COMPOSITION FOR PREPARING FLAME-REDUCING SURFACES OR OBJECTS

专利摘要:
The invention relates to a composition for the production of flame retardant surfaces or articles comprising: a) animal protein and b) base selected from alkali metal and alkaline earth metal hydroxides, bicarbonates and carbonates, and flame retardant surfaces and articles made therefrom.
公开号:AT511015A1
申请号:T79/2011
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:

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The invention relates to compositions for producing flame retardant surfaces, preferably compositions of natural raw material components.
STATE OF THE ART
Flame protection always has special significance in areas where there are opportunities for overheating or open flame exposure in living spaces or certain applications, and the potential for human and environmental hazards arises through self-combustion. Certain products must therefore be flame retardant or flame retarded before use.
Flame retardant or flame retardant effect is controlled by chemically active substances and / or physical properties. The common flame retardancy techniques are divided into 5 main groups, each based on different mechanisms of action.
Flame retardants that due to their reactivity bind the heat released fission products (radicals) or the oxygen to prevent reactions with oxygen (e.g., halides, phosphate and sulfur compounds).
Flame retardants that extract heat energy in the heat due to endothermic reactions and / or formation of H20 in order to hinder or terminate the thermal decomposition and decomposition process under heat (cooling effect, energy absorber).
Flame retardants that form a protective insulating layer with soot by incomplete combustion on the surfaces to prevent the access of oxygen and thermal energy (encapsulation and thermal insulation).
Flame retardants that by their own incombustibility shift the ratio between flammable mass and incombustible mass and thus exert a "dilution effect".
Physically effective flame retardancy is also achieved by the fact that a shrinking or melting process is triggered by heat to the contact -1 -.
Reduce surfaces or the heat exchange surfaces and to interrupt the thermal degradation by retreating from the heat source or by appropriate distance to minimize the effect of temperature.
All systems fulfill their purpose if the energy input (the effect of heat) and the formation of reactive fission products and / or reactions with oxygen are reduced or prevented by thermal decomposition in organic substances.
The worldwide use of flame retardants is (according to the Danish Environmental Protection Agency) composed as follows (percentages rounded): 50% inorganic, 25% halogenated, 20% nitrogen-based and 5% organophosphorus flame retardants. Each group of flame retardants has its own advantages in addition to a number of disadvantages.
Although inorganic flame retardants have advantages in the environmental and cost sector, but must be used in high concentration to achieve the desired effect, undesirable accompanying properties such as increased mass, loss of elasticity and / or increased brittleness to product-specific quality losses (eg heat insulation, electrical conductivity, etc.) often limit their applications.
Halogenated flame retardants are preferably used in the form of modern hydrocarbon compounds (plastics), where characteristic properties must be maintained and low thermal stability of the molecular chains in the case of thermally induced cleavage (cracking) are effectively blocked by oxidation processes with oxygen. These substances are already highly effective in the formation of combustible pyrolysis gases, but are questionable and controversial in connection with their gaseous reaction products. In addition, halogenated flame retardants prevent the recycling and easy disposal of appropriately equipped products after their use. - 2 -
Phosphorus and sulfur compounds are used in both organic-synthetic and natural forms. The combination options are partly limited due to their chemical behavior and their reactivity with other materials. In technical leaflets of branded products is often the indication that with phosphorous or sulfur-containing compounds subsequently equipped or surface-treated products remain reactive and can lose their effectiveness through environmental, aging and weathering processes over time. It should also be noted that here too, similar to halogenated products, the gaseous reaction products released in the event of fire are not safe.
Nitrogen-based flame retardants consist largely of organic-synthetic products (eg based on urea or melamine), whose mode of action is designed to generate the highest possible nitrogen concentration in the form of aliphatic or aromatic organic compounds, which then turn under thermal stress are cleaved into radicals to bind the oxygen as NOx compounds and release H20 as a fission product {oxygen blocker and energy absorber). Apart from the fact that the nitrogen compounds used for this purpose, similar to halogenated compounds based on phosphorus or sulfur, can diffuse out of the suitably equipped products over time, they can only be combined to a very limited extent with modern plastics or material mixtures.
Many flame retardants are therefore of health and / or environmental concern. For example, steadily increasing concentrations of some flame retardants in house dust, blood serum and breast milk have been detected for years.
Against this background, the object of the invention was to provide a highly effective flame retardant composition which is as harmless as possible in terms of health and environmental protection, in particular a largely biologically structured one, which meets the diverse fire protection requirements in combination with any materials and materials and which can be produced and used in an economical manner. - 3 -
DISCLOSURE OF THE INVENTION
This object is achieved by the invention by providing a composition for producing flame retardant surfaces which comprises: a) animal protein and b) base selected from alkali metal and alkaline earth metal hydroxides, bicarbonates and carbonates.
The invention is based on the discovery of the inventor that from a combination of animal protein and one or more suitable bases with appropriate digestion and crosslinking of the components, a composition can be produced which represents a highly effective flame retardant without any addition of other components. The animal proteins used as component a) are all natural or nature-identical substances, so that disposal without any environmental or health concerns is possible, although, depending on the selection of other optional components, recycling and recycling are in most cases easily possible - and most of the time without any quality degradation of the recycling products.
Although animal proteins may have a whole range of different or at least different nuanced properties, as a component to be crosslinked in a composition according to the invention but in most cases cause the resulting flame retardant surfaces are relatively hard, solid and rigid, the composition preferably contains an additional component c), namely a proportion of vegetable polymers, in particular vegetable proteins, which, in addition to other inherent properties, also serve as a crosslinkable and therefore binding component and as such tend to cause a higher elasticity and flexibility of the flame retardant surfaces. Furthermore, the composition according to the invention may contain, as additional optional component d), various fillers and / or additives as long as these do not impair the flame-retardant effect of the invention. By a suitable choice of the mixing ratio between the components, the desired properties of the flame-retardant products made therefrom can be set very precisely in very wide ranges.
As natural components a) and c) it is possible, by way of example and preferably, to use natural products, such as, for example, milk or milk products or cereal products, but also natural waste products, e.g. from slaughterhouses, dairies, saw mills, mills and other grinding operations, but also as the base of component b) and as fillers or additives of component d), natural substances are used, at least in preferred embodiments of the invention. Thus, for example, a preferred base according to the invention is lime, which will be discussed in more detail later.
All this makes it possible to produce and use the flame-retardant composition of the invention in an extremely advantageous manner from an economical and ecological point of view. Particularly preferably, the components a), c) and d), if present, are all food, food ingredients, food waste or waste products from food production and thus completely harmless from a health and environmental point of view.
A composition of the invention may either be applied as a coating to a substrate for flame retardant finishing of materials or used as a molding compound or binder and made into a three dimensional article having flame retardant surfaces, in all cases more or less proportions of the optional components c) and d ) can be taken into account. The transitions between (relatively unfilled) molding compound and (more or less strongly filled) binder are flowing here.
The optional component d) is not particularly limited and includes, for example, pigments, dyes, plasticizers, flow or thickening agents, mixing aids and fillers, as long as they do not impair the flame retardant properties of the composition according to the invention, but even enhance these in preferred embodiments. Preferably, optional fillers are provided.
Fabrics are therefore selected from the group consisting of stone meal, bone ash, cork granules, pulps, volcanic ash, glass foam, coconut shells, cocoa and coffee powder, polystyrene and polyurethane foam granules, and mixtures thereof, as will be explained in more detail below. The optional component d) also includes blowing agents in order to foam the composition in a targeted manner if a foamed flame-retardant surface or a flame-retarded 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), b) and optionally c) and their mixing ratio in the composition according to the invention, which is why will be discussed in particular later on these three basic components.
The invention makes use of the known fact that proteins are fundamentally difficult to ignite. However, it has hitherto not been possible to produce flame-retardant coatings or articles from proteins or even natural protein sources which in their natural form are not stable to external and biological-natural degradation processes and decomposition influences and hardly combinable with other materials and products. This has now been achieved for the first time by the inventor by appropriate selection and combination of such natural components as well as suitable digestion and crosslinking with, preferably natural, metal hydroxides, bicarbonates or carbonates. The flame retardant properties of the natural proteins are only fully activated, enhanced by optional other vegetable polymers and especially by the base and thus used specifically for flame retardancy. Surprisingly, it was found that proteins, especially animal proteins, after the corresponding digestion and crosslinking reactions with bases also have an unusually good wetting ability and binding power. This brings about a multiplicity of applicability of the composition according to the invention as a coating agent, binder or molding compound.
In contrast to many existing flame retardants, which sometimes severely alter the properties of the products equipped therewith, the invention makes it possible to obtain the desired properties of the end product by appropriate selection of the components, coordination of the particular formulation and control of the crosslinking reactions during processing of the composition into flame retardant products set wide limits and adapted to numerous materials. The efficiency of the protein flame retardants according to the invention is decisively influenced by the particular materials and products to be equipped, especially since non-absorbent, synthetic and closed-line products require different formulations than open-cell, absorbent materials and products to which a superficial flame retardant is more firmly anchored and which in part chemical reaction can be included in the crosslinking process. Therefore, even with low concentrations and with the simplest combinations of disrupted proteins, different materials can be equipped with flame-retardant and even flame-resistant properties.
