Classifications

• • 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 paper sheet resistant to wrinkling 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 therefore 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. According to yet another of its aspects, 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 at heart with 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.
• the fibers of the substrate are essentially in contact with the hydroxylated polymeric binder.
• said fibrous substrate is also impregnated in its 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.
• the invention also relates, in another of its aspects, to a method of manufacturing a sheet of paper with high resistance to wrinkling and folding, in particular for the manufacture of banknotes as described above, from a fibrous substrate comprising (i) impregnating said substrate with an aqueous solution of a hydroxyl polymeric binder, especially in a proportion ranging from 1 to 10% by dry weight relative to the weight of the dry fibers,
• 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 sizing agent provides hydrophobicity to the treated fibrous substrate to enhance repellency of the aqueous solutions (water) contacted by the substrate.
• 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).
• these silanol derivatives are advantageously devoid 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 .
• this siloxane derivative corresponds to formula (I)
• - ⁇ represents a covalent bond with a fiber, another silicon atom or the hydroxylated polymeric binder
• - A represents a divalent hydrocarbon group, saturated or not, the hydrocarbon chain may be optionally interrupted by one or more nitrogen atom (s), oxygen, sulfur or phosphorus, and substituted by one or more grouping (s) hydrocarbons comprising one or more nitrogen, oxygen, sulfur, phosphorus and halogen atoms, in particular fluorine atoms and / or by one or more C3 cyclic group (s) C6 or aromatic (s) and whose hydrocarbon chain may be interrupted if necessary by one or more nitrogen atom (s), sulfur or phosphorus oxygen, - B represents
• hydrocarbon group saturated or unsaturated, linear or branched or cyclic, with or without one or more cyclic group (s) and whose hydrocarbon chain may be interrupted by one or more nitrogen atom (s), oxygen or sulfur,
• halogen atom and preferably a fluorine atom, or
• hydrocarbon group saturated or unsaturated, linear or branched or cyclic, with or without one or more cyclic group (s) and whose hydrocarbon chain may be interrupted by one or more nitrogen atom (s), oxygen or sulfur.
• hydrocarbon group or
• Hydrocarbon chain more particularly denotes a linear or branched group C1 to C30, especially C1 to C18.
• B represents a link
• R represents a hydrogen or fluorine atom in the formula I 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.
• oxygen atom s
• R represents the unit of formula (II) as described above, and B and B 'represent a bond ⁇ ⁇ .
• A advantageously comprises one or more nitrogen atom (s) and / or oxygen atom (s).
• siloxane derivatives present in the fibrous substrate of the paper sheet according to the invention may in particular be cited as follows:
• n 2 to 10 and from 2 to 7
• R represents the unit of formula (II) as described above, and B and B 'represent:
• a monovalent hydrocarbon group saturated or unsaturated, linear or branched or cyclic, with or without one or more cyclic group (s) and whose hydrocarbon chain can be interrupted by one or more nitrogen atom (s), of oxygen or sulfur.
• 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:
• n varying from 2 to 10 and preferably from 2 to 7
• 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 hydroxylated 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.
• Polyvinyl alcohol may for example be dissolved in water at
• 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 can 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 1 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 uraray 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 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 ⁇ .
• the fibrous substrate considered according to the invention may comprise one or more watermark (s) and / or one or more safety 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 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.
• the composition intended to form the outer layer also preferably comprises a mineral filler chosen from silica, kaolin, talc or calcium carbonate.
• the 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.
• the paper sheet according to the invention can be obtained according to the method comprising
• 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 the era impregnated 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 in the sense of the invention are trialkoxysilanes.
• the substrate may be brought into contact with a silanol derivative of formula (III):
• 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,
• 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 shown, in which B is a bond and R is a hydrogen or fluorine atom.
• the substrate may be brought into contact with two silanol derivatives of formula (IV) and (V): OH OH
• the groups G 1 and G 2 can for example be of the amino, epoxy, sulphide, mercapto, methacryl, vinyl, ureido or fluorine type.
