EP2794989B1 - Folie aus faltenfreiem papier - Google Patents

Folie aus faltenfreiem papier Download PDF

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Publication number
EP2794989B1
EP2794989B1 EP12824715.2A EP12824715A EP2794989B1 EP 2794989 B1 EP2794989 B1 EP 2794989B1 EP 12824715 A EP12824715 A EP 12824715A EP 2794989 B1 EP2794989 B1 EP 2794989B1
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EP
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Prior art keywords
sheet
paper
atom
paper according
substrate
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EP12824715.2A
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English (en)
French (fr)
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EP2794989A1 (de
Inventor
Pierre Sarrazin
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ArjoWiggins Security SAS
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ArjoWiggins Security SAS
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Priority to PL12824715T priority Critical patent/PL2794989T3/pl
Priority to SI201230461T priority patent/SI2794989T1/sl
Publication of EP2794989A1 publication Critical patent/EP2794989A1/de
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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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/13—Silicon-containing compounds
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/18—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with itself, or other added substances, e.g. by grafting on the fibres
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes

Definitions

  • the invention relates to a sheet of paper resistant to crumpling and its method of manufacture.
  • "wrinkle-resistant” means that the sheet has, following wrinkling, a low crease marking.
  • carrier layer is meant a layer blocking the pores of the substrate considered, for example a sheet of paper, and dedicated to confer on this support enhanced protection.
  • This layer may be hydrophobic and / or oleophobic.
  • oiling is meant in particular aqueous or oleaginous liquids, or even sub-millimeter particles, and mixtures thereof.
  • a first wrinkle resistance gain regarding the maintenance of zero porosity after creasing was achieved via incorporation into the cellulosic material dedicated to forming the safety document of a flocculated latex.
  • the latex is flocculated in the interstices of the fibrous mat thus conferring on it a localized elasticity and thus a gain in resilience.
  • the present invention therefore aims to provide a security document based on cellulosic fibers which has a resistance to wrinkling enhanced both in terms of resilience and crease marking.
  • the object of the present invention is to provide a security document based on cellulosic fibers whose mechanical properties are not altered by the treatment aimed at reinforcing their resistance to wrinkling.
  • the object of the present invention is to provide a security document capable of satisfactorily satisfying all paper manufacturing constraints.
  • the invention relates to a sheet of paper with a high resistance to wrinkling and folding, in particular for the production of banknotes, comprising a fibrous substrate impregnated with the core by at least one hydroxyl polymeric binder characterized in that said binder and the fibers of said substrate are at least partially covalently bound to at least one siloxane derivative.
  • core impregnation is meant that the hydroxyl polymeric binder is established deep in the substrate and is found on the surface as well. Thus, the fibers of the substrate are essentially in contact with the hydroxylated polymeric binder.
  • said fibrous substrate is also impregnated to the core by at least one siloxane derivative.
  • the sheets of paper according to the invention show, against all expectations, good resistance to wrinkling both in terms of resilience and crease marking, without altering its mechanical characteristics.
  • step (ii) can be performed beforehand, simultaneously or consecutively to step (i).
  • step (ii) is performed simultaneously or consecutively to step (i).
  • the present invention relates to a multilayer structure comprising a sheet of paper as described above.
  • a multilayer structure may be formed of a superposition of several layers of identical or different chemical nature with at least one of them being represented by a sheet of paper according to the invention.
  • it may be a structure formed of a sheet of paper according to the invention, the latter being coated on one of its outer faces or both, a plastic film.
  • the invention relates to the use of a silanol derivative as an insolubilization agent in the paper industry.
  • An insolubilization agent makes it possible to avoid the solubilization of the hydroxylated polymer present in the paper during a long-term contact with an aqueous solution (water).
  • This agent consists of reactive chemical functions, when subjected to thermal energy, with the hydroxyl functions of the hydroxylated polymer.
  • the invention relates to the use of a silanol derivative as a sizing agent in the paper industry.
  • a bonding agent is used to provide hydrophobicity to the treated fibrous substrate in order to improve the repulsion by the substrate of the aqueous solutions (water) brought into contact with it.
  • the inventors have indeed found that the silanol derivatives in particular as defined below prove to be effective in increasing the insolubilization of the hydroxylated polymeric binder while permitting the production of a sheet of paper resistant to water. 'water.
  • the inventors have also found that the insolubilization with the silanol derivatives is particularly increased when step (ii) of the process defined below, is carried out simultaneously or consecutively to step (i).
