed of different proteins with approximately 11% protein content. The dispersing and firming properties are pronounced as with all animal proteins, however, elaborate processing and economic disadvantages over the milk proteins do not add up to an overall advantage in the production of non-slip coating and binder formulations. It should be noted that in combination with alkali metal hydroxides a strong, permanently unstable gelation occurs, which can be reversed by further heating to a maximum of 65-70 eC before further processing and addition of further components, after which the composition no longer gels.
Egg yolks: The egg yolk contains in comparison to egg white / protein in addition to a higher protein concentration and high levels of animal fat (about 30%), which must be saponified with higher concentrations of alkaline digestion and crosslinking agents, the emulsifying effect in the mixture but clearly strengthen. Too high (digested) fat contents in the overall formulation (from about 3%), however, reduce the moisture and water resistance, the stickiness and the adhesion in the final product significantly and reduce the internal strength of the cured products. Although this can be countered inter alia by the addition of other proteins and vegetable polymers, so that egg yolks can be used in significant proportions in formulations of the invention. For the production of non-slip and water-resistant surfaces, however, the use of egg yolk is more problematic, costly and uneconomical than those of other protein sources. Egg yolk protein is therefore especially a valuable protein-containing formulation component for anti-slip products, when it is deliberately used in relatively low concentration as a property-enhancing Nunancier excipient.
With regard to the effects of various starting vegetable products, several preferred representatives are given below for illustration, again as a guideline for the person skilled in their use in compositions according to the invention, and compared with the formulations of the later embodiments, which contain wheat flour as a particularly preferred vegetable component.
Roqqenmehl: When using rye flour, which contains no gluten and a lower starch content, instead of wheat flour is obtained in the same other formulation composition a consistency and effect comparable coating and binder mass, which mainly differs in that the slip-resistant and cross-linking effect are slightly weaker. Nevertheless, even such a composition adheres sufficiently well to the substrate as a coating on absorbent or open-porous materials. Although smooth and closed surfaces are also well wetted, the adhesion thereto is weaker and may be present in some materials, e.g. Sometimes insufficient, unless additional measures are taken, such as Change in the composition of animal proteins or increase their proportion.
Potato flour: If the composition of the recipe is otherwise the same as in the examples, potato instead of wheat flour will produce a much more viscous and tougher consistency. The elasticity is greatly reduced after the drying and curing process and is also significantly more crosslinked. Alkali-digested potato flour remains slightly "gritty" in structure. and does not form a homogeneous uniform film in the thermally assisted digestion. With appropriate recipe optimizations, such as Reduction of the proportion of potato flour and adaptation of the other reaction components, can be used with potato flour to create targeted product properties for non-slip coating and binder mixtures.
Pea flour: Pea flour behaves very similar to potato flour and differs only by the slightly higher protein content, which leads to a slightly more elastic behavior in the final product than potato flour recipes.
Corn and rice flour: Corn and rice flour have similar properties to wheat flour. Both are thermally very well digestible, lead to uniform and homogeneous, highly viscous, well-crosslinkable masses and differ from other cereal flours only by their slightly lower protein content, which leads to somewhat inflexible, less elastic combinations with the latex. The slightly higher fat content in cornmeal (about 3.8% instead of 2.2%) additionally supports the emulsifying effect, but limits the water resistance slightly, as shown by example 7, where, in addition to skin glue as animal protein maize flour as vegetable Component was used.
Soia and other oil crops: These contain high protein content, but in their natural form also high levels of vegetable fats, which are hardly suitable for use for latex-based slip-resistant coating and binder compositions. Soy meal or other press residues from oil extraction, on the other hand, are suitable for use as a formulation component due to their low residual fat content. In practical trials, for reasons of easy availability, unsweetened soy milk containing 4% protein, 0.1% fat and 4% starch has been investigated, which has proven to be a suitable source of vegetable polymers. To keep the water content of the composition low, use -29- 94 4 4 4 • 4 4 * · · • · · 94 • 9 94 9 4 4 4 • · * · · «· I · * · * 1 44 9444 4 4 m 9 44 4 944 • 4 4 4 9 4 9 49 44 444 soymilk may be used as a source of animal protein (instead of milk or cottage cheese).