Proteins are macromolecules composed of amino acids with high proportions of nitrogen, which, when used in a flame retardant composition according to the invention - without wishing to be limited to one theory - trigger two effective mechanisms even with low heat exposure: 1) The protein macromolecules are already under thermal stress split early, which shows with increasing temperature development on the basis of color changes from yellow over yellow brown to black (charring). Proteins usually do not burn and char with elimination of H 2 O, N 2, CO, CO 2 and NO x. For this reason, large amounts of energy are consumed for cleavage of a protein and formation of fission products, and at the same time deoxygenated the environment, so that complete combustion is hardly possible. The residue, i. the combustion product is a predominantly carbonaceous mass that forms a charred, soot-like layer. It should be noted that soot is produced by incomplete combustion along with carbon monoxide and is a visible indication of oxygen deficiency during combustion. 2) Under the action of flame, a heat-insulating soot layer builds up on a surface produced from the composition according to the invention, which at the same time blocks the access of oxygen and makes the transfer of heat difficult and, in the optimum case, even prevents both.
Natural protein sources and plant components with protein moieties usually contain undesirable concomitants, e.g. Fats, sugars, starches, cellulose, etc., which actually have the opposite effect in terms of fire resistance or flame retardancy. Starch, for example, is a polysaccharide that has sufficient oxygen in its structure and can release it on thermal decomposition of the molecule, which rather promotes fire behavior. Starch products can therefore also burn without external oxygen supply, as for example as an independent " glow " is known. Of the optional herbal component c) of the composition according to the invention, therefore, primarily its protein content is to be regarded as advantageous.
However, the invention uses all components of animal and optional vegetable protein sources with all accompanying substances, since they can be crosslinked in complete and joint digestion with the natural reaction and crosslinking components to highly effective flame retardant and preferably non-combustible coating and binding agents. The individual components of a composition according to the invention are described in more detail below.
Component a) - Animal protein
Without wishing to be bound by any particular theory, it is believed from the results obtained that of the possible components of the composition of the invention, the animal protein is responsible for the internal cohesion of the constituents of the composition due to the functions explained below. Through targeted and suitable selection of the animal -8- ·· * ······ * # * * · · · · · · · · · · · · · · · · · · · · ·. φ • · * > ι **! ! ··· * · «; ι · * * · · · «« «ι
Protein can also be prepared or improved compatibility with optional fillers and additives. The following statements apply in part also to vegetable proteins described in more detail later: Proteins, especially animal proteins, have after the reaction, i. including cross-linking, with other components of the composition according to the invention 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 flame-retardant surfaces in the targeted application in a flame-retardant 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 crosslinking, increase the internal strength of flame retardant coating and binder systems, which are enhanced by the particular reactants selected, i.e., the 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. Non-limiting examples include collagen, gelatin, skin glue, bone glue, bone meal and eggs. Animal proteins are of 100% natural origin and are therefore fully biodegradable and, moreover, relatively inexpensive. In preferred -9-
Embodiments of the composition of the invention include as animal protein milk proteins, more preferably in the form of 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. Particularly preferred are milk and milk products with a low fat content, since these are the most effective and at the same time most efficient animal protein source, since besides the protein at the same time further, highly effective dispersants are introduced into the accompanying substances. In addition, the amount of water in the formulation can be specifically adjusted by selecting the milk product.
Furthermore, the composition of milk and dairy products is not as volatile as those of other natural protein sources, since casein proteins account for about 80% of the protein content in milk as the main ingredients. The accompanying substances present in the original and naturally occurring protein source milk, such as, for example, sugar and fat, are not directly desired in the composition according to the invention because of their ease of flammability, but they do not interfere even in small amounts since they increase the compatibility of the components with one another Support and improve those with the additional, optional components.
In addition to the milk protein and skin glue compositions described in the later examples, other animal proteins were also tested and compared for their suitability and effectiveness for the preparation of flame retardant coatings and articles in simple parallel experiments. 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.
Purified, concentrated and industrially processed proteins, e.g. Casein, or synthetically produced proteins are, of course, equally applicable according to the present invention and in combination with the other components have a comparable flame retardant effect as the corresponding natural product; For example, flame retardant products produced with casein as component a) have similar properties to those produced with milk or milk products. Due to the weaker dispersing properties, the economy and the limited availability of " pure " Proteins, however, are not preferred according to the invention.
Component b) - 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 proteins into 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 ensured that by the in 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 slow natural rotting of the coatings or articles made from the composition of the invention after deposition thereon. In addition, light metals react with alkaline systems, so that the composition of the invention for flame retardant finishing of light metal surfaces or at the same time as a binder or adhesive for other combinations with light metals can be used. It should also be noted that alkaline systems saponify fats and thus neutralize both fat deposits in the formulation as well as traces of grease or grease contamination on surfaces to be coated, which represents a significant advantage for a coating system.
Among others, NaOH, KOH, Ca (OFI) 2, NaHCC > 3, NFI4HCO3, potash, wood ash, soda and ammonia have proved to be preferred reactants and components of action. For cost, availability, handling and toxicity reasons, the base used in the composition according to the invention is preferably Ca (OH) 2, NaOH or KOH or a mixture thereof, more preferably Ca (OH) 2 in the form of lime, more preferably a mixture from lime lime and at least one alkali metal hydroxide, in particular a mixture of lime 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 cost reasons, should be premixed with the animal protein and optionally also with optional vegetable components and optionally heated together to provide at least one causing partial, preferably complete, digestion of these components before adding the lime and optional fillers or additives, as further detailed below. If the base comprises a carbonate or bicarbonate, by means of which the water resistance can be increased, this is preferably likewise added only in the last mixing step, in order to prevent any foaming of the mixture, if this effect is not explicitly desired.
Various optional components may be incompatible with strong bases. However, according to the present invention, this effect is due to the proportion of protein in the protein. "* * * * * * * * I ·» · · 1 * * ·· · ♦, * * * * * ···· * 4 ······························································································ NaOH is used, of which NaOH is pre-mixed as digestion and reaction component with component a), before the otherwise incompatible component and - at the same time or only afterwards - the slaked 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 (i.e., react with water) for at least three months to fully convert the calcium 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 optionally vegetable constituents and the degree of crosslinking of the polymers contained can be controlled. For example, larger proportions of NaOH which are preheated together with components a) and optionally c) cause the properties of the animal proteins and of any vegetable polymers to become 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.
It depends above all on the quality of the starting materials and their combination, but also on the desired properties of the flame retardant composition, whether the base component is more or less diluted dissolved or used as a solid or as a combination thereof. For example, hydrogen carbonates are used specifically for pulping and / or when foaming is desired in the later thermal processing process. In this case, the released CO2 is used to enhance the carbonation in the system and / or to accelerate it by reaction with other components. -13 -
It is important to keep the composition alkaline overall and to reconstitute it with at least slight excess of alkali. Especially when using natural vegetable products, it is advantageous if their protein and starch portions are also attacked by the base and partially dissolved before curing and cross-linking and thus involved in the reactions with the animal protein. However, in combinations with synthetic products, alkalinity is also advantageous because it aids wettability and chemically digests residual traces of fats or other interfering surfaces of contaminants, e.g. especially by saponification.
Optional component c) - Vegetable polymers
Of the herbal polymers, which are not to be understood here exclusively, but in particular vegetable proteins and polysaccharides and the latter especially starch and cellulose, it is assumed, on the basis of their characteristic properties (again without wishing to be limited to a particular theory) primarily support the adhesive and adhesion promoting functions of the coating and binder systems of the invention and stabilize and reinforce the internal strength of the targeted systems.
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 accompanying substances of vegetable proteins, which are rather disturbing in pure adhesive systems because of 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 and fire-resistant behavior are combined with a high degree of crosslinking. Upon complete digestion of the starch and sugar ingredients and subsequent carbonation / cross-linking with calcium hydroxide, the " glow effect " of starchy products.
In the present invention, plant proteins may be an important means to enhance the binding and adhesive power to a carrier medium or to any fillers, as well as to optimize the crosslinking and water resistance of the flame retardant products produced from the composition.
Divided into main groups, the following vegetable protein sources are particularly suitable. - cereal products containing gluten (gluten), e.g. Barley, Wheat - Other vegetable proteinaceous fruits such as rice, corn, potato, lentils, beans, peas - high protein protein plants and plant fruits, e.g. Soya - Protein waste products from the production of starch, oil or alcohol - Protein-containing waste and food-processing waste products, e.g. Breadcrumbs - Protein-containing products that are digested and cross-linked in the course of the flame-retardant finishing or binding of a vegetable material only in the second processing step, as specified below, for example, grasses, bovine granules, vegetable fiber - 15-
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 invention. Glues in particular aid and improve the adhesion and adhesion of compositions of the invention, while maintaining elasticity through their flexibility while increasing the internal strength of elastic blends ,