  • silanol derivatives are advantageously free of undesirable effects, particularly in terms of toxicity, in contrast to polyamide-epichlorohydrin or polyamine-amide-epichlorohydrin resins conventionally considered for this function in the paper industry.
  • a siloxane derivative covers any compound comprising at least one silicon atom bonded to at least one oxygen atom. They are obtained from silanol derivatives according to the invention which have reacted with fibers, other silanol derivatives and / or the hydroxylated polymeric binder.
  • the paper sheet according to the invention has infrared absorption bands characteristic of the CO-Si bonds in which C originates from cellulose or a hydroxyl polymeric binder. These bands are respectively observed between 1100 cm -1 and 1250 cm -1 .
  • hydrocarbon group or “hydrocarbon chain” more particularly denotes a linear or branched C1 to C30, especially C1 to C18, group.
  • B represents a bond -O- ⁇ and R represents a hydrogen or fluorine atom in formula I of siloxane derivative.
  • A preferably represents a saturated or unsaturated divalent hydrocarbon group, the hydrocarbon chain being interrupted by one or more oxygen atom (s), optionally substituted with an epoxide group.
  • R represents the unit of formula (II) as described above, and B and B 'represent a bond -O- ⁇ .
  • A advantageously comprises one or more nitrogen atom (s) and / or oxygen atom (s).
  • the siloxane derivatives present in the fibrous substrate of the paper sheet according to the invention may in particular be cited as follows: with n varying from 2 to 10 and preferably from 2 to 7 with ⁇ representing a covalent bond with a fiber, another silicon atom or the hydroxylated polymeric binder.
  • A advantageously comprises one or more nitrogen atom (s) and / or oxygen atom (s).
  • siloxane derivatives may in particular be cited as the following derivatives: with n varying from 2 to 10 and preferably from 2 to 7 with ⁇ representing a covalent bond with a fiber, another silicon atom or the hydroxylated polymeric binder.
  • the siloxane derivative may be present in the fibrous substrate in a proportion ranging from 5 to 30% and in particular from 10 to 20% by dry weight relative to the total weight of the fibers in dry form.
  • the siloxane derivative may be present in the fibrous substrate in a proportion ranging from 100 to 350% and in particular from 200 to 300% by dry weight relative to the total weight of hydroxylated polymeric binder.
  • the hydroxyl polymeric binder according to the invention comprises at least one hydroxyl group, and advantageously more than one hydroxyl group.
  • the hydroxylated polymeric binder impregnating the substrate is preferably based on polyvinyl alcohol (PVA), starch, pullulan, polyhydroxyalkyl methacrylate, polyglycerol monomethacrylate or a polysaccharide.
  • PVA polyvinyl alcohol
  • starch starch
  • pullulan polyhydroxyalkyl methacrylate
  • polyglycerol monomethacrylate polyglycerol monomethacrylate
  • it is based on PVA.
  • Said hydroxylated polymeric binder is in a proportion ranging from 1 to 10% by dry weight relative to the total weight of the fibers in dry.
  • the compound considered to form the polymeric binder is generally contacted with the fibrous substrate in the form of an aqueous preparation, preferably in line on the paper machine, preferably with the aid of an impregnator and / or a surfacing device.
  • the polyvinyl alcohol may for example be dissolved in water at a level of 1% to 10% by weight, preferably between 3% and 6%, before impregnation of the paper substrate.
  • aqueous PVA preparation can be used an impregnator and / or an in-line surfacing device, including in particular predosage rollers, engraved rollers, transfer rollers before dosing output.
  • Another alternative may be to soak the fibrous substrate in an aqueous bath containing the compound for forming the polymeric binder.
  • the aqueous solution containing this hydroxyl polymeric binder may be further supplemented with other additives usually used in the paper industry.
  • the substrate useful for the implementation of the present invention may be any paper or nonwoven suitable for making paper and more particularly security documents like banknotes.
  • nonwoven fibrous papers including natural fibers, in particular cellulosic fibers or synthetic fibers, or a mixture of natural and synthetic fibers.
  • said fibers may be cellulosic fibers mixed with synthetic fibers.
  • wood fibers for example of hardwood, softwood or their mixture, of eucalyptus, cotton, bamboo, viscose, straw, abaca, asperto, hemp , jute, flax, sisal or mixtures thereof.
  • the fibers may be bleached, semi-bleached or unbleached.