In all three applications of the composition of the invention, i. as a coating composition, as a molding composition and as a binder, the composition may also be self-foamed prior to curing to produce a foamed coating or foamed article. The foaming can be effected both by using a carbonate or bicarbonate as the base component and by adding an additive containing a blowing agent, preferably CO2, or a combination thereof, or even using a forced-ventilated technical system.
In a final aspect, the invention relates to an antislip surface on a non-slip surface article consisting of a composition according to the first aspect in a cured state, which, as described above, is applied to a backing or, for example, in FIG cast a mold and dried, cured and crosslinked. Such an anti-slip surface on a wear-resistant article may preferably be used for securing cargo, i. to prevent the slipping of cargo, are used.
A special feature is an anti-slip surface that is in the form of an imprint on the wearer. By this are meant cases in which the composition according to the invention can also serve as an ink with anti-slip function, with which, using a conventional printing process, an imprint such as e.g. a label on a support such as Paper or cardboard is applied. Curing takes place in the printing process customary in series, where printing inks are thermally dried and thus no additional working step or expense is required for heating the composition according to the invention. In this way, the coating produced from the composition of the invention not only acts slip-resistant, but also serves as an information carrier. -30- ΦΦ • 9 «• 499 φ • Φ ΦΦ ΦΦ ΦΦ ΦΦ # 4 ···· • 9 4 · · 9 9 • 9 4 · · 9 999 • Φ · r« 4 9 9 9 9 9 9 9 94 99 * · ΦΦΦ
Viewed the other way around, a non-slip printed packaging can also be equipped as a packaging and load protection device.
The present invention will now be further described with reference to specific examples, which are given by way of illustration only and not by way of limitation.
EXAMPLES
In the following examples, different formulations were prepared for different application scenarios as well as several articles from such formulations, whereby care was taken to continue and extend and further expand the qualitative and economic advantages of the coating and binder system in the subsequent process steps and in the end product. For example, concentrated lumps and mixtures were used to work with as little water as possible, optimizing the drying process in an aqueous system. In addition, practical and industry-relevant tests were carried out by experts to test and compare the frictional resistance of anti-slip coatings produced on different substrates. In cooperation with Transport-Technik Günther GmbH & Co. KG in Augsburg, DEKRA Automobil GmbH in Augsburg and the Fraunhofer Institute for Material Flow and Logistics (IML) in Dortmund were identified and confirmed with the following load characteristics and friction partners. -31 -
Examples 1 to 7 - Preparation of compositions and articles of the invention
example 1
Highly adhesive and highly elastic composition with moderate water resistance
Recipe 1
Component_Ingredient_Part weight a) Milk, approx. 1% fat content 50.0% by weight b) Cereal flour W450 9.5% by weight c) NaOH powder 0.5% by weight _d) _ Natural latex (TS approx. 50% ) 40.0% by weight 100.0% by weight
The components a) to c) were premixed, then heated with constant stirring to boiling temperature (95-100 ° C) and, as soon as the mass had turned from milky white to transparent-turbid, without additional cooling to about 30-35 C. until the latex component d) was mixed in and stirred and dispersed for at least 10 minutes. It is - as with all later examples - to make sure not to stir too much air and not to use a stirrer, which heats the composition by high shear forces during stirring.
This formulation clarifies the mode of action and the interaction of the individual components quite clearly in that the wettability, the adhesion forces, the binding forces as well as the adhesion to the respective carrier material compared to pure latex were significantly improved and enhanced, but the elasticity somewhat reduced and the coating against water not yet stabilized, ie not sufficiently networked is. This recipe is therefore suitable for applications in the field of application and for those in which highly effective slip resistance is achieved and must be achieved even with the least amount of contact pressure. -32-
Example 2
Elastic composition with good water resistance (and basic formulation for anti-slip products for load securing)
Recipe 2
Component Component Weight percentage a) Milk, approx. 1% fat content 43.0% by weight b) Cereal flour W450 6.8% by weight of Ci) NaOH powder 0.2% by weight of c2) Sumpf lime (at least 3 months old) 10.0% by weight _d) _ natural latex CTS approx. 50% ϊ 40.0% by weight 100.0% by weight
The components a), b) and ci) were premixed, then heated with constant stirring to boiling temperature (95-100 ° C) and, as soon as the mass had turned from milky white to transparent-turbid, without additional cooling to about 30- Allowed to cool 35 ° C before the latex component d) was mixed and stirred for at least 10 minutes and dispersed. In the last mixing step, the slow admixture of the reaction component C2) took place, which was predispersed and therefore contained no lumps or agglomerates. This was followed by a 10-minute thorough dispersion with a suitable stirring and mixing unit.