Other preferred vegetable protein sources contain, in addition to their emulsifying, wetting and more or less strongly adhesive and elastic action, water-binding pentosans or slime-forming hemicelluloses, i. Substances which ensure sufficient surface wettability in wet or wet conditions in highly crosslinked (water-resistant) mixtures.
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 of digested proteinaceous substances, starch components can be uniformly crosslinked with alkaline earth metal hydroxides and "carbonated" with C02 to water resistant, very stable, solid, flame retardant products.
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. Particularly preferred in the composition according to the invention is, as a source of vegetable polymers, legume flour, e.g. Pea flour, or cereal flour contain, since this simple availability and correspondingly low price 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, at a relatively low fat content. 2% fat, oats: about 63% starch, about 12% protein, about 7% fat). Wheat flour, rice flour, maize flour, potato flour and soybean meal (reduced fat) have proven to be particularly advantageous and economical, which, in addition to their precisely defined composition, quality and quantity, are also the most economical.
From the viewpoint of fully digesting and crosslinking natural vegetable protein sources, preference is given to products which can be ground to a fine powder or already present in an open-ended state, for example after a cooking or baking process, e.g. Breadcrumbs. In addition, the vegetable components (with the exception of any targeted oilseeds) have a low fat content and should be composed of few and well-known constituents so as not to disturb complete digestion and cross-linking. The use of a slurry of the vegetable component with the lowest possible water content is also provided according to the invention and is preferred in some cases, e.g. when the animal protein is used in powder form.
As already described for the animal proteins, it is also possible with the vegetable components to utilize waste products or residues or to use purified industrial individual components of vegetable raw materials (for example starch, gluten, bran, pomace, etc.) in a targeted manner.
Optional component d) - Fillers, additive fillers
Almost all natural and synthetic fillers and additives are included in this group. Critical to the selection are the properties of the filler and its proportion in the composition. To illustrate the various possibilities of optimizing the effect of the compositions according to the invention by means of fillers, some preferred, non-limiting representatives of this group are characterized in addition to those mentioned in the examples below.
Bone ash (Spodium): Bone ash is a highly interesting and at the same time very effective filler and, due to its chemical composition, an additional effective flame retardant. Spodium consists of 73-84% calcium phosphate, about 10% calcium carbonate, 2-3% magnesium phosphate and about 4% calcium fluoride. This filler is useful in flame retardant coating systems, especially for paints, since its heat resistance and flame resistance are very high and it optimizes its effectiveness in the new natural protein system of the invention. The only small drawback is the halide content, i. calcium fluoride, which is relatively low and because of the high reactivity of fluorine hardly pose a significant problem in combustion gases. However, this point should be considered in the recipe selection.
Cork granules or cork powder: Cork has basically fire-resistant and fire-retardant properties. In a composition of the invention, its flame-retardant properties in the formulation can be additionally enhanced or optimized. When using the composition as a binder for such cork fillers, absolutely non-combustible cork products can be produced.
Natural Fibers: In addition to inherently incombustible fibers such as metal fibers and glass fibers, it may also be advantageous to use natural pulp, wool, hair, etc. based on pulp or collagen as fillers. The fibers may be treated with a specially formulated formulation of the composition of the invention, e.g. With a slightly increased base content, chemically digested, are thus cross-linked and thus flame retardant, fire-resistant and are inextricably included in the drying and curing process. Depending on -18-
Concentration and quality of the pulp can be made using such natural pulps from the composition either an optimized binder system (adhesive pulp), or it can be cured and crosslinked as a filled molding compound to form an extremely stable lightweight component.
An adhesive slurry with fibrous materials additionally has advantages where the adhesive strength of the unfilled binder system is insufficient to provide a strong, non-releasable coating on certain materials, e.g. those with smooth surfaces. For example, straw, reeds, bamboo, grass, polyolefins, etc. all have smooth surfaces and are therefore hardly bondable. In this case, the surfaces may be enveloped with a fiber filled composition, thereby overcoming the poor bondability. The same principle can be transferred to other, not or poorly bondable material mixtures.
Volcanic ash, glass foam: Volcanic ash and glass foam are available in a wide variety of qualities and shapes. However, the most decisive product characteristic can be seen in the foamed, open-pore structure of the particles and the silicate-containing composition. Above all, the advantage of this filler is that on the basis of inorganic and incombustible materials, the flame retardant products prepared from the composition according to the invention can be given high stability, light weight and thermal insulation, which significantly increases their fire resistance and resistance. With these fillers also heat insulation products such as polystyrene foam or polyurethane foams can be effectively flame retardant without sacrificing any significant degree of insulating properties. Using the composition as a binder for larger amounts of volcanic ash results in new flame resistant, lightweight and heat and sound insulating products.
Coconut shells: Coconut shells are extremely strong and permanently stable products which, in the milled state according to the present invention, are outstandingly suitable as fillers in order to increase the strength and durability of the products. The effect -19-
is similar to the natural fiber materials mentioned above, when the starch and protein components are chemically digested and inseparably crosslinked and integrated in the system. The products obtained from the composition are thereby given a particular hardness and stability. Coconut shells show almost no swelling and are therefore especially suitable for waterproof fire-resistant products.
Cocoa, coffee: Both products have the property to react with the components of the composition according to the invention to form complexes and to support their flame retardant effect. An additional positive effect is the optimization of the water and moisture resistance of the system. Coffee powder swells strongly on first contact with water and shrinks accordingly during the curing process. This must be taken into account in its use and, if necessary, compensated by low concentration, fine grinding or use of dissolving coffee.
additives
In addition to the previously mentioned representatives of this group is a variety of other, preferably natural, auxiliaries or stabilizers for the purpose of optimizing the composition of the invention for their determination and optionally also introduce additional functions.
By way of illustration, three preferred and partly also used in the later examples representatives to illustrate the effect of this group.
Citric acid: This is mainly used in formulations in which, in addition to NaOH, Ca (OH) z is also used as base in certain mixing ratios. The two base components in such formulations tend to react very rapidly and violently in the curing and drying process at temperatures above 90 ° C, causing a short (but not stable) foaming. Therefore, when using the composition as a coating composition, the cured end product does not form a coherent, uniform flame retardant film. Although this is not necessarily a disadvantage, since at the same time a good distribution of the composition on the flame-retardant carrier and a penetration into the smallest pores thereof can be achieved. However, in order to prevent this effect for certain applications and to increase the fire resistance, the composition (preferably in the last mixing step), for example, about 0.1% to 1% citric acid are added. While citric acid itself is not thermostable and rapidly decarboxylates upon heating above 175 ° C, which can be used for targeted foaming (i.e., citric acid blowing agent). However, in the presence of Ca 2+, it is converted to insoluble and incombustible calcium citrate. With citric acid, a radical and ion scavenger is thus introduced into the composition, which bind the otherwise explosively released, excess base components and can be selectively used both for stabilization (foam prevention) and to increase the fire resistance.
Silica: An inert inorganic product available in a wide variety of natural and industrial grades. This product family has exceptional properties by which the composition of the invention can be stabilized and their reactions can be homogenized. In combination with selected reactants, the hardness, strength and weather resistance are increased, the chemical resistance is optimized and the fire protection effect is significantly improved. Depending on the product and quality, noticeable changes in properties are already achieved with very small amounts (for example, from 0.1%).
The following known silica-based products may be mentioned by way of example: quartz flour, diatomaceous earth, volcanic rock or volcanic ash, or else the industrially produced products glass foam and Aerosil. Each of them has its own specific characteristics and modes of action and can be used for different purposes and considerations.
Alginates: These polysaccharides are known natural thickeners and emulsifiers that are industrially used mainly in the food industry. -21 -
In the presence of free calcium ions, alginates react by crosslinking to form long-chain, branched macromolecules, also known as " bridge-building support structure " is understood. In addition to the positive effect that, when used in a composition according to the invention settling of pigments or other massive components can be avoided, a similar stabilizing effect can also be used selectively where foamed masses are permanently foam-stabilized and converted into solid, stable foam products , The crosslinking reaction of alginate with calcium also has the advantage that the alginates themselves are stabilized against the otherwise usually rapidly onset of biodegradation and protected against rotting in an alkaline environment.
Short fibers: This means fibers from about 0.1 mm fiber length, which have an emulsifying, stabilizing effect as well as a wetting and adhesion promoting effect. The use of short fibers as additives may be due to different objectives. Depending on the fiber type and type, the drying of the aqueous system can be accelerated or slowed down. Short fibers counteract crack formation during the drying process even in very low concentrations and ensure smooth continuous layers or thin films. In foamed systems, short fibers perform foam-stabilizing functions and, thanks to the support effect, ensure sufficiently uniform and stable foam structures until hardened. Kurfasern also have adhesion enhancing effect of coating or binder systems on smooth surfaces. When using non-combustible short fiber grades, the flame retardant effect of a coating or article of the composition of the invention can be further improved and, if desired, the solids content in the formulation increased.
production method
Due to the large number of possible optional components and their properties, it is difficult to provide a general process for the preparation of the composition according to the invention and for its processing into anti-flocculating agents.
* * * * I! I! I ····· »9 0, ·· ** · * · ♦ · f» t