  • polyester polyamide
  • rayon rayon and viscose fibers.
  • the fibers can be short or long.
  • the fibers may have an average length ranging from 0.1 to 30 mm, in particular from 1 to 15 mm.
  • the fibrous substrate may for example consist solely of cellulosic fibers.
  • the fibers used in the composition of the sheet may comprise synthetic fibers.
  • This embodiment is particularly advantageous because it makes it possible to further improve the tear-resistance properties of the sheet according to the invention.
  • the paper sheets according to the invention comprising synthetic fibers have a tear strength greater than 1300 mN.
  • the synthetic fibers are in a proportion ranging from 5 to 30% by dry weight relative to the total weight of the fibers.
  • the sheet comprises cotton fibers in a proportion of at least 70% by dry weight relative to the total weight of the fibers and synthetic fibers in a proportion varying from 10 to 30% by dry weight relative to the total weight of the fibers, the sum total of cotton fibers and synthetic fibers being equal to 100%.
  • said synthetic fibers are selected from polyamide fibers and / or polyester fibers. It may be, for example, polyamide 6-6 fibers or polyester fibers sold by the company Kuraray under the trade name EP 133.
  • the fibrous substrate may for example consist of cellulosic fibers and synthetic fibers of polyamide 6-6, advantageously in a proportion of 90% by weight of cellulosic fibers relative to the total weight of dry fibers.
  • the fibrous substrate according to the invention may further comprise a flocculated latex in particular in a proportion ranging from 6 to 50% by weight relative to the total weight of dry fibers, advantageously in a proportion of 10% by weight relative to the total weight of dry fibers.
  • the sheets of paper according to the invention, comprising such a flocculated latex may be prepared according to the patent FR 2 916 768 .
  • the fibrous substrate may have, as finished and dry paper, before treatment according to the invention, a grammage of between 20 and 120 g / m 2 and a thickness ranging from 30 to 180 microns.
  • the fibrous substrate considered according to the invention may comprise one or more watermark (s) and / or one or more security element (s).
  • security elements that can be incorporated in the fibrous substrate, some are detectable to the eye, daylight or artificial light, without the use of a particular device.
  • These security elements comprise for example colored fibers or boards, fully or partially printed or metallized wires. These security elements are called first level.
  • Additional security elements are detectable only with a relatively simple apparatus, such as a lamp emitting in the ultraviolet (UV) or infrared (IR).
  • UV ultraviolet
  • IR infrared
  • These security elements comprise, for example, fibers, boards, strips, wires or particles. These security elements may be visible to the naked eye or not, being for example luminescent under a lighting of a Wood lamp emitting in a wavelength of 365 nm. These security elements are said to be second level.
  • security elements require for their detection a more sophisticated detection device. These security elements are for example capable of generating a specific signal when they are subjected, simultaneously or not, to one or more external excitation sources. The automatic detection of the signal makes it possible to authenticate, if necessary, the document.
  • These security elements comprise, for example, tracers in the form of active materials, particles or fibers capable of generating a specific signal when these tracers are subjected to optronic, electrical, magnetic or electromagnetic excitation. These security elements are said to be third level.
  • the sheet of paper as described above is a security document.
  • a security document according to the invention may also include a booklet.
  • a security document according to the invention is a bank note.
  • the fibrous substrate can be obtained beforehand on an inclined table, "to form", flat table (Fourdrinier) or round form or any other tool capable of forming a sheet of fibers from their mixture by dry way as according to the technologies "Dry-laid” or their mixture in suspension in wet water as in “wet-laid” (wet) technologies.
  • the substrate can be obtained, for example, by means of an aqueous suspension in any proportion of natural and / or synthetic fibers. These fibers once suspended are preferably refined and supplemented with adjuvants well known to those skilled in the art for their implementation.
  • defoamers, retention agents, binders, pigments, mineral fillers, wet strength agents and tackifiers can be used.
  • This fibrous mixture can then be drained onto a web to result in the formation of the expected fibrous substrate which is then dried prior to being treated in accordance with the invention, in line.
  • the security sheet may further comprise an outer layer.
  • This outer layer applied on at least one side of a sheet, is well known to those skilled in the art and allows, for example to enhance the durability properties of the sheet.
  • the composition of such a layer is for example described in the application EP 1 319 104 .
  • the outer layer is initially, preferably, a preparation in aqueous phase, in particular an emulsion or a dispersion.