As an alternative to predispersing, component C2) may also be slurried with water at 10% dilution, and instead of the final dispersion, the composition may be subjected to fine dispersion on a roll mill or a bead mill shortly after blending reaction component C2). This dispersing system is best suited when dyes, pigments or other auxiliaries have been mixed in order to sufficiently finely disperse them.
Compared to Example 1, it can be seen in the formulation that by increasing the base shares and the additional basic reaction component, the cross-linking -33-
and Stabilization against water exposure is the optimization goal of this coating quality, which illustrates the relationships and modes of action mentioned above.
Due to the additional base component, (CaOhfe) in the form of limestone, and the correspondingly reduced protein content, the mixing ratios are shifted in favor of better crosslinking and stabilization. The originally high elasticity was intentionally and deliberately reduced in this formulation, and the internal strength and the viscoelastic effect in the overall system are reinforced. This formulation was specially developed for load securing products, is geared to different carrier materials and friction partners and also stabilized for high mechanical loads. It was therefore tested under practical conditions for its slip-inhibiting action on coated carrier materials (compare Examples 8 to 18). Recipe 2 is due to its special properties but also for the production of articles with anti-slip surface effect, especially as an effective and sustainable binder system for products with different amounts of filler.
Example 3
Composition with reduced elasticity, high internal strength and very good water resistance
Formulation 3 Component Ingredient Weight fraction a) Quark, approx. 1% fat content 30.0% by weight b) Cereal flour W450 10.0% by weight of Ci) NaOH solution, 10% by weight 10.0% by weight of C2) Lime lime (at least 3 months old) 10.0% by weight ... d) Natural latex (TS approx. 50%) 40.0% by weight 100.0% by weight -34-
The components a), b) and ci) were premixed, wherein first a) and Ci) were mixed to form a slightly viscous, digested protein mass, and only then component b) was added and mixed. Subsequently, the mixture was heated with constant stirring to 90-95 ° C and allowed to cool again to 30-35 ° C before the latex component d) and then the lime c2) were mixed with continuous stirring, after which the mixture for a further 15 minutes was stirred.
In this formulation it can be seen that the use of puarkjanstelle of milk increased the concentration of animal protein, whereby the base Ca (OH) 2 and its cross-linking, water-stabilizing effect are optimized. The amount of natural latex as an elastomer was reduced because in this case the goal was to create a very stable, strong yet tough-flexible coating and binder formulation. This formula is designed for particularly demanding and strong mechanical strength. Hard, stable carriers such as wood or light metal in combination with high contact pressures and weights of the friction partners achieve the best effect with such stable and solid surface-active equipment.
Another and important aspect of this formulation is the ability to produce a highly elastic carrier material, such as e.g. Flexible foams or elastic rubber products to be equipped with this low elastic coating and binder system to reduce undesirable and ineffective " overstresses " of the starting product and to optimize for the applications in the load securing.
At the same time, this formulation is excellently suited to form durable stable foams and also as a very stable and permanently elastic binder system, where in addition to the addition of freely selectable fillers, high-quality components with non-slip outer surfaces are also created via the joining technique (bonding). -35-
Example 4
Highly adhesive and well-water resistant formula Formulation 4
Component Ingredient Weight percentage a) Skin glue, 4% in water 37.0% by weight b) Cereal flour W450 7.5% by weight of Ci) NaOH powder 0.5% by weight of C2) Sumpfkalk (at least 3 months old) 10.0% by weight _d) _ natural latex (TS approx. 50%) 45.0% by weight 100.0% by weight
The mixing and preheating of the components a), b) and Ci) was carried out analogously to Example 2, after which the latex component d) was mixed and stirred for at least 10 minutes and dispersed. In the final mixing step, the slow admixture of the reaction component C2), which was slurried with 10% dilution with water to prevent lump formation. Shortly after the mixing of component C2), a 10 minute fine dispersion was carried out on a roll mill.
This formula forms the basis of simple optimizations and product adaptations to various carriers to be coated by adjusting the stickiness and adhesion to the carrier surface by simply varying the concentration of the skin glue.
Skin glue lathers little to no milk compared to milk protein. On the one hand, this ensures bi-layer-free coating application and processing, but on the other hand makes skin glue largely unsuitable for uses in which foaming of the coating or binder is intended. -36-
Example 5
Highly elastic composition with moderate water resistance
Recipe 5
Component Component Weight fraction a) Skin glue, 4% in water 37.0% by weight b) Corn flour 5.0% by weight of Ci) NaOH solution 10% by weight 3.0% by weight of C2) Sumpfkalk (min. 3 months old) 5.0% by weight d) natural latex (TS approx. 50%) 50.0% by weight 100.0% by weight
