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    • 专利摘要:
    The present invention relates to a method for manufacturing a slab comprising solid fillers and organic binders. More in detail the present method comprises a method for manufacturing slab consisting of a front layer, a middle and a rear layer, said slab comprising fillers, organic binders and additives. The present method furthermore relates to a slab obtained according to the present method.
    公开号:NL2019729A
    申请号:NL2019729
    申请日:2017-10-13
    公开日:2018-06-28
    发明作者:Schoneveld Erik
    申请人:Innovative Stone Tech B V；
    IPC主号:
    专利说明:

    Description
    The present invention relates to a method for manufacturing a slab comprising solid fillers and organic binders. The present method furthermore relates to a slab obtained according to the present method.
    Methods for manufacturing slabs are known from the prior art. For example, International application WO 2005/014952 (corresponding to US2006119002) relates to a thin, i.e. a thickness of 3.5 to 6 mm, stratified, reinforced slab consisting of two outer layers and at least one resistant middle layer wherein the outer layers and the at least one middle layer consist of the same permanently hardened mix, comprising inert materials and a binding resin. The mass of the middle layer is a fibrous layer where linear elements or filaments made of glass. The mix forming outer layers and at least one middle layer is a Breton stone mix. The technology according to Breton stone envisages using a mix consisting of inert materials and a cement binder or a binder consisting of a synthetic resin with the addition of fillers, wherein the mix, which is deposited in a suitable thickness inside a forming support, preferably in the form of two rubber sheets with dimensions matching those of the final slab desired, is subjected inside a vacuum chamber to the action of a press, the ram of which is kept vibrating at a redefined frequency. After the vacuum compaction accompanied by a vibratory movement, the resulting slab is transferred to a hot hardening station where, owing to the effect of heat, the resin hardens. The slab is then freed from the rubber sheets so that it can be conveyed away for the normal finishing operations (such as sizing, polishing, etc.).
    US Patent application publication 2012/119414 relates to a process for manufacturing a slab having an average thickness of about 2.5 mm to about 50 mm from a composite material, said process comprising: (a) mixing solid filler and thermoplastic binder in a kneading device at a pressure in the range of about 100 kPa to about 1500 kPa to obtain a composite material; and (b) forming the composite material into a shaped article; wherein the thermoplastic binder comprises about 60 wt.% to about 100 wt.% of a thermoplastic polyester, based on the total weight of the binder, and wherein the thermoplastic polyester comprises about 90 wt.% to about 100 wt.% of recycled polyethylene terephthalate.
    US Patent application publication 2012/049413 relates to a process for manufacturing a shaped article from a composite material, said process comprising mixing solid filler and thermoplastic binder in a mixing device to obtain a composite material, forming the composite material into a shaped article; and cooling the shaped article at a cooling rate of at least about 5 °C./min to about 120 °C./min, wherein the weight ratio of the solid filler to the thermoplastic binder is about 2:1 to about 15:1. shaped article is a slab. The shaped article is a slab having a thickness of about 0.3 cm to about 5 cm, wherein an upper surface and a bottom surface slab are cooled simultaneously by belt cooling.
    US Patent application publication US 2013/130009 relates to an isotropic slab of engineered stone, having a thickness of about 2 mm to about 10 mm, the slab comprising a composite material comprising about 50 to about 95 wt.% of solid filler and about 5 to about 50 wt.% of a thermoplastic binder, based on the total weight of the isotropic slab. Such a slab has been manufactured according to a process comprising the following subsequent steps: feeding solid filler and a thermoplastic binder to a mixing device, mixing the solid filler and the thermoplastic binder in the mixing device at a temperature of 230 °C to 350 °C. to obtain a composite material, forming the composite material into a thin slab; and cooling the thin slab to a temperature greater than about 75 °C. by belt cooling.
    International application W002/090288 relates to a process for the preparation of a composition, which comprises a matrix of solid particles, i.e. a combination of aggregate, filler and sand, embedded in a binder, wherein the binder is present in an amount in the range of from 1 to 50 % by weight and comprises a synthetic thermoplastic polymer, i.e. waste or recycled polymer selected from the group of polypropylene, polyethylene terephthalate, polybutylene terephthalate and mixtures thereof, which process comprises mixing heated particles and binder, shaping if desired, and allowing the mixture to solidify, wherein solid particles and binder are heated independently of each other prior to mixing such that on mixing the temperature of the mixture is in the range of from 230 to 300 °C, and wherein the solid particles are heated to a higher temperature than the binder.
    US Patent application publication US 2003/122273 relates to a method of manufacturing a building product from a mix including particulate material and a binder, wherein the binder being a thermoplastic binder which binder is an asphaltenes-containing binder, which comprises heating the mix including the thermoplastic binder at least to a temperature at which the thermoplastic binder in the mix liquefies, subjecting the heated thermoplastic mix to a pressing action that shapes the heated mix, and cooling the shaped heated thermoplastic mix to solidify the thermoplastic binder and form the building product.