  • the external printability layer is preferably based on polyurethane.
  • the polyurethane is preferably applied as an aqueous dispersion of polyurethane or pro-polyurethane particles.
  • the polyurethane may be present in the composition intended to form the outer layer in a mass content of between 40 and 100% relative to the total weight of the composition.
  • the composition intended to form the outer layer may comprise a crosslinking agent chosen from isocyanates, carbodiimides or aziridines.
  • the crosslinking agent may be in a mass content, by dry weight, of between 1 and 15%, better still 1 to 3%, relative to the total weight of the composition before coating.
  • composition intended to form the outer layer also preferably comprises a mineral filler chosen from silica, kaolin, talc or calcium carbonate.
  • composition intended to form the outer layer also preferably comprises a filler in a mass proportion by dry weight of between 1 and 60%, more preferably 3 and 10%, relative to the total weight of the composition.
  • step (ii) can be performed beforehand, simultaneously or consecutively to step (i).
  • step (ii) is performed simultaneously and / or consecutively in step (i).
  • the word "and" means that the substrate can undergo a 1 st impregnation with an aqueous solution of a hydroxylated polymeric binder and at least one silanol derivative and a 2 nd impregnation with only an aqueous solution at least one silanol derivative.
  • silanols can be of monopodal or dipodal type.
  • dipodal silanol is meant a silanol which comprises only one silicon atom, the latter being bonded to at least one hydroxyl group.
  • dipodal silanol is meant a silanol which comprises two silicon atoms, each bonded to at least one hydroxyl group.
  • the monopodal silanols that may be used according to the invention may or may not be obtained beforehand by a hydrolysis reaction of a corresponding alkoxysilane. This reaction is within the skill of those skilled in the art.
  • the alkoxysilanes used in hydrolysis reactions to provide monopodal silanols for the purposes of the invention are trialkoxysilanes.
  • the substrate may be brought into contact with a silanol derivative of formula (III): in which - A represents a divalent hydrocarbon group, saturated or not, the hydrocarbon chain may be optionally interrupted by one or more nitrogen, oxygen, sulfur or phosphorus atom (s), and substituted by one or more a plurality of hydrocarbon groups comprising one or more nitrogen, oxygen, sulfur, phosphorus and halogen atoms, in particular fluorine, and / or one or more cyclic group (s) (s) hydrocarbon and whose hydrocarbon chain may be optionally interrupted by one or more nitrogen atom (s), sulfur or phosphorus oxygen,
  • formula (III) in which - A represents a divalent hydrocarbon group, saturated or not, the hydrocarbon chain may be optionally interrupted by one or more nitrogen, oxygen, sulfur or phosphorus atom (s), and substituted by one or more a plurality of hydrocarbon groups comprising one or more nitrogen, oxygen, sulfur, phosphorus and halogen atoms, in particular fluorine, and / or
  • the A-R unit is inert with respect to the fibers and the associated polymeric binder.
  • the silanol is obtained according to a hydrolysis reaction of an alkoxysilane
  • the A-R unit present on the alkoxysilane is such that it does not prove to be detrimental to the hydrolysis reaction.
  • sterically hindered and / or highly hydrophobic A-R units are to be avoided.
  • the paper sheet obtained according to the invention comprises siloxane derivatives of formula (I) as previously represented, in which B is a bond -O- ⁇ and R is a hydrogen or fluorine atom.
  • the groups G 1 and G 2 can for example be of amino, epoxy, sulphide, mercapto, methacryl, vinyl, ureido or fluorine type.
  • the substrate may be contacted with a silanol derivative having as G1 an epoxide group and a silanol derivative having as G2 an amine group.
  • the sheet of paper obtained according to the invention comprises siloxane derivatives of formula (I) as previously represented, in which B and B 'are -O- ⁇ bonds and R is a unit of formula (II). ) as previously shown.
  • the substrate may be brought into contact with two silanol derivatives of formula (IV) and (V), with G1 and G2 respectively representing a reactive functional group according to a covalent coupling reaction but no not being complementary to one another, in the presence, simultaneous or not, of an auxiliary compound bearing two functional groups reactive according to a covalent coupling reaction and complementary to G1 and G2, respectively.
  • the substrate may be brought into contact with silanol derivatives comprising, as G1 and G2, an epoxide group and a derivative comprising two terminal amine groups.
