• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a method for manufacturing a laminated material (S) comprising a fibrillated cellulose layer, characterized in that it comprises the following steps: (a) depositing a suspension (1) of fibrillated cellulose on a membrane (2) for filtering and draining said suspension through the membrane so as to form a fibrillated cellulose wet layer (A) having a dryness of between 5 and 18%, (b) pressure transfer of said wet layer (A) on an at least partially hydrophilic surface of a substrate (B), so as to form said laminated material (S), (c) drying said laminated material. The invention also relates to a device for implementing said method.
    公开号:FR3035611A1
    申请号:FR1553818
    申请日:2015-04-28
    公开日:2016-11-04
    发明作者:Valerie Meyer
    申请人:Centre National de la Recherche Scientifique CNRS；Centre Technique du Papier；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to a method of manufacturing a laminated material comprising a fibrillated cellulose layer, as well as to a device for manufacturing a fibrous cellulose layer. such a material. BACKGROUND OF THE INVENTION The laminated materials comprising a substrate and a fibrillated cellulose layer are of particular interest because the fibrillated cellulose layer provides the substrate with barrier properties, particularly useful in the packaging. Four types of processes are known for making such materials. A first method, said paper-making, consists in depositing on a fabric a very dilute suspension (that is to say having a concentration of less than 5% by weight) of cellulose and then spraying a very dilute suspension of cellulose fibrillated with so as to obtain, after drainage through said fabric, a stratified wet fibrous mat having a concentration of about 20% by weight of cellulose, the fibrillated cellulose layer having a lower concentration. The use of the spray, given the speed of the machine, does not achieve a high thickness of the fibrillated cellulose layer once dried, the thickness is generally less than 3-5pm. A second method, used for the manufacture of the cartons, consists in depositing on a canvas a very dilute suspension of cellulose and, on an adjacent web, a very dilute suspension of fibrillated cellulose; drainage is exerted through each fabric to obtain a fibrous mat having a concentration of 10 to 15% by weight of cellulose, and then the two mattresses are assembled. This method does not achieve a low thickness of the fibrillated cellulose layer once dried, the thickness of the fibrillated cellulose layer being generally greater than 15-20pm.
    [0002] The drainage of a fibrillated cellulose suspension through a fabric is described in WO 2013/171373. In both of these processes, the water content of the laminated fibrous mat is reduced by means of a sometimes heated press. A problem associated with this technique is that the fibrillated cellulose layer adheres to the surface of the press, which makes implementation difficult. Moreover, such a wet mattress is difficult to dehydrate. A third method, called coating / coating, consists in spreading a suspension of fibrillated cellulose on the substrate so as to form a wet layer which is dried by infrared radiation (gas or electric), convection (hot air) or conduction (at 3035611 2 contact of a drying cylinder). However, for a concentration of the order of 2% by weight of fibrillated cellulose, the suspension has the consistency of a gel which is difficult to spread. To facilitate the implementation of this suspension, the fibrillated cellulose concentration should be decreased by increasing the amount of water. However, this increase in water content degrades the properties of the fibrous substrate, makes it difficult to dry the fibrillated cellulose layer and makes it difficult to achieve sufficient layer thickness to show improved performance. A fourth method consists of manufacturing a self-supporting film of fibrillated cellulose, as described in WO 2013/060934 and then laminating it to a dry fibrous mat already manufactured. This method does not make it possible to achieve low thicknesses of the fibrillated cellulose layer (less than 15 μm), since the thin fibrillated cellulose films have a fragility which makes their handling difficult. On the other hand, this technique requires the use of a glue to adhere the self-supporting fibrillated cellulose film to the fibrous mat. The laminated material thus obtained thus comprises a layer of glue. Furthermore, it is not known at present process to manufacture a laminate comprising a layer of fibrous cellulose very thin (eg of the order of 3 to 20 pm), which is also continuous and homogeneous.
    [0003] BRIEF DESCRIPTION OF THE INVENTION An object of the invention is to overcome the aforementioned drawbacks and to design a method of manufacturing a laminated material which is simpler to implement and which makes it possible in particular to produce a homogeneous layer of Fibrillated cellulose, deposited in a single operation, thicker than known processes, minimizing drying requirements. According to the invention, there is provided a method of manufacturing a laminated material comprising a fibrillated cellulose layer, characterized in that it comprises the following steps: (a) depositing a fibrillated cellulose suspension on a filtering membrane and draining said suspension through the membrane so as to form a fibrillated cellulose wet layer having a dryness of between 5 and 18%; (b) pressurizing said wet layer to a surface at less partially hydrophilic of a substrate, so as to form said laminated material, (c) drying said laminated material.