    US Patent No. 6,177,179 relates to a process for the production of an Integral, board-like component with a visible side and a rear side which comprises the steps: filling a casting mold with a first hardenable casting mass which contains a first syrup with a first monomer and a first filler for forming the visible side layer, further filling the casting mold with a second hardenable casting mass which contains a second syrup with a second monomer and filling a second inorganic filler into the casting mold, wherein the filler forms the rear side layer together with the second casting mass, closing the casting mold, and initiating the hardening of the first and the second casting masses, beginning on the visible side of the component, wherein the first filler has a greater specific density than the syrup of the first casting mass, wherein the barrier layer is essentially impermeable for the first monomer and can be securely bonded to the visible side layer as well as the rear side layer.
    From International application WO 2013/011360 is known a method for obtaining a hybrid polymer coating for petrous or ceramic substrates, the coating having a thickness between 0.1 and 2 mm and comprising a mixture of micronized powder, gravels, base resin selected from polyurethane, polyester, epoxy or acrylic and in general pigments and additives for said resin. The method comprises a step of preparing a base mixture comprising at least one first gravel of quartz, silica or silica sand in a mixer, preparing a base resin selected from polyurethane, polyester, epoxy or acrylic, adding the resin to the mentioned mixture and stirring in a mixer, creating a vacuum inside the mixer, applying a layer of the semi-fluid mixture obtained on a substrate and retaining on the same, vibrating the substrate to displace the larger gravels towards the bottom; accelerating the curing of the mixture by providing or generating heat, the mixture being consolidated on the substrate, and mechanical finishing including a mechanical polishing of the coating polymer to obtain the mentioned thickness required and a smooth surface.
    Such a vibration process for causing a degree of migration of particles from one layer to another layer is also known from International application WO 2004035502. This document discloses a method of forming a particle mass comprising at least two particle populations arranged in a desired graded relationship, the method comprising: forming in a container a first layer of dry particles constituting a first particle population having a desired particle size distribution, superimposing on the first layer a second layer of dry particles constituting a second particle population having a desired particle size distribution, the second layer being in direct contact with the first layer at a contact interface, and causing the particle mass in the container to vibrate to cause a desired degree of migration of particles from one or both layers across the contact interface under the influence of force experienced by particles in the mass.
    JP2006137807 relates to an epoxy resin compact obtained by impregnating epoxy resin into a fiber glass mat as reinforcing material. A mixture (250-350 weight parts) of hydrated aluminum-powder of large particle size group having particle size of 15-100 micrometer and small particle size group with particle size of less than 4 micrometer is mixed with an epoxy resin (100 weight parts) to obtain a varnish. The varnish was impregnated into a fiber glass mat and heated at 120[deg] C for 10 minutes, to obtain a prepreg. The initial and final filler distribution is the same across the final product.
    JP2005089648 relates to an insulating plate of electric switch used for motor circuits, prepared by impregnating a fiber glass mat with a mixture containing granular filler for improving arc resistance, a resin binder, and hardener for resin binder to form a prepreg and molding the formed prepreg. Such a mixture contains filler, binder and hardener, wherein the filler, i.e. aluminum hydroxide, contains particles of large size (15100 micron) and particles of small size (less than 4 micron), in mass ratio of 10:6-10:14. The initial and final filler distribution is the same across the final product.
    JPS54-37174 relates to a moulding fibre reinforced plastic material by pulverizing components, forming a slurry, applying the slurry to web, drying and moulding under heat and pressure. This document discloses the pulverization of an epoxy resin and hardener to particles smaller than 50 micrometer and the subsequent preparation of a slurry with silica powder, colloid silica and methanol. The slurry was applied to a glass fibre mat and five sheets of the web were laminated under pressure and heat to obtain a flame retardant sheet. The initial and final filler distribution is the same across the final product.
    JPS54162781 relates to insulating boards for tightening rails with slabs, prepared by moulding glass fibre reinforced unsaturated polyester, quartz sand filler and additives mixture at specific temperature and pressure. The mixture as disclosed therein contains unsaturated polyester, calcium carbonate powder and quartz powder containing 99.9% of Si02, 50% of the particles having a size of 2 -10 micrometer and is impregnated into a glass mat, and moulded in a mould. The initial and final filler distribution is the same across the final product.
    On basis of the above discussion of relevant prior art one must realize that nowadays a wide range of polymer-filler composite products is used in the construction of buildings, cars, aviation etc. These products are manufactured with different technologies that can basically be divided into two categories, namely i) chemical processes employing a liquid thermoset resin that solidifies via chemical reaction (like two component adhesives) and ii) mechanical processes using a thermoplastic resin at high temperature, that subsequently solidifies by cooling.
    In the technical area of artificial (or engineered) stone products for the building industry require very high levels of fillers, e.g. up to 90% by weight, to mimic the stone like features of natural stone products. A very important technical challenge is how to effectively mix such very highly filled polymer-mineral composites, while at the same time keeping the wear of the mixing devices at an acceptable level.