• the substrate may be brought into contact with a silanol derivative comprising, as G1, an epoxide group and a silanol derivative comprising, as G2, an amino 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 ⁇ 1 bonds and R is a unit of formula (II) such as than previously represented.
• the substrate may be brought into contact with two silanol derivatives of formula (IV) and (V), with Gl and G2 respectively representing a reactive functional group according to a covalent coupling reaction but not 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 respectively to G1 and G2.
• the substrate may be brought into contact with silanol derivatives comprising as G1 and G2 an epoxide group and a derivative having 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 ⁇ 1 bonds and R is a unit of formula (II) such that previously represented.
• 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.
• 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.
• alkoxysilanes By way of illustrative and nonlimiting examples of alkoxysilanes, mention may be made of: vinyltriethoxysilane, in particular that marketed by Momentive
• octyltriethoxysilane in particular that marketed by Momentive (reference Silquest A-137 silane), ⁇ -glycidyloxypropyl-trimethoxysilane, in particular that marketed by Struktol (reference SCA 960).
• 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.
• 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.
• This impregnation can also be achieved via the implementation of devices usually considered for surfacing, gluing or coating the paper.
• 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 impregnation "heart".
• 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 respect 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
• a) a device for rolling the paper test specimen into a cylinder This device consists of a split sleeve inside which is placed a movable fork with two teeth, b) a tube whose one end is provided with a movable cover, c) a sliding cylinder guide to the inside said tube, d) a cylindrical guide for maintaining inside and in vertical position said piston whose lower base rests at the end of a lever.
• the cylindrical guide is designed such that the tube can slide between said guide and the piston, e) a lever mounted on a pivot, and
• 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.
• a square sample of 6.7 cm x 6.7 cm is crimped 8 times using the above-mentioned apparatus. It is then extracted from the device and then held at the four corners.
• the analysis of four images (rotation of the sample 1 ⁇ 4 turn) high resolution of the sample via software allows to express the average rate of folds present on the analyzed surface. This analysis is done in three steps:
• the result of the thresholding is a binary image containing black and white pixels, calculation of the ratio black pixels / white pixels on the whole image (1800x1800 pixels) corresponding to the percentage of hollow (% hollow).
• 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 ( Kl) and 12.7 g of diiodine (3 ⁇ 4 in 1 liter of distilled water in a 50 ml volumetric flask)
• Kl potassium iodide
• diiodine 3 ⁇ 4 in 1 liter of distilled water in a 50 ml volumetric flask
• 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 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 consists 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 in the following manner: 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.
• each sample is immersed in a first bath, dried at 110 ° C. for 10 minutes, then immersed in a second bath, for the samples of Series 1 (not according to the invention), the bath 1 is standard (that is to say devoid of hydrolyzed ⁇ -glycidyloxypropyl-trimethoxysilane). It contains polyvinyl alcohol (PVA), glycerin and water,
• the 2nd bath is standard, and contains PVA, a sizing agent, glycerin, an insolubilizing agent and water,
• the treated papers are then dried at 110 ° C for 10 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 mechanical properties were characterized as follows: 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 results of the sample 2C from Example 1 appear for comparison.
• Example 2 differs from Example 2 in that:
• silanol coating was carried out after impregnation in the two series 1 PVA baths of Example 1.
• 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.
• Example 4 38 60 6 68
• the papers obtained according to Example 4 have hydrophobic properties since the water absorption has decreased by 70% compared to the control. Comparing the fold, resilience, cobb and solubilized PVA values for the samples of Examples 4 (comprising besides silanol an insolubilizing agent and a sizing agent) and 4 bis (devoid of insolubilizing agent and bonding agent), it appears that it is possible to overcome the insolubilization agent and the bonding agent.
• This example represents a visualization of the measurement of the fold rate for two samples:
• 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. Samples Photos Folding rate (% hollow)

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• 2011
  • 2011-12-21 FR FR1162208A patent/FR2984926B1/fr not_active Expired - Fee Related
• 2012
  • 2012-12-21 EP EP12824715.2A patent/EP2794989B1/fr active Active
  • 2012-12-21 WO PCT/IB2012/057597 patent/WO2013093872A1/fr active Application Filing
  • 2012-12-21 ES ES12824715.2T patent/ES2562905T3/es active Active
  • 2012-12-21 SI SI201230461T patent/SI2794989T1/sl unknown
  • 2012-12-21 PL PL12824715T patent/PL2794989T3/pl unknown

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