    [0004] By "fibrillated cellulose" is meant cellulose converted at least 50% into fibrils of nanometric diameter. By "at least partially hydrophilic surface" is meant a surface exhibiting non-dispersive, acid-base type interactions in the sense of the theory of Van Oss, Chaudhury and Good as described in the work of [Darque-Ceretti et al. Felder]. According to one embodiment, the fibrillated cellulose concentration of the suspension used in step (a) is between 0.5 and 2% by weight.
    [0005] Preferably, the dryness of the fibrillated cellulose wet layer formed in step (a) is between 7 and 15%. In a particularly advantageous manner, the dryness of the fibrillated cellulose layer in the laminate at the end of step (c) is between 80% and 99%. According to other advantageous features of the invention, taken alone or in combination: the fibrillated cellulose wet layer at the end of step (a) has a thickness of between 20 μm and 750 μm; Wet fibrous cellulose at the end of step (b) has a thickness between 15 pm and 500 pm. The fibrillated cellulose layer at the end of step (c) has a thickness of between 3 μm and 100 μm. According to one embodiment of the invention, the substrate is a paper or a cardboard. Particularly advantageously, in step (b), the fibrillated cellulose wet layer adheres to the substrate by direct contact with the at least partially hydrophilic surface of said substrate. According to one embodiment, the substrate is driven in scrolling and the wet fibrillated cellulose layer is transferred to said substrate continuously. In another embodiment, the fibrillated cellulose layer is discontinuously transferred to the substrate in step (b).
    [0006] Another object of the invention is a device for producing a laminate material comprising a fibrillated cellulose layer. Said device comprises: a unit for manufacturing a fibrillated cellulose wet layer, comprising a device for depositing a fibrillated cellulose suspension on a filtration membrane and means for draining said suspension through the membrane so that to form a fibrillated fibrous cellulose wet layer having a dryness of between 5 and 18%; - a pressure transfer unit of the fibrillated cellulose wet layer at the outlet of the manufacturing unit onto a substrate so as to form a material laminate, - a drying unit of said laminated material at the output of the transfer unit.
    [0007] BRIEF DESCRIPTION OF THE DRAWINGS Other characteristics and advantages of the invention will emerge from the detailed description which follows, with reference to the appended drawings, in which: FIG. 1 is a schematic view of an installation allowing the implementation of FIG. 5 of an embodiment of the method of manufacturing the laminated material, in which the fibrillated fibrous cellulose layer is entirely carried on a moving substrate, - Figure 2 is a schematic view of an installation for the manufacture of the material. laminate according to another embodiment, wherein the fibrillated cellulose wet layer is locally carried on a moving substrate; - Fig. 3 is a schematic view of an apparatus for manufacturing a fibril material in another mode. embodiment, in which the fibrillated cellulose wet layer is cut to pick up portions of layers reported suc terminally on a plurality of distinct substrates.
    [0008] DETAILED DESCRIPTION OF THE INVENTION Fibrillated cellulose is a heterogeneous nanomaterial composed of micrometric size elements (fiber fragments) and at least 50% by number of nano-objects (i.e. objects of which at least one of the dimensions is between 1 and 100 nanometers).
    [0009] These cellulosic nano-objects are called "micro-fibrils" or "micro-fibrils" or "nano-fibrils", NFC or CNF (acronym for the English words "Nano Fibrillated Cellulose"). And "Nanofiber Cellulose"). The cellulose micro- or nano-fibrils typically have a diameter in the range of 20 to 60 nm and a length of 0.5 to 5 μm.