    As discussed above, some processes employ thermoset resins in very low contents below 10%, mainly in a batch process. The batch mixers are designed in such a way that they can cope with the high shear and wear created by the very abrasive quartz/resin mix. The batch vacuum vibration presses are dimensioned such a way that they are able to press out all air and create a non-porous product. However, such a batch process is capital intensive, generates industrial waste; uses (toxic) chemicals and limits plant productivity and the flexibility of product dimensions. The slab produced according to these batch processes has generally a minimum thickness of typically 10 mm (due to process constraints and mechanical properties) and the length of the slabs cannot be tailor made. The length of the slab will always be the same from batch to batch due to the dimensions of the batch press. In addition, a lot of waste in the down-stream cut process will be generated since most of the final applications do not have the same dimensions as the dimensions of the batch press.
    It has also been attempted to use thermoplastic or thermoset resins in a continuous (mechanical) process. Such a technology would need less capital investment having higher productivity and would lead to a reduction of waste, avoidance of toxic
    Chemicals and increase of flexibility in product dimensions. However, such attempts have proven to be unsuccessful, because machine wear is too high when high concentration of hard coarse minerals are used for manufacturing high quality end products and degassing the end product to a final product free of air pores has shown to be unviable at such low binder content in a continuous process. This could be overcome by using a higher binder content in the mixing unit, but in order to reduce significantly the wear in the mixing unit the binder content has to be increased to at least 25% or higher (30%). At those high binder contents the hardness of the final product decreases significantly and the final product does not have the appearance of a stone like material which will be an important barrier for the selling argument of these materials.
    In addition, an important aspect of the final slab is the geometrical dimension. The slab as such is a flat panel and any kind of warping or undulation should be prevented.
    An aspect of the present invention is to provide a method for manufacturing a slab wherein one or more of the shortcomings of the cited art as discussed above are overcome.
    More in detail, an aspect of the present invention is to provide a method for manufacturing a slab wherein a slab having excellent product properties is obtained.
    The present invention relates thus to a method for manufacturing a slab comprising solid fillers and organic binders, said method comprises the following steps:
    i) providing a first mixture comprising organic binders and solid fillers, wherein said solid fillers comprise fine particles and coarse particles;
    ii) providing a second mixture comprising organic binders and solid fillers, wherein said solid fillers comprise fine particles and coarse particles;
    iii) providing a substrate layer;
    iv) contacting the substrate layer of step iii) with the first mixture of step
    i) and the second mixture of step ii) such that said substrate layer is positioned between said first mixture and said second mixture;
    v) exerting a force on the composite obtained in step iv) for migrating at least a part of said organic binder of said first mixture and at least a part of said organic binder of said second mixture into said substrate layer;
    vi) cooling the construction obtained in step v) thereby obtaining said slab.
    The present inventors found that by using such a method for manufacturing a slab one or more of the above identified aspects can be achieved. According to the present method the composition of the first mixture in step i) and of the second mixture in step ii) has a significantly higher organic binder content than desired in the final product, i.e. the slab. This high organic binder content in the first mixture in step i) and the second mixture in step ii) will have a positive influence on the reduction of wear in the mixing equipment, and the substrate layer as used in step iii) will function as a kind of sponge for absorbing at least a part of the organic binders that was originally present in the starting first mixture in step i) and the starting second mixture in step ii).
    During step v), wherein a force is exerted on the composite obtained in step iv), wherein the composite is such that said substrate layer is positioned between the first mixture and the second mixture, at least a part of said organic binder of said first mixture and at least a part of said organic binder of said first mixture will migrate into the substrate layer. Due to this migration the concentration of the coarse particles in both the first and second mixture will increase. And these first and second mixture are positioned on either side of the substrate layer. Since the solid fillers comprise both fine particles and coarse particles some parts of the fine particles will also migrate into the substrate layer. The organic binder absorption capacity of the substrate layer is chosen such that the coarse particles of both the first and second mixture will not migrate into the substrate layer and that consequently the coarse particles are concentrated on either side of the substrate layer. In other words, the substrate layer will form a barrier for the coarse particles to migrate into the substrate layer. The present inventors found that the concentration of those coarse particles on both sides of the substrate layer will have a beneficial effect on the mechanical properties of the final slab. This enrichment of coarse particles on both sides of the substrate layer will result in an increase of the surface hardness of the final slab.
    In an embodiment of the present method step v) is carried out in such a way that both the concentration of coarse particles in the first mixture of step i) and the concentration of coarse particles in the second mixture of step ii) is lower than the concentration of coarse particles in the mixture after step v).
    In an embodiment of the present method at least a part of said fine particles of both the first mixture and the second mixture migrates in step v) into said substrate layer.
    In an embodiment of the present method step v) is carried out in such a way that the coarse particles of both the first mixture and the second mixture are concentrated in an area adjacent to the substrate layer.
    The present method will thus result in a change in particles distribution during the manufacturing process, i.e. the formation of a particles concentration profile across the thickness of the final slab after the manufacturing process. The present method thus relates to a selective migration of at least a part of the organic binder and particles from the initial mixtures of step i) and ii) into the substrate layer, i.e. at least a part of the organic binder and fine particles migrate into the substrate layer, while the coarse particles are retained in the initial mixtures of step i) and ii). In practice some parts of the organic binder and fine particles will remain in the starting mixtures and thus this organic binder will function as a “matrix” for coarse particles.
