DE2753651A1 - COMPOSITE MATERIAL - Google Patents

Description

PATE IMTAN ΛΑ '. Γ Ε

-40-

A. GRÜNECKER

Kjeld Holbek APS

Lejrevej 74-, DK-4320 Lejre

H. Kl

OR ING

W. STOCKMAIR

K. SCHUMANN

to FER HAJ OPL PMYS

P. H. JAKOB

dr. iNa

G. BEZOLD

n «wi Μ, οβι

8 MUNICH 22

MAXIMILIANSTRASSE 43

1- Dec 1977

P 12 191

Composite material

The invention relates to a composite material containing cellulosic fibers. The invention also relates to a method of making this material and certain materials for use in the composite material and methods of making these materials.

The invention is based on the concept of uniform incorporation of a polymer material consisting of solid

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individual particles or solid individual fibers with a polymer on at least their surfaces and optionally of inorganic particles or fibers, into a cellulose fiber structure by a wet process using polyelectrolytes to prevent effective flocculation of cellulosic fibers, polymer particles or fibers and optionally inorganic particles or fibers. On this yieise, after dehydration and drying, a product becomes obtained in which the additives are uniformly distributed in the cellulose fiber structure and in which the cellulose fibers are essentially undenatured and bonded together in the normal manner such as in paper or cardboard. The polymer or polymers of the polymer material is or are such that the polymer material at P ^ umemperatur is not tacky and after being incorporated into the cellulose fiber structure and drying is essentially in Remains in the form of individual particles or fibers. On the other hand, the polymers are such that they are capable of doing this are able to flow and have a binding effect or form a film when one puts energy in a suitable Forms supplies, for example by heating.

The cellulose fiber structure with the polymer material incorporated in the form of individual elements and optionally with the incorporated inorganic material represents a valuable semi-finished product which, depending on the special components and their relationship, can be used for a variety of important applications, in which the ability of the uniform incorporated polymers, in the supply of energy in a suitable form, for example by heating, to flow and to exert a binding effect or to form a film, use is made.

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The form in which the polymer is incorporated is one Form that is essentially chemically inert to water and cellulose fibers (which is contrary to the use of the so-called "dispersions" or "emulsions", which are often in the form of polymer forms for incorporation into cellulose pulp be used). As a result, the inherent binding properties of the cellulose fibers are practically not disturbed and it is possible to have coherent structures of the composite material even with very low levels of cellulosic fibers to obtain. A wide variety of polymer forms already on the market for other uses, are suitable for very uniform incorporation into the cellulosic fiber structure according to the invention.

The polyelectrolytes contribute to the uniform distribution of the polymer material and the inorganic material in the cellulose fiber structure. They also contribute to a high Retention when the process is carried out on a papermaking machine, resulting in a maximum Applicability in practice is contributed.

In the state in which the film formation of the polymer has not yet been initiated or brought about, the composite materials according to the invention can be in the form of paper or cardboard-like sheets, webs, plates, rods, profiles, strings or granules. By subsequent application of heat or equivalent forms of energy under sufficient conditions that the binding or film-forming properties of the polymer are triggered, these composite materials can be converted into materials of many different types depending on the ratio between cellulose fibers and polymer material, the type of polymer material , the

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Content of optional additional materials (especially inorganic materials) and of the implementation and Sharpness of the heat treatment and any pressure treatment carried out, etc., can be converted. By The end products obtained the final heat treatment can therefore be made of polymer-impregnated paper, cardboard or cardboard-like Materials up to soft, elastic or hard cellulose fiber reinforced polymer articles and even up to panels or molded articles that appear to have an inorganic character vary. Determine the properties to a large extent from the added inorganic materials, e.g. minerals, including mineral or metal particles or fibers. All of the end products in question are regardless of the large differences that may be possible Their character in common is that they contain cellulose fibers and a polymer as defined above, bsi that the film formation has been triggered. They are therefore made from a semi-finished product or "plastic product", the cellulose fiber, being uniform between the cellulose fibers the polymer material as defined above is distributed and contains polyelectrolyte. The semi-finished product is for most practical purposes a continuous (i.e. a product linked by the cellulose fiber ^) sheet, sheet, plate, rod, profile or string-shaped material. In accordance with some aspects of the present invention make the cellulose fibers a relatively large proportion of the end product and / or they carry in one contributes greatly to the character of the end product, while other end products made from the semi-finished product exhibit properties essentially those of the polymer material used and the additives used. In such cases the cellulose fiber structure primarily as a carrier material in the

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finished product and as an aid to obtaining a uniform Distribution of the polymer material and the added inorganic material and for obtaining further advantages, which emerge from the following statements, served.

The invention therefore contemplates a composite material in semi-finished or finished form. The semi-finished material or the semi-finished material is a cellulose fiber structure in which uniformly dispersed a polymer material is distributed, which consists of solid individual particles or fibers which have a polymer at least on their surfaces, the polymer being a water-insoluble solid synthetic polymer , which is film-forming at temperatures above 80 ^{° C.} The particles or fibers of the polymer material are bound in the composite material by means of a polyelectrolyte. The cellulose structure optionally also contains inorganic particles or fibers made from minerals or metals with the inclusion of hydraulic binders. In the finished form, the film-forming properties of the polymer have been triggered by the application of energy. The finished products or the finished products can be v / oak, elastic or hard materials or moldings. In a process for producing this material, the procedure is that a polymeric material and optionally inorganic material are flocculated together with a cellulose fiber pulp by means of a polyelectrolyte and that the resulting suspension is dewatered on a paper-making machine. The finished product or the finished product is obtained from the semi-finished product by the application of heat and usually pressure.

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The invention therefore provides a composite material which, through a cellulose fiber structure in which the cellulose fibers are connected to one another by bonds, such as in cardboard or paper, is a polymer material uniformly distributed in the structure, the polymer material consisting of solid individual particles or fibers The particles or fibers consist of a polymer on at least their surfaces, the polymer or the polymers of the polymer material being water-insoluble and non-swellable in water, solid, synthetic polymers which are not sticky at room temperature and at temperatures above 80 ⁰ C are film-forming, the particles or fibers of the polymer material being bound in the composite material by means of a polyelectrolyte and the proportion of the polymers being at least 2% by weight of the composite material, and optionally inorganic material in the form of mineral or metal particles or -fa sern, wherein the inorganic material is uniformly distributed throughout the cellulosic fiber structure, is characterized, as well as composite materials made from the composite material defined above by the application of energy to induce film formation of the polymer.

Another object of the invention is a method for producing the composite material described above, which is characterized in that a polymer material consisting of solid individual particles or fibers, wherein the particles or fibers consist of a polymer at least on their surfaces, the polymer or the polymers of the polymer material are synthetic, water-insoluble and water-non-swellable, solid, synthetic Polymers are non-sticky and non-sticky at room temperature

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are film-forming at temperatures above 30 ⁰ C, mixed with a cellulose fiber pulp and optionally with an inorganic material in the form of mineral or metal particles or fibers, the polymer material with the cellulose fibers and with the inorganic material, if this is available, coherently flocculated by means of a polyelectrolyte and then dewatered the resulting suspension to form a coherent sheet, web or extrudate material, the coherent material dries under conditions that do not trigger the film formation of the polymer, the polymer of the polymer material is such that the polymer material after drying essentially remains in the form of individual particles or fibers, and that if necessary the dry material is subjected to a treatment which triggers the film-forming properties of the polymer, for example giner Αην.'βηάνηΓ, from warmth and optionally pressure.

The above-mentioned semi-finished product, which is obtained on drying under conditions which do not trigger the film-forming of the polymer, can, if desired, be subjected to a treatment which triggers or causes the film-forming of the polymer, if desired immediately after drying, optionally in the same production series. This can be carried out, for example, by treatment with heat and, if appropriate, pressure. Alternatively, the semi-finished product can be sold as it is or after granulation, ie in other places, as a "plastic" or semi-finished product for the later production of end products from the semi-finished product by a desired deformation and release the film-forming properties of the polymer.

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The phrase "film formation at temperatures above 80 ^° C." used herein is intended to characterize a polymer which, when applied in the form of a dry powder to a surface and ^{heated to above 80 °} C., is able to undergo within 60 min at the most Formation of a film to dissolve. Under the conditions mentioned, the film formation preferably takes place in the course of about 10 seconds or less to about 15 minutes. It is often preferred to use polymers whose film formation is only initiated at temperatures above 120 ° C. within such shorter periods of time. Due to the water-insoluble and water-non-swellable character of the polymers used according to the invention, they are able to form a film which is practically waterproof and water-resistant.

Polymers that meet the above requirements are various thermoplastic polymers that can, but cannot, continue to polymerize during heat treatment necessarily further polymerize, as well as various thermosetting polymers including such thermosetting ones Polymers produced by a built-in curing or crosslinking agent polymerize, the effect of which is released by a certain heat treatment and the effect may have a more or less rapid onset.

Polymers which are in the form of "dispersions", "emulsions ^II or" sols ", in which the particles grow together to form a film after the water has evaporated, are not considered to be polymer materials for the purposes of the present invention. such dispersions, sols or emulsions of more or less sticky resin materials are widely used as additives for cellulose pulps prior to sheet formation

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used, for example the paper material a better one To give letting resistance. What these resin materials have in common is that they have at least a certain affinity for them Water and the wet cellulose fibers have, but that they also show the tendency to migrate with the water. Farther the procedural measures, additives and modifications tend to emulsify or disperse such polymer forms are used in water and / or for imparting emulsifiable or dispersible properties v / ground, at the same time, to reduce the ultimate strength properties. In general, they are unable to to give solid films or bonds, as is the case with the water-insoluble and water-non-swellable solid Polymers that are used according to the invention is the case, which under the incorporation and drying conditions ~ ur-g2n not grow together and. which as practically chenisch Can be characterized inert to water and cellulose fibers and the d; ihcr the pH conditions of the cellulose pulp or the hydrogen bonds between the cellulosic fibers do not bother.

The polymer forms used according to the invention are for the most part forms which are intended for incorporation into cellulose pulps have not been formulated or adapted. It was found that it is by means of the polyelectrolytes in the cellulosic structure can be effectively uniformly distributed without migration occurring during tissue formation. Only when the film-forming properties of the polymer are triggered or brought about does the polymer flow in this essentially inert elements and forms bonds or even a coherent film in the material.

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Examples of polymers suitable for the purposes of the invention include polyolefins such as polyethylene and polypropylene, vinyl polymers such as polyvinyl chloride, polyvinyl acetate and polystyrene, polyimides, polyamides, polyacrylates, ABS, epoxy resins, epoxy / phenolic resins, phenolic resins, urea resins, melamine and polyester resins , Melamine / polyester resins, crosslinked acrylic resins, silicone resins, polyurethane resins and copolymers thereof such as copolyamides can be mentioned. Such polymers are available in solid form and they can be converted ^{into a coherent film by heat treatment at temperatures above 80 °} C. over a period of about 10 seconds to about 15 minutes. The heating treatment can be carried out by high frequency treatment, ultrasonic treatment, infrared irradiation, microwave irradiation and / or conventional application of heat.

A polymer material of interest for the purposes of the invention is a finely divided polymeric material which has been made from waste, e.g. a suitable thermoplastic Material such as polyethylene that has been ground at a low temperature.