    [0010] The formation of fibrillated cellulose from cellulose fibers is known per se and will therefore not be described later in the text. Fibrillated cellulose is typically provided in the form of an aqueous suspension. Optionally, additives may be included in the suspension, for example binders, dispersants, inorganic particles, metal oxides, plasticizers, rheological, dry or wet resistant, crosslinkers, antimicrobials or cellulosic fibers. or synthetic or silver nanowires or other molecules that will, after the process, trapped in the fibrillated cellulose layer. The concentration of the fibrillated cellulose suspension is typically from 0.1% to 4% by weight. Preferably, said concentration is between 0.6% and 2% by weight. In a first step of the process, the suspension is deposited in the form of a layer on a filtration membrane. This membrane has an aperture 3035611 large enough to promote water removal by filtration while being low enough to promote retention of the fibrillated cellulose on the membrane. A woven fabric with a small opening (Opm mesh opening, free surface <10%), commonly used in the field of filtration, is suitable for this purpose. As a purely indicative, a web marketed under the reference SEFARTM PETEXTM 07-1 / 2 is suitable for this purpose. The membrane may also be a synthetic membrane. There is a frontal filtration through the membrane, which allows the drainage of a part of the water and therefore a certain dehydration of the fibrillated cellulose layer. This drainage step is continued until a dryness of the fibrillated cellulose layer of between 5 and 18%, preferably 7 to 15% by weight, is obtained. Dryness, which is the ratio of the mass of the dry matter to the total mass of the fibrillated cellulose layer (that is, the sum of the masses of the dry matter and the water contained in the layer) can be measured, conventionally, by means of an oven or a thermobalance.
    [0011] In such a range of dryness, the fibrillated cellulose layer has sufficient cohesion to be manipulated. Moreover, as will be seen below, this range of dryness provides the layer with advantageous adhesion properties on a surface that is at least partially hydrophilic. At the end of this step, the thickness of the fibrillated cellulose wet layer is advantageously between 20 and 750 μm, preferably between 30 and 200 μm. The fibrillated cellulose wet layer is then transferred onto an at least partially hydrophilic surface of a substrate having a dryness greater than 60%, and preferably greater than 85% (said substrate then being considered "dry") and a pressure is used to promote intimate contact between the fibrillated cellulose wet layer and the substrate. Under the aforementioned dryness conditions, the fibrillated cellulose wet layer behaves like a gel which, by virtue of its water retention properties, prevents excessive wetting of the substrate. According to one embodiment, the method of manufacturing the laminate is continuous, the substrate being in the form of a flexible strip driven in scrolling. According to another embodiment, the manufacturing process is discontinuous, the wet layer being sequentially carried on the substrate or on separate parts. The transfer is advantageously carried out under conditions allowing intimate and direct contact between the substrate and the fibrillated cellulose layer, that is to say in particular: at a temperature of between 20 ° C. and 140 ° C., a duration up to 15 s, usually between 10 ms and 1s; a pressure of between 0.1 and 40M Pa.
    [0012] The inventors have found that in the dryness range mentioned above (5-18%, preferably 7-15%), the fibrillated cellulose wet layer adheres to the substrate by direct contact with the at least partially hydrophilic surface. No intermediate bonding material is therefore necessary to ensure this adhesion.
    [0013] The transfer is followed by drying of the laminated material, resulting in a final dryness of the fibrillated cellulose layer of between 80 and 99%, preferably between 88 and 95%. The drying can be carried out by any appropriate means, including in particular convective drying means (heating roller for example), radiative (infrared lamp for example), microwave or convective.
    [0014] Figure 1 illustrates an embodiment of an installation for carrying out the method described above. This installation comprises three main parts: Part I comprises a system for forming the fibrillated cellulose wet layer; Part II comprises a system for transferring the wet layer to the dry substrate; - Part III comprises a drying system of the laminate material formed in Part II. The arrows indicate the direction of movement of the fibrillated cellulose wet layer, paper and laminate. Part I comprises a system for depositing a suspension of fibrillated cellulose 1 on a filtering membrane 2. The filtering membrane may be in the form of a continuous strip which may be driven by rollers 3 over organs suction 4 which promote drainage through the filter membrane. Part I makes it possible to form a fibrillated cellulose wet layer A. In the embodiment illustrated in FIG. 1, substrate B is in the form of a paper reel. A strip of paper B is driven in scrolling between a rewinder 6 and a reel 7. The part I and part II are contiguous, so that when the wet layer A has the required dryness (between 5 and 18%), said layer A may be applied to the paper B through a rolling mill 8. In the case where the substrate does not have the same properties on each of its faces, it is made to be an at least partially hydrophilic surface of the paper B which is brought into contact with the wet layer A. Thus, by direct contact between the wet layer A and said at least partially hydrophilic surface, good adhesion of the wet layer to the substrate is obtained. In Part III, the laminate S formed from the layer A and the substrate B is driven in a high temperature atmosphere to dry the wet layer. The means used in Part III are means conventionally used in a paper dryer or dryer placed at the output of a coating machine, and are therefore not described in detail here. At the exit of Part III, the laminate is wound by the reel 7 so as to form a reel. Of course, Figure 1 is given for illustrative and not limiting. In particular, the manufacture of the laminate can be achieved by means other than those shown schematically in Figure 1 without departing from the scope of the present invention. FIG. 2 thus illustrates an installation allowing the implementation of another method of manufacturing a laminate according to the invention. Parts I and III are similar to those of Figure 1 and are therefore not described again. As in Figure 1, the substrate B is in the form of a paper reel. A strip of paper B is driven in scrolling between a unwinder 6 and a reel 7. Part II 'comprises a portion cutting means A, of the fibrillated cellulose wet layer. Each of said portions Ai is carried under pressure, for example by means of a roll 9, on the strip of paper B running. The falls A 'resulting from this cutting are advantageously recovered for recycling.