    Examples of materials for the substrate layer are materials chosen from the group of paper, cardboard, textile fibres, glass fibre mat, carbon fiber, basalt fibers natural fibre mat, such as flax fibers, Abaca fibers, coir fibers, hemp fibers and jute fibers, or a combination thereof. These materials enable the “sponge” function of the substrate layer, i.e. the absorption of at least a part of the organic binder during present step v).
    The present substrate layer has an organic binder absorption capacity preferably in a range of 100-3000 g/m2, more preferably 500-3000 g/m2, even more preferably 1000-3000 g/m2. Although the term “substrate layer” has been used here, such a substrate layer may comprise several sub layers.
    The number and the size of voids in the substrate layer is such that during step v) the coarse particles will not migrate into the substrate layer. The number and the size of voids of the substrate layer is chosen such that the substrate layer will function as a selective filter or membrane wherein only specific components of the starting mixture according to step i) and ii) having a size smaller than the voids present in the substrate layer can migrate into the interstices or voids of the substrate layer. The result of such a selective filtering or absorbing property of the substrate layer is that specific components of the starting mixture having a size bigger than the interstices or voids of the substrate layer will remain in the originally provided mixture according to step i) and ii).
    The substrate layer in step iii) is preferably in the form of a mat.
    In an embodiment the present method further comprises a step vii) of processing at least of one of the outermost layers of the slab, said processing is chosen from the group of one or more of milling, planing, sanding, sawing, polishing, etching and abrasion, or a combination thereof. Such a step will remove a part of the hardened outermost layers of the slab resulting in an exposure of a layer of hardened material, that layer being composed of coarse particles. The hardness of that layer is crucial for the use of the slab in specific applications. Examples of such a removal step vi) comprise one or more of milling, planing, sanding, sawing, polishing, etching and abrasion, or a combination thereof. According to an embodiment of the present method the thickness of the layers to be removed in step vii) is about 0,1 -1,0 mm, preferably in a range of 0,2-0,5 mm.
    In another embodiment of the present method the substrate layer is a layered structure, wherein said layered structure comprises at least two substrate layers. Such a layered structure preferably comprises solid fillers comprising fine particles and coarse particles, wherein solid fillers are positioned between two substrate layers, wherein the substrate layers are of the same type or of a different type of material.
    Such a layered structure comprises thus solid fillers comprising fine particles and coarse particles, wherein said solid fillers are positioned between two substrate layers. In such an embodiment the “core” of the final slab is not a single substrate layer but a combination of substrate layers, wherein a layer of solid fillers is positioned between these substrate layers. One can say that such a slab is a five layer slab, made on basis of a first mixture- a substrate layer- solid fillers- a substrate layer- a second mixture. In another embodiment the slab is a three layer slab, made on basis of a first mixture- a substrate layer- a second mixture. Such a sandwich construction of substrate layers and solid fillers positioned between these two substrate layers will further minimize the occurrence of warpage.
    In an embodiment the first mixture in step i) and/or the second mixture in step ii) further comprises one or more additives chosen from the group of glass fibers, flax fibers, Abaca fibers, coir fibers, hemp fibers, jute fibers, carbon fibers and basalt fibers, or a combination thereof.
    In the present method the organic binder is preferably chosen from the group of thermoset and thermoplast type binders, or a combination thereof.
    In case of the application of thermoset type binders in step i) and step ii) the present method may further comprise a step of heating during one or more of step i), step ii), step iv), step v). Thus, in an embodiment the present method for manufacturing a slab comprises a step of heating the mixture of step i) and /or step ii) before step iv) is carried out, wherein the heating takes place at a temperature of 100 - 160 °C in case of a thermoset type organic binder and at a temperature above the melting point Tm in case of a thermoplast type organic binder. Such a step of heating is preferred for facilitating present step v), i.e. the migration of at least a part of the organic binder into the substrate layer. In other words, in the present method step v) is carried out under high temperature conditions in case of thermoplastic resin binder and in case of thermoset resin the step v) of migration can be done under ambient temperature followed by high temperature curing.
    Present steps i) and ii) may further comprise mixing organic binders, additives and fillers at an elevated temperature.
    In a preferred embodiment step iv) further comprises applying said first mixture comprising organic binders and fillers on a support, applying said substrate layer on top of said mixture laying on said support, and applying said second mixture comprising organic binders and fillers on said substrate layer in a continuous mode.
    In another preferred embodiment the step of applying said substrate layer comprises a step of applying a layered structure, namely a step of applying a substrate layer, applying a layer of solid fillers comprising fine particles and coarse particles on top of said substrate layer and applying a substrate layer on top of said layer of solid fillers in a continuous mode. This embodiment refers to the manufacture of a five layer slab, made on basis of a first mixture- a substrate layer- solid fillers- a substrate layer- a second mixture, as discussed above..
    An example of such a support is an endless conveyor belt.
    For obtaining a high pressure in a continuous mode of the present method step i) further comprises transferring the support, the support comprising the substrate layer(s) and the mixtures comprising organic binders and fillers through a slit between rotating rolls. By adjusting the width of the slit between the rotating rolls both the pressure exerted on the feed material and the thickness of pressed feed material can be set at a desired range.