  • the paper sheet according to the invention comprises siloxane derivatives of formula (I) as previously represented, in which B and B 'are -O- ⁇ bonds and R is a unit of formula (II) as shown previously.
  • the substrate may be brought into contact with a dipodal-type silanol derivative of formula (VI) so as to create a flexible bridge between fibers:
  • A may for example be an entity derived from a polyethylene glycol such as diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, a polypropylene glycol such as dipropylene glycol or tripropylene glycol, triethylene glycol diamine, 2 , 2'-oxy (bisethylamine) or tetraethylene glycol amine.
  • the paper according to the invention comprises siloxane derivatives of formula (I) as previously represented, in which R is a unit of formula (II) as previously represented.
  • the monopodal silanols that may be used according to the invention may or may not be obtained beforehand by a hydrolysis reaction of a corresponding alkoxysilane. This reaction is within the skill of those skilled in the art.
  • silanols are also commercially available, for example hydrolyzed fluoroalkyl-triethoxysilane, in particular that marketed by Degussa (reference Dynasylan® F 8815).
  • Dynasylan ® SIVO 110 Dynasylan ® SIVO 121
  • Dynasylan ® SIVO 160 marketed by Evonik
  • silanols and alkoxysilanes marketed by Gelest Inc. and selected from those referenced in the "Silane Coupling Agents" brochure available from the address http://www.gelest.com/gelest/forms/GeneralPages/literature.aspx may also be in particular SILICLAD ® , SIT 8378.5, SIC 2263.0, SIS 6984.0 and SIT 8378.3.
  • the step (ii) of impregnating said substrate with at least one silanol derivative is carried out with an aqueous solution of at least one silanol derivative.
  • the silanol derivative (s) are used in a proportion greater than 0.5%, preferably ranging from 5 to 30%, preferably from 10 to 20% by dry weight relative to the total weight of the fibers in dry form. .
  • a silanol may for example be dissolved in water at a level of more than 0.5%, preferably between 5% and 50% and more preferably between 10% and 50% by weight, preferably between 15% and 40%, before impregnation of the paper substrate.
  • the silanol (s) in question (s) can be contacted simultaneously or not with said hydroxylated polymeric binder with the fibrous substrate.
  • the impregnation operation it can be carried out by dipping, that is to say, immersion of the fibrous substrate in an aqueous bath containing at least one silanol derivative and said hydroxylated polymeric binder, or in two consecutive baths containing respectively at least said hydroxyl polymeric binder and a silanol derivative.
  • the one or more aqueous solutions are contacted with the fibrous substrate via an on-line impregnator.
  • the aqueous solution (s) are deposited on the surface of the fibrous substrate by means of an in-line surfacing, gluing or coating device, comprising in particular predose rollers, engraved rollers, transfer rollers before dosing. output.
  • Said surfacing, sizing or coating device is preferably a size-press or a coater. It is more preferably a press-gluing machine to promote a "heart" impregnation.
  • this impregnation can be carried out by spraying.
  • the impregnation steps (i) and (ii) are carried out independently of one another by dipping, surfacing, sizing, spraying or coating.
  • the impregnation steps (i) and (ii) are carried out simultaneously and by dipping.
  • the process according to the invention is particularly advantageous insofar as it makes it possible to incorporate silanol via a conventional method of manufacturing a sheet of paper, that is to say concomitantly with the conventional manufacturing steps.
  • silanol makes it possible to dispense with the insolubilizer usually required with regard to the hydroxylated polymeric binder.
  • the silanol is furthermore used as the insolubilizing agent of said hydroxylated polymeric binder.
  • the drying of the substrate thus treated can be carried out for example by hot air or infrared, possibly seconded by driving rollers.
  • the surface temperature reached will be at least 30 ° C and at most 180 ° C, and this in relation to the residence time of the coated paper in the heating unit.
  • the fibrous substrate is for example passed through a drying section formed of steam heated cylinders contacted with both sides of the fibrous substrate, or subjected to infrared radiation, or passed through a tunnel blowing hot air through the fibrous substrate.
  • the drying can be carried out at a temperature ranging from 50 to 250 ° C., in particular from 60 to 150 ° C.
  • the water is for example evaporated to a content ranging from 4 to 6% by weight in the finished fibrous substrate.
  • This drying step is also conducive to the crosslinking of the silanol derivatives with each other and / or with the hydroxyl groups of the fibrous substrate and / or the hydroxylated polymeric binder due to the dehydration conditions.