Synthetic vulcanizable elastomers, e.g. SBR, in suitable forms as polymers useful for the purposes of the invention.

For the production of composite materials in the form of finished products or molded articles for outdoor use can be used, it is advantageous to use inherently weather resistant polymers, such as single component addition polymers, e.g. cross-linked acrylic resins, polyesters, epoxy polyesters and polyurethanes. However, there are e.g. Polyvinyl chloride, polypropylene and polyethylene are also suitable

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Polymers used in the manufacture of products for outdoor use. For other purposes, such as the manufacture of containers for liquid products including beverages, such as milk or juice, are polyethylene, polypropylene and copolymerized or otherwise hydrophobized Home amine products, e.g. Kelamin polyester, the preferred polymers.

It is also within the scope of the present invention to use more than one polymer material. For example, a cross-linked synthetic polymer such as a polyester with a thermoplastic polymer such as polyethylene, polyvinyl chloride or polypropylene. It is also possible to use the crosslinked polymer together with, for example Bitumen powder or bitumen emulsion, which is used as an inexpensive structure-filling and waterproofing component, preferably along with the incorporation of a water film disrupting surfactant material, e.g. Surfactant to use.

Another example of a suitable combination of two polymer materials is a combination of non-plasticized Polyvinyl chloride and plasticized polyvinyl chloride. It was found that the combination of an im substantial non-calibrated polymer and a relatively highly plasticized polymer often over the Use of a plasticized polymer to a lesser extent is preferable.

If the polymeric material used in the invention consists of particles which consist entirely of the polymer then has the powdery polymeric material has a particle size in the region of 1 to 500 microns, preferably about 1 to 200 and

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especially 10 to 80 µm. Alternatively, the polymer material can also consist of a polymer which is deposited on an inorganic carrier, e.g. metal particles, such as brass, iron, zinc, aluminum, copper or bronze particles, or on mineral or other inorganic particles such as TiOg, Iron oxide, volastonite, kaolin, devitrified glass, calcium carbonate, quartz with inclusion of sand, silica, steatite, talc, aluminum silicate, synopal, barite, diatomaceous earth or amorphous SiOp, are applied. Such particles of a polymer which is applied to an inorganic support typically have a particle size of 1 to 500 µm, preferably 1 to 200 µm. Another suitable polymer material is a polymer that is applied to mineral fibers such as glass wool, rovings, rock wool, slag wool, kaolin wool or metal fibers such as fibers made of brass, copper, aluminum, bronze or iron. The length of such inorganic fibers with the polymer coated thereon is typically about 100 µm to about 3 mm and the thickness is typically about 5 to about 30 µm. Certain minerals are available in particles that are fairly elongated, such as wollastonite. Here, however, they are viewed as particles and not as fibers.

Some polymeric materials, with the polymer applied to an inorganic carrier, are commercially available products made, for example, for use in powder coating processes. The fraction of such products in the range below 30 µm and above 80 µm is usually considered waste. However, such fractions, as well as the fraction in the range from 30 to 30 µm, are also well suited for the purposes of the invention. Examples of such commercially available powder coating materials are polyolefins or epoxy, polyester, acrylic or poly

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amide resins, applied to TlO ^ particles, wherein the amount of the polymer 40 to 90 Gevr .-% _t based on the Gesamtnaterial, is. Higher weight levels are usually used when the polymer is a polyolefin. An amount by weight of AO to 60% by weight represents the normal range when the polymer is an epoxy, polyester, acrylic or polyamide resin.

For the purposes of the present invention, a significantly smaller amount of the polymer is applied to the inorganic Carrier, suitable for most purposes, e.g. 2 to 40 wt .-? J, with 2 to 20 wt .- Si typical values for fibrous Carrier materials and 5 to 40 wt .-? 4 typical values for particulate materials are.

Toiletries or fiber-like or fiber-containing polymer materials, in which the polymer is applied to an inorganic carrier, can be produced in various ways v / earth. One way of preparing particulate polymer materials on an inorganic carrier is by extrusion a mixture of the carrier and the polymer and the subsequent grinding of the mixture. If at this If a thermosetting polymer is used, then the extrusion should be carried out at a temperature which does not cause hardening of the polymer. The best compatibility between the polymer and the inorganic Carrier material is obtained when one of these materials has a positive electrical surface potential and the other has a negative electrical surface potential. Most of the polymers used for the purpose of the invention are inherently negative surface potential. Most carrier materials also have

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have a negative surface potential. If such materials are combined, both of which inherently have a negative surface potential, then it may be useful to to treat the carrier material with an agent that has a negative surface potential of the inorganic material changed too positively. Various so-called coupling agents, i.e. compounds that are able to bond with both the polymer and the inorganic materials to combine and in this way the compatibility between the Polymers and the inorganic carrier or additive material have this property.

Such coupling agents are e.g. silanes (e.g. Silane A 1100, i.e. a) f-aminopropyltriethoxysilane from Union Carbide Corporation, New York, N.Y., USA), and Dyna3ylan Memo (Jf-MethacryloTcypropylxriinethoicysilar-) or Dynasylan Glymo (Jf-Glycidyloxypropyltrimethoxysilane) from Dynamit Nobel, Germany, and chromium complexes (such as Volan (an Ilethacryl-Chrom-Complex of the Y / erner type from Seppic, Paris, France)).

In order to bring about a particularly effective distribution of the polymer on the carrier particles or fibers and to provide a coherent one To obtain polymer coating with maximum uniformity on the particles or fibers, one proceeds according to one specific methods according to the present invention for manufacture of polymer-coated particles or fibers in such a way that the particles or fibers of the carrier material, while they are in the dried and optionally heated state, holds with vigorous agitation, for example by stirring or in a stream of air while the polymer is in small amounts in liquid or semi-liquid Condition sprayed or otherwise added

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will. (The polymer can also be added in the solid state if the carrier material has a sufficiently high temperature during the application process, since the polymer, which is in the form of solid particles, for example, is then transformed into the liquid or semi-liquid required for coating due to the heat State is converted). For example, a powder of volastonite particles is heated to about 350 ° C. to remove the water film on the surface. Thereafter, at a temperature of above 100 ^° C. (to ensure that no water film is formed on the particles again during the process), a polymer in solid, liquid or semi-liquid state can be added to the agitated powder, e.g. a polyester or a paste-like solvent-free one-component -Epoxy resin, e.g. 3. Araldit AV8 (from Ciba-Geigy, Switzerland), which is a thermosetting epoxy resin paste, or polyethylene can be added.

The agitation of the inorganic carrier particles or fibers can be obtained in various ways. It is within the scope of this invention to coat fibers in the fluidized bed with the polymer, where optionally an opposite electrostatic charge is used on the fibers and the polymer and the polymer (and optional processing aids such as surfactants) immediately after the formation of glass wool fibers or Rock wool fibers and while these are transported v / ground by means of a vacuum or an air stream from the spinning elements where they are formed, applied.

Mineral fibers with a coating made of a polymer which forms a film at temperatures above 80 ^° C., in particular a coating which. 2 to 40% by weight of the combined material represents a particularly interesting polymer material

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material that can be produced in the manner described above and that apart from the method according to the invention and can also be used for many other purposes for incorporation into the products according to the invention, where a film-forming polymer is used. Because such materials exhibit a large free surface area of the film-forming polymer compared to the amount of polymer they as very economical substitutes for polymer materials that consist exclusively of the polymer in question, can be used, for example, in the manufacture of various composite materials of the otherwise known type. Apart from that, they can be used for the production of various new products, their special properties depend on the bond between such mineral fibers with a coating of the film-forming polymer.

Fibers composed solely of the film-forming polymer or a combination of film-forming polymers can also be used. An advantage of polymeric materials comprised of a polymer coated on particles or fibers , in addition to the fact that they also inherently contain the desired inorganic component of the composite material through their incorporation, is that when the polymer has an inherent density below one Polymer materials having a density above 1 can be obtained when combined with the inorganic carrier in a sufficient amount. Particles or fibers having a density above 1 are more effectively co-flocculated with cellulosic fibers.

According to a specific aspect of the invention, the polymer of the polymeric material may contain a blowing agent which, at the temperature conditions at which the film-forming

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the properties of the polymer caused simultaneously the polymer foams while maintaining a cell structure. This can be caused, for example, by violent evaporation or a chemical reaction occurs with the release of a gas. In this way, cellulose fiber reinforced Additional materials that have been added are preserved. Polymers, such as polystyrene, which contain blowing agents or foaming agents, are commercially available. The blowing system of the selected polymer should be one that is only suitable for one high temperature triggered, so that during drying of the composite material no undesirable foaming occurs.

If an inorganic material in the form of mineral or metal particles or fibers is to be incorporated into the composite material, such dipping or fibers are preferably the same particles or fibers as they are above as possible carriers for polymer materials have been mentioned, ie metal particles such as particles of brass, iron, zinc, aluminum, copper or bronze, or mineral or other inorganic particles such as TiO ₂ , iron oxide, wollastonite, kaolin, devitrified glass, calcium carbonate, quartz, with inclusion of sand, silica, steatite, talc, aluminum silicate, synopal, barite, diatomaceous earth or amorphous SiOp. The particle size of such inorganic particles is typically 1 to 500 µm. It can also be mineral fibers, for example glass wool, rovings, rock wool, slag wool, kaolin wool, or metal fibers, for example fibers made of lies3ing, copper, aluminum, bronze or iron. A particular type of inorganic material that can be incorporated is a hydraulic binder, such as cement or kaolin cement. In order to ensure the compatibility between the

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mers and to improve the added inorganic material, if the film-forming properties of the polymer are triggered later, a coupling agent can use the above described type, for example a silane, can be used. The inorganic material can be previously mixed with the coupling agent be treated or the coupling agent can be added to the cellulose pulp, for example simultaneously with the inorganic Material, can be added.

In the process according to the invention, the polymer material is incorporated into an aqueous suspension of cellulose fibers, which is also referred to as cellulose fiber pulp, optionally with the inorganic material described above. The cellulose fiber pulp can be produced in the usual way from, for example, sulfate or long-fiber suIfit cellulose, waste paper and waste cardboard, straw cellulose, tlaermonechanical silulose fibers and, if appropriate, synthetic cellulose fibers such as rayon fibers. Waste cardboard is a particularly suitable starting material. The board may in a cellulosic fiber pulp by treatment in a Pulpiereinrichtung, optionally at an elevated temperature of up to 60 ⁰ C, to be converted. The Ceiiulosefaserkonzentration in the resultant cellulose pulp can, for example 1/2 to A wt -.% Amount. Usually it is about 2 wt% or less. In conventional papermaking machines, it is often 1/2 to 1% by weight. The cellulosic pulp can be treated by conventional paper technology processes, for example in a hydrocyclone and in deflocculators.