    The present inventors found that the presence of air bubbles in the binder containing mixture will have a negative influence on the final mechanical properties of the final slab. It is thus preferred to further include in step i) and/or step ii) a step of deaeration, preferably during or after mixing said organic binders, additives and fillers. Such a step of de-aeration can be carried out by vibrating the mixture with an under pressure,
    i.e. vacuum conditions in the mixing unit and or the press. Such a step of de-aeration may also comprise the application of an under pressure without vibration.
    The particle size distribution of the fine particles in the mixture of step i) and step ii) is preferably chosen from a range below 63 micron.
    According to another preferred embodiment the particle size distribution of coarse particles is chosen from a range of 63-1200 micron, especially 100-800 micron. This particle size distribution of coarse particles will be chosen such that the final volume fraction of coarse minerals in the front layer is very high (> 0.75) yielding high product hardness.
    The thickness of the slab obtained after step vi) and/or vii) is in a range of 2 to 10 mm.
    According to a preferred embodiment the weight percentage of organic binder is in a range of 5 - 40 wt.%, the weight percentage of solid fillers is in a range of 50 to 95 wt.%, the weight percentage of additives is in a range of 0,1-10 wt.%, all weight percentages being based on the total weight of the slab obtained after step vi) and/or vii).
    According to another preferred embodiment organic binder comprises 60 - 100 wt.% of thermoplastic polyester and 0 - 40 wt.% of a polyolefin, based on the total weight of the organic binder.
    It is preferred that 90 - 100 wt.% of said thermoplastic polyester is one or more chosen from the group of polybutylene terephthalates, modified polyethylene terephthalates, recycled polyethylene furanoate, polycarbonates, polylactates and recycled polyethylene terephthalates, based on the total weight of the thermoplastic polyester.
    The organic binder is preferably a thermoset type binder chosen from the group of unsaturated polyester resin, acrylic resin, epoxy resin or phenolic resin, or a combination thereof.
    Examples of the coarse particles are chosen from the group of inorganic minerals, such as quartz, glass, silica sand (S1O2), calcium carbonates, such as marble (CaCC>3) or dolomite (CaMg(CC>3)2), aluminum tri-hydrate (ATH), wollastonite (CaSiCF), coesite, cristobalite, keatite, moganite, seifertite, stishovite and tridymite, especially inorganic minerals having a Mohs hardness of at least 7.
    The present method is preferably carried out as a continuous process,
    i.e. steps i) -vii) are carried out in a continuous mode.
    The present invention furthermore relates to a slab consisting of a front layer, a middle and a rear layer, obtained according to the method as discussed above, wherein the concentration profile of coarse particles in both the front layer and the rear layer shows a gradient over the thicknesses thereof, the coarse particles of both the front layer and the rear layer are concentrated in an area adjacent to the middle layer.
    In a preferred embodiment of the present slab the concentration profile of fine particles in both the front layer and the rear layer shows a gradient over the thicknesses thereof, the concentration of fine particles of both the front layer and the rear layer is lowest in an area adjacent to the middle layer.
    In a slab according to the present invention the particle size distribution of the coarse particles is chosen from a range of 63-1200 micron, especially 100-800 micron.
    The present slab is further characterized in that the Barcol Hardness as measured on the front layer of said slab exceeds a value of 65, preferably 75, in case of an organic thermoset type binder (according to ASTM D 2583-07 Standard Test Method for Indentation Hardness of Rigid Plastics by Means of a Barcol Impressor).
    The present slab is further characterized in that the Barcol Hardness as measured on the front layer of said slab exceeds a value of 55, preferably 70, in case of an organic thermoplast type binder (according to ASTM D 2583-07 Standard Test Method for Indentation Hardness of Rigid Plastics by Means of a Barcol Impressor).
    Various aspects of the present invention are now illustrated by way of examples and comparative examples.
