Patent Application
20130260627
The present invention concerns a method for producing wet-laid non-woven, in particular non-woven glass fiber fabrics, which have a very low binder content, as well as the non-woven glass fiber fabrics produced according to this method and the use thereof.
The production of wet-laid non-woven fabric has been known for more than 50 years and uses the methods and devices initially developed for paper manufacturing.
For the production of wet-laid, for example non-woven glass fiber fabrics, the glass fibers are dispersed in a so-called pulper in water, wherein the content of glass fibers is approx. 0.1-1% by weight. Here, one must pay attention to the fact that the the glass fibers are damaged as less as possible during the dispersion, i.e. essentially no fiber breaking occurs. the dispersed glass fibers are temporarily stored in one or more storage vessels. The discharge takes place through the material outlet, wherein the concentration of glass fibers is reduced by a factor 10 to 20. The discharge takes place to a circumferential Fourdrinier wire through which the water is sucked up and the wet-laid non-woven glass fiber fabric is formed. The sucked up water is supplied again to the process, i.e. recycled.
Following this, a binder is applied onto the non-woven glass fiber fabric, which has just been formed, which binder effects consolidation of the non-woven glass fiber fabric after drying resp. hardening so that it can be rolled up resp. post-treated.
Depending on the range of application, the glass fiber materials, glass fiber lengths and glass fiber diameters as well as the weights per unit area and the binder application are set up. In particular during the production of wet-laid non-woven glass fiber fabrics with a low binder content, problems arise, for example, through rupture.
For a number of applications, it is required to apply a binder, which is only partially cross-linked, on non-woven fabrics. In particular for production of such wet-laid non-woven fabrics with a low application of a B-stage binder, significant problems arise during production, since the non-woven fabrics are very sensitive due to the missing strength and can practically not be used in conventional processing tasks.
During production of wet-laid non-woven fabrics, tensile forces arise, which can be compensed, for example, during transfer of the non-woven fabric from the furnace to the winder only through corresponding tensile strength of the non-woven fabric. Furthermore, shearing forces during winding inevitably lead to delamination and decomposition of the non-woven structure in case of unsufficient strength of the non-woven fabric. Enhancement of the tensile strength is of course possible by using completely cross-linked binders. If, however, non-woven fabrics with a very low binder content are required and, besides this, the binder may not be completely cross-linked (B-stage), this solution cannot be realized.
The object of the present invention is therefore to provide a method for the production of wet-laid non-woven fabrics with a low binder application, with which non-woven fabrics for which the binder is still in the B-stage state can by no means be produced and with which handling of these non-woven fabrics is enhanced.
Therefore, the object of the present invention is a continuous method for producing wet-laid non-woven fabrics, comprising the measures of:
characterized in that
The wet-laid non-woven fabrics produced by means of the method according to the invention have a good mechanical strength along with a low binder content and are to be used in particular for the production of composite materials, in particular composite materials with a low fire load.
Fibers
The fibers used in measure (i) are discontinuous fibers, i.e. so-called staple fibers resp. chopped fibers. The fiber-forming materials are preferably natural fibers and/or fibers of synthesized or natural polymers, ceramic fibers, carbon fibers, mineral fibers or glass fibers, wherein they can also be used in the form of mixtures.
The mineral and ceramic fibers are aluminosilicate fibers, ceramic fibers, dolomite fibers, wollastonite fibers or fibers of vulcanites, preferably basalt fibers, diabase fibers and/or melaphyre fibers, especially basalt fibers. Diabases and melaphyres are designated collectively as paleobasalts and diabase is also often designated as greenstone.
The average length of the mineral fibers is between 5 and 120 mm, preferably 10 to 90 mm. The average fiber diameter of the mineral fibers is between 5 and 30 μm, preferably between 8 and 24 μm, especially preferably between 8 and 15 μm.
Suitable materials made of synthetized polymer materials are, e.g., polyamides such as, e.g., polyhexamethylene diadipamide, polycaprolactam, aromatic or partially aromatic polyamides (“aramids”), aliphatic polyamides such as, e.g., nylon, partially aromatic or fully aromatic polyesters, polyphenylene sulfide (PPS), polymers with ether and keto groups such as, e.g., polyetherketones (PEK) and polyetheretherketone (PEEK), polyolefins such as, e.g., polyethylene or polypropylene, cellulose or polybenzimidazoles. In addition to the previously cited synthetic polymers, even those polymers are suited that are spun from solution.
Preferably, however, the fibers consist of melt-spinnable polyesters. The polyester material can, in principle, be any known type suitable for fiber production. Polyesters containing at least 95 mole % of polyethylene terephthalate (PET) are particularly preferred, especially those composed of unmodified PET.