Specify surfaces or objects, as many component-specific considerations are to be made. Basically, however, a distinction must be made between the following cases. A) Reactive, i. airborne self-crosslinking compositions consisting essentially of animal proteins and base and containing no or very low levels of vegetable components. These have a very short pot life and can therefore be processed very quickly. B) Non-reactive compositions composed only of animal or animal plant components. These have a significantly longer shelf life. This group is still divided into: B1) digested and precrosslinked compositions and B2) undigested and non-precrosslinked compositions. A) Reactive, self-crosslinking compositions
These are essentially produced by simply mixing components a) and b). Depending on the protein concentration and type of animal protein, the addition of the base as a reaction and crosslinking component, preferably an alkaline earth metal hydroxide such as Ca (OH) 2, the digestion of the protein and at the same time the crosslinking effect started, depending on the protein concentration relatively quickly to complete Networking can lead. The fully cross-linked animal protein forms a compact, gelled mass that loses its stickiness with increasing drying and is difficult to process. Therefore, it is important to process the mass prior to its complete crosslinking.
This self-contained airborne process can be supplemented, if necessary, either by the addition of water or by cooling, e.g. to 5-15 X, significantly inhibited or at least slowed down.
The advantages are rapid and economical processability, low water input and, with a high degree of crosslinking, good water resistance of the final product. -23-
The disadvantage is that until complete crosslinking a thermally assisted drying and curing must be carried out at not more than 65-70 ° C, so as not to provoke premature degradation of the macromolecular protein. ΒΪ Non-reactive compositions
Here, the following general procedures should be followed to obtain optimum compositions and flame retardant products made therefrom. BP Non-reactive, disrupted and precrosslinked compositions In addition to the animal protein, these preferably contain an alkali metal hydroxide as base component bi) and lime limestone as base component b2) and optionally optional components c) and d).
The first step in the preparation is to mix component a) with alkali metal hydroxide bi), digest the protein by uniform mixing and then optionally optional components c) and / or d) mix and disperse uniformly without lumps.
In the second step, the non-protein impurities of component a) and optionally also component c) are thermally digested in a cooking process. In order to ensure complete and uniform dispersion of component b2), the digested and cooked mass should be cooled to at least 30-35 ° C and only then, in the third step, the crosslinking component Sumpfkalk be mixed and dispersed. In subsequent, further steps, further components d) can be added.
This procedure ensures the compatibility of the mixture components with each other and the long-term storage stability of the composition.
Compositions which are based exclusively on animal proteins, but can also be formulated non-reactive without thermal process and subsequently -24- be digested during processing, crosslinking. For this purpose, component a) with reaction component bi) is first digested in the first working step. The composition is already flame retardant in this state, but not water resistant. Therefore, reaction component b2) is preferably mixed in a second working step in order to increase the degree of crosslinking and thus also the water resistance, at the same time processing into flame-retardant coatings or articles.
This procedure results in the protein being first digested and thus losing its reactivity, and preferably only in the later thermal processing for producing flame-retardant products therefrom (which in this case can also be carried out well above 70 ° C.), with the reaction component c2). is offset and networked.
Such compositions are usually storage-stable for only a few hours or days, since the chemical digestion and cleavage process of the proteins in the alkaline medium continuously continues and degrades. The cross-linking effect in the presence of both base components is not as pronounced in pure animal protein recipes as when using lime alone. However, animal protein after digestion with component Ci) has the advantage that higher processing temperatures can be replaced because the protein is already digested. B2) Non-disrupted and non-precrosslinked compositions This applies in particular to compositions containing animal and vegetable proteins, where thermal digestion occurs only during processing in a thermal processing process in which the boiling point is reached.
For this purpose, the components are mixed in the same sequence as described under B1) without thermal digestion of the accompanying substances. The result is again a composition that can be stored for only a few days and only at the
Processing is completely unlocked and networked. The mass is characterized by the lack of thermal digestion and the unreacted pre-crosslinking in their behavior "biologically marked". and is therefore not stabilized against biodegradation processes (molecular degradation, segregation and mold formation on prolonged storage). However, this deficiency can be remedied by appropriate stabilizing additives if necessary.
The invention will be described in more detail below with reference to illustrative, non-limiting embodiments.
EXAMPLES
To illustrate the mode of operation and the broad scope of the present invention, various formulations have been developed for the preparation of compositions according to the invention, which were used either as a coating for the production of flame-retardant surfaces on carriers or as a molding material / binder for the production of flame-retardant articles. The respective behavior under flame exposure or fire behavior of these products was examined by a simple and at the same time effective test procedure and compared with each other.
Regardless of the type and size of specimens, both an edge and the main surface of the specimens were heated with a propane gas torch at full power, loading and evaluating the parts to be tested in a horizontal position relative to the flame and perpendicular to the flame. The distance to the burner was adjusted so that the tip of the flame just touched the sample. The firing time was limited to a maximum of 3 minutes continuous load, depending on the fire behavior of the respective test specimen, and was noted as well as special events, e.g. Smoke, unusual, intense odor, noise and the like.
In order to check the different formulations for their effect and properties, paper, nonwovens (natural fiber and -26- synthetic fiber), cork (granules and plate products), wood (wood chips) and polystyrene foam (EPS granules) were used in the examples below Equipped with protein flame retardant or compositions of the invention used as a binder and made of flame-resistant components.
For economic reasons, all formulations were each designed for the highest possible concentration, but can be adapted to any conditions in practice for each application.
example 1
Reactive, self-crosslinking composition of milk proteins and filler
Component Ingredient Weight proportion a) Pot / quark, approx. 1% fat content 40.0% by weight b) Lime lime (at least 3 months old) 20.0% by weight _d). _ Blähqlimmer flour 40.0% by weight 100.0% by weight
Alternatively to the expanded mica flour, any available finely powdered stone meal or inorganic pigment, e.g. White pigment, used or mixed in addition. Their effect is comparable, although the hardness of the dried coating differs. Bloating Mica is characterized by the fact that a " schup-penförmige " Microstructure is present, which leads to smooth and smooth coatings with high surface hardness. Similar effects were also observed with color pigments, e.g. Titanium dioxide, observed, which influence the surface properties smoothing due to their structure.
Step 1: Quark and swamp lime were thoroughly mixed and completely digested to basal binder.
Step 2: Blähglimmer flour was stirred and finely dispersed (roller mill, bead mill or dissolver stirrer disc, depending on the fineness of the powdered stone powder) care being taken that no lumps were formed or a to -27-
developed high frictional heat, which would accelerate the independent reaction in addition.
The mass can be diluted depending on the desired consistency with water. It is important that this approach is processed quickly, ideally within 1 hour. With a foreseeable longer processing time, small amounts of water may be added after mixing to reduce the reaction rate, i. to extend the pot life.
The system is self-crosslinking, the coating dries and crosslinks at room temperature within a few minutes. Thermally assisted, the drying process can be additionally accelerated, but should not be charged above 70 ° C until fully cured. The fully cured coating was and remained durably heat-resistant and fire-resistant. At higher coating levels, shrinkage or drying cracks in the coating can occur on hard and stable substrates, such as by adding 1-2% short fibers {e.g. 0.2 mm long) to the recipe.
Result and effect: Used as a coating, surfaces are equipped with a fire-resistant and wet-resistant and firm protective layer. The viscosity can be adjusted by changing the rock flour concentration or by adding water to the respective application technique. Dyes or pigments do not disturb this flame retardant, but should be carefully selected for their chemical composition so as not to produce toxic hydrolysis products. In temperature-sensitive or thermally shrinking products, the thermal stability is increased by external heat. In the case of wood and other natural carrier materials, the coating adhesion is markedly enhanced by the chemical disruption effect of the coating. The fire-protective effect is given up to the time at which the carrier material behind the fire-retardant protective layer pyrolysis gases developed. Stronger and lasting heat does not prevent the formation of pyrolysis gases in the carrier medium that burn in the open flame of products coated in this way. To avoid or improve this, this flame retardant can also be used as a binder in the carrier material.
Example 2
Non-reactive, thermally digested and precrosslinked composition
Component Ingredient Weight fraction a) Milk, approx. 1% fat content 60.0% by weight bi) NaOH solution, 10% 5.0% by weight b2) Sumpf lime (at least 3 months old) 20.0 wt. -% c) soy flour (Hensel) * 5.0 wt .-% d) _ SiO (Acematt) 10.0% by weight 100.0% by weight *: "Flensel soy low in fat", 48% protein protein, 15% starch, 8.5% sugar, 3% fat
Step T. Milk was predispersed with SiO 2 and digested with the NaOFI solution, then soy flour was mixed in and dispersed.
Step 2: The milk-flour mass was brought to cooking temperature and completely digested, then cooled.
Step 3: The lime lime was mixed in and dispersed finely on the roller mill.
This formula is non-reactive and storage stable for months. The drying can be carried out at room temperature, but better in a thermally supported drying and curing process. The viscosity can be adjusted to the desired consistency by adding water. This composition is suitable for both paint systems and as a fire retardant binder.
Result and effect: Comparable with Example 1, except that the coating contained no granular constituents, was more crosslinked and better stabilized against external influences. -29- «· * ·« · · «
Example 3
Composition with animal protein from eggs (whole egg or egg white)
Depending on the application and the technology used, different formulations for surface flame protection can be selected. Fuller has the advantage of better dispersibility and very good wettability due to the fat content in the egg yolk, which can be additionally digested (i.e., saponified) with a higher base level, as otherwise it may affect the water resistance. However, this fat content has the advantage of producing a flexible film or a somewhat more flexible and smoother coating. Protein on the other hand leads to harder flame retardant layers and is slightly tackier in the beginning than whole egg.
Both raw material sources can be easily prepared as non-water-resistant coating and binder compositions by digestion with alkali metal hydroxides, during mixing a strong gel formation occurs immediately, which can be eliminated by means of temperature control to about 60-70 ° C to facilitate the processability,
Hydroaluminum hydroxides lead to water resistant and reactive compositions, and their handling in the preparation of the composition and its processing is more demanding. A mixture of Akalimetallhydroxiden and alkaline earth metal hydroxides and / or bicarbonates and / or ammonia acts with whole egg and protein property-optimizing and can be implemented in appropriate formulations for processing and quality-optimized products.