    [0015] Thus, a paper web is formed of which only the regions on which the A portions of fibrillated cellulose have been reported are laminated. Figure 3 illustrates an installation for implementing another method of manufacturing a laminate according to the invention, wherein the substrate is no longer a scrolled paper web but a plurality of unitary parts.
    [0016] Part I is similar to that of Figure 1 and is therefore not described again. Substrates B are provided in a container 12 from which they can be removed successively for the manufacture of a respective laminate. The installation comprises a device II 'for cutting and transferring a portion of fibrillated cellulose layer This device comprises a cutting means 11, for example a punch, which samples successively in the layer A a plurality of portions A, and which transfers, thanks to a delivery system 10, said portion A, above a mat 13 on which B substrates. During the establishment of the portion A, on the substrate B, a pressure is exerted by the means 11 to promote adhesion.
    [0017] The portion A may cover the entire surface of the substrate B or, as shown schematically in FIG. 3, cover only a portion of the surface of the substrate B. In the latter case, the laminate S is located on the surface of the substrate B.
    [0018] Although shown in FIG. 3, the substrate B may have any other shape. Thus, in the field of packaging, the substrate B may for example be a cardboard tray. In this case, the postponement of the fibrillated cellulose wet layer portion is advantageously carried out by means of a complementary counterform to that of the substrate. The installation also includes a III laminate drying system. This system comprises, facing the belt 13, a dryer 14 below which scroll laminates. At the outlet of the dryer, the laminates S are stored in a container 15 for transport and / or storage. The laminated material obtained can give rise to multiple applications. The substrate can be any material of the family of papers, including paper and board for printing-writing, paper and paperboard for packaging, paper for sanitary and domestic use, specialty paper and board, non-paper woven, etc. The substrate may consist of a single layer or a stack of several layers. The fibrillated cellulose layer provides the laminate with improved surface properties which can be exploited particularly in packaging applications (for imparting barrier properties to gas or liquids for example) in printing / writing applications ( to immobilize inks or varnishes on the surface and limit their penetration into the fibrous network of the substrate) or in specialty applications. The laminated material can thus be used in the field of building, energy or electronics.
    [0019] Furthermore, the complex formed improves the mechanical properties of the substrate by virtue of the fibrillated cellulose layer (especially in terms of stiffness, tensile strength) and is thus advantageously used in all kinds of paper. Finally, it goes without saying that the examples cited above are only particular illustrations that are in no way limiting as to the fields of application of the invention.
    [0020] WO 2013/171373 WO 2013/060934 [Darque-Ceretti and Felder]: Adherence and adhesion, Evelyne Darque-Ceretti, Eric 35 Felder, Engineering Sciences and Techniques, CNRS Editions, ISBN 2-271-06092-3 , 2003, Chapter 2.3.2.1 Decomposition of Accession Work, pp. 97-99.
    权利要求:
    Claims (12)
    [0001]
    REVENDICATIONS1. A process for producing a laminated material (S) comprising a fibrillated cellulose layer, characterized in that it comprises the following steps: (a) depositing a suspension (1) of fibrillated cellulose on a membrane (2) filtering and draining said suspension through the membrane so as to form a fibrillated cellulose wet layer (A) having a dryness of between 5 and 18%, (b) pressurizing said wet layer (A) on an at least partially hydrophilic surface of a substrate (B), so as to form said laminate material (S), (c) drying said laminated material.
    [0002]
    2. The method of claim 1, wherein the fibrilated cellulose concentration of the suspension is between 0.5 and 2% by weight.
    [0003]
    3. Method according to one of claims 1 or 2, wherein the dryness of the fibrillated fibrous cellulose layer formed in step (a) is between 7 and 15%.
