EP2479343B1 - Structure en nids d'abeille basée sur des matériaux ligno-cellulosiques et son processus de production - Google Patents

Structure en nids d'abeille basée sur des matériaux ligno-cellulosiques et son processus de production Download PDF

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EP2479343B1
EP2479343B1 EP12164779.6A EP12164779A EP2479343B1 EP 2479343 B1 EP2479343 B1 EP 2479343B1 EP 12164779 A EP12164779 A EP 12164779A EP 2479343 B1 EP2479343 B1 EP 2479343B1
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Prior art keywords
lignocellulosic
boric acid
sio
layer
acid derivative
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EP2479343A1 (fr
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Michael Fritz Sailer
Arjen Boersma
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Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D21H27/40—Multi-ply at least one of the sheets being non-planar, e.g. crêped

Definitions

  • the invention relates to honeycomb structures based on lignocellulosic materials and processes for producing these structures.
  • Honeycomb paper is applied as an intermediate (“sandwich”) layer having a low specific mass in various types of constructions.
  • Honeycomb structures based on recycled paper provide certain advantages, such as a light weight and a relatively high compression strength, at low costs.
  • Another advantage of paper based honeycomb structures is their high flexibility. This makes it possible to fold the honeycomb structures and reduce the diameter of the honeycomb structures, as a result of which the required amount of space for storage, transport and handling can be relatively low.
  • honeycomb structures based on paper often have a limited biological stability ( viz , they are susceptible of attack by microorganisms, such as moulds), a limited water stability ( viz. their mechanical strength may drop considerably when wet or when in humid atmosphere) and have a limited fire resistance.
  • substances are combined with the paper material, e.g. by impregnating the paper.
  • these (fire resistant) resins this generally results in a product having an increased stiffness, as a result of which the honeycomb structures often can not be compacted by folding and so they take up a lot of space.
  • the paper should have a glueability that is sufficient to produce the honeycomb structures therefrom.
  • a glueability that is sufficient to produce the honeycomb structures therefrom.
  • water glass an aqueous solution of sodium silicate, is commonly employed as a glue in this type of applications.
  • an endless honeycomb structure can be made, which would be very desirable from a process economic point of view.
  • the paper itself has a certain elasticity (especially if compression pressure is applied), because this facilitates the production of composites with a core layer of honeycomb. If the core layer is more elastic, the compression strength can be better maintained in the composite after assembling the composites (gluing and pressing the skins onto the core layer),
  • the amount of compounds that are brought into contact with the paper material should be as low as possible but still homogeneously distributed in a thin layer on surfaces of the paper (and fibers), viz , sufficient to bring about the desired effect, while avoiding any detrimental effect,
  • the present invention aims at providing this.
  • the present invention is directed to a lignocellulosic structure comprising a thin layer comprising SiO 2 on at least part of its surface.
  • the thin SiO 2 based,layer can be applied in various ways.
  • a highly preferred method comprises contacting the lignocellulosic structure with a suitable precursor e.g. by submerging the lignocellulosic structure in a bath of SiO 2 precursor or by spraying the SiO 2 precursor on the structure or application of the silica using plasma technology,
  • SDBD surface dielectric barrier discharge
  • Silica sol-gel is a suitable precursor.
  • the silica sol-gel component is typically based on silicon alkoxide, Si(OR) 4 , wherein R is an alkyl, preferably methyl or ethyl. These compounds can be subjected to hydrolysis and gelation, whereby silane groups (Si-OH) and and siloxane groups (Si-O-Si) are broken and formed, respectively.
  • Commercially widely available sol-gel components are TEOS (tetraethylorthosilicate) and TMOS (tetramethylorthosilicate).
  • the silica content of the SiO 2 precursor typically ranges from 1-10% silica and the solvent (such as ethanol, isopropanol or other alcohols, acetone or other ketones) content typically ranges from 10-70%.
  • solvent such as ethanol, isopropanol or other alcohols, acetone or other ketones
  • ethanol as a solvent has a very limited risk, because these solvents have limited toxicity.
  • solvents tend to evaporate easily. It is highly preferred to collect the vapours comprising the evaporated solvents and thus recover the solvent therefrom so that it may be recycled.
  • materials can be provided that provide excellent fire-retardant properties, while at the same time conserving all other requirements and where the transport volume of structures produced is minimized.
  • the thin SiO 2 based layer preferably has a thickness of 0.01 ⁇ m to 10 ⁇ m, preferably about 0.2 to 5 ⁇ m, more preferably about 0.5 to 2.5 ⁇ m.
  • the paper surface may be treated with further substances, such as fire retardants, These further components may be applied together with the SiO 2 film, but it is also possible to apply them in a separate process step e.g. a subsequent dipping or spraying step or a plasma treatment.