By way of example, two recipe examples follow that describe the modes of action and possibilities of using eggs as the source of the animal protein.
Component Ingredient Weight percentage a) Egg white 80.0% by weight b) NaOH solution. 10% iq 20.0% by weight 100.0% by weight 30%
This formulation immediately formed a non-stable gel, which under the action of temperature (maximum 70 ° C) in a permanently medium viscous, viscous mass passed. The wetting ability of the digested protein was very pronounced, which has the advantage that thin layers of this composition are well anchored mechanically due to the strong capillary action on open-cell products.
When this composition was applied evenly and richly on paper on both sides, e.g. with about 20 g / m2 total coating / dry substance, this resulted in self-extinguishing (though not waterproof) paper products.
Component_component_weight% a) whole egg 60-80.0% by weight _b) _slow lime (at least 3 months old) 40-20.0% by weight _ 100.0% by weight
Such formulations are highly reactive, with gel formation and crosslinking starting within a few minutes. The higher the Ca (OH) 2 content, the stronger the crosslinking, the flame retardancy and also the water resistance. They are interesting from an economic and qualitative point of view, because in the processing process an effective coating result can be achieved very quickly.
The drying can be carried out simply at room temperature or else with thermal support, preferably with radiant heat. The strength of the coating or the coating film is influenced by the heat of drying. At room temperature or thermally assisted drying up to 60 ° C stable and solid films and coatings were obtained. At drying and curing temperatures above 70 ° C, the flame retardancy remained, but the strength of the coating degraded with increasing drying temperature. It has proven to be advantageous to use a two-stage drying system in which, in a first step at room temperature or slightly thermally assisted (up to 60 ° C.), a fully-filled ... - .. -: ...... ..: V * '' Continuous crosslinking takes place and then the drying takes place without loss of quality at temperatures of up to 90-95 ° C.
Optional additives can be mixed in, for example, to optimize the appearance or the flame-retardant effect.
Paper was fully coated on both sides with about 20-25 g / m 2 (dry matter) with the above whole egg / Ca (OH) 2 formulation and dried at room temperature and cured. This resulted in a ratio of 80:20 a clearly established, self-extinguishing and conditionally water-resistant product. A coating test on the same paper quality with a composition of whole egg and Ca (OH) 2 in the ratio 60:40 resulted in an even stronger, stable and water-resistant product, which burned in the open flame, but extinguished immediately without flame exposure. In both cases, no afterglow of the thermally stressed paper was observed. The coatings were chemically and mechanically anchored in the paper, which is thus permanently flame retardant.
Example 4
Reactive and highly cross-linked mixed animal composition
Component Ingredient Weight fraction ai) Quark, approx. 1% fat 50.0% by weight 82) Skin glue, 40% 20.0% by weight b) _ Sumpfkalk imind. 3 months old) 30.0% by weight 100.0% by weight
Step 1: The quark was digested with the swamp lime.
Step 2: The skin glue warmed to about 60-70 ° C was mixed with stirring into the digested quark mass and dispersed lump-free. - 32-
The processing of this composition must be done quickly because it is very reactive and sometimes gelled within an hour. Pot life can be significantly increased by adding small amounts of water (e.g., 2-5%).
Paper and PET nonwoven fabrics (PET spunbonded fabric having a basis weight of 60 g / m 2) were coated on both sides with the composition, resulting in stable and consolidated fabrics. The pyrolysis gases of the carriers burned under the action of flame, but the flame retardant products extinguished immediately upon settling of the flame.
The coating can be cured both at room temperature and thermally, preferably between 60 and 100 ° C, more preferably at about 65 ° C, cured and crosslinked. Temperatures above 100 ° C are possible for a short time, but then rapidly lead to the thermal degradation of the proteins, which is reflected by a corresponding yellow-brown color. The flame retardancy is not lost though.
The wettability is unusually high due to the amount of skin glue and additionally increases the adhesion to carriers or fillers.
Paper was coated with this composition and spun fleece and PU foam were impregnated. All products were dried at 65 ° C in a convection oven for 20 minutes and cured and immediately subjected to the fire test. All products so charred on the surface and extinguished immediately when the flame was removed. -33-
Example 5
Non-reactive and highly cross-linked animal-vegetable composition
Component Ingredient Weight fraction a) Milk, approx. 1% fat content 60.0% by weight bi) KOH solution, 10% 10.0% by weight b2) Lime lime (at least 3 months old) 20.0% by weight -% ___ c) __ Soybean meal (Hensel) 10.0% by weight 100.0% by weight
The high protein content (animal and vegetable) of this composition causes the digestion with potassium hydroxide immediately increases the viscosity very strong and forms a tough, sticky mass. The flame retardant effect is very pronounced due to the high protein content.
Step 1: Milk was predispersed with KOH and then soy flour was mixed in and dispersed.
Step 2: The digested milk-flour mass was brought to boiling temperature to completely digest the starch portions, and then cooled.
Step 3: The lime lime was mixed in and finely dispersed in a bead mill.
Although drying, curing and crosslinking at room temperature is possible, it is recommended that thermal drying processes up to 130 ° C, preferably in the range 90-100 ° C, use. Temperatures above 130 ° C are possible for a short time. Then, however, there is a thermal degradation of the proteins, but without the flame retardancy is lost.
Open-cell foam (PU foam) and various textile fiber fabrics were thoroughly soaked with the flame retardant compound and cured, resulting in stable and consolidated, flame-retardant and water-resistant fabrics. Under the action of flame, the pyrolysis gases of the excipients occasionally burned with them;
Setting off the flame extinguished all flame-retardant products but immediately.
Example 6
Non-reactive, non-open-minded and non-pre-crosslinked composition
In this example, the same components were used as in Example 5, but in the preparation of the composition, step 2 (heating the batch to digest the starch portion) was omitted.
Component Ingredient Weight fraction a) Milk, approx. 1% fat content 60.0% by weight bi) KOH solution, 10% 10.0% by weight b2) Lime lime (at least 3 months old) 20.0% by weight -% c) _ Soybean meal (Hensel) 10.0% by weight 100.0% by weight
Step 1: Milk was predispersed with KOH and then soy flour was mixed in and dispersed.
Step 2: The lime lime was mixed in and finely dispersed in a bead mill.
This composition, after wetting and / or impregnating an open-celled carrier, requires a thermal manufacturing process beyond 100 ° C to break up and crosslink the starch portion in the soybean meal during processing. It has its greatest economic advantages in those cases where materials are subjected to thermal drying processes in a processing process, so that they only have to be equipped (coated, soaked, etc.) with the composition at room temperature, after which the composition is completely digested in the given process , reacts and finally hardens. -35-
The composition can not be stored for long and should be processed within a few days.
Both compositions, from Example 5 and Example 6, can be used without problems as a coating composition, as a molding composition and as a binder.
The following are examples of the production of components made of synthetic foams.
It is generally very difficult to subsequently retrofit synthetic foams and foam products. A distinction is made here between closed-cell and open-cell systems, which in the event of fire raise the problem of favoring the burning behavior due to their large surfaces and the high proportion of air or gas in the cells. In addition, there are the strong heat-insulating properties of these materials, which cause thermal energy can penetrate only slowly, but at the same time also hinders cooling-acting flame retardant and sometimes even ineffective.
Flame retardants that are not incorporated into the polymer matrix of these foams but are subsequently applied as an outer layer can only hinder, but not prevent, the burning off of pyrolysis gas in the flame. This effect can be counteracted by shifting the concentration ratios in favor of the flame retardant agents, or by additional nonflammable fillers adapted to the properties of the starting material. In each of these cases, although the properties of the starting product are changed, this can be advantageously used to create new product qualities.
From this point of view, recipe examples for polystyrene foam (EPS) and polyurethane foam (RG 55) were created, resulting in stable and strong parts. -36-
Example 7
Reactive, self-crosslinking binder system
weight proportion
component
Component a) b) dl
Quark, approx. 1% fat content 40.0% by weight
Lime lime (at least 3 months old) 20.0% by weight 40.0% by weight
Bone ash 100.0% by weight
Step 1: Quark and swamp lime were thoroughly mixed and completely digested to basal binder.
Step 2: The bone ash was stirred in and finely dispersed by means of a dissolver stirring disc.
The viscosity of the composition was low after fine dispersion, i. it was almost fluid, allowing further adjuvants (e.g., aluminum hydroxide) or drugs to be easily mixed.
This mass can be used as a protective coating or as a flame retardant filling and binding agent. Paper and nonwoven fabrics that were coated or soaked with the mass were nonflammable and self-extinguishing.
In order to produce a flame-retardant component based on polystyrene foam (EPS) re-granules (ie granular recycled styrofoam®), the above composition may be mixed as binder preferably in a ratio in the range of 50:50 to 90:10 with the granules. since the flame retardant effect is sufficiently pronounced only from about 50 wt .-% binder content. At proportions of less than about 50% flame retardant binder, the processing to new products is still possible because of the high binding power of the formulation, but the flame retardancy is then hardly in the case of polystyrene foam products to advantage. - 37-
It should be noted that between the foam, in the specific case the polystyrene foam, and the binder due to the large density differences, a volume ratio of up to 1: 100 may be present, so that a sufficient (weight) amount of flame retardant is required to Surfaces of the granules throughout and completely wet and thus build up the flame retardant. For example, with a mixing ratio of 50% by weight of the above composition according to the invention and 50% by weight of polystyrene foam granules, a volume ratio of around 1: 1000 exists because 100 g of the binder corresponds to approximately 90 ml volume while 100 g of polystyrene foam granulate corresponds to approximately 10,000 ml. The flame retardant composition must therefore have very strong flame retardant properties. However, it can be enhanced in its effect by foaming it, so as to reduce the volume difference and best almost balanced.
The flame retardant binder is mixed with the polystyrene foam granules, introduced into a shaping tool and compacted as desired and required. The higher the compaction, the lower the binder usage can be. After about 30 minutes holding time at room temperature, the pre-reacted and already stable component can be removed and either dried in the air or, more efficiently, by means of thermally and technically optimized manufacturing processes with heating (to a maximum of 60 ° C) and cured.
Polyurethane foam is usually open-celled and offers the advantage, up to a density of 80-100 kg / m3, of being continuously soaked and wetted with the composition according to the invention. Dipping methods are recommended here, according to which the excess of flame retardant can be pressed out in a second step if necessary.