  • This measurement is carried out at 23 ° C and 50% humidity on a sample of 10cm x 2.5cm. It allows to visualize "the nervousness or spring effect" of the treated paper.
  • the sample is folded on itself, without marking the fold beforehand, under the action of a weight of 2 kg for 30s. The weight is then removed and a reading of the resilience angle is performed after 30s. The more “nerve” the paper, the greater the angle of resilience, the less the crease will be marked.
  • the figure 1 in the appendix provides an illustration of this measure.
  • the creasing force is adjusted by the weight position on the lever arm so that the pressure on the piston is 10kg / cm 2 ⁇ 0.1 kg / cm 2 .
  • the different cylindrical tracks namely, the guide, the tube and the piston must be able to slide freely and in particular slide under the weight. With the tube and the piston in place in the guide, the piston must fall or rise as one raises or lowers the weight at the end of the lever. In case of impediment, check that there is no foreign body and wipe these parts.
  • the Erlenmeyer flask is closed and then placed in a water bath at 50 ° C. for 45 minutes with magnetic stirring.
  • the extract is then filtered in a filter crucible of porosity No. 1 and then diluted in a volumetric flask of 200 ml.
  • a test portion of 20 mL is taken, to which 15 mL of boric acid at a concentration of 40 g / L and 3 mL of an iodine solution made by mixing 25 g of potassium iodide ( KI) and 12.7 g of diiodine (I 2 ) in one liter of distilled water in a 50 ml volumetric flask.
  • KI potassium iodide
  • I 2 diiodine
  • the different types of paper are called A, B, C, and D.
  • Paper A consists of cellulosic fibers (100% cotton fibers). (samples 1A and 2A)
  • Paper B is made of cellulosic fibers and 10% of latex based on the weight of the fibers, it is prepared according to the patent FR 2 916 768 . (samples 1B and 2B)
  • Paper C is made of 90% cotton cellulosic fibers and 10% polyamide 6-6 synthetic fibers. (samples 1C and 2C)
  • the paper D is made of 90% of cellulosic cotton fibers, 10% of synthetic polyamide 6-6 fibers and 10% of latex based on the total weight of the fibers, it is prepared according to the patent FR 2 916 768 . (1D and 2D samples)
  • the substrate may comprise adjuvants known to those skilled in the art and commonly used in the paper industry, including retention agents and wet strength.
  • the ⁇ -glycidyloxypropyltrimethoxysilane was first hydrolysed as follows: in a beaker containing the alkoxysilane with magnetic stirring is added a mixture of water and acetic acid so as to adjust the pH to 3, 5. The solution is stirred for 15 minutes.
  • the papers thus obtained have hydrophobic properties since the water absorption has decreased for all the samples in a comparable manner according to the nature of the paper (from 22 to 25%).
  • the wet tensile strength and the dry tensile strength were thus measured on the 8 samples.
  • the wet strength (ReH) is equal to the ratio of the wet tensile strength to the dry tensile strength.
  • the security documents according to the invention have hydrophobic properties, resilience and crease resistance, without the mechanical properties of said documents being altered. As regards more particularly wet strength, it is even improved for the security documents according to the invention.
  • the silanol used was obtained as in Example 1, by hydrolysis of ⁇ -glycidyloxypropyl-trimethoxysilane (reference SCA 960 marketed by Struktol) according to the procedure of Example 1.
  • Example 2 The results obtained are reported in the following Table 3. Similarly, the results of the sample 2C from Example 1 appear for comparison. The only difference between Example 2 and Sample 2C of Example 1 lies in the functionalization mode. Indeed, sample 2C had been functionalized by impregnation. ⁇ b> Table 3 ⁇ / b> Sample Removal (g / m 2 ) Fold rate (% hollow) Resilience (°) Witness 0 47 35 Example 2 11 35 66 2C 10 33 78
  • the papers obtained according to Example 3 have hydrophobic properties since the water absorption has decreased by 70% compared to the control.
  • Example 3 differs from Example 3 only in the silanol used for functionalization. Indeed in this example the silanol used and the SIVO 160 from Evonik Degussa.
  • a variant 4bis of this example was produced without insolubilization agent or bonding agent in the 2nd bath of series 1 of Example 1.