  • Phosphorus based fire retardants are very suitable for this purpose,
  • the combination of phosphorus based fire retardants and silica sol-gel provides materials that have excellent flre-retardant properties, while at the same time conserving all other above-mentioned requirements and where the transport volume of structures produced is minimized.
  • the (phosphorus based) fire retardant used in the present invention is preferably a phosphate ester and more preferably an oligomeric phosphate ester.
  • the .fire retardant composition of the present invention can be used to impregnate paper in order to create honeycomb structures. The structures thus obtained show excellent properties with respect to water resistance, fire retardant properties, compressibility and durability, At the same time, the product can still be combined with water glass in the conventional method of lamination.
  • the composition of the invention typically comprises 1 to 90 wt,% oligomeric phosphate ester, preferably from 5 to 50 wt.%, based on weight of the total composition.
  • the contacting of the lignocellulosic material with the SiO 2 precursor can be carried out in a continuous fashion by using a conventional paper treatment process, e.g . by submerging a continuous belt of lignocellulosic material (paper) through a bath containing the sol-gel composition and optionally the fire retardant composition, application of coating processes as used in the paper industry or plasma treatment under atmospheric pressure.
  • the impregnated paper maintains its flexibility in the length direction, by which it can be stored and transported without requiring much space, due to its compactness.
  • the structures that are thus produced have dimensions that are "enmess", viz . up to e.g . 50 m or more. Also no emission of harmful compounds occurs during the production process, If a silica sol-gel comprising ethanol is used, the solvent can be collected as vapor and recycled.
  • Suitable (oligomeric or monomeric) phosphate esters may be represented by the following formula I: wherein each of R 1 , R' 1 , R 2 , R' 2 and R 3 is independently hydrogen or hydrocarbon side chain, in particular straight, branched or cyclic C 1 -C 10 alkyl or alkenyl (preferably C 2 -C 8 alkyl or alkenyl), optionally substituted, e.g . with halogen, epoxide hydroxyl, amino; and n is an integer from 0 to typically about 10. In case n is zero, the compounds of formula I are monomeric phosphate esters. Examples of suitable oligomeric phosphate ester compound s and their production are given e.g . in US-A-3 767 732 and US-A-4 382 042 .
  • Single compositions of the present invention can be prepared by admixing the ingredients in any order.
  • the (oligomeric) phosphate esters are mixed into the sol-get composition.
  • a boric acid derivative is present in the compositions of the present invention, in particular those described in DE-A-198 33 479 . It was found that the,addition of these boric acid compounds has a positive effect on the durability of the lignocellulosic products that are impregnated with the compositions of the present invention.
  • Suitable boric acid derivatives for this purpose are boric acid, trialkylborate ( e.g . tributyl borate; tri-isopropyl borate; or tri-tert-butyl borate).
  • the boric acid derivatives may be present in amounts of typically 0 to 10 wt.%, preferably 0.5 to 5 wit.%, based on weight of the total composition.
  • the boric acid provides further protection against biological degradation (that may be caused by degrading organisms like fungi and insects) and has positive effects on the fire resistance.
  • Honeycomb structures can be prepared by known process, e.g . the paper honeycomb production processes described in Pflug et al. (5th Global Wood and Natural Fibre Composites Symposium, Kassel (DE), 27-28 April 2004 ) typically out of low cost recycled paper (e.g . Testliner).
  • Figure 3 shows schematically the different process steps in a suitable production process for making expanded honeycombs.
  • adhesive lines are printed on the paper, which may come from one or several paper rolls (1).
  • a stack of several sheets is made and bonded together (2). Those sheets can be cut to strips prior or after stacking to a slice (3).
  • the third step many slices are stacked and bonded together to produce an unexpanded endless paper honeycomb core (4).
  • the sheets are pulled apart (5) expanding the stack onto a hexagonal honeycomb core (6).
  • the residual stresses in paper honeycombs can be relaxed after expansion by a controlled application of heat.
  • the structures that are produced in this way comprise walls formed of paper strips having a width of several cm, e . g . about 1-6 cm.
  • a typical honeycomb structure is has a diameter of the cells of e.g. 5 - 50 mm and a thickness of the total honeycomb layer of e . g . 5 - 60 mm.
  • the paper weight is usually between 80 g/m 2 and 250 g/m 2 .
  • Figure 4 shows a scanning electron micrograph (SEM), of a sample that is prepared in accordance with the present invention. A thin silica film on a cell wall of a paper fiber can be seen.
  • Paper 140 g/m 2 was treated with silica in ethanol (concentration 18 %) using a coating treatment.
  • the coated paper was dried at 105 oC over a period of 12 hours.
  • the paper that is treated in accordance with the present invention maintains it strength after the first and second measurement. Furthermore, the flexibility of the honeycomb structure in the length direction was maintained. Also the paper had an excellent glueability so that it could be easily glued with water glass.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)