The single titers of the staple fibers in the non-woven fabric are between 1 and 16 dtex, preferably 2 to 10 dtex. The staple length is 1 to 100 mm, preferably 2 to 500 mm, particularly preferably 2 to 30 mm.
The natural fibers are plant fibers, fibers derived from grasses, straw, wood, bamboo, reed and bast, or fibers of animal origin. The generic term “plant fibers” comprises cotton, kapok or poplar fluff, bast fibers, such as bamboo fiber, hemp, jute, linen or ramie, hart fibers, such as sisal or manila, or fruit fibers, such as coconut. Fibers of animal origin are wool, animal hairs, feathers and silks.
The textile surfaces of fibers of natural polymers are cellulose fibers, such as viscose, or vegetable or animal protein fibers, in particular cellulose fibers.
The average length of the cellulose fibers is between 1 and 25 mm, preferably 2 to 5 mm. The average diameter of the cellulose fibers is between 5 and 50 μm, preferably between 15 and 30 μm.
Suitable glass fibers comprise those manufactured from A-glass, E-glass, S-glass, T-glass or R-glass.
The average length of the glass fibers is preferably between 5 and 120 mm, preferably 10 to 90 mm. The average fiber diameter of the glass fibers is preferably between 5 and 30 μm, in particular between 8 and 24 μm, especially preferably between 10 and 21 μm.
In addition to the previously cited diameters even so-called glass microfibers can be used. The preferred average diameter of the glass microfibers is between 0.1 and 5 μm.
Fiber Dispersion
The measures for dispersion of the fibers used in step (i) are known to those skilled in the art. The exact process conditions depend on the fiber materials and the desired weight per unit area of the non-woven fabric to be formed.
The processes described hereinafter refer to the production of non-woven glass fiber fabrics; however, the corresponding process steps are similar also for other fiber materials are known to those skilled in the art.
Basically, the fibers are dispersed in a so-called pulper in water, wherein in the case of glass fibers the content of the glass fibers is approx. 0.1% by weight to 1% by weight.
The dispersed glass fibers are usually temporarily stored in one or more storage vessels, wherein the deposition of the glass fibers must be prevented. This measure is also known to those skilled in the art.
The discharge of the glass fiber/water dispersion resp. the application according to measure (ii) takes place through the material outlet, wherein the concentration of glass fiber is reduced by a factor 10-20. This measure is also known to those skilled in the art.
Further auxiliary materials can be added to the water used for production of the glass fiber/water dispersion. Here, it is usually thickening agents and surfactants. This measure is also known to those skilled in the art. Additionally, the B-stage capable binder system responsible for the reinforcement can be added to the water, so that measure (iv) can be cancelled wholly or at least partially.
The discharge of the fiber/water dispersion takes place to a circumferential Fourdrinier wire through which the water is sucked up and the wet-laid fiber fabric is formed (measure (iii)). The sucked up water is supplied again to the process, i.e. recycled. For the production of the wet-laid glass non-woven fabrics, known apparatuses are used, such as Voith Hydroformer® or Sandy Hill Deltaformer®, which are known in the market.
The weight per unit area of the non-woven fabric formed, in particular the non-woven glass fiber fabric formed, is between 20 and 500 g/m2, preferably between 50 and 300 g/m2, wherein these values refer to a non-woven glass fabric with binder and without taking into account the residual humidity, i.e. after drying and complete cross-linking of the binder.
The wet-laid non-woven fabric can also consist of mixtures of different fibers. Non-woven fabric, which consist of synthetic fibers, polymeric fibers and of glass fibers are particularly suitable. The glass fiber content is between 20-80% by weight, in particular between 30-60% by weight, wherein these values refer to the total weight of the non-woven fabric without binder.
Binder
In measure (iv), a B-stage capable binder system is applied onto the wet-laid glass non-woven fabric, which has just been formed and still is on the circumferential Fourdrinier wire. Excess binder can be sucked up via the Fourdrinier wire, so that the binder system is available uniformly distributed in the glass non-woven fabric.
Here, it has proved that when using B-stage binders and with low binder application, no sufficient stability of the non-woven glass fiber fabric can be achieved, so that they can not be produced in this way. Missing longitudinal and transverse strengths lead to rupture of the non-woven fabric, to delamination during winding or even to decomposition of the non-woven structure, but at least to extreme product inhomogenities and thus to significant loss in yield.
To avoid said problems, a B-stage capable binder system is used. The B-stage capable binder system according to the invention comprises (i) at least one B-stage capable binder and (ii) one further self-cross-linking binder, preferably a thermally cross-linking binder.
The applied quantity of the B-stage capable binder system in measure (iv) is at most 20% by weight, preferably 15% by weight, wherein the value refers to the total weight of the non-woven fabric after complete drying.