At an appropriate time during or after pulping and prior to web formation, surfactants, e.g., nonionic Surfactants, antifoam agents, aluminum hydroxide, ammo

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Non-phosphate, diphosphate or polyphosphate can be added. The non-ionic surfactants reduce the surface activity and they break up the molecular water film on the particles and fibers. They help to remove small air bubbles from the polymeric material and the optional inorganic material. They also help to obtain a more compact end product . Aluminum hydroxide gives the resulting product a higher fire resistance. The above amino phosphate materials are well known defibrillants used in the paper industry and they help to make the material more fire resistant. At this stage, other non-ferrous agents, such as antimony trioxide or halogen-containing compounds, can also be added.

satisfy '/ erts and the zeta-potential following conditions, which are known in paper technology, that they give good retention - uL.'j auszuf iocliionä ^ suspension sollto respect do-s pri.. The pH is usually in the range from 5 to 3, but can also be higher, for example up to 9. The zeta potential is preferably kept at a low numerical value between +20 and -20 millivolts, preferably in the range from +10 to -10 millivolts and in particular in the range from +5 to -5 ilillivolts. It is known that changes in the pH value and / or the ionic strength of the suspension change the zeta potential. Furthermore , the addition of strongly cationic or strongly anionic surfactants, for example, changes the zeta potential considerably, and in certain cases can even change the zeta potential from positive to negative or vice versa. It has been shown that silanes and polyelectrolytes also exert a considerable influence on the zeta potential of suspensions of the type under consideration here.

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To further improve flocculation, the opposite can be used electrical surface potential of the cellulose fibers and the polymer material can be applied. Cellulose fibers inherently have a relatively high negative surface potential. The same is true for certain polymer materials, such as polyester and epoxy resins. In such cases it may be useful to convert the surface potential of the polymer material, for example by using a cationic Surfactant of a type used that, after application to the polymer and subsequent drying in water can no longer be dissolved again, such as Fintex 577, which is explained in more detail in the examples. Even treatment with silanes and subsequent drying to form a monomolecular layer can be inherent negative surface potential on the polymer convert positive. The treatment of the polymer sr iali en with cationic surfactants can be carried out in such a way that, for example, the cationic surfactant to an aqueous one There is suspension of the polymer material and then the polymer material dries. There is another possibility in treating the dried heated polymer particles with a cationic surfactant. A third possibility is to incorporate a cationic surfactant into the right polymer.

The Schopper-Riegler grade of the cellulose fibers in the cellulose pulp can vary within wide limits, for example from about 15 to about 80. The Schopper-Riegler degree is often the same in the range from 30 to 60, for example 30 to 40 or especially 40 to 60. If the cellulose fiber !! thermomechanical Are fibers, then the Schopper-Riegler level is preferably lower, for example about 15.

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According to the invention, the cushioning material is incorporated by common flocculation by means of a polyelectrolyte. Polyelectrolytes are macromolecules with built-in ionic groups (see, for example, Römpps Chemie-Lexikon, 7th edition, Stuttgart 1975, pages 2755 to 2756). The polyelectrolytes preferred for this purpose are synthetic water-soluble polyelectrolytes which have been formulated for flocculation purposes, but not necessarily polyelectrolytes which have heretofore been proposed for use in cellulose pulps. The best results are often obtained with cationic polyelectrolytes, but anionic polyelectrolytes can also be used. In certain cases, both an anionic and a cationic polyelectrolyte are suitable in order to ensure that all components are flocculated together. Examples of suitable polyelectrolytes are Proieiloc AC (a soluble anionic flocculant, a polyelectrolyte, namely aluminum chlorohydrate, from Prodeco, San Donato Milanese, Italy) and Prodefloc N / 2M (a high molecular weight water-soluble anionic polymeric flocculant). Examples of cationic polyelectrolytes are Prodefloc CL2, Prodefloc C1, Prodefloc C4, Prodefloc C6 and Prodefloc C3. All of these products are water-soluble cationic polyelectrolyte flocculants. It has been shown that Prodefloc C1 is a very suitable polyslectrolyte for the purposes of the invention. Other suitable cationic polyelectrolytes are Hercufloc 829.3 (strongly cationic) and Hercufloc 859, both of which are polyacrylamides from Hercules Powder Company.

The polyelectrolyte is usually used in a concentration of 0.005 to 2% by weight, for example 0.01 to 2 % by weight, based on the dry weight of the constituents of the suspension to be flocculated

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pension, added. Often very satisfactory results are obtained with about 0.1 to 0.25? S of a cationic polyelectrolyte, e.g. from Prodefloc C1.

The polyelectrolyte or polyelectrolytes are preferably added to the mixed suspension immediately before the suspension is dehydrated, added. It is preferred to give a vigorous agitation after adding the polyelectrolyte avoid.

In some cases retention is improved when using a conventional one Cellulosic fiber flocculants, e.g., alum and / or a silane, to the cellulosic fiber pulp prior to adding the Polyelectrolyte is added. When a silane is added, its concentration is usually 0.1 to 2% by weight, preferably 0.2 to 1 weight-i-j, based on the 'Trockeu ^ evrichö d ^ r Components of the suspension. In addition to supporting the improved flocculation in systems where an inorganic Material is added, the silane is later after the release of the film-forming properties of the polymer because of this advantageous because e3 acts as a coupling agent.

When silane and conventional cellulose fiber flocculants such as alum are added, these are usually added or added during the mixing of the components of the suspension.

The person skilled in the art can determine the optimum flocculation in the respective system by means of a few preliminary experiments will.

The Polymernaterial can with the cellulose in the fabric - vat are combined, where an effective mixing of these

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Components and the optional inorganic materials with suitable mixing devices, for example an agitator, can be made. The polyelectrolyte is then added immediately before the suspension is transferred to the dewatering stage.

It is often preferred to add the polymer material to the cellulose pulp as an aqueous suspension rather than as a dry material. Such a suspension can suitably be prepared in high concentration, for example with a solids content of 30 to 90%, by vigorous agitation, for example surfactants such as Berol 373 can be used. The values of these surfactants are given in the examples. Furthermore, thixotropic agents can be added to the suspension, \ jXCi ei.ie oe'iiae: ita ^- cior, to v ~ rr.eiao; -i. The suspension of the L ¹ O Iymernaterials is suitably kept at room temperature. If an inorganic material is to be added, then this can either be added separately in dry form or in aqueous suspension, or it can be added to the suspension which contains the polymer material.

If the polymer material and / or the inorganic material consists of fibers, then it is expedient for these to be present in defibrillated form before they are combined with the cellulose pulp. Effective defibrillation can be obtained by grinding the fibers in the presence of a suitable surfactant. It has been found that a through movement over short periods of time of at most 1 min the fibers with a polyelectrolyte to an effective Deitibril-regulation leads the fibers. The fiber materials are preferably defibrillated in an aqueous suspension, for example with a concentration of less than V / * _t. One

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effective method for defibrillation of glass wool for example, the glass v / ole in one concentration of 0.5? j in water over a period of no more than 1 min in the presence of a cationic polyelectrolyte, e.g. of Prodefloc C1, in a concentration of, for example, 0 to grind.

If the composite material is to be used for objects that will last for long periods of time in their end use to be stable under conditions of exposure to moisture, the cellulose fibers can be protected from destruction by adding an antimicrobial agent such as a fungicide. The antimicrobial agent can act on the Surface of finished objects after final heat treatment, for example in the form of antioicrobial sprays or as components of a paint coating or one other coating.

When manufacturing composite materials for objects that are exposed to moisture, for example roof panels or building panels, it can be useful to add an anti-moisture irapregnant, e.g. a "wood preservative", never Pinotex, Goriol or Bondex, preferably in colorless form . The wood preservative oils can be easily emulsified and flocculated together with the cellulose pulp. Bitumen emulsion and paraffin emulsion are other suitable impregnating agents that can be added to the cellulose pulp prior to flocculation. A interest impregnating agent is an oil-emulsion with an added cationic surfactant, which decomposes at temperatures of about 100 ⁰ C. The following effects can be obtained by adding such an emulsion: The emulsion is first applied together with the cellulose pulp.

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flocked and in the web molding the cellulose fibers ^! bound by hydrogen bonds. During the drying process the surfactant of the oil emulsion is decomposed due to the drying heat, whereby the cellulose fibers are effectively impregnated with the oil v / ground, which has a tendency to penetrate the ends of the cellulose fibers. When the film-forming properties of the polymer, a solid water-resistant material is obtained.

With regard to the water resistance of the articles made from the composite material, it may be preferable to use surfactants and polyelectrolytes which are decomposed during the heat treatment, since surfactants and polyelectrolytes tend to be hygroscopic.

In connection with the J-Tor3 tziluaz von Zeuant- containing composite materials, it was found that optimum flocculation and retention is obtained if a cationic polyelectrolyte is added first and then a polyelectrolyte is added (cf. Examples 50 to 54).

In the following description of the method according to the invention, a papermaking machine of the endless Fourdrinier type will be used described. However, the method can just as well be used with any other type of papermaking machine or another machine capable of dewatering a flocculated suspension to form a web or a sheet, such as a hydroforming device or a rotoform type ("non-woven" Type).

809823/081 3

Successful co-flocculation manifests itself in the fact that the added particles or fibers dos the polymer material and the optional other additives, in particular the inorganic material, practically completely are retained in the flakes on the Fourdrinier wire and that they are not carried away with the water which the Fourdrinier passes through. This is not the case even if the particles are very small, for example 5 µm or less, acts. The dehydration treatment is carried out in a manner known per se. It becomes a Fourdrinier speed applied to the character of the cellulose pulp, the content of added materials, the suction power, the desired sheet thickness etc. is adapted. In some embodiments of the invention it is useful to produce relatively thick sheets or sheets with sheet weights of up to boispieisv / aise 2 to 3 kg / a "(dry weight). In these cases it may be useful to adjust the Fourdrinier wire speed in certain types of papermaking machines to keep it small. The fourdrinier wire speeds in conventional papermaking machines are between 10 and 500 m / min. If webs with high sheet weights of up to e.g. 2 to 3 kg are to be produced, then Fourdrinier wire speeds of only 2 to 10 m / min are used.

Thereafter, the web that is passed through the bond is seen Cellulose fiber ^ (hydrogen bonds) has been formed, from the Fourdrinier in a known way to the drying and reel-up stages. This happens e.g. by passage between conventional wet press rolls and over heated drums, with optionally a cooling drum is provided immediately before winding. It is

809823/0813

It is important that the drying is carried out at time / temperature conditions which do not trigger the film-forming properties of the polymeric material. Suitable drying temperatures are in the range of up to about 110 ^° C., for example in the range from 80 to 100 ^° C. In order to obtain good results when the binding or film-forming properties of the polymer are later released, it is necessary for the web to be dried effectively beforehand preferably to a water content of at most 5% by weight or most preferably to constant weight. In principle it could be possible to ship the semi-finished product with a higher water content, for example up to 50 wt .- / ό, whereby the further drying could be carried out in connection with a deformation treatment before the final heat treatment. A most suitable dry, semi-finished product, however, has a content of at most 25, in particular at most 15% by weight and preferably at most 5% by weight.

The composite material according to the invention can be in the form of the semi-finished product in the form of rolls, sheets or strips are sent. If dewatering has been done in an extruder, then so can it be sent in the form of an extrudate. Alternatively, it can also be given the desired shapes in the manufacturing station and sizes punched or cut according to the products or articles into which it is in the final heat treatment is converted. The waste material from the cutting or punching process can be recycled. It can be simple can be ground in the pulping machine and part of the raw material can be used for later production form.