The preparation of the composition was carried out analogously to Example 4.
This formulation is optimized in elastic behavior, not as highly cross-linked as those of Examples 2 to 4, and, considering its reduced water resistance, has been specially developed for indoor applications without permanent moisture and wetness.
Example 6 - slip-resistant cork plate
Strong adhesive and elastic composition filled with cork granulate
Formulation 6 Component Components Weight percentage a) Milk, approx. 1% fat content 40.0% by weight b) Cereal flour W450 9.5% by weight of Ci) NaOH powder 0.5% by weight of c2) Sumpfkalk (min. 3 months old) 10.0% by weight d) _ natural latex (TS approx. 50%) 40.0% by weight 100.0% by weight -37- φ φ • φ
The composition according to the invention from formulation 6 was prepared as described in Example 2 and then mixed in a ratio of 30:70 with cork granules, particle size 2-3 mm. The resulting mixture of binder and cork filler was compacted in a 3: 1 ratio in a platen tool and heated at 130 ° C for 3 minutes to obtain a cured cork sheet of 3 mm thickness, which has excellent slip resistance and good flexibility.
Example 7 - antislip polystyrene foam board
Highly adhesive and elastic composition filled with polystyrene foam granules
Recipe 7
Component_Ingredient_Weight% a) Milk, approx. 1% fat content 40.0% w / w b) Cereal flour W450 4.5% w / w Ci) NaOH powder 0.5% w / w C2) Lime limestone (at least 3 months old) 5.0% by weight _d) _ natural latex (TS approx. 50%) 50.0% by weight 100.0% by weight
The composition according to the invention from formulation 7 was prepared as described in Example 2 and then mixed in a weight ratio of 50:50 with polystyrene foam granules, grain size 2-3 mm. The resulting mixture of binder and polystyrene foam filler was compacted in a 4: 1 ratio plate mold, heated to 30 ° C. for 5 minutes and then allowed to dry for 45 minutes at room temperature in an unheated convection oven and cured to form a cured polystyrene foam sheet 3 mm thick, which in addition to excellent slip resistance also has good stability and flexural strength. -38-
Examples 8 to 18 - Preparation of Coatings from a Cured Composition and Anti-Slip Resistance Tests Therewith
The composition of example 2 was applied to four different support materials by means of different coating methods and cured, as indicated in the individual examples.
The carrier materials thus finished with the compositions according to the invention were tested for their frictional resistances μ. Although there are different laboratory measuring methods for evaluating the frictional resistance, their results often do not allow any concrete statements on the behavior of load during transport. For comparative testing under standardized conditions (which are not available in practice and application), these laboratory test methods and procedures remain an important and guiding reference, but are not accepted for industrial qualification and commercial release. Therefore, to assess the slip-resistant effect of fabrics, practical tensile tests are carried out with original cargo and friction partners in all weather conditions. Only in this way will the legally recognized principles be developed, which will lead to a test certificate associated with the product and the application and to the test certificate required for the production and marketing of load securing equipment in order to document the effectiveness of a system or product.
For this purpose, a load of known mass is placed on a non-slip surface to be tested, which has been placed on a practical base (for example, screen-printed floor or wooden pallet). About tensioning and lashing straps a shifting force is built up by a tractor and held by means of an intermediate load cell, the measured tensile force, which is applied to the load. It will determine the restraint forces that are required to bring the load in motion (holding force or static friction). In addition, the load is continuously shifted further to determine the sliding resistance of a moving load (sliding friction). This process is repeatedly interrupted and restarted on a sample -39- in order to record and document the lasting effect and mechanical degradation of a product.
The holding force (static friction) to move a mass is always higher than the moving mass (sliding friction). The measurement results given in the examples correspond to the official and accepted test procedures, where the sliding friction (ie the lowest value in the test procedure) is shown and documented. These results are defined and expressed as a coefficient of friction or coefficient of friction μ.
The statutory minimum friction coefficient for anti-slip underlays in load securing is 0.6 μ. Good and high-quality products for load securing have friction resistance values of about 0.8 μ. The papers and paper products known on the market currently achieve measurement results in the range of 0.5 to 0.6 μ and are preferably used as packaging aids (intermediate layers) against slipping of entire load units. Multilayer systems, such as Carrier made of cardboard combined with PU foam as antislip coating, can exceed the legal minimum requirement of 0.6 μ and are used with 0.6 to 0.7 μ friction as a cost-effective disposable system for load securing.
Examples 8 to 11 - Coating on corrugated cardboard
Carrier: Corrugated cardboard with 2 mm or 4 mm thickness