B-stage capable binders are understood to mean binders that are only partially consolidated or hardened, i.e. are available in the B-stage state, and can still experience a final consolidation, e.g., by thermal post-treatment. Such B-stage binders are described in detail in U.S. Pat. No. 5,837,620, U.S. Pat. No. 6,303,207 and U.S. Pat. No. 6,331,339. The B-stage binders disclosed therein are also an object of the present invention. B-stage binders are preferably binders based on furfuryl alcohol formaldehyde resins, phenol formaldehyde resins, melamine formaldehyde resins, urea formaldehyde resins and mixtures thereof. Preferably, these are aqueous systems. Further preferred binder systems are formaldehyde-free binders. B-stage binders are characterized in that they can be subjected to a multistage hardening, that is, they still have a sufficient binding action after the first hardening or after the first hardenings (B-stage state) so that they can be used for the further processing. Such binders are usually hardened in one step after the addition of a catalyst at temperatures of ca. 350° F.
In order to form the B-stage, such binders are optionally hardened after the addition of a catalyst. The amount of hardening catalyst is up to 10% by weight, preferably 0.1 to 5% by weight (based on the total binder content). For example, ammonium nitrate as well as organic aromatic acids, e.g., maleic acid and p-toluenesulfonic acid, are suitable as hardening catalyst since it allows the B-stage state to be reached quicker. In addition to ammonium nitrate, maleic acid and p-toluenesulfonic acid, all materials are suitable as hardening catalyst that have a comparable acidic function. In order to reach the B-stage, the textile fabric impregnated with the binder is dried under the influence of temperature without producing a complete hardening. The necessary process parameters are dependent on the binder system selected.
The lower temperature limit can be influenced by the selection of the duration or by adding more or stronger acidic hardening catalysts.
B-stage binders based on urea formaldehyde (UF), melamine formaldehyde (MF), epoxide, or mixtures of UF binders and MF binders are particularly preferred.
Self-cross-linking binders are binders, which completely react through chemically without any additive of a catalyst. The cross-linking is preferably induced thermally. It has proved that, in particular aqueous polymer dispersions, polymer dispersions of vinyl acetate and ethylene, or similar self-cross-linking, in particular thermally self-cross-linking binders are suitable. Acrylate binders are particularly suitable.
The content of the self-cross-linking binder in the B-stage capable binder system is at most 20% by weight, preferably at most 15% by weight and particularly preferably at most 10% by weight, wherein the values refer to the B-stage capable binder system (B-stage binder and self-cross-linking binder), without taking into account the residual humidity, i.e. after drying and complete cross-linking of the binder,
The content of the self-cross-linking binder in the B-stage capable binder system is at least 2% by weight, preferably at least 5% by weight, wherein the values refer to the B-stage capable binder system (B-stage binder and self-cross-linking binder), without taking into account the residual humidity, i.e. after drying and complete cross-linking of the binder.
The application of the B-stage capable binder system can take place by means of known methods. In addition to spraying, impregnating and pressing, the binder can also be applied by coating or by means of rotary nozzle heads. Furthermore, foam application is also possible.
The drying in measure (v) takes place at temperatures between 90° C. and 200° C. max., wherein the dwell time in the dryer is typically between 30 and 60 seconds for the aforementioned temperature range. The drying according to measure (v) effects that the B-stage capable binder hardens at least partially, but not completely, and the additional, self-cross-linking binder is completely hardened.
The degree of hardening of the B-stage binder is usually determined through measurement of the condensation humidity, which is produced during complete hardening.
The residual humidity is determined as relative change in weight of a sample at a temperature of 170° C. for 2 minutes. A complete hardening leads to residual humidity of less than 1%. Incompletely cross-linked binders, i.e. binders in the B-stage state, show in the non-woven fabrics produced according to the invention a residual humidity of between 1% and 5%, preferably between 1.5% and 4%.
Alternatively, it is possible to determine the degree of hardening using the tensile strength of the non-woven fabric. A complete hardening of the B-stage capable binder system is supposed at a tensile strength of at least 95% or more of the highest possible tensile strength. The drying in measure (v) has the effect that the B-stage binder is not yet completely cross-linked and the non-woven fabric has a tensile strength of less than 20% of the highest possible tensile strength (gem. DIN EN 29073T3).
For drying of the wet-laid glass non-woven fabric, known drying apparatuses are used.
The wet-laid glass non-woven fabric produced by means of the method according to the invention have a low binder content. The content of all binders is at most 20% by weight in relation to the total weight of the non-woven fabric. Preferably, the content of all binders is between 5% by weight and 15% by weight. Preferably, the wet-laid non-woven fabric produced by means of the method according to the invention, in particular glass non-woven fabrics, exclusively contain the B-stage capable binder system used according to the invention and no further additional binder.