    Table : Test results
    bomoienumberR iet 1 Quartz tn•wetmix6b ft m t o 5 f t 1 orptionLayer on out stdejGiass fibre mats in middle of z3 exactly the same wet mix layerscommentsBarcolHardnessjWarpedVlBQ-89-1577%NONoPressed Without Impregnation45(80-92-15-) t 77%NO3 NO:Pressed without Impregnation46.7.......................................1IBQ130 52179%2 8axial 280 g/m2 Bottom only[ Nox-layer system. 15x15 cm Jab tite59,5IbQ l-> IS1 y3 3axial z80 g/ m2 Bottom onlyJ NO2-layer system. ibxl5 cm tab tile72 38Q 31 121%79%7vRΛΧ13! 7RQ g/m7 Bo’Tom onlyi no7-tayer system ' 5x15 cm lab tile69,5 tsssssssssssssssssssssssssssssssssssssssIBQ-134-152179%2 8axial z8u g/m2 8ottom only3 No2-tayer system. 15x15 cm tab tile68,8fell 515•Ί79%Ά3axial zSO a/ m2 Bottom only3 :'«·2-tayer system. 15x15 cm tab tile72,0IBQ-142-1521%79%Noί 3xBl-axlal 280 s/m23-tayer system, 15x15 cm lab tile71,0brt G billy yy t±ed1BQ-143-TS21%79%NojsxBi-axtat 280 %'m2 '3-layersystem, 15x15 cm tab tile73,3................(8Q-14S-1521%79%Noj3xBl-axial280g/m23-tayer system, 15x15 cm lab titenaIBQ-1S0-1521%79%No13>,Bi-axial 286 g/m23-layer system. 15x15 cm tab tile7S,C18Q-163-1523%77%NoJ 3x Bi-a xtat 280 < /m2 '3-tayer system, 15x15 cm lab tile72,0IBQ-164-1523%77%NoJ 3x Bl-axlal 280 a/m 23-tayer system, 15x15 cm lab tile69,7jfffiteMsK-M ......................IBQTS8-1SI8Q-169-1522%21,5%79%79%No3xFlax fibre mat Bottom only2xRef2 280g/m2 + dr^Quartt in b Ί........ NoS-layer system. 15x15 cm tab tile 2-tayer system, 15x15 cm lab tite72,866.0IBQ-170-1521,5%79%2xBasalt fibre: mat Bottom onlyNo2-layersystem, 15x15 cm tab tite69,31BQ-171TS21,5%79%NoUxf lax fibre mat300 e/m23-layer system, 15x15 cm tab tile69,83sot38b 230-1620%80%3x onoriented GF300e/m2 bottom] NO2-layer system 4Sxl2Dcmsiab48.3 SSS8S8S3SÈSSS8öi8!58i!8SSfciSfcS5S8S88S8SS8&83D 23T1820%80%No3 3x unoriented GF 300g/m23-tayer system, 45x120 cm stab63,3380 232-1620:%30%No’3xtmorientedGF300g/m23-layer system, 45x120 cm slab57.3BBD233-1620%80%Nounoriented Gf 300g/m23-layer system, 45x120 cm slab70,5jiGööicilëPlytb'tityièèüdiitSiSibëi::::::::::lBQ-246-17IBQ-256-1721%21%79%,79%Absorption paper on both sidesAbsorption paper on both sidesi2xp nonentedGF300g/m23<tx unoriented GF 300g/m25-layer system, 15x15 cm lab tile5-layer system, 15x15 cm lab tile67 871,5URWfffSffieSWtiSi..............tt&txi F&t iNtiwte1BQ-257-1721%79%Absorption paper on both sidestax unoriented GF300g/m25-layer system, ISxlS cm tab tile69,7jGsixiifei &·#$&...................
    The first column of the Table refers to the sample number, the second column to the amount of resin in both the first mixture and the second mixture, the third column to the amount of quartz particles in both the first mixture and the second mixture, the fourth column to the construction of the layers of the final slab, the fifth column to type of the substrate layer, the sixth column to the comments on the layered construction, the seventh column to the Barcol Hardness and the last column to geometrical aspects of the final slab after step vii).
    The experiments shown in the Table clearly indicate that a two layer system, i.e. Examples IBQ-130-15, IBQ-131-15, IBQ-133-15, IBQ-134-15 and IBQ-13515, shows a significant sign of warping.
    For the three layer system, see Example IBQ-164-15, a perfect flat tile,
    i.e. no warping, has been obtained.
    For a five layer system, see Example IBQ-246-17, IBQ-256-17 and IBQ257-17, a flat sample has been obtained as well.
    The type of resin used in the examples is a thermoset resin (50% Epoxidised Linseed Oil (ELO) + 46% methyl hexahydro phthalic anhydride (MHHPA) + 3% 2-methyl imidazole (Melm)/alcohol mixture + 1% GLYMO). The “wet mixture” comprises XX wt.% quartz powder 45 (fines), YY wt.% quartz 63-200 particles (coarse) and ZZ wt.% quartz 200 - 500 particles (coarse).
    In the table a sacrificial absorption layer is a layer that has been removed after manufacturing of the slab.
    Hereafter several sample numbers, i.e. IBQ-142-15, IBQ 168 and BBD 231-233, will discussed in more detail.
    IBQ-142-15
    A mixture of 21 wt.% of a thermoset resin ( 50% Epoxidised Linseed Oil (ELO) + 46% methyl hexahydro phthalic anhydride (MHHPA) + 3% 2-methyl imidazole (Melm)/alcohol mixture + 1% GLYMO) is mixed with 27 wt.% quartz powder 45 (fines) and 21 wt.% quartz 63-200 particles (coarse) and 31 wt.% quartz 200 - 500 particles (coarse) and heated to 60 °C. An amount of 100 g hot mixture is transferred into a hot mould (15x15 cm at 60 °C) and contacted with an aggregate comprising 18 g woven glass fiber mat (three layers of 300 g/m2). On top of that another 100 g hot mixture is transferred and spread out over the glass fibre mat. The hot product was pressed to > 50 bar for 4 minutes and cured at 140 °C during one hour and then cooled to ambient temperature. The hardness was measured after at least 1 hour cooling, according to ASTM D2583-07 and found to be 71.