Coating technology: two-sided application by means of coating and filling technique; Drying and curing at room temperature or with contact heating, 1 min at 160 ° C
Coating: recipe 2 with 30 g / m2 (dry weight)
Sample sizes: 2 pcs. Blanks 800 mm x 150 mm as slip-resistant base Friction partner below: Truck loading floor (screen-printed bottom)
Friction partner above: wooden pallet with load, total weight 803 kg, and standing paper roll with 1404 kg weight • · · * · * · ♦ «· · · · · · · · · * ♦ * · · * · · · · * * φ φφφ φ · ···· «· · · · ·
Measurement results: 0.30 to 0.40 μ 0.30 to 0.40 μ 0.70 to 0.75 μ 0.71 to 0.75 μ 0.70 to 0.80 μ 0.74 to 0.80 μ
Comparative Example 1 (2 mm, without coating) Comparative Example 2 (4 mm, without coating) Example 8 (2 mm thickness, room temperature) Example 9 (2 mm thickness, heating)
Example 10 (4 mm thickness, room temperature) Example 11 (4 mm thickness, heating)
The test results themselves are hardly affected by the different thicknesses and drying methods, although the thicker pad tends to give better values. However, it was found that tempered drying and curing causes slight scattering in the case of cardboard as the carrier material.
Example 12 - Coating on kraft paper
Carrier: kraft paper, 120 g / m2
Coating technology: two-sided application by roll coating; Drying and curing by means of IR radiation, both sides, at 160 ° C for 20 s Coating: Formulation 2 with 25 g / m.sup.2 (dry weight)
Sample sizes: 1 pc. Cutting 1200 x 800 mm as slip-resistant intermediate layer Reiboartner below: wooden pallet
Friction partner above: BigBag (PP fabric) with plastic granule filling with 1056 kg weight
Measurement results:
Comparative Example 3 (without insert) 0.20 to 0.25 μ
Comparative Example 4 (paper insert without coating) 0.32 μ
Example 12 0.68 μ-41- * t * * * * e t · φ • e · · «· ·« Φ «· e
• · · · «· · ·· · V •••• es» · t ·
Examples 13 and 14 - Coating on cork granule plate
Carrier: cork granules plate, thickness 3 mm, grain size 2-3 mm Coating technology: two-sided application by means of coating and filling technique; Drying and curing at room temperature or with contact heating, 1 min at 160 ° C
Coating: Formulation 2 with 40 g / m2 (dry weight)
Sample size: 2 pcs. Blanks 800 mm x 150 mm as slip-resistant base Friction partner below: Truck loading floor (screen-printed bottom)
Friction partner above: Paper roll standing with 1404 kg weight
Measurement results:
Comparative Example 5 (cork plate without coating) 0.65 μ Example 13 (room temperature) 0.91 μ
Example 14 (heating) 0.92 μ
As already shown in Examples 8 to 11, the test results are comparable with different drying technology, but it is advantageous for absorbent materials such as paper and cork to use temperature-assisted drying techniques to ensure the consistent and uniform curing and drying in the overall composite.
Example 15 coating on cork granule plate
Carrier: cork granules plate, thickness 3 mm, grain size 2-3 mm Coating technology: two-sided application by means of coating and filling technique; Drying and curing with contact heating, 1 min at 160 ° C Coating: Formulation 2 with 40 g / m2 (dry weight)
Sample size: 1 pc. Cutting 800 mm x 150 mm as slip-resistant intermediate layer Friction partner below: wooden pallet
Friction partner above: beverage cartons stacked with 531 kg weight
Comparative Example 6 (cork plate without coating) 0.65 μ
Example 15 0.91 μ-42- •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• Φ Φ # · · Φ ·· «· · ··· ♦ * · Φ · Φ ·
Examples 16 and 17 - coating on XPS foam
Carrier XPS foam, thickness 2.2 mm
Coating technology: two-sided application by means of dipping and doctor blade stripping technology; Drying and curing in tempered circulating air drying channel, 2 min at 70 ° C Coating: Formulation 2 with 25 g / m2 (dry weight)
Sample size: 2 pcs. Cutting 800 x 150 mm as anti-slip surface or 1 pc. Cutting 1200 x 1000 mm as slip-resistant base Friction partner below: Truck loading floor (screen-printed bottom)
Friction partner above: Paper roll standing with 1404 kg weight
Measurement results: 0.55 to 0.60 μ 0.88 μ 1.28 μ
Comparative Example 7 (without coating)
Example 16 (800 x 150 mm)
Example 17 (1200 x 1000 mm)
Example 18 - Coating on XPS foam
Carrier: XPS foam, thickness 2.2 mm Coating technology: double-sided application by means of dipping and doctor blade stripping technology; Drying and curing in tempered circulating air drying channel, 2 min at 70 ° C Coating: Formulation 2 with 25 g / m2 (dry weight)
Sample size: 2 pcs. Blank 800 x 150 mm as slip-resistant base Friction partner below: Truck loading floor (screen-printed bottom)
Friction partner above: wooden pallet with load, total weight 803 kg
Measurement results:
Comparative Example 8 (without coating) 0.55 to 0.60 μ
Example 18 0.96 μ
The above practical test results for the examples show that the coatings of compositions according to the invention for the production of slip-resistant surfaces have an excellent slip-inhibiting effect on a variety of surfaces. [001] * • I * I * I * # * * · · + ····· · * »· chen carrier materials. It was not only in all cases, the legal minimum value of the coefficient of friction for the load transport exceeded, and sometimes even significantly, but also significantly improved the coefficient of friction of commercial products for the load securing by coatings according to the invention. -44-