In the case of both finished foams, ie polystyrene foam and polyurethane foam, the effect described above was that, in the case of both products, under severe fire, some of the pyrolysis gases co-burned in the open flame, upon settling However, the thermal energy input of the self-firing process was prevented and the materials were stabilized against melting and dripping.
Example 8
Non-reactive, open-minded and pre-crosslinked composition with plant flour
Component Component Weight fraction a) Milk, approx. 1% fat content 50.0% by weight bi) NaOH solution, 10% 5.0% by weight b2) Lime lime (at least 3 months old) 25.0% by weight -% cl cereal flour W450 20.0% by weight 100.0% by weight
Step 1: The milk was digested with NaOH solution and the cornmeal was mixed in and dispersed,
Step 2: The milk-flour mass was brought to boiling temperature and completely digested.
Step 3: After cooling, the lime lime was mixed in and dispersed thoroughly (lump-free).
This approach is a high viscosity paste with thixotropic properties and can be stored for months at room temperature. The composition cross-links, dries and hardens completely and rapidly only with thermal support.
However, polystyrene foam itself can hardly be thermally stressed and reaches the limits of its thermal capacity at contact heat even at approx. 65 ° C. At this temperature, shrinkage processes are first initiated in the material, and at even higher temperatures, the plastic melts. -39-
• · · I
In order to avoid this and to improve economic efficiency, the shrinkage and melting effect can be significantly delayed in the thermal crosslinking and curing of prefabricated molded parts with contactless heating systems (infrared or microwave). In the contactless heating, drying and reaction process, temperatures of the binder of well over 70 ° C can be set.
In combination with open-celled polyurethane foam, the uniform wetting and distribution of the flame retardant system is more difficult because of the high viscosity, but the formulation itself is more effective than that of Example 7 above.
Example 9
Reactive, digested, pre-reacted composition with pulp
Component Ingredient Weight fraction a) Quark, approx. 1% fat content 40.0% by weight b) Lime lime (at least 3 months old) 20.0% by weight c) Pulp fibers (moist-wet) 40.0% by weight 100 , 0% by weight
The pulp fibers used here can either originate from softened and paperboard recycled waste paper from which the excess water was pressed out and which has a residual moisture content of about 60%, or pulp fibers having a fiber length of preferably not more than 5 mm are mixed with water softened and the excess water again removed by squeezing, The pressing is crucial for the effect and processability to create a homogeneous flame retardant binder pulp.
Step 1: Quark and limestone lime were thoroughly mixed and completely disrupted.
Step 2: The digested binder mass was foamed, after which, with constant stirring, the wet pulp mass was mixed in small portions and thoroughly dispersed. As the pulp mass increased in concentration, the foam was destroyed / dissolved and the mass turned into a tough and viscous slurry.
This approach is not so much reactive in comparison to the other quark recipes, as introduced via the humidified and swollen pulp inhibiting water and run the crosslinking reactions at room temperature slowed down.
Alternatively, however, the moistened pulp mass can also be mixed and homogenized in a compulsory mixer suitable for fibrous materials without a foaming process.
It is very difficult to uniformly disperse dry pulp mass in higher concentrations in aqueous and tacky binders, since the viscosity increases sharply due to water absorption and swelling of the fibers.
Reactive compositions should be dried cured and cross-linked in two stages. After the batch has been blended with all of the components and the part has been shaped, self-crosslinking of the composition, usually at room temperature for at least 60 minutes, at 50-60 ° C for at least 10-15 minutes, should be complete, before with thermal support at temperatures above 70 ° C, but preferably not above 130 ° C, the complete curing / drying and crosslinking takes place.
The cured product was a very compact, hard, nonflammable and water resistant article.
The present composition exhibits the best effect in cases where smooth and / or hard-to-bond surfaces of products (e.g., straw, reeds, bamboo, etc.) prevent firm bonding. -41 -
The pulp flame retardant slurry had a relatively high drying shrinkage and caused by the swollen pulp more expensive drying processes. This effect can be achieved by reducing the water content, e.g. by adding fillers, reduced and optimized.
Example 10
Non-reactive, open-minded composition with vegetable residues
Component Component Weight fraction a) Milk, approx. 1% fat content 55.0% by weight bi) NaOH solution, 10% 10.0% by weight b2) Sumpf lime (at least 3 months old) 10.0 wt. -% cL wheat bran 25.0% by weight 100.0% by weight
Step 1: The milk was digested with NaOH solution and the wheat bran blended.
Step 2: The milk-bran mass was heated to boiling temperature for about 2-3 minutes and thereby fully digested.
Step 3: After cooling, the lime lime was mixed in and dispersed thoroughly (lump-free).
This approach was compact and doughy, had sticky properties and was storable at room temperature for a longer time. It is extremely suitable as a lightweight fire protection filling system in a material mixture and has a similar mode of action as the composition described in Example 9. This binder slurry with bran shrinks more in the drying process than other formulations and should preferably be combined with elastic components to avoid shrinkage cracks. -42-
A combination with cork granules was prepared by mixing in a weight ratio 50% of the composition as a flame retardant binder with 50% cork granules with 2-3 mm grain size and from a plate of 3 mm thickness was produced.
Manufacturing parameters: Shaping tool 300x200 mm, heated on both sides and set to 3 mm nominal thickness; Temperature 120 ° C; Compression of the filling compound 3: 1; Drying and curing time 4 minutes.
The result was a dimensionally stable, lightweight and non-combustible plate that is lighter compared to equivalent commercial products.
Example 11
Non-reactive, open-minded composition with breadcrumbs
Component Ingredient Weight fraction a) Milk, approx. 1% fat content 50.0% by weight bi) NaOH solution, 10% 10.0% by weight b2) Sumpfkalk (at least 3 months old) 10.0 wt. -% _ cl breadcrumb 30.0% by weight 100.0% by weight
Step 1: The milk was digested with the NaOFi solution, the breadcrumbs mixed in and thoroughly dispersed to a homogeneous mass.
Step 3: The lime lime was mixed in and dispersed thoroughly (lump-free).
A thermal exclusion is not required here, because due to the baking process, the starch components of the breadcrumbs are already open-minded.
This approach had only weak tacky properties and was storable for months at room temperature. This composition results in hard and porous flame retardant products and fillers in a material mixture.
A combination with cork granules was prepared by mixing in a weight ratio of 50% of the composition as a flame retardant binder with 50% cork granules with 2-3 mm grain size and from a plate of 3 mm thickness was produced.
Manufacturing parameters: Shaping tool 300x200 mm, heated on both sides and set to 3 mm nominal thickness; Temperature 120 ° C; Compression of the filling compound 3: 1; Drying and curing time 4 minutes.
The result was a hard, light and non-flammable plate, which is significantly more stable and dense compared to equivalent commercial products because the cavities are filled with the hard binder, which is also more crosslinked.
Example 12
Non-reactive, open-minded composition with vegetable flour
Component Ingredient Weight fraction a) Milk, approx. 1% fat content 50.0% by weight bi) NaOH solution, 10% 10.0% by weight b2) Sumpfkalk (at least 3 months old) 20.0 wt. -% c) Chickpea flour 20.0% by weight 100.0% by weight d) NH4HCO3 (powder) (optional) 2.0% by weight
Step 1: The milk was digested with NaOH solution and the chickpea flour was mixed in.
Step 2: The milk-pea flour mass was heated to boiling temperature for about 2-3 minutes, so completely disrupted and then allowed to cool to about 35-40 ° C.
Step 3: After cooling, the lime lime was mixed in and dispersed thoroughly (lump-free). -44-
This approach had only slightly tacky properties and was storable at room temperature for a long time. This formulation is excellently suited as a filling fire-resistant binder in cases where very hard and stable end products are desired.
As an alternative potato flour was used in the same concentration, which led to comparable results.
A combination with chopped straw (grain size about 10 mm) was prepared by mixing in a weight ratio of 50% of the composition as a flame retardant binder with 50% chopped straw and from a plate-shaped component with 3 mm thickness was produced.
Manufacturing parameters: Shaping tool 300x200 mm, heated on both sides and set to 3 mm nominal thickness; Temperature 120 ° C; Compression of the filling compound 1: 1; Drying and curing time 5 minutes.
The result was a very compact, strong, moisture resistant, non-flammable plate.
In a parallel experiment, an additional 2% by weight of NH4HCO3 as blowing agent was mixed into the above formulation, which was then dried by means of microwave heating without a shaping tool. This gave after a curing time of 2 minutes a hard and dimensionally stable, incombustible foamed body.
Example 13
Composition for producing stable flame retardant foams
Component Ingredient Weight fraction a) Quark, about 1% fat content 50.0% by weight b) lime lime (at least 3 months old) 20.0% by weight of Ci) alginate solution, 3% strength in water 5.0 % By weight of Oz) Zelistoff short fibers 2.0% by weight - _d) _ Rock flour 23.0% by weight 100.0% by weight
Step 1: The quark and the limestone lime were thoroughly mixed and opened up.
Step 2: The digested binder mass was foamed by rapid stirring, and after achieving the desired foam consistency, the pulp fibers were mixed in small portions with further stirring and then the alginate solution and thoroughly dispersed.
Step 3: The stone meal was mixed into the foam.
In a first experiment, a base foam having a wet weight per liter of about 0.35-0.40 kg / l was obtained from components a) to c) using a household hand mixer. With forced-ventilated industrial foam blenders, on the other hand, reproducible wet-weight weights of 0.10 kg / l were obtained.
The foam compositions produced in each case from components a) to c) were already permanently stable flame-retardant base foams, which were then mixed with rock flour as filler.
The drying and curing of such flame retardant base foams (without filler) is tedious, since on the outer sides quickly forms a dried-on skin, which hinders a continuous drying and curing. This effect can
be met by the use of fillers or other aids that support the moisture transport or reduce skin formation.
Thermally assisted drying is generally more advantageous in such cases, but care should be taken to ensure that the foam continues to expand if the heat generation is too high. The best drying conditions were previously found at temperatures of about 65-70 ° C with circulating air or with careful radiation energy. Radiation energy has the advantage over ventilated systems that the heat energy is transported continuously and in the medium from the inside to the outside, which significantly reduces skin formation and supports and accelerates the drying and curing process.
The final cured products in this example were hard, rigid, non-flammable foams with a density of 0.3 kg / L, which were flashed and cured as 5 mm thick plates at room temperature without additional drying technique; Drying and curing time: 2 days.
Flame retardant foams, when used as a coating or binder, have a higher surface area and the release of " fire retardant shielding gases " In most cases a much stronger flame retardancy than non-foamed products, but it also "consumes" faster. In the case of permanent flame exposure, it may be decisive how concentrated and how long the flame-retardant active ingredients are available.
The above examples clearly demonstrate that the present invention provides compositions from which highly effective flame retardant surfaces and articles having a wide variety of other properties can be made in a very economical manner. These are preferably composed of purely natural constituents and are both readily recyclable and completely biodegradable upon landfilling. -47-