Claims (14)

  1. Structure lignocellulosique comprenant une couche ayant une épaisseur de 0,01 µm à 10 µm comprenant du SiO2 sur au moins une partie de sa surface, laquelle structure a la forme d'une structure en nid d'abeilles, et laquelle structure peut être obtenue en mettant en contact la structure lignocellulosique avec un précurseur de SiO2, la structure comprenant de plus un dérivé d'acide borique.
  2. Structure lignocellulosique selon la revendication 1, dans laquelle le dérivé d'acide borique est sélectionné parmi le groupe constitué d'acide borique et de trialkyle borate, tel que tributyle borate, tri-isopropyle borate et tri-tert-butyle borate.
  3. Structure lignocellulosique selon les revendications 1 ou 2, dans laquelle la couche a une épaisseur de 0,2 µm à 5 µm, de préférence de 0,5 à 2,5 µm.
  4. Structure lignocellulosique selon l'une quelconque des revendications 1 à 3, dans laquelle les cellules ont un diamètre moyen de 5 à 50 mm et dans laquelle l'épaisseur de la couche en nid d'abeilles et de 5 à 60 mm.
  5. Procédé pour produire une structure lignocellulosique comprenant une couche ayant une épaisseur de 0,01 µm à 10 µm comprenant du SiO2 sur au moins une partie de sa surface, laquelle structure a la forme d'une structure en nid d'abeilles, le procédé consistant à imprégner la structure lignocellulosique d'une composition qui comprend un précurseur de SiO2 et un dérivé d'acide borique.
  6. Procédé selon la revendication 5, dans lequel la composition comprend en outre un retardateur de feu et dans lequel un retardateur de feu est appliqué dans une étape de traitement séparé, lequel retardateur de feu est de préférence un retardateur de feu à base de phosphore, de manière plus préférée un ester phosphorique oligomèrique.
  7. Procédé selon la revendication 6, dans lequel l'ester phosphorique est représenté par la formule qui suit :
    Figure imgb0004
     dans laquelle chacun parmi R1, R'1, R2, R'2, et R3 est de manière indépendante un hydrogène ou un alkyl ou un alcényle en C1 à C10 cyclique, rectiligne ou ramifié, facultativement substitué ; et n est un entier de 0 à 10.
  8. Procédé selon l'une quelconque des revendications 5 à 7, dans lequel la composition est constituée de 1 à 90 % en poids d'ester phosphorique oligomèrique, de préférence de 5 à 50 % en poids sur la base du poids de la composition totale.
  9. Procédé selon l'une quelconque des revendications 5 à 8, dans lequel le précurseur de SiO2 est un sol-gel de silice, qui est de préférence un alkoxide de silice, Si(OR)4, où R est un alkyle, de préférence un méthyle ou un éthyle.
  10. Procédé selon l'une quelconque des revendications 5 à 9, dans lequel le dérivé d'acide borique est sélectionné parmi le groupe constitué d'acide borique et de trialkyle borate, tel que tributyle borate, et tri-tert-butyle borate.
  11. Procédé selon l'une quelconque des revendications 5 à 10, dans lequel le dérivé d'acide borique est présent selon une quantité de 0,5 à 5% en poids sur la base du poids de la composition totale.
  12. Utilisation d'un dérivé d'acide borique dans une structure lignocellulosique pour renforcer la durabilité, dans laquelle la structure lignocellulosique comprend une couche ayant une épaisseur de 0,01 µm à 10 µm comprenant du SiO2 sur au moins une partie de sa surface, laquelle structure a la forme d'une structure en nid d'abeilles.
  13. Utilisation d'un dérivé d'acide borique dans une structure lignocellulosique pour protéger à l'encontre d'une dégradation biologique, dans laquelle la structure lignocellulosique comprend une couche ayant une épaisseur de 0,01 µm à 10 µm comprenant du SiO2 sur au moins une partie de sa surface, laquelle structure a la forme d'une structure en nid d'abeilles.
  14. Utilisation d'un dérivé d'acide borique dans une structure lignocellulosique pour améliorer la résistance au feu, dans laquelle la structure lignocellulosique comprend une couche ayant une épaisseur de 0,01 µm à 10 µm comprenant du SiO2 sur au moins une partie de sa surface, laquelle structure a la forme d'une structure en nid d'abeilles.
EP12164779.6A 2007-01-12 2008-01-14 Structure en nids d'abeille basée sur des matériaux ligno-cellulosiques et son processus de production Not-in-force EP2479343B1 (fr)

