EP3172379B1 - Security sheet resistant to crumpling and hard creasing - Google Patents
Security sheet resistant to crumpling and hard creasing Download PDFInfo
- Publication number
- EP3172379B1 EP3172379B1 EP15741536.5A EP15741536A EP3172379B1 EP 3172379 B1 EP3172379 B1 EP 3172379B1 EP 15741536 A EP15741536 A EP 15741536A EP 3172379 B1 EP3172379 B1 EP 3172379B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- fibres
- dry weight
- security
- fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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- 125000002091 cationic group Chemical group 0.000 