809823/0813

If desired, the semi-finished product to a final heat treatment in the factory before the semi-finished product is manufactured, then the dried Or can be passed directly to a further treatment, where the temperature of the Drying temperature is increased to film formation temperature. Before or simultaneously with the increase in temperature the film forming temperature can subject the web or sheet to a deforming operation, usually under pressure will. This deforming operation can be done at a stage where the web has not been completely dried and wherein the further drying is then carried out in a later stage.

As stated above, the additional set according to the invention Material in the form of the semi-finished product can also be produced in the form of an extrudate, the wet material being extruded in a manner known per se. The drying can be carried out simultaneously with or after the extrusion. The extrusion technique can can be used to produce very thick materials in the form of large plates or tubes.

If the semi-finished product according to the invention is to be in a laminated, possibly cross-laminated form, then such a material can either be obtained by having moist webs on or after the Fourdrinier treatment Laminated in the papermaking machine, or it can be done by making dry sheets or webs slightly moistened, for example with steam, and then through the hydrogen bonds of the cellulose fiber ^ zur Brings liability.

• 08823/0813

The composite material according to the invention can easily be adhered to granular surfaces, for example metal or glass surfaces, since the polymer acts as an adhesive towards the interfaces in question after the film-forming properties have been triggered. In this way, both a cohesive and an adhesive effect are obtained during the heat treatment. This can e.g. be used in the manufacture of electrically insulating components which are to be arranged between interfaces of metals, for example in the manufacture of commutators, in which the insulating material can be introduced into the form of the material according to the invention and attached to the metal interfaces in a very simple and effective manner . Another possible application is the production of sandwich materials in which the combined materials according to the invention are wound as "binding sheets" for example, metal or glass plates.

When a hydraulic binder is incorporated into the composite material as an inorganic material, it is usually not preferable to perform a pressing operation after the hydraulic binder has hardened. Composite materials containing a hydraulic binder can be treated in two different ways according to the invention after forming. Thus, one can either dry the composite material only to a stage where sufficient water remains in the material to set the hydraulic binder, and then allow the hydraulic binder to set. The heat treatment is carried out after hardening of the hydraulic binder wherein one but substantially during the heat treatment no

809823/0813

Exerting pressure. On the other hand, one can also proceed in such a way that the composite material is removed before the hydraulic binder is dried and heat-treated, after which the hydraulic binder is allowed to harden. this can either be done by simply exposing the composite material to ambient moisture or positive addition of water to the composite material after the heat treatment.

The products of this invention, the proportion of CeI-lulosefasern can vary within wide limits, from about 5 to about 95 parts by 5>, based on the Trockenge ^T .vicht the material.

The products with a cellulose fiber content in the upper part of this range, for example with ép / i cellulose fiber !! and 5% polymer material, can be paper or cardboard-like materials, the strength and water resistance properties of which are improved by the incorporated polymer material. If the polymer is one that easily fills all voids, e.g., low density polyethylene, then such composite materials, after heat treatment, can be used as water-resistant or liquid-tight packaging materials, e.g., for making containers for beverages such as milk or juice. With appropriate polymer selection, such as low density polyethylene, these materials may be heat weldable. By incorporating polymer materials that improve strength properties, such as polyester-coated fibers, very strong packaging materials can be obtained. Another example of a material of interest for milk containers with improved rigidity

809823/0813

ness is a composite Ilaterial a laminate with cement and polymer material in the outer layers, \ lerm materials of this type are to be dyed in accordance with the invention in the form, then a color pigment can be used as the inorganic material in the above-described V / else incorporated v / ground or For example, a polymer material can be used which consists of a polymer which has been applied to an inorganic color pigment or carrier. However, the coloring can also be carried out in a conventional manner after the formation of the sheet or web. The cellulose fibers should, however, be dyed before the final heat treatment, since otherwise the cellulose fibers become completely or partially unsuitable for the dyeing treatment. Printing on the material should also preferably be carried out before the final heat treatment.

From webs with a high content of cellulose fibers it is also possible to manufacture products with properties which are similar to those of wood or hardwood fiber boards. Such products can be obtained by subjecting a thick layer or several superimposed layers of the semi-finished product with a polymer suitable for this purpose to a heat and pressure treatment. The material becomes stronger and more rigid, the higher the pressure applied. The strength characteristics of a laminate of this type can be further improved by that in an alternating direction of production, such as plywood, arranging the layers having alternating fiber direction. It may also be layers of other materials included, for example aluminum foil, lead foil or composite materials with different 'content, which also produced suitably in accordance with the invention

809823/0813

have been. The bond between the layers of such laminates can be achieved solely by a heat and pressure treatment can be obtained, whereby the polymer binds the layers. The lamination can also be used to produce other types of composite materials according to the invention applied. The laminates can be used for subsequent heat treatment expelled v / earth. A suitable composition for a wood or wood fiber board product is, for example, 35% cellulose fibers and 155a polypropylene particles or polyvinyl chloride particles. If desired, some of the cellulose fiber content can be used be replaced by, for example, wood chips or straw particles. For example, the composition can contain 15% polypropylene particles, 60 $ 3 cellulose fiber ^ and 25 / j wood chips or Be straw particles.

The products that are in addition to cellulose fiber :! and the Polymers contain an inorganic material, either incorporated as such or as a carrier in the polymer material, often have cellulose fiber contents in the range from 15 to 35% by weight. Such materials are of interest semi-finished products Products for the manufacture of a wide range of end products. Examples of such and similar Materials are as follows:

A composite material used in the manufacture of various articles, traditionally made entirely of one polymer or made of other materials, e.g. toy bricks or other shaped objects such as plates, disposable cutlery, Rice bowls, serving trays, cassette housings, packing drums, Heating pipes etc. Such materials can consist of about 30 to 70% by weight of cellulose fibers, about 40% by weight Mineral wool fibers and about 30 wt .- 55 polymer material, in which

809823/0813

the film-forming polymer has been applied in an amount of about 15 to 40 % by weight to mineral wool fibers. This composite material in the form of a single layer, a laminate, a wound strip or an extrudate can be converted into the above-mentioned shaped bodies by compression by heating, for example at a pressure of 2 to 10,000 kg / cia and a temperature of about 100 ^° C (it is generally valid that in triggering the filmbildonden properties of Polymarmaterialien temperatures above 170 ⁰ C does not stop for prolonged periods of / should be, when it is desired to avoid damage to the cellulose fibers. However, usually a short (e.g., up to 60 see) heating to higher temperatures, such as 250 ⁰ C, can be tolerated). If the moldings are to be colored, then pigment can be found instead of a part of the mineral wool fibers or the polymer can be colored in the correct amount. The surface smoothness and the material strength of the finished molded body depend to a large extent on the deformation conditions, the higher the pressure, the smoother the surface and the better the strength. Typical pressures are 10 to 100 kg / cm and es

can be worked at pressures up to 1000 to 10000 kg / cm. By properly selecting the polymer such as a thermosetting polyester resin or a melamine polyester with a short curing time, a very short cycle time can be obtained in the press die. E.g. for Toy brick a suitable polymer, for example an ABS, epoxy or polyester resin. A suitable polymer for plates or bowls and rice bowls is a melamine copolymer. A suitable polymer, for example for glasses frames, knife handles and artificial counters, 3ind e.g. epoxy polyester, polyester or acrylic resins.

809823/0813

A strong construction material for producing, for example, laminate panels, boats, drums, plates, chairs or automotive bodies may be made of 15 wt -.% Cellulose fibers and 85 parts by weight S $ mineral wool fibers, which are covered with about 15 weight Sa polyester consist. The laminate panels can be made as described above. They can be used for the same purposes as conventional technical laminate boards, e.g. for interior walls, tops of kitchen tables, 7 / and tiles for bathrooms, etc. They are advantageous in that they can be manufactured extremely easily from cheaper raw materials than the conventional laminate boards. For the manufacture of boats, for example, panels or strips of the semi-finished product according to the invention can be deformed in the moistened state to the desired configuration, after which the release of the forming properties of the polymer under pressure (e.g. 100 kg / cm) and heat is provided.

A fibrous material that is used, for example, as roof felt and floor felt is suitable, can be made of 15 to 20 wt .-? o cellulose fibers, 50 to 70% by weight of mineral wool fibers and 15 to 25 Gew.-So a polymer material, for example glass, stone or Slag wool fibers with lengths of about 3 mm, or rovings with a coating of 15 to 20% by weight of the film-forming Polymer or inorganic particles, for example sand or wollastonite, with a coating of 20 to 40 wt of the film-forming polymer. Alternatively, the film-forming polymer may be present as particles that only consist of the polymer. The above inorganic materials are added as such, in which case the amount of polymer is preferably 5 to 10% higher.

809823/0813

A wear-resistant flooring material according to the invention Can be made from 15 wt. SS cellulose fibers, 50 wt. JS glass fibers and as polymer material, for example, a combination of 20 wt. S-S polyvinyl chloride and 50 wt. S-S polymer-coated Mineral wool fibers are made.

A composite material used in the manufacture of hard, strong and electrically insulating moldings, e.g. electrical For example, insulators such as commutator materials, hair curlers, printed circuits, etc. can be about 15 By weight cellulose fibers, suitably straw cellulose, and 8550 of a polymer material consisting of wollastonite particles 5 to 200 µm with a coating of 10 to 50 wt a polymer, for example a polyester or epoxy polyester resin, exist. ! after heat treatment with or iiacii ain ^ .Q high pressure, i.e. at a pressure above 1000 kp / cr.

preferably above 4000 kp / cm, an almost mineral or earthenware-like compact product with a high strength is obtained. Similar products can also be obtained when the wollastonite particles and the polymer are added separately. Composite materials similar to these can also be made from powders of the respective mineral and polymer components, but the use of the composite materials according to the invention avoids any problems of incompatibility or segregation. Furthermore, the sheet-shaped or plate-shaped blank made of the composite material can be easily handled, and the composite material can be used in a laminate form including rolls or as an extrudate for the production of molded articles having a larger thickness. Granules can also be used. Similar materials can be used for the same area of application

809823/0813

- ν

2.3. of 20% by weight of cellulose fibers, about 60% by weight of Y / ollastonite powder with a particle size in the range from about 5 to 200 μm Concrete) and 20% by weight of a commercially available particulate powder coating material consisting of epoxy resin on 43/5 TiO ₂ and 2% BaSO ^.