The winding of the finished wet-laid glass non-woven fabric takes place by means of known methods.
The above-mentioned preferred ranges for fiber length, fiber diameter, fiber weight, binder and porosity can be combined freely, independently of each other, and any possible combination of the respectively preferred ranges is thus explicitly part of the present description.
Reinforcement
The wet-laid non-woven glass fiber fabric produced by means of the method according to the invention method can additionally have further reinforcement.
The supply of planar reinforcement typically takes place on the top side of the circumferential Fourdrinier wire on which the wet-laid non-woven glass fiber fabric is formed.
The supply of reinforcement fibers and/or yarns takes place as in the case of planar reinforcement or individually, i.e. from above or the side, wherein the reinforcement fibers and/or yarns are incorporated centrally in the non-woven fabric formed or on the top side and/or underside. The assembly position results from the exact positioning of in the area of non-woven formation on the Fourdrinier wire. Finally, restrictions merely apply due to the type of construction of the non-woven makers used.
Reinforcements include preferably reinforcing filaments and/or yarns whose Young module is at least 5 GPa, preferably at least 10 GPa, particularly preferred at least 20 GPa.
The reinforcing filaments, i.e. the monofilaments, rovings as well as the yarns have a diameter between 0.1 and 1 mm or 10-2400 tex, preferably 0.1 and 0.5 mm, particularly 0.1 and 0.3 mm and have an elongation at rupture of 0.5 to 100%, preferably 1 to 60%.
Filaments, in particular multifilaments and/or monofilaments on the basis of polyester, aramids, preferably so-called high-modulus aramids, carbon, glass, glass rovings, mineral fibers (basalt), high-strength polyester monofilaments or multifilaments, high-strength polyamide monofilaments or multifilaments, as well as so-called hybrid multifilament yarns (yarns containing reinforcing fibers and lower-melting binding fibers) or wires (monofilaments) composed of metals or metal alloys, are preferably used as reinforcing filaments. The selection of the material is predefined through the drying temperatures in measure (v).
For economic reasons, preferred reinforcements consist of glass multifilaments in the form of—essentially—parallel warp sheets or scrims. In most cases, the glass non-woven fabrics are reinforced in the longitudinal direction by—essentially—parallel warp sheets.
The reinforcement filaments can be used arranged as net, lattice or scrim. Reinforcements with reinforcing yarns running parallel to each other, that is warp sheets, as well as scrims or lattice fabrics are preferred.
Depending on the wanted property profile, the density of the filaments may vary in wide limits. Preferably the filament density is between 20 and 250 filaments per meter. The filament density is measured vertically to the running direction. The reinforcement filaments are preferably supplied prior to the formation of the glass non-woven fabric on the top side of the circumferential Fourdrinier wire. It is, however, possible to supply the filaments during the formation of the glass non-woven fabric, so that they are incorporated.
Non-woven glass fiber fabrics are produced by means of the usual wet laid method. The glass fibers used are 13μ E-glass fibers with a length of 18 mm.
The formation of the non-woven fabric is followed by the binder application using a MF binder (Madurit MW 830 by the company INEOS) while adding an hardener (0.3% Deuracure KF by the company Deurawood). Then, the drying takes place at 120° C. for 35 sec in a furnace. The strengths were measured according to DIN EN 29073T3 with samples with a width of 5 cm. The residual humidity was determined after the drying in the furnace on the final product. The wet strength of the non-woven fabric is determined on test items at room temperature (approx. 21° C.) after 10 min. of watering in the water bath according to DIN EN 29073T3.
Example 1 (comparison):
Total area weight of the non-woven fabric: 240 g/m2
Binder: 100% MF
Binder content (ignition losses): 15%.
Tensile strength (longitudinally): 11 N/5 cm
Tensile strength (transversally): 8 N/5 cm
Wet strength: not measurable
Residual humidity: 2.8%
Total area weight of the non-woven fabric: 240 g/m2
Binder: 95% MF+5% Acronal
Binder content (ignition losses): 15%.
Tensile strength (longitudinally): 202 N/5 cm
Tensile strength (transversally):
Wet strength: 1.75 N/5 cm
Residual humidity: 2.52%
Total area weight of the non-woven fabric: 240 g/m2
Binder: 90% MF+10% Acronal
Binder content (ignition losses): 15%.
Tensile strength (longitudinally): 269 N/5 cm
Tensile strength (transversally): 8 N/5 cm
Wet strength: 1.11 N/5 cm
Residual humidity: 2.08%
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2012 006 689.9 | Mar 2012 | DE | national |