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EP12164779.6A EP2479343B1 (fr) 2007-01-12 2008-01-14 Structure en nids d'abeille basée sur des matériaux ligno-cellulosiques et son processus de production

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EP07075034A EP1944413A1 (fr) 2007-01-12 2007-01-12 Structure en nids d'abeille basée sur des matériaux ligno-cellulosiques et son processus de production
EP08705093.6A EP2106485B1 (fr) 2007-01-12 2008-01-14 Structure alvéolaire à base de matériaux ligno-cellulosiques et procédé de production de celle-ci
EP12164779.6A EP2479343B1 (fr) 2007-01-12 2008-01-14 Structure en nids d'abeille basée sur des matériaux ligno-cellulosiques et son processus de production

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EP2479343B1 true EP2479343B1 (fr) 2013-07-24

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EP08705093.6A Not-in-force EP2106485B1 (fr) 2007-01-12 2008-01-14 Structure alvéolaire à base de matériaux ligno-cellulosiques et procédé de production de celle-ci
EP12164779.6A Not-in-force EP2479343B1 (fr) 2007-01-12 2008-01-14 Structure en nids d'abeille basée sur des matériaux ligno-cellulosiques et son processus de production

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EP08705093.6A Not-in-force EP2106485B1 (fr) 2007-01-12 2008-01-14 Structure alvéolaire à base de matériaux ligno-cellulosiques et procédé de production de celle-ci

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CN102516786B (zh) * 2011-12-19 2014-02-19 南京林业大学 硅改性木质素膨胀阻燃成炭剂及其制备方法和应用
CN103321098B (zh) * 2013-05-24 2016-04-13 吴江曦屹欧阻燃纸有限公司 一种新型阻燃纸蜂窝专用阻燃剂及其制备方法
JP6241843B2 (ja) * 2013-06-06 2017-12-06 国立研究開発法人産業技術総合研究所 シリカ被膜付きペーパーハニカム構造体及びその製造方法
CN107244087A (zh) * 2017-07-14 2017-10-13 苏州云逸航空复合材料结构有限公司 复合材料蜂窝结构的制造方法及用于制造复合材料蜂窝结构的设备

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GB1323381A (en) 1970-07-23 1973-07-11 Knapsack Ag Polyols containing halogen and phosphorus and process for making them
US4382042A (en) 1978-04-03 1983-05-03 Stauffer Chemical Company Method of preparing oligomeric phosphate esters
US5254195A (en) * 1992-05-08 1993-10-19 Industrial Technology Research Institute Process for manufacturing moisture exchange element
US5626945A (en) * 1993-09-28 1997-05-06 International Paper Company Repulpable, water repellant paperboard
DE19833479C2 (de) 1998-07-24 2003-06-26 Kallies Feinchemie Ag Holzschutzmittel, Verfahren zur Behandlung von Holz und Verwendung des Holzschutzmittels
SE515614E (sv) * 2000-03-01 2009-06-16 Proflute Ab Förfarande för framställning av avfuktningselement samt användning av en suspension för impregnering av papper vid förfarandet

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CN101627162A (zh) 2010-01-13
EP1944413A1 (fr) 2008-07-16
EP2106485B1 (fr) 2013-05-15
EP2106485A1 (fr) 2009-10-07
EP2479343A1 (fr) 2012-07-25
WO2008085054A1 (fr) 2008-07-17

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