    IBQ 168
    A mixture of 21 wt.% of a thermoset resin ( 50% Epoxidised Linseed Oil (ELO) + 46% methyl hexahydro phthalic anhydride (MHHPA) + 3% 2-methyl imidazole (Melm)/alcohol mixture + 1% GLYMO) is mixed with 27 wt.% quartz powder 45 (fines) and 21 wt.% quartz 63-200 particles (coarse) and 31 wt.% quartz 200 - 500 particles (coarse) and heated to 60 °C. An amount of 100 g hot mixture is transferred into a hot mould (15x15 cm at 60 °C) and contacted with an aggregate comprising 12 g woven glass fiber mat (two layers of 300 g/m2) and 75 g of dry hot (60 °C) quartz 500-800 particles (coarse) is added in the middle of the two glass fiber mats. On top of that another 100 g hot mixture is transferred and spread out over the glass fibre mat. The hot product was pressed to > 50 bar) for 4 minutes and cured at 140 °C during one hour and then cooled to ambient temperature. The hardness was measured after at least 1 hour cooling, according to ASTM D2583-07 and found to be 72,8.
    BBD 231, 232, 233
    A mixture of 21 wt.% of a thermoset resin ( 50% Epoxidised Linseed Oil (ELO) + 46% methyl hexahydro phthalic anhydride (MHHPA) + 3% 2-methyl imidazole (Melm)/alcohol mixture + 1% GLYMO) is mixed with 27 wt.% quartz powder 45 (fines) and 21 wt.% quartz 63-200 particles (coarse) and 31 wt.% quartz 200 - 500 particles (coarse) and heated to 60 °C. An amount of 5 kg hot mixture is transferred into a hot mould (45x120 cm at 40 °C) and contacted with an aggregate comprising 0,9 kg woven glass fiber mat (three layers of 300 g/m2) and 75 g of dry hot (60 °C) quartz 500-800 particles (coarse) is added in the middle of the two glass fiber mats. On top of that another 5 kg hot mixture is transferred and spread out over the glass fibre mat. The hot product was pressed inside a continuous double belt press (to > 30 bar) for 2 minutes and cured at 140 °C during one hour and then cooled to ambient temperature. The hardness was measured after at least 1 hour cooling, according to ASTM D2583-07 and found to be 71.
    权利要求:
    Claims (31)
    [1]
    CONCLUSIONS
    A method of manufacturing a panel comprising solid fillers and organic binders, the method comprising the steps of:
    i) providing a first mixture comprising organic binders and solid fillers, said solid fillers comprising fine particles and coarse particles;
    ii) providing a second mixture comprising organic binders and solid fillers, said solid fillers comprising fine particles and coarse particles;
    iii) providing a substrate layer;
    iv) contacting the substrate layer of step iii) with the first mixture of step i) and the second mixture of step ii) such that said substrate layer is positioned between said first mixture and said second mixture;
    v) applying a force to the assembly obtained in step iv) for migrating at least a portion of said organic binder from said first mixture and at least a portion of said organic binder from said second mixture into said substrate layer;
    vi) cooling the structure obtained in step v) to thereby obtain the panel.
    [2]
    Method according to claim 1, wherein step v) is carried out in such a way that both the coarse particle content in the first mixture of step i) and the coarse particle content in the second mixture of step ii) are lower than the coarse content particles in the mixture after step v).
    [3]
    Method according to one or more of claims 1-2, wherein in step v) at least a part of said fine particles of both the first mixture and the second mixture migrates into said substrate layer.
    [4]
    Method according to one or more of claims 1-3, wherein step v) is carried out in such a way that the coarse particles of both the first mixture and the second mixture are concentrated in an area adjacent to the substrate layer.
    [5]
    Method according to one or more of claims 1-4, wherein said substrate layer has an absorbency for organic binder in a range of 100-3000 g / m 2 , preferably 500-3000 g / m 2 , in particular preferably 1000 3000 g / m 2 .
    [6]
    The method of claim 5, wherein said substrate layer is made from a material selected from the group of paper, cardboard, textile fibers, fiberglass mat, carbon fibers, basalt fibers, natural fiber mat such as flax fiber, Abaca fiber, coconut fiber, hemp fiber and jute fiber, or a combination of these.
    [7]
    Method according to one or more of claims 1-6, wherein said substrate layer is a porous layer, provided with pores with a size in a range of 10-100 micrometres, preferably in a range of 20-80 micrometres, in particular at preferably in a range of 30-60 micrometers.
    [8]
    A method according to any one of claims 1-7, wherein said substrate layer is a layered structure, wherein said layered structure comprises at least two substrate layers.
    [9]
    The method of claim 8, wherein said layered structure comprises solid fillers, comprising fine particles and coarse particles, wherein said solid fillers are positioned between two substrate layers, wherein said substrate layers are of the same type of material or of a different type of material.
    [10]
    Method according to one or more of claims 1-9, further comprising a step vii) of processing at least one of the outer layers of said panel, said processing being selected from the group of one or more of milling, planing , sanding, sawing, polishing, etching and abrasion, or a combination of these.
    [11]
    The method of any one of claims 1 to 10, wherein said first blend in step i) and / or said second blend in step ii) further comprises one or more additives selected from the group of glass fibers, flax fibers, Abaca fibers , coconut fibers, hemp fibers, jute fibers, carbon fibers and basalt fibers, or a combination thereof.
    [12]
    The method of any one of claims 1 to 11, wherein said organic binder comprises a thermosetting type binder.