权利要求:
Claims (20)
[1]
A composition for producing slip-resistant surfaces, comprising: • I · Φ I · 0 0 ft ft 1 ········································································································· a) animal protein, b) vegetable polymers, c) base selected from alkali metal and alkaline earth metal hydroxides, hydrogencarbonates and carbonates, d) polymer latex.
[2]
2. Composition according to claim 1, characterized in that as animal protein one or more milk proteins are contained.
[3]
3. Composition according to claim 2, characterized in that the milk proteins are contained in the form of milk and / or one or more milk products.
[4]
4. Composition according to one of claims 1 to 3, characterized in that the source of the vegetable polymers is cereal flour.
[5]
A composition according to claim 4, characterized in that the cereal flour is or comprises wheat flour.
[6]
6. Composition according to one of the preceding claims, characterized in that as the base Ca (OH) 2, NaOH or KOH or a mixture thereof is contained.
[7]
7. The composition according to claim 6, characterized in that as the base Ca (OH) 2 is contained in the form of limestone lime.
[8]
8. The composition according to any one of the preceding claims, characterized in that is contained as latex polymer latex. "· ·" ·· "···" t · · t t ai · iv · t * § ···· »· *» ··· w ·········
[9]
9. A process for producing a composition according to any one of claims 1 to 8 by mixing the components a) to d), wherein in a first mixing step, first the components a) and b) are mixed with at least a portion of component cj before in a second mixing step component d) is added, wherein optionally the remainder of component c) is mixed simultaneously with component d) in the second mixing step or thereafter in a third mixing step.
[10]
10. The method according to claim 9, characterized in that in the first mixing step, first the component a) with component c) or a part thereof is mixed, after which the component b) is mixed.
[11]
11. The method according to claim 9 or 10, characterized in that the mixture of the components a), b) and at least a part of c) is heated to boiling temperature between the first and the second mixing step to the components a) and b) unlock and interlink.
[12]
12. The method according to any one of claims 9 to 11, characterized in that component c) comprises both Ca (OH) 2 and at least one alkali metal hydroxide, of which the at least one alkali metal hydroxide in the first mixing step with the components a) and b) is mixed and the Ca (OH) 2 is mixed in the second or third mixing step.
[13]
13. Use of a composition according to any one of claims 1 to 8 as a coating composition for producing slip-resistant surfaces on substrates.
[14]
14. Use of a composition according to any one of claims 1 to 8 as a molding composition for the production of articles with anti-slip surface.
[15]
15. Use of a composition according to any one of claims 1 to 8 as a binder for the production of articles with anti-slip surface. -47-
[16]
16. Use according to any one of claims 13 to 15, characterized in that the composition for producing the slip-resistant surface on a support or an article with anti-slip surface at a temperature between 25 ° C and 160 ° C dried, cured and crosslinked.
[17]
17. Use according to claim 16, characterized in that the composition is foamed before or during its drying / curing.
[18]
An antislip surface on a non-slip surface article consisting of a composition according to any one of claims 1 to 8 in a cured state.
[19]
19. Slip-resistant surface on a support or article with slip-resistant surface according to claim 18, characterized in that the slip-resistant surface is used for securing cargo.
[20]
20. Slip-resistant surface on a support according to claim 18 or 19, characterized in that the slip-resistant surface is in the form of an imprint on the support. Vienna, 19 January 2011 Austria Wirtschaftsservice Gesellschaft mbH Johann Kiss