权利要求:
Claims (21)
[1]
Claims 1. A composition for producing flame retardant surfaces or articles comprising: a) animal protein and b) base selected from alkali metal and alkaline earth metal hydroxides, bicarbonates and carbonates.
[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 as the base Ca (OH) 2, NaOH or KOH or a mixture thereof is contained.
[5]
5. A composition according to claim 4, characterized in that as the base Ca (OH) 2 is contained in the form of limestone lime.
[6]
6. Composition according to one of the preceding claims, characterized in that as additional component c) vegetable polymers are contained.
[7]
7. The composition according to claim 6, characterized in that the source of the vegetable polymers are shredded or ground plants or plant constituents.
[8]
8. The composition according to claim 7, characterized in that the source of the vegetable polymers is cereal flour.
[9]
A composition according to claim 8, characterized in that the cereal flour is or comprises wheat flour.
[10]
10. The composition according to any one of the preceding claims, characterized in that as additional component d) one or more fillers and / or additives are included.
[11]
A composition according to any one of the preceding claims, characterized in that the optional filler is selected from the group consisting of stone meal, bone ash, cork granules, pulps, volcanic ash, glass foam, coconut shells, cocoa and coffee powder, polystyrene and polyurethane foam granules and mixtures thereof.
[12]
Composition according to any one of the preceding claims, characterized in that components a), c) and d), if present, are foodstuffs, food ingredients, food waste or waste products from food production,
[13]
13. A process for preparing a composition according to any one of claims 1 to 12 by mixing the components a) to d), if present, wherein in a first mixing step, a part of the components contained is premixed, after which the remaining components are mixed in a second mixing step .
[14]
14. The method according to claim 13, characterized in that in the first mixing step component a) and optionally component c) with component b) or a part thereof is premixed before the remainder of component b) and optionally component d) is mixed in the second mixing step /become.
[15]
15. The method according to claim 14, characterized in that the mixture of component a) and at least a portion of component b) and optionally component c) between the first and the second mixing step