  • Example 3 The measures of removal, resilience, Cobb, fold rate and solubilized PVA are reported in the following Table 5. Similarly, the results of Example 3 appear for comparison. ⁇ b> Table 5 ⁇ / b> Sample Removal (g / m 2 ) Fold rate (% hollow) Resilience (°) Cobb (g / m 2 ) PVA solubilized (mg / 100g of paper) Witness 0 41 45 20 771 Example 4 8 38 60 6 68 Example 4bis 8 38 60 6 68 Example 3 15 33 82 6 Not measured
  • the papers obtained according to Example 4 have hydrophobic properties since the water absorption has decreased by 70% compared to the control.
  • Table 6 shows the relationship between the fold rate measured according to the method explained above and the visual assessment of the samples after creasing according to the BNIP 07 90 standard. ⁇ b> Table 6 ⁇ / b> Samples Pictures Fold rate (% hollow) Reference Figure 2a 41% Treated paper Figure 2b 31%

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Claims (15)

  1. Papierblatt mit hoher Beständigkeit gegen Knittern und Falten, insbesondere zur Herstellung von Banknoten, mit einem Fasersubstrat, welches im Inneren mit mindestens einem hydroxylierten polymeren Bindemittel imprägniert ist, dadurch gekennzeichnet, dass das Bindemittel und die Fasern des Substrats zumindest teilweise kovalent an mindestens ein Siloxanderivat gebunden sind.
  2. Papierblatt nach Anspruch 1, dadurch gekennzeichnet, dass das Siloxanderivat die folgende Formel (I) aufweist:
    Figure imgb0018
     worin:
    - □ eine kovalente Bindung mit einer Faser, einem anderen Siliciumatom oder dem hydroxylierten polymeren Bindemittel darstellt,
    - A eine zweiwertige, gesättigte oder ungesättigte Kohlenwasserstoffgruppe darstellt, wobei die Kohlenwasserstoffkette gegebenenfalls durch ein oder mehrere Stickstoff-, Sauerstoff-, Schwefel- oder Phosphoratom(e) unterbrochen sein kann und durch eine oder mehrere Kohlenwasserstoffgruppe(n) substituiert sein kann, die ein oder mehrere Stickstoffatom(e), Sauerstoffatom(e), Schwefelatom(e), Phosphoratom(e) oder Halogen, insbesondere Fluor, aufweisen, und/oder durch ein oder mehrere zyklische Gruppe(n) mit C3 bis C6 oder aromatischen Gruppen, wobei die Kohlenwasserstoffkette gegebenenfalls durch eine oder mehrere Stickstoffatom(e), Sauerstoffatom(e), Schwefelatom(e) oder Phosphoratom(e) unterbrochen sein kann,
    - B
    - eine Bindung -O-□ darstellt, oder
    - ein Halogen oder
    - eine gesättigte oder ungesättigte, lineare oder verzweigte oder zyklische Kohlenwasserstoffgruppe, die ein oder mehrere zyklische Gruppen aufweist oder nicht, und wobei die Kohlenwasserstoffkette durch ein oder mehrere Stickstoffatom(e), Sauerstoffatom(e) oder Schwefelatom(e) unterbrochen sein kann,
    - R
    - ein Wasserstoffatom darstellt,
    - ein Halogenatom, bevorzugt Fluor, oder
    - eine Gruppe der Formel (II)
    Figure imgb0019
     worin B'
    eine Bindung -O-□ darstellt, oder
    - ein Halogen oder
    - eine gesättigte oder eine nicht gesättigte, lineare oder verzweigte oder zyklische Kohlenwasserstoffgruppe, die ein oder mehrere zyklische Gruppen aufweisen kann oder nicht, und wobei die Kohlenwasserstoffkette durch ein oder mehrere Stickstoffatom(e), Sauerstoffatom(e) oder Schwefelatom(e) unterbrochen sein kann.
  3. Papierblatt nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass B eine Bindung -O-□ darstellt und R ein Wasserstoffatom oder Fluor darstellt.
  4. Papierblatt nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass A eine zweiwertige, gesättigte oder ungesättigte Kohlenwasserstoffgruppe darstellt, deren Kohlenwasserstoffkette durch ein oder mehrere Sauerstoffatom(e) unterbrochen sein kann und gegebenenfalls durch eine Epoxidgruppe substituiert ist.
  5. Papierblatt nach Anspruch 2, dadurch gekennzeichnet, dass R die Gruppe der Formel (II) wie in Anspruch 2 definiert darstellt und B und B' eine Bindung -O-□ darstellen.