    [13]
    A method according to any one of claims 1-12, further comprising a step of heating said first mixture of step i) and / or said second mixture of step ii), before step v) is performed, wherein said heating takes place at a temperature above 100-160 ° for the thermosetting type of binders.
    [14]
    A method according to any one of claims 1-13, wherein step iv) further comprises applying said first mixture, comprising organic binders and fillers, to a support, applying said substrate layer on top of said mixture lying on said support and applying said second mixture, including organic binders and fillers, to said substrate layer in a continuous manner.
    [15]
    Method according to claim 14, wherein the step of applying said substrate layer comprises a step of applying a layered structure, namely a step of applying a substrate layer, applying a layer of solid fillers, comprising fine particles and coarse particles, on top of said substrate layer and applying a substrate layer on top of said layer of solid fillers, in a continuous manner.
    [16]
    The method of any one of claims 14 to 15, wherein step v) further comprises transferring said support through a gap between rotating rollers.
    [17]
    Method according to one or more of claims 1-16, wherein step i) and / or step ii) further comprises a step of venting, preferably after mixing said organic binders and fillers.
    [18]
    The method of any one of claims 1-17, wherein the particle size distribution of the fine particles is selected from a range of less than 63 micrometers.
    [19]
    Method according to one or more of claims 1-18, wherein the particle size distribution of the coarse particles is selected from a range of 63-1200 micrometers, in particular 100-800 micrometers.
    [20]
    The method according to one or more of claims 1-19, wherein the thickness of the panel obtained after step vi) and / or vii) is in a range of 2 to 10 mm.
    [21]
    A method according to any one of claims 1-20, wherein the weight percentage of organic binder is in a range of 5 -40% by weight, the weight percentage of solid fillers is in the range of 50 to 95% by weight, the weight percentage of additives is in the range of 0.1-10% by weight, all weight percentages are based on the total weight of the panel obtained after step vi) and / or step vii).
    [22]
    The method of claim 21, wherein said organic binder comprises 60-100% by weight of thermoplastic polyester and 0-40% by weight of polyolyphine compound, based on the total weight of the organic binder.
    [23]
    The method of claim 22, wherein 90-100% by weight of said thermoplastic polyester is one or more selected from the group of polybutene terephthalate compounds, modified polyethylene terephthalate compounds, recycled polyethylene furanoate, polycarbonate compounds, polylactate compounds and recycled polyethylene terephthalate compounds, based on the total weight of the thermoplastic polyester.
    [24]
    The method of claim 21, wherein said organic binder is a thermosetting type binder selected from the group of unsaturated polyester resin, acrylic resin, epoxy resin or phenolic resin, or a combination thereof.
    [25]
    The method of any one of claims 1-24, wherein said coarse particles are selected from the group of inorganic minerals such as quartz, glass, silica, sand (S102), calcium carbonate such as marble (CaCl3) or dolomite (CaMg (¢ 03) 2), aluminum trihydrate (ATH), wollastonite (CaSiOs), coesite, cristobalite, keatite, moganite, seifertite, stsishovite and tidymite, in particular inorganic minerals with a Moh hardness of at least 7.
    [26]
    The method of any one of claims 1-25, wherein steps
    i) -vii) are conducted in a continuous manner.
    [27]
    A panel consisting of a front layer, a middle layer and a back layer, obtained according to the method as described in one or more of the preceding claims, wherein the concentration profile of coarse particles in both the front layer and the back layer shows a gradient over its thickness, the coarse particles from both the front layer and the back layer are concentrated in an area adjacent to the middle layer.
    [28]
    The panel according to claim 27, wherein the concentration profile of fine particles in both the front layer and the back layer shows a gradient over the thickness thereof, the content of fine particles of both the front layer and the back layer is lowest in an area adjacent to the middle layer.
    [29]
    Panel according to one or more of the claims 27-28, wherein the particle size distribution is coarse particles selected from a range of 200-1200 micrometers, in particular 63-800 micrometers.
    [30]
    The panel according to one or more of claims 27 to 29, wherein the Barcol hardness, as measured on the front layer of said panel, exceeds a value of 55, preferably 70, in an embodiment of an organic thermoplastic type binder ( according to ASTM D 2583-07 "Standard Test Method for Indentation Hardness or Rigid Plastics by Means of a Barcol Impressor").
    [31]
    The panel according to one or more of claims 27 to 29, wherein the Barcol hardness measured on the front layer of said panel is a value of 65, preferably
    75, in an embodiment of an organic thermoset type binder (according to ASTM D 2583-07, exceeds "Standard Test Method for Indentation Hardness or Rigid Plastics by Means or a Barcol Impressor").
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    同族专利:
    公开号 | 公开日
    US11260562B2|2022-03-01|
    US20190329458A1|2019-10-31|
    NL2018010B1|2018-06-26|
    NL2019729B1|2018-10-12|
    EP3554803A2|2019-10-23|
    WO2018111106A2|2018-06-21|
    CN110312612B|2021-08-03|
    CN110312612A|2019-10-08|
    WO2018111106A3|2018-07-26|
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    法律状态:
    优先权:
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    NL2018010A|NL2018010B1|2016-12-16|2016-12-16|A method for manufacturing a slab|
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