Hard, weatherproof and durable board materials, for example for external panels of buildings, for example roof tiles or roof panels, can be made from a composite material be produced, the 15 to 40 wt. Sb cellulose and the remainder contains inorganic material and polymer, the polymer content being 15 to 40% by weight and the content being des inorganic material is 20 to 70 wt .-%. An example is a in composite material, w-alolies 35 wt .-> · '; Cellulose fibers and 65% by weight of a polymer material made of mineral wool fibers with a coating of 15% by weight Polyester. Various other composite materials suitable for this purpose are disclosed in US Pat Examples 1 to 24 and 45 to 54 are described. A preferred roofing sheet material contains about 20 wt .-? 5 cellulose fibers, for example of cardboard, about 40 to 50 wt. so inorganic particulate material, e.g. wollastonite or sand with a particle size below 300 µm, and etv / a 30 to 40% by weight polymer particles. The polymortel loans can e.g. consist of a relatively rigid polymer and a softer, to a greater extent structure-filling polymer. For example, the relatively rigid polymer may be non-plasticized polyvinyl chloride and the other may be used in combination Polymers can be plasticized polyvinyl chloride. A crosslinked polyethylene is a softer good polymer for use for such roof tiles or tiles. In the

809823/0813

-ZT-Ul

Manufacture of roof panels is the composite material, either as a single layer or as a laminate of several layers (e.g. formed by web lamination of several webs by suitably directing the suspension from several tanks onto one and the same fourdrinier wire, in which case expediently one greater content of the polymer in the bottom and top layers), deformed to the desired shape while it is still wet. This is done, for example, using corrugated rollers to produce corrugated roof panels. Thereafter, the shaped panels can be dried either in the oven or between drying rollers and then subjected to a temperature which triggers the film formation of the polymer, for example 170 ^° C., which if necessary or if desired under pressure, either between rollers or a plate press,

... 1 ^ T ¹ Q T_ 'T j ip'"3""V ^ _{1 m}

A composite material that is used as an underlay natorial for floor coverings, for example as underlay material for Carpet, e.g. a polyvinyl chloride foam floor covering, -suitable-t is can, for example, from stv / a 15 to 25, preferably about 20 percent by weight of cellulose fibers, about 40 to 60% by weight, preferably about 50% by weight, mineral fibers, for example glass wool or rock wool fibers, and about 30 to 40 wt. So, preferably about 30 to 35 wt. Polymer are produced. Such backing materials have heretofore been made from asbestos fibers, but it is the health hazards of asbestos fibers make it necessary to find substitutes for products containing asbestos. The backing material contemplated according to the invention is dimensionally stable, acceptable and compatible Underlay for polyvinyl chloride floor coverings. Examples

809823/081 3

suitable polymers for this purpose are polyethylene such as crosslinked polyethylene and polyvinyl chloride. Yfenn the polymer is polyvinyl chloride, then the backing material with the other components of the polyvinyl chloride floor covering simultaneously with the release of the film-forming Properties are welded.

The composite material of the present invention can also be used to make friction materials such as brake linings. For this purpose materials are incorporated which are suitable in friction materials, for example bronze powder, barium sulfate, graphite, bronze powder and wollastonite and synopal or slag wool fibers. Composite materials suitable for brake pads are described in Examples 33-36. In the manufacture of material for brake linings, it is particularly preferred that the fan assembly of the finished brake linings or brake bodies be perpendicular to the contact side to the extent possible. For this purpose, a laminate is produced from several layers of the composite material containing the friction material, the fiber direction being the same in all layers. The laminate is subjected to heat and pressure to induce the film-forming properties of the polymer and the resulting material is then cut into brake pads in a direction perpendicular to the fiber orientation.

The invention is illustrated in the examples. All percentages therein are not related to the ^ β \ · τ , unless otherwise stated.

Example A.

25 wt .- # V / ollastonitpulver (FW200

809823/0813

von Pargas, Finland) with a particle size of 1 msec 200 µm mixed with 75 wt. The resulting mixture was extruded in a conventional plastic extruder, solidifying the polyester. Then, the resulting material was treated in a hammer mill, to 80 ^c; o of the material have a particle size of v / ess than 70 had to.

Corresponding to each other and from the same starting materials, powdered V / ollastonite / polyesterGr-I materials with a content of 35% V / ollastonite and 65% polyester, 45% wollastonite and 55/3 polyester, 70% V / ollastonite and 30? Ί Epo :: ypolye3ter or 70 / j V / ollastonit and 3O $ 5 polyurethane her-

Example B.

75% by weight of viollastonite powder (FV / 200 from Pargas, Finland) and 25% w / y particulate solid Polyester with a particle size such that 30% of the part were less than 70 µm in size. The energy added during mixing softened the polyester particles to such an extent that a part of them adhered to the volastonite particles.

Beis-Qiel C flocculation in different systems:

Flocculation attempts were made with the two starting batches given below carried out.

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- it »-

Approach # 1:

70 g of cardboard (2 Lge aqueous suspension, ground to 33 SR ⁰⁾ 10 g polypropylene particles, particle size below 100 g to 30 Wollastonite / Polyoster-Haterial, polyester content of 75 $ o,

produced according to example A
30 g of wollastonite / polyester material, polymer content 65> 1,

produced according to example A
30 g wollastonite / polyester-II material, polyester content 55? '),

produced according to example A.

Approach # 2:

70 g of cardboard (2? Aige v / äßrige suspension, ground to 33 SR ⁰⁾ 10 £ polypropylene, particle size below 100 microns jO s i '/ ollastonit / i-'olyastör-I-latiiris.I, poly ^ ^ most olialc 75 / 0,

produced according to example A
30 g 1 / ollastonit / polyester material, polyester content 65 / ί,

produced according to example A
30 g ¥ ollastonit / polyester material, polyester content 55 / y,

produced according to Example A 104 g of wollastonite powder.

The above suspensions are used in a concentration of 0.2 $ ό in V / water applied / ends.

The experiments are carried out in a graduated 1000 ml Cylinder carried out:

1. Measure 1000 ml of the suspension v / earth.

2. Flocculant is added.

809823/0813

BATH ORIGINAL

3. Shake it thoroughly.

4. Leave to stand on the table and start timing.

5. The sample is taken (on the surface) and the zeta potential and the pH value are measured.

6. The time (^ 400 ^ 'when the "precipitation" dia 400 ml line happens, it is recorded.

7. The time (t _20Q ) when the "rainfall" passes the 200 nl line is recorded. If the 200 ml line is not passed within 10 minutes, the volume of the precipitate is measured.

3. Bai t = 5 r.iin : rtvi d: 3 sample? Box taken from the 900-nl-Lini-i for the optical determination of the water clarity (percentage permeability) in the Beckmann photometer. The first samples were not measured in the photometer. For this reason, in the following table no Mert is indicated for the percent transmittance.

809823/0813

BATH ORIGINAL

Flocculation test fc; with approach 1

Flocculants

'200

OO

negative control 0.4% alum

0.5% AC

0.4% alum + 0.5% AC

0.4% alum + 0.5% AC + 0.5% Sil

CD

0.4% alum + 1.0% AC 0.4% alum + 2.0% AC 1.0Ji alum + 1.0% AC 0.4% K-alum + 1.0% AC

0.4% K-alum + 1.0% AC (after 10 min)

0.4% K-alum + 1.0% AC + 0.5% silane

0.4% alum + 0.25% 329.ö Hercufloc

Permeability zeta-poten- pH

tlal, mV

Remarks

2 : 10 6: 40 rather cloudy 6: 40 semi-clear 6: 40 semi-clear 2 ; 15th 7: 20th semi-clear 2 : 10 6: 30th very clear 2 ί 40 205 ml clear, 91% 2 : 36 205 ml clear, 39% 2 : 07 7: 40 clear, 87% 2 : 20 8th : 20th clear, 82% 2 i 03 7: 40 clear, 86% 1 i 55 6: 20th clear, 35% clear, 93%

-26.4 -30.9 -30.5 -25.3

-29.2 -15.6 -13.9 -14.7 -21.5

-20.5 -21.3 + 6.3

5.5 6.0 6.0 5.5

5.0 5.5 6.0 6.0 6.0

5.0

5.5

6.0 very fast

AC: Prodefloc AC Silane: Silane A1100

Hercufloc 829.8: polyelectrolyte, water-soluble cationic polymer, polyacrylamide

cn co

cn

cn

-HD-

Flocculation attempts with approach 2

Flocculants

'400

'200

Permeability zeta-poten- pH remarks

tial, mV

negative control

$ 45 alum + 1.0Si AC

$ 45 alum + $ 0.259 829.3 Hercufloc

OO

O U) OO

oo

η ^r -

0,

0,

$ 0.255 829.3 Hercufloc

$ 0.45 alum + $ 0.255 N / 21! 0:30

$ 0.45 alum + $ 0.255 Ν / 2ΙΊ + $ 0.55 AC 0:25 $ 0.45 alum + $ 0.255 AX special

$ 0.45 alum + $ 0.255 A7 0:32

0.4> $ alum + 0.25? $ A7 + $ 0.55 AC 0:26 $ 0.45 alum + $ 0.25 Cl

$ 0.255 Cl 0:27

0.125 * $ Cl 0:26

$ 0.255 C4 0:36

$ 0.255 CS 0:25

$ 0.255 C6 0:30

quite cloudy, 6d% 9O5'e $ 965 $ 825 -27.6 6.0 h = 1 05 ml clear, 3750 $ 965 $ 775 - 7.5 5.0 very fast clear, semi-clear, $ 955 $ 335 +13.3 6.0 very fast half k: $ 975 +14.5 6.5 very fast lar, $ 975 -19.3 7.0 very s c line U Vj silly, $ 085 -16.5 6.5 7.0 very fast 7.0 very fast -17.9 7.0 very fast i.lar, + 3.6 6.0 very fast clear, + 2.6 7.0 clear, , 98% - 6.0 7.0 very fast clear, +13.1 5.5 clear, + 7.4 6.0 clear + 9.7 6.0

N / 2M: Prodefloc N2M: polyelectrolyte, water-soluble, high molecular weight anionic polymer flocculant ^ J

AX-Special: Polyelectrolyte, water-soluble, anionic polymeric flocculant ς-A7: Polyelectrolyte, water-soluble, anionic polymeric attractant _ω

C1: Prodefloc C1, polyelectrolyte, water-soluble, high molecular weight linear polymeric flocculant cn

C4: Prodefloc C4: Polyelectrolyte, water soluble, high molecular weight, cationic polymer flocculant

C8: Prodcfloc C8, Polyslcktrolyte, water-soluble, cationic polymeric flocculant C6: Prodefloc C6, polyelectrolyte, water soluble, high molecular weight, cationic polymer

Flocculants

Flocculation attempt: -, with approach 2

Flocculants

'400 permeability

zeta-poten- pll remarks tial, mV

IF O

to

<A>

negative control

0.4% alum + 1.0% AC

0.4% alum + 0.25% 829.8 Hercufloc 0.25% 829.8 Hercufloc

0.4% alum + 0.25% N / 2M 0

0.4% alum + 0.25% N / 214 + 0.5% AC 0 0.4% alum + 0.25% AX-Special

0.4% alum + 0.25% A7 0

0.4% alum + 0.25% A7 + 0.5% AC 0 0.4% alum + 0.25% C1

0.25% Cl • 0

0.125% Cl 0

0.25% C40

0.25% C8 0

0.25% C6 0

30 25

32 26

27 26 36 25 30

1 1

1 0

quite cloudy, 68%
clear, 90%
clear, 87%
semi-clear, 82%
semi-clear, 77%
semi-clear, 33%

8d%

clear, 96%

clear, 96%

clear, 95%

clear, 97%

clear, 97%

clear, 98%

-27.6
- 7.5
+13.3
+14.5

-19, a

-16.5

-17.9
+ 3.6
+ 2.6
- 6.0
+13.1
+ 7.4
+ 9.7

6.0 5.0 6.0 6.5 7.0 6.5 7.0 7.0 7.0 6.0 7.0 7.0 5.5 6.0 6.0

h = 105 ml very quickly very quickly very quickly very quickly,

very fast »very fast very fast very fast

very söhnsll

cn co

CJ)

cn

Example D

0.7 g Fintex 577, an irreversible cationic surfactant type einor quaternary ammonium compound ~ n, was mixed with 100 ml of v / ater and 10 g of a powdery polymer material consisting of '55 / j polyester, is applied to 43/3 TiO _2/2 ? O BaSO ^, particle size distribution 0.1 to 30 µm, added. The resulting suspension was left to stand for 10 minutes. The aqueous phase was filtered off and the polymeric material v / urde in an oven at about 60 ⁰ C dried. The resulting polymer material, which was coated with the irreversible surfactant, was added to 1.5 l of a 1.5% suspension of cellulose fiber in water. It was seen that a considerable attraction between the cellulosic fibers and the polymer material was obtained when the particles δ-, 3-oly :: vsrniat-jrv-ils flocculated together with the cellulosic fibers :: on. The resulting suspension was applied to a sieve with a mesh size of 100 mesh. The flocculated product was retained on the sieve and the water that passed through the sieve was practically free of polymer particles.