  6. Papierblatt nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das hydroxylierte polymere Bindemittel auf Polyvinylalkohol (PVA), Stärke, Pullulan, Polyhydroxyalkylmethacrylat, Polyglycerolmonomethacrylat oder einem Polysaccharid basiert, wobei das Bindemittel bevorzugt auf PVA basiert, wobei das hydroxylierte polymere Bindemittel bevorzugt in einem Anteil im Bereich von 1 bis 10 Trockengew.-% bezogen auf das Gesamttrockengewicht der Fasern vorliegt.
  7. Papierblatt nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Fasern Cellulosefasern im Gemisch mit synthetischen Fasern sind.
  8. Papierblatt nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Fasersubstrat weiterhin ein geflocktes Latex umfasst, insbesondere in einem Anteil von 6 bis 50 Gew.-% in Bezug auf das Gesamttrockengewicht der Fasern, bevorzugt in einem Anteil von 10 Gew.-%.
  9. Papierblatt nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Fasersubstrat ein oder mehrere Wasserzeichen und/oder ein oder mehrere Sicherheitselement(e) aufweist.
  10. Papierblatt nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es sich um ein Sicherheitsdokument handelt, insbesondere um eine Banknote.
  11. Mehrlagenstruktur, welche ein Papierblatt nach einem der vorhergehenden Ansprüche umfasst.
  12. Verfahren zur Herstellung eines Papierblatts mit hoher Beständigkeit gegenüber Knittern und Falten, insbesondere zur Herstellung von Banknoten, wie in einem der vorhergehenden Ansprüche beschrieben, aus einem Fasersubstrat, umfassend:
    (i) Imprägnieren des Substrats mit einer wässrigen Lösung eines hydroxylierten polymeren Bindemittels, insbesondere in einem Anteil im Bereich von 1 bis 10 Trockengew.-% in Bezug auf das Trockengewicht der Fasern,
    (ii) Imprägnieren des Substrats mit einer wässrigen Lösung mindestens eines Silanolderivats und
    (iii) Trocknen des gemäß den Schritten (i) und (ii) modifizierten Substrats,
    wobei der Schritt (ii) vor, gleichzeitig oder nach dem Schritt (i) durchgeführt werden kann.
  13. Verfahren zur Herstellung eines Papierblatts nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, dass das oder die Silanolderivat(e) in einem Anteil im Bereich von 5 bis 30 %, bevorzugt 10 bis 20 Trockengew.-% in Bezug auf das Trockengewicht der Fasern eingesetzt werden.
  14. Verfahren zur Herstellung eines Papierblatts nach Anspruch 12 oder 13, dadurch gekennzeichnet, dass die Imprägnierschritte (i) und (ii) unabhängig voneinander durch Einweichen, Bedecken, Leimen, Zerkleinern oder Beschichten erfolgt, wobei die Imprägnierschritte (i) und (ii) bevorzugt gleichzeitig und durch Einweichen durchgeführt werden.
  15. Verwendung eines Silanolderivats in dem Herstellungsverfahren eines Papierblatts mit hoher Beständigkeit gegenüber Knittern nach Anspruch 12 als unlöslich machendes Mittel für das hydroxylierte polymere Bindemittel.
EP12824715.2A 2011-12-21 2012-12-21 Folie aus faltenfreiem papier Active EP2794989B1 (de)

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FR1162208A FR2984926B1 (fr) 2011-12-21 2011-12-21 Feuille de papier resistante au froissement
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JPS5365352A (en) * 1976-11-24 1978-06-10 Toray Silicone Co Ltd Composition for finishing and processing of resin
FR2668507B1 (fr) * 1990-02-09 1996-06-21 Arjomari Europ Feuille pour documents de securite, ayant une imprimabilite elevee en meme temps qu'une resistance a la circulation elevee.
FR2814476B1 (fr) 2000-09-11 2003-04-11 Arjo Wiggins Sa Feuille de securite comportant une couche transparente ou translucide
FR2864557B1 (fr) * 2003-12-30 2006-10-27 Arjo Wiggins Secutity Sas Papier de securite possedant une resistance au double-pli elevee et son procede de fabrication
FR2916768B1 (fr) * 2007-05-31 2009-07-24 Arjowiggins Licensing Soc Par Feuille de securite resistante au froissement, son procede de fabrication et un document de securite la comprenant

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WO2013093872A1 (fr) 2013-06-27
FR2984926A1 (fr) 2013-06-28
FR2984926B1 (fr) 2014-02-21

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