The boiling temperature is heated to decompose and pre-crosslink component a) and optionally component c).
[16]
16. The method according to any one of claims 13 to 15, characterized in that component b) comprises both Ca (OH) 2 and at least one alkali metal hydroxide, of which at least one alkali metal hydroxide in the first mixing step with component a) and optionally component c) is mixed and the Ca (OH) 2 is mixed in the second mixing step.
[17]
17. Use of a composition according to any one of claims 1 to 12 as a coating composition for the production of flame-retardant surfaces on carriers.
[18]
18. Use of a composition according to any one of claims 1 to 12 as a molding material or binder for the production of flame-retardant articles.
[19]
19. Use according to claim 17 or 18, characterized in that the composition for producing the flame-retardant surface is dried on a support or a flame-retardant article at a temperature between 25 ° C and 160 ° C, cured and crosslinked.
[20]
20. Use according to claim 19, characterized in that the composition is foamed before or during its drying / curing.
[21]
21. A flame retardant surface on a support or flame retardant article which consists of a composition according to any one of claims 1 to 12 in a cured state. Vienna, 19 January 2011 Austria Wirtschaftsservice Gesellschaft mbH Johann Kiss by:

- 51 -

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同族专利:

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公开号 | 公开日

---

EP2665781A1|2013-11-27|

---

AT511015B1|2017-01-15|

---

WO2012097395A1|2012-07-26|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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ATA79/2011A|AT511015B1|2011-01-19|2011-01-19|COMPOSITION FOR PREPARING FLAME-REDUCING SURFACES OR OBJECTS|ATA79/2011A| AT511015B1|2011-01-19|2011-01-19|COMPOSITION FOR PREPARING FLAME-REDUCING SURFACES OR OBJECTS|

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PCT/AT2012/050008| WO2012097395A1|2011-01-19|2012-01-18|Use of protein-containing compositions for producing flame-retardant coatings and articles|

---

EP12716181.8A| EP2665781A1|2011-01-19|2012-01-18|Use of protein-containing compositions for producing flame-retardant coatings and articles|