-48-

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同族专利:

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AT511047B1|2014-08-15|

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WO2012006651A1|2012-01-19|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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GB245540A|1924-10-21|1926-01-14|Thomas Marshall Rigby|Improvements in and relating to rubber latex compositions and the application thereof|

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US2121087A|1936-08-20|1938-06-21|Labra Joseph|Ship deck mortar-like adhesive plastic|

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EP0407059A2|1989-06-30|1991-01-09|Japan Synthetic Rubber Co., Ltd.|Process for producing copolymer latex and paper coating composition, carpet backing composition or adhesive composition comprising said latex|

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DD156612A1|1981-02-25|1982-09-08|Joachim Antemann|METHOD FOR RECYCLING CARPET MATERIAL|

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JPH04208487A|1990-08-03|1992-07-30|Mitsubishi Paper Mills Ltd|Alteration preventing single layer type color forming pressure-sensitive copy paper|

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DE4339642A1|1993-11-20|1995-05-24|Henkel Kgaa|Aqueous anti-slip agent|

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KR100476099B1|2003-11-26|2005-03-14|김덕수|Composition for coating of nylon gloves and process for preparation of the same|DE102012102330A1|2012-03-20|2013-09-26|Adam Dromert|Material with a binder and dry baked goods, useful in dry bakery bread, rolls, biscuits and/or cake, for producing a solid shaped body, and as a substitute for the construction, furniture, plastics and packaging industry|

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WO2013185819A1|2012-06-14|2013-12-19|Intier Automotive Eybl Gmbh& Co Ohg|Method for producing a moulded part and moulded part|

法律状态:
2016-10-15| PC| Change of the owner|Owner name: JOHANN KISS, AT Effective date: 20160908 |

优先权:

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申请号 | 申请日 | 专利标题

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AT782011A|AT511047B1|2011-01-19|2011-01-19|COMPOSITIONS FOR PREPARING SLIP-RESISTANT SURFACES|AT782011A| AT511047B1|2011-01-19|2011-01-19|COMPOSITIONS FOR PREPARING SLIP-RESISTANT SURFACES|

---

PCT/AT2011/000305| WO2012006651A1|2010-07-15|2011-07-15|Composition for producing anti-slip surfaces|

---

EP20110751785| EP2593413B1|2010-07-15|2011-07-15|Composition for producing anti-slip surfaces|