In the following examples, they have not yet been defined Designations have the following meaning:

Newsprint: cellulose pulp made by grinding from old newspapers.

Cardboard: cellulose pulp made by grinding waste cardboard .

Sulphate: sulphate cellulose pulp Sulphite: sulphite cellulose pulp ⁰ SR: Schopper-Riegler grade

809823/081 3

Y / ollastonit Fv / 50: wollastonite powder with a particle size from 1 to 500 µm from Pargas, Finland ♦

V / ollastonit FW200: wollastonite powder with a particle size from 1 to 200 µm from Pargas, Finland

Synopal: Synopal (a synthetic mineral made from sand, dolomite, chalk and a material containing aluminium), dust ¹ , particle size below 100 µm

Slag fiber, glass fiber brick wool: acted in all cases these are fibers with a diameter of 5 µm, logarithmically distributed, down to 1 µm and up to 30 µm. The length ranged from 1 mm to 10 mm, predominantly about 3 mm.

Polyester: polyester powder from Smser-Werke, Switzerland, with 70-5 of the particles having a size below 30 µm and the remainder were up to 200 µm in size.

Polyesters Tiü ^ / ^ BaLJO. Rcoat Commercially available product of PuIv =, Germany, consisting of 55/5 polyester, is applied to k3% TiO _2/2 $ a BaSO _2, particle size 30 to 80 UE.

Polypropylene: particle size below 100 µm.

Epoxy polyester: from Emser-Werke, Schvreiz, vrobei 30; S of the particles Its size below 70 µm and the PLO is one Up to 200 µm in size.

PVC: 80-5 of the particles were below 70 µm in size the rest a size of up to 200 µm,

Urethane: Isonate 123 P (caprolactar-blocked polymeric isocyanate) from Upjohn Company, Kalamazoo, Michigan.

CopoVamid: Gril-tex 2P, melting temperature 120 to 130 ⁰ C, a copolyamide with monomer units of polyamide 12, polyamide 6 and polyamide 6,6, from Emser-Werke. Particle size below 30 µm.

809823/0813

- fr -

Borol 373: a non-ionic surfactant, consisting of a Alkylane oxide adduct based on a normal primary Alcohol. The surfactant has a hydrophilic (water-soluble) character. The product is a clear one Liquid with an active ingredient content of 100? S. From Berol Kemi AB, 44401 Stenungsund 1, Sweden.

Triton CF10 can also be used instead of Berol 373.

Triton CF10: alkylphsnoxypolyethoxyethanol from Röhn & Haas, Philadelphia, USA.

Nopco, MXZ: Antifoam agents containing a non-ionic Emulsifier, from Nopco Chemical Company, 60 Bark Place, ITew Ark, New Jersey, USA.

Fintex 577: A quaternary ammonium type cationic surfactant by Berol Kemi AB. This surfactant has an irreversible character, i.e. it can, after it has acted on the ou ^ s ^ at ang-ii-Ug'o been isx (single alschiciic structure), cannot be dissolved again in water.

Sand: Danish brook sand, particle size below 300 µm.

Cement, white: White Portland cement, Blaine value 3400 cra ² / g, 77 to 33% C ₃ S.

Polyethylene, cross-linked: product of Sigma, whereby 67.3 / o der Particles are greater than 200 µm in size.

PVC 3107/11/2: a plasticized product (32 $ ά plasticizer + Soot).

PVC 3035 / 92Λ / 1: a non-plasticized (rigid) product PVC 3035/91 A / 3: a v / calibrated product (32.% plasticizer) PVC O-VI-107-1: a non-plasticized (rigid) Product PVC 5 WSW 67-951: a plasticized product.

The above PVC products were all from British Industrial Plastics Limited, Darlington, England. Retention: determined visually.

809823/0813

Uasserabsorption, %, day: percentage weight gain after about / a 24 h. ·

Examples 1 to 23 were all run on a laboratory sheet former. All components were mixed into the sheet former jar prior to the onset of suction. The hold time in the jar after mixing was about 5 minutes After sheet formation, the sheets were dried in a ventilated oven and then heat treated in a heated press.

809823/0813

St.

Mr.

"Newsprint, Jo, 60 ° SR cardboard, &, 40 ⁰ SR

Sulphate, Ji, 35 ⁰ SR 8Sulphite, %, 35 ⁰ SR wollastonite F \ J50 _t ^C , 0

ΐ / ollastonit Fi72OO, % XPolyester, So Silan Λ 1100, ^C A from anorg.

Dynasylan. Glymo, / ί from anorg.

Volan, / 3 from ar.org.

Triethylamine, % of inorg.

Prodefloc AC, % leaf weight, g / n retention,?. ' pH (installed) drying temperature ^{, 0 C}

O _n

Heating temperature, heating time, min.heating pressure, kg / cm * density, g / cxP ignition residue, % tensile strength, kg / cn water absorption, $ S, day

V / water vapor absorption at a relative humidity of 35? Ό, 50 30

50 15th 15th 15th 25th 65 65 40 65 20th 30th 20th 20th 0.5 0.5

0.5

0.5

0.5 0.5 0.5 0.5 0.5 2000 2000 2000 0.5 2000 97 -93 2000 6th 6th 6th 6th 30th 80 ao ö 30th 190 190 190 30th 190 4th 4th 4th 190 4th 40 40 40 4th 40 1.2 1.3 1.3 40 1.1 51 66 66 1.2 41 42 42 43 66 30th 8th 4th 4th 43 10 5

809823/0813

275365Ί

eisOiel Ur.

10

Papp: ·, 55, AO ⁰ SR "rfollastonit FV / 50, %

^ Polypropylene, % epoxy polyester, ^c / o PVC, %

J. Ur ethane, ⁰ A silane A 1100, % of anorg. Prodofloc AC, % leaf weight, g / m retention, % pH (adjusted) dry ^{temperature, 0} C 3hitzur.gst - ^. P * ratur, ⁰ C heating time, min heating pressure, kg / cm density, g / cm 'residue ,? o Tensile strength, kg / cm \ 7water absorption, %, day

25th

50

20th

25 50

25th

25 50 20

25 50

0.5 0.5 5.5 0.5 25th 0.5 0.5 0.5 00 0.5 0.5 0.5 2000 2000 200 2000 0.5 2000 • · · · Ζ7 / "* y * ^ · · · 4th 2000 • · · · · 5.5 40 5.5 • «· · · 5.5 80 1.3 30th 5.5 30th 190 51 190 30th ! 90 4th 50 4th 200 4th 40 9 40 4th 40 1.3 1.3 40 1.3 51 51 1.3 51 45 36 51 42 6th 3 43 9 6th

809823/0813

At SOi c-1 Mr.

12th

13th

15th

"Cardboard, %, 40 ⁰ SR Wollastonat FW200, % Synopal, %

Mineral wool, slag fibers,% § mineral wool, glass fibers, % ^ i mineral wool, rock wool, % J. polyester, % silane A 1100, % of anorg.

Prodefloc AC, %

Leaf density, g / m retention, % pH (installed), drying temperature ^{, 0 C}

Heating time, min

, Kg / cm V asserabsorption heating pressure, kg / cm density, g / cn residue on ignition,? Ά tensile strength, ^T, $ ί, Day

20th

60

20th

60

20th

20th 20th 20th 60 20th 0.5 0.5 0.5 20th 0.5 0.5 0.5 0.5 0.5 0.5 2000 2000 2000 0.5 2000 97 93 93 2000 97 5.5 5.5 5.5 93 5.5 ao 80 30th 6.5 80 190 190 190 80 ! 90 4th 4th 4th 190 4th 40 40 40 4th 40 1.3 1.1 1.1 40 1.3 61 61 61 1.1 61 33 52 63 61 42 6th 3 10 50 7th 7th

809823/0813

Beis-Diel No.

16 17

20th

Cardboard, «5, 5O ⁰ SR 20

tfollastonit, FV / 50,? S 43

^ Mineral wool, slag fibers, yes 15 2 polyester, JS 20

Polypropylene, %

Aluminum hydroxide, % 1

JLAmmoniumpho sphat, % 1

Berol 373 %

ITopco, NXZ, Jo

Silane A 1100, % of inorg.

Triethylamine, % of inorg.

Prodefloc AC, %

Sheet weight, g / m *

pH (adjusted)
Drying temperature, ⁰ C heating temperature, heating time ⁰ C, min
Heating3 pressure, kg / cm density, g / cnr
Residue on ignition, %
Tensile strength, kg / cm water absorption, %, day

0.5 0.4 0.4 2000

5.5 80 190 4 40

1.3

60

44

20th
43
15th
20th

1
1

0.2

0.5
0.4
0.4
2000

... 97-

20th
43
15th
20th

0.1
0.2
0.5
0.4
0.4
2000

20 43 15 17

0.1 0.2 0.5 0.4 0.4 2000

1.3
60
44 7

5.5
80
190
4th
40
1.3
60
46
6th

P, 3 30 190 4 40

1.3 60 46 6

20 43 15 15

0.1 0.2 0.5 0.4 0.4 2000

5.5 80

190 4

40

1.3 60

47 6

809823/0813

Ur.

Prodefloc C1, ^c / o
Leaf density, g / m
Retention, %
pH (adjusted)
Drying temperature, ° C heating temperature, ° C heating time, min
Heating pressure, kg / cia density, g / cnr
Ignition residue, $ 4
Tensile strength, kg / cm

0.4 0.5

2000 2000 ... 97-93 .. 5.5 5.5 30
190

40

1.3

60

52

30th
190
4th
40
1.2

59
40

Cardboard, tf, 50 ⁰ SR 20th 20th 25th Wollastonite FW50, % 43 44 35 Ilineralv / olle, slag fibers. ,% 15 Polyester, % 15th Polyaster on TiO ₂ and BaSO ^ 36 Copolyamide, % 5 Toilet, % 40 Aluminum hydroxide,; j 1 Ammonium phosphate, yes 1 Berol 373 % 0.1 Nopco, IKZ, ⁰ A 0.2 Silane Λ 1100, X from anorg. 0.5 0.5 Triethylamine, % before. anorg. 0.4

0.1

5.5

ao

190 4 40

2753S51

Example 24

During a technical operational test on a papermaking machine the mixture used consisted of 400 kg of cardboard cellulose, which had been ground to 25 ° SR, 500 kg

809823/081

Polyester material, consisting of 55% polyester, applied to 4353 TiO _2/2 ? S BaSO ^, particle size 30 to 80 μm, 100 kg of wollastonite FW200 and 5 l of silane A 1100. Prodefloc AC was continuously in an amount corresponding to 0.5 $, calculated on the dryness level of the batch, added. The correct addition for the Prodefloc AC was in the pipe that led from the overflow vat into the inlet vat. The fourdrinier wire of the papermaking machine was from Hordiskafilt AB, "Vatvira", quality 6050/0 (double plastic linear wire). The fourdrinier wire speed was 8 m / min.