    [0004]
    4. Method according to one of claims 1 to 3, wherein the dryness of the fibrillated cellulose layer in the laminate (S) at the end of step (c) is between 80% and 99%.
    [0005]
    5. Method according to one of claims 1 to 4, wherein the fibrillated cellulose wet layer at the end of step (a) has a thickness between 20 pm and 750 pm.
    [0006]
    6. Method according to one of claims 1 to 5, wherein the fibrillated cellulose wet layer at the end of step (b) has a thickness between 15 pm and 500 pm.
    [0007]
    7. Method according to one of claims 1 to 6, wherein the fibrillated cellulose layer at the end of step (c) has a thickness between 3 pm and 100 pm.
    [0008]
    8. Method according to one of claims 1 to 7, wherein the substrate (B) is a paper or a cardboard. 3035611 10
    [0009]
    9. Method according to one of claims 1 to 8, wherein in step (b), the fibrillated cellulose wet layer (A) adheres to the substrate (B) by direct contact with the at least partially hydrophilic surface of said substrate. 5
    [0010]
    10. Method according to one of claims 1 to 9, wherein the substrate is driven scroll and the wet fibrillated cellulose layer is transferred to said substrate continuously.
    [0011]
    The method of one of claims 1 to 9, wherein the fibrillated cellulose layer is discontinuously transferred to the substrate in step (b).
    [0012]
    12. A device for producing a laminated material (S) comprising a fibrillated cellulose layer, characterized in that it comprises: - a unit (I) for manufacturing a fibrillated cellulose wet layer, comprising a device for depositing a suspension of fibrillated cellulose on a membrane (2) for filtration and means (4) for draining said suspension through the membrane so as to form a fibrillated cellulose wet layer (A) having a dryness between 5 and 18%, a unit (II, II ', II ") of pressurized transfer of the fibrillated cellulose wet layer at the outlet of the manufacturing unit (I) onto a substrate (B) so as to form a laminated material (S); - a unit (III) for drying said laminated material at the outlet of the transfer unit (II).
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    法律状态:
    2016-04-18| PLFP| Fee payment|Year of fee payment: 2 |
    2016-11-04| PLSC| Search report ready|Effective date: 20161104 |
    2017-04-07| PLFP| Fee payment|Year of fee payment: 3 |
    2018-04-26| PLFP| Fee payment|Year of fee payment: 4 |
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    2021-04-07| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1553818A|FR3035611B1|2015-04-28|2015-04-28|METHOD AND DEVICE FOR MANUFACTURING LAMINATED MATERIAL COMPRISING A FIBRILED CELLULOSE LAYER|
    FR1553818|2015-04-28|FR1553818A| FR3035611B1|2015-04-28|2015-04-28|METHOD AND DEVICE FOR MANUFACTURING LAMINATED MATERIAL COMPRISING A FIBRILED CELLULOSE LAYER|
    EP16722316.3A| EP3288670B1|2015-04-28|2016-04-27|Process and device for manufacturing a laminated material comprising a fibrillated cellulose layer|
    KR1020177033946A| KR20180016363A|2015-04-28|2016-04-27|Method and apparatus for producing a laminate material comprising a fibrillated cellulose layer|
    CA2984128A| CA2984128A1|2015-04-28|2016-04-27|Process and device for manufacturing a laminated material comprising a fibrillated cellulose layer|
    ES16722316T| ES2852025T3|2015-04-28|2016-04-27|Method and device for manufacturing a laminated material comprising a fibrillated cellulose layer|
    JP2017555799A| JP6827956B2|2015-04-28|2016-04-27|Methods and Equipment for Producing Laminated Materials Containing Fibrilized Cellulose Layers|
    US15/570,090| US10618015B2|2015-04-28|2016-04-27|Process and device for manufacturing a laminated material comprising a fibrillated cellulose layer|
    CN201680023886.9A| CN107820463B|2015-04-28|2016-04-27|Method and apparatus for manufacturing a laminate comprising a fibrillated cellulose layer|
    PCT/FR2016/050986| WO2016174348A1|2015-04-28|2016-04-27|Process and device for manufacturing a laminated material comprising a fibrillated cellulose layer|
    PL16722316T| PL3288670T3|2015-04-28|2016-04-27|Process and device for manufacturing a laminated material comprising a fibrillated cellulose layer|
    BR112017023255-3A| BR112017023255A2|2015-04-28|2016-04-27|process and device for making a laminated material|
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