The cellulose was ground in the normal way and the polyester was added together with the volastonite powder to the pulp chest, which was provided with a powerful stirrer. The temperature of the cellulose pulp was about 50 ° C and. the dry matter content was 2fo. The dry matter content in the end sheet before rolling up was 50 to 55%. Sheet weights of 1200 g / m 2 to 2000 g / m were produced. Examination of the final material with a surface microscope showed that the wollastonite had been uniformly distributed throughout the leaf. The fourdrinier side had no greater wollastonite content than the upper side. A sample of this cardboard-like composite material was shaped into a corrugated shape in a profile dryer and dried. The dried material was pressed into the corrugated panels in a smaller pressing die at a pressure of about 8 kg / cm and at a temperature of about 170 ⁰ C over a period of 15 minutes. The resulting panel is excellent for use as a roof coating panel.

809823/0813

Example 25

Three layers of the cardboard-like composite material produced according to Example 24 were placed on top of one another in a Bakelite press die. At a pressure of 200 kg / cn and a temperature of 170 ⁰ C in the course of 15 min vrurde excellent bowl with sharp Konturan, good mold release properties and a Aigen Ilaterialcharakter obtained which corresponded to that of glass fiber reinforced polyester.

Examples 25 to 36

These examples were used in a pilot plant papermaking facility carried out. It was like playing in the Bs! 1 to 24, i.e. cellulose pulps were placed in the pulp chest, Polymer material and optionally inorganic additives as well as the specified processing aids mixed with the Ausnal.uns that the flocculants also already were added in this stage. The flocculants immediately before transferring the suspension to it don Fourdrinier '(vira) added. In the following table the fourth of these examples are compiled. The various abbreviations have the same meaning as in Examples 1 through 23. The barium sulfate material was a barium sulfate powder with a particle size below 100 um. The Hessing powder had a particle size of below 200 µm. Instead of Hsrcufloc 329.3, e.g. Ilercufloc 853 has also been used.

809823/081 3

Example Mr. 26 27 23 29 30 31 32 33 34 35 36

Straw illulose,

& ™ SR 25 15

Sulphate, # _f 35 ° SR 80 20 17 20 15 Sulphite, JS, 35 ° SR 90 15 thermone chani s ehe

Cellulose fiber ^,

%, 40 ° SR 95

Glass fibers, % 60 55

Slag fibers, % 51.5 20 20 10 15

Rock wool fibers, % 60

t / ollastonite

Fl / 200,; i 15 10 10

Synopal, Jo

Barium sulfate,? 5 25 10 10

ο Hessing powder, % 22 23 25 25

Polyester on

Ti0 ₂ / BaS0 ₄ 20 30 13 18 12 20 15

Polypropylene, V * 5 20

_Copolyamide, % 10 20 3.510

Ammonium polyphosphate 0.2 0.2 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

Ammonium hydroxide 1 »5

Triton CF10 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

Silane A 1100,

% of anorg. 0.4 0.6 0.6 0.6 0.6 0.7 0.7 0.7 0.7

Mopco ITXZ,

55 by anorg. 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

Alum, % 2.1 2.1 2 0.5 0.4 0.5 0.5 0.4 0.5 0.6 0.6

Prodefloc AC 0.5 0.3 0.5 0.6 0.7 0.4 0.5 0.5 0.4 0.6 0.5

Hercufloc 829.3 0.05 0.1
Prodefloc CL 2 0.5

While the materials produced according to Examples 1 to 24 after the release of the filra-forming properties

809823/0813

of the polymer has a relatively hard and patty-like character show those produced according to Examples 26-26 li materials have a cardboard-like character after the polymer has formed a film. However, they show a better one Hatefulness than ordinary cardboard. The one according to the examples 29 to 32 produced limaterialien show a character like non-Gev / ebte flat structures (fleece), while the materials prepared according to Examples 33 to 36 for Use as friction materials, in particular for brake pads, are suitable.

Bronze powder can also be used instead of liessing powder i / ground. In place of the polyester applied to the inorganic carrier, carrier-free polyester particles can also be used will. An epoxy polyester can also be used been. Instead of polypropylene, polyethylene can also be used.

Example 37

As in Examples 26 to 36, a composite material was horgestallt with 20% sulfate cellulose and 8O? 5 one Polymer material consisting of rock wool fibers with a coating of a phenol / formaldehyde resin that to an extent of 8O5o had been polymerized, with the resin 3 to 4? o of the polymer material consisted. The resulting product is useful for making hard plate-like panels and molded articles by heat treatment at one Pressure of 200 kg / cm suitable.

In a further experiment, the same resin-covered rock wool fibers were used in a narrow range of 35%, with

809823/081 3

the amount of sulfate cellulose was 15 / S. It became a similar one Material suitable for the same purpose was obtained.

Example 53

As described in Examples 26-36, a composite material was made from the following approach:

about 200 l of water

1350 g sulfate cellulose
300 g polyethylene powder (SA65), particle size

about 300 to 500 by 0.2 % (3 g) Prodefloc C1.

The sheet weight of the product was 228 g / m. After drying the product had a slightly uneven cardboard-like character. After the polymer has been released from film formation under a pressure of 50 kg / cm and over a period of time A uniform parchment-like material with good waterproof properties was obtained in about 2 minutes.

Example 39

The procedure was as in Examples 26 to 36, the the following approach was used:

about 200 l of water

1350 g sulfate cellulose
300 g polypropylene (LM 229), particle size 300

up to 500 µm

5 to 10? 5 of a $ 1 solution of Prodefloc AC 0.2 $ i (3 g) Prodefloc C6.

809823/0813

-W-

The zeta potential of the resulting suspension was -6.0 ilillivolt. The sheet weight of the product was 263 g / m 2. The product was similar to the composite material of the example 3 <3.

Example 40

The procedure was as in Examples 26 to 36, with the following approach was used:

100 l water
675 g sulphate cellulose 150 g polypropylene (LM229)

about 5 % of an ISbigen solution of Prodsfloc AC 0.2 % (1.5 g) Prodefloc C6 1/2 ml Silane A 1100.

The sheet weight of the product was 316 g / m Example 41

The procedure was as in Examples 26 to 36, the following approach being used:

about 200 liters of water, 1000 g of sulphate cellulose, 1000 g of glass wool

800 g polyester resin (polyester lacquer, 861-0984) 0.11 % (1.65 g) Prodefloc C1 0.89 % (1.35 g) Prodefloc C4.

809823/0813

Di3 suspension of water, sulphate cellulose, glass wool and Polyester resin was initially passed through a de-icing facility directed.

The pH of the suspension was 6.5 and the zeta potential +4.6 millivolts. The sheet weight of the product was 330 g / in

Example 42

The same procedure was followed in Example 41, using the following approach was used:

about 200 l of water

500 g of sulphate cellulose
1500 g glass wool
800 g polyester resin (polyester lacquer, 861-0934).

The above mixture was distributed in a deflocculator.

Then 0.15% (2.25 g) Prodefloc C1 was added.

The pH of the suspension was 6.5 and the zeta potential was +4.0 millivolts to -9.2 millivolts.

The sheet weight of the product was 310 g / m. The product, like the product of Example 41, is pretty and uniform.

Example 43

The procedure was as in Examples 26 to 36, the following approach being used:

809823/0813

about 200 l of water

500 g sulphate cellulose g rock wool fibers

The following mixture was added to this mixture:

300 g gray epoxy powder (epoxy to 45% 0.15% Prodefloc C1 (2.25 g) 10 ml Fintex 577 1 1 water.

The pH was 6.5 and the zeta potential was +6.8 millivolts.

The sheet weight of the product was 432 g / m, Example 44

The procedure was as in the previous examples, using the following approach:

about 100 liters of water

75 g cellulose fibers (old cardboard, 42 ° SR) 375 g glass wool
519 g polyester with a content of 35% by weight 5

Wollastonit 606 g wollastonite FW50 10 g surfactant WKT 15 ml 1 oiges Prodefloc. C1.

The pH was 7.0. The zeta potential was -10.1 millivolts.

809823/081 3

Examples 45 to 54

Examples 45-54 were all run on a LaboratoriuQs sheet forming machine as follows: Cardboard Cellulose was ground and sand was added to the resulting pulp. Then the polymer was added, the polymer in the wet state through a sieve (430 µm) had been directed. The resulting mixture was stirred at 1000 rpm for 2 minutes. A flocculant was added and stirring was continued for 15 to 20 seconds at 200 to 400 rpm. After this flocculation, the approach was in given a vessel to the sheet-forming machine and approximately Stirred for 1/2 min. Sucking was then started. After the sheet formation, the sheets were ventilated in a Oven dried and then treated in a heating press.

809823/0813

Example IJr. 45 46 47 48 49

"[Cardboard, %, 50 ° SR ^ sand, %

° PVC (3107/11/2), %

j) 35) 35) 35) 35) 35

IPVC (3085 / 92A / 1), % 15) 20) 25) 3θ) 35)

Prodc-floc C1, % of anorg. 0.125 0.125 0.125 0.125 0.125

Sheet weight, g / m ² 3000 3000 3000 3000 3000

Retention, % <~ Ί00 ~ 100 ~ 100 λ ^ ΙΟΟ λ-ΊΟΟ

Drying temperature, ° C 60 60 60 60 60

Heating temperature, ° C 250 250 250 250 250

Heating time, min 1/2 1/2 1/2 1/2 1/2

Heating pressure, kg / cia ² 40 40 40 40 40

* Addition of 35% of a mixture of the two types of PVC to the specified weight ratio

809823/0813

Example no.

50 51

53

Cardboard, %, 50 ⁰ SR sand, #
Cement, white polyethylene, cross-linked, % PVC (3035 / 91A / 3),%

PVC (O-VI-107-1), % PVC (5WSW67-951),% Prodefloc C1, $ from anorg.

Prodefloc N2M sheet weight, g / m Retention,% dry temperature ⁰ C heating temperature, heating time ⁰ C, min-heating pressure, kg / cm

20th 20th 20th 20th 20th 45 30th 45 45 30th 30th 15th 15th 30th 15th 20th 20th 10 85) *
) 20
15) 85) * '
) 20
15) 10

0.125 2) ** 2) ** 2) ** 2) **

) 0.125) 0.125) 0.125) 0.125 1) DDD

3000 3000 3000 3000 3000 <> Ί00 - ^ 90> ^ 90 «^ 90 '^ 90 60 60 60 60 60 250 250 250 250 1/2 1/2 1/2
40 40 40

1/2 1/2

40 40

* Addition of 2OJo of a mixture of the two types of PVC in the specified weight percentage ratio.

** Addition of a total of 0.125% of the two polyelectrolytes in the specified weight ratio. First were
the 2 parts by weight of Prodefloc C1 was added and then 1 part by weight of Prodefloc N2M was added.

Example 55

A material used as a base for polyvinyl chloride flooring suitable, was made from the following:

809823/0813

Cellulose fiber] * (20 to 40 ° SR) 20% glass wool 50 ^

Polyvinyl chloride (10 to 70 µm) 30%.

The cellulose fibers and the glass wool were defibrillated separately in a Hollander. (The glass wool was ground to a 0.5% suspension in water, v / o at 0.01 ° a Prodefloc C1 was added. Stirring was limited to a maximum of 1 min). The suspensions were combined and the polyvinyl chloride was added. Just before the inlet stock chest of the paper machine, 0.2 μa of Prodefloc C1 was added and the resulting flocculate was dewatered and the web was dried. The web is suitable for the application of the polyvinyl chloride show fabric and the top finishing coat of the floor covering. The pad can be self-supporting during manufacture. The heat applied in combining the polyvinyl chloride foam and the top finishing liner intimately binds the backing to the foam.

Example 56

Using the same procedure as in Example 55, a composite material was obtained from the following manufactured:

Cellulose fibers 20% by weight

Glass wool 45% by weight PVC (3107/11/2) 80 #)

PVC (3035 / 92A / 1) 20Si < ³⁵

809823/081 3

Example 57

As in Example 55, a composite material was made from:

Cellulose 2O? O

Glass wool 45? $

cross-linked polyethylene 35? o.

Example 58

As in Examples 45 to 54, a material was made from the following manufactured that was suitable as roof panels:

Cellulose 20 wt .-? 6

Sand 45 wt .-? *

Polyethylene, cross-linked 35 Gexr .-%.

Example 59

A composite material suitable for making roof panels was made according to Examples 45 to 54 made from the following:

Cellulose 4.8 wt .- #

Glass wool 23.8 wt .- #

Wollastonite FW50 38.4 parts by weight

Polyester 33 wt .- #.

Example 60

As in Examples 45 to 54, a material suitable for roofing panels was made from the following:

809823/0813

- 6T -

Cellulose 20 wt .- #

Sand 40 wt .-? £

PVC (3107/11/2)
PVC (3035 / 92A / 1)

Example 61

In Examples 44 to 53, a material suitable for use as roofing panels was made from the following:

Cellulose 20% by weight

Cement, white 20 wt .- #

Sand 25 wt -.%

PVC (3035/91 A / 3) 85? O

PVC (O-VI-107/1) 15% \ ^{35 wt} '~ ⁵ '

809823/0813

Claims (1)

Claims 1. Composite material, characterized by a cellulosic fiber structure in which the cellulosic fibers are connected to one another by bonds, such as in cardboard or paper, a polymer material uniformly distributed in the structure, the polymer material consisting of solid individual particles or fibers, the particles or fibers on at least their surfaces consist of a polymer, wherein the polymer or polymers of the polymeric material water insoluble, and are in v / ater non-swellable, strong, synthetic polymers which are not tacky at room temperature and are film-forming at temperatures above 8O ⁰ C, wherein the particles or fibers of the polymer material are bound in the composite material by means of a polyelectrolyte and wherein the proportion of the polymers is at least 2% by weight of the composite material, and optionally inorganic material in the form of mineral or metal particles or fibers, the inorganic Ma material is uniformly distributed throughout the cellulosic fiber structure, as well as composite materials made from the composite material defined above by the application of energy to induce film formation of the polymer. 2. Composite material according to claim 1, characterized in that the polymer material from the group 1) Particles of the polymer with a particle size of 1 to 500 µm, preferably 1 to 200 µm, 809823/0813 2) Particles of an inorganic carrier with the polymer applied thereon, the particles having a particle size of about 1 to 500 µm, preferably 1 to 200 µm, 3) fibers of polymer and 4) inorganic fibers with the polymer applied thereon is selected. 3. Composite material according to claim 1 or 2, characterized in that the polymers from the group polyolefins, vinyl polymers such as poly vinyl chloride, polyvinyl acetate, polystyrene, polyimides, poly amides, polyacrylates, ABS resins, epoxy resins, epoxy / phenolic resins, Phenolic resins, urea resins, melamine resins, polyester resins, kelamin polyester resins, crosslinked acrylic resins, silicone resins, polyurethane resins, and copolymers thereof, such as copolyamides, are selected. 4. Composite material according to claim 3 »characterized in that the polymer is a synthetic vulcanizable elastomer, e.g. SBR, is. 5. Composite material according to claim 3 _t characterized in that the polymer is a crosslinked synthetic polymer such as a polyester, and a thermoplastic synthetic polymer such as polyethylene, polyvinyl chloride or polypropylene, 809823/0813 and / or the crosslinked polymer together with bitumen powder or bitumen emulsion is used. 6. Composite material according to claim 3, characterized in that the polymers a non-plasticized polymer and a plasticized polymer such as a non-plasticized polyvinyl chloride together with a plasticized polyvinyl chloride. 7. Composite material according to one of the preceding claims, characterized in that that it contains a water film-breaking surface-active material such as a surfactant. 8. Composite material according to one of claims 1 to 7, characterized in that the particles of the polymer material are particles of an inorganic carrier material with the polymer applied thereon, the carrier material being composed of metal particles such as particles of brass, iron, zinc, aluminum, copper or bronze, or mineral or other inorganic particles such as TiO ₂ , iron oxide, wollastonite, kaolin, devitrified glass, calcium carbonate, quartz with inclusion of sand, silica, steatite, talc, aluminum silicate, synopal, barytes, Oatomaceous earth or amorphous SiO ₂ . 9. A composite material according to any one of claims 1 to 7, characterized in that it rejects, that the polymer material consists of polymer-coated inorganic fibers, the fibers being mineral fibers such as Glass wool, rovings, rock wool, slag wool, kaolin wool, 809823/0813 or metal fibers such as brass, copper, aluminum, bronze or Iron fibers, are. 10. Composite material according to any one of claims 1 to 9, characterized in that that the polymer of the polymer material contains a blowing agent or foaming agent, which under the temperature conditions in which the film-forming properties of the polymer are triggered, at the same time the polymers are retained foamed in a cell structure. 11. A composite material according to any of the preceding claims, characterized in that it comprises impregnating agents Anti-humidity an which a wood preservative oil, a bitumen emulsion or a paraffin emulsion, or which is decomposed at temperatures of about 100 ⁰ C, an oil emulsion containing a cationic surfactant, , is. 12. Composite material according to one of the preceding claims, characterized in that that it is in the form of an extrudate or granulate. 13. Composite material according to any one of claims 1 to 11, characterized in that that it is in the form of a laminate including a cross laminate of layers of the composite material, wherein the polymer content in the surface layers is optionally higher than in the inner layers. 14. Composite material according to claim 8, characterized in that the part 809823/0813 Chen of the Polyiaermaterials made of a polyolefin or a Epoxy, polyester, acrylic or polyamide resin, applied to TiOp particles, consists of the amount of polymer 40 to 90? 6 of the polymer material. 15. Composite material according to claim 8 or 9, characterized in that the proportion of the polymer is 2 to 40% by weight of the polymer material, typically 2 to 20 wt .- # if the carrier is fibrous, and 5 to 40 wt .- 56 if the carrier is particulate is. 16. Composite material according to one of claims 1 to 3, characterized in that that there are 15 to 40% by weight of cellulose fibers, 15 to 40% by weight Polymeric material and 20 to 70% by weight of inorganic material. 17. Composite material according to claim 16, characterized in that it is the inorganic material mineral particles such as TiO ₂ , wollastonite, kaolin, devitrified glass, calcium carbonate, quartz with inclusion of sand, silica, steatite, talc, aluminum silicate, synopal, barite , Diatomaceous earth or amorphous SiO ₂ *. 13. Composite material according to claim 17, characterized in that the polymer Is polyvinyl chloride, a polyolefin, polyvinyl acetate or a polyamide. 19. Composite material according to claim 16, characterized in that it is used as an- 809823/0813 - 73 "- organic material synthetic mineral fibers such as glass wool, rovings, rock wool, slag wool, kaolin wool or contains calcium silicate wool. 20. Composite material according to claim 19, characterized in that it is glass fibers, such as mineral wool fibers, and polyvinyl chloride as a polymer. 21. Composite material according to any of the preceding Claims, characterized in that the inorganic material is hydraulic Contains binding agents, e.g. cement or kaolin cement. 22. Roof panel, characterized in that sia made of a composite material according to Claim 16 has been made. 23. Roof panel according to claim 22, characterized in that it contains about 20% by weight of cellulose fibers, about 40 to 50% by weight of inorganic particulate material, for example wollastonite or sand with a particle size of below 300 contains up to 40 wt .- # polymer . In that it is made of a composite material according to claim 24, 16 backing sheet for a floor covering, characterized in that. 25. Underlay for a floor covering according to claim 24, characterized in that it contains 15 to 25% by weight of cellulose fibers, 40 to 50% by weight of glass wool or rock wool and about 30 to 40% by weight of polymer. 809823/0813 26. A method for producing a composite material according to claim 1, characterized in that a polymer material consisting of solid individual particles or fibers, the particles or fibers at least on their surfaces consisting of a polymer, the polymer or the polymers of the polymer material are synthetic, water-insoluble and water-non-swellable, solid, synthetic polymers which are not sticky at room temperature and form a film at temperatures above 80 ^° C., mixed with a cellulose fiber pulp and optionally with an inorganic material in the form of mineral or metal particles or fibers, the polymer material with the cellulose fibers and with the inorganic material, if this is present, co-flocculates by means of a polyelectrolyte and then dehydrates the resulting suspension to form a coherent sheet, web or extrudate material, drying the coherent material under conditions et, which do not trigger the film formation of the polymer, the polymer of the polymer material is such that the polymer material remains after drying essentially in the form of individual particles or fibers, and that optionally the dry material of a treatment which the film-forming properties of the polymer triggers, preferably subjected to the application of heat and optionally pressure. 27. The method according to claim 26, characterized that a synthetic polyelectrolyte flocculant is used as the polyelectrolyte in an amount of 0.005 to 2% by weight, based on the dry weight of the constituents to be flocculated. 809823/0813 2β. Process according to Claim 27, characterized in that the polyelectrolyte added immediately before the dehydration of the suspension. 29. The method according to claim 23, characterized that one adds the polymer material to the cellulose pulp as an aqueous, a surface-active agent containing suspension added. 30. The method according to claim 29, characterized in that the inorganic material added to the cellulose pulp as an aqueous suspension. 31. The method according to any one of claims 26 to 30, characterized in that the zeta potential of the suspension to be flocculated between -20 and +20, in particular between -10 and +10 and preferably holds between -5 and +5 millivolts. 32. The method according to any one of claims 26 to 31 »characterized in that as Polyelectrolyte uses a water-soluble cationic synthetic polyelectrolyte. 33. The method according to claim 26, characterized in that a hydraulic binder is incorporated as the inorganic material, that the composite material is dried after dewatering, heat-treated to trigger the film-forming properties of the polymer and that the hydraulic binder is then optionally added with water allowed to harden into the material after the heat treatment. 809823/0813 34. The method according to claim 26, characterized in that fiber-like or fiber-containing material is incorporated as polymer material or the inorganic material and that the fiber-like material is incorporated
Material defibrillates by moving it through in an aqueous suspension with an added polyelectrolyte. 809823/0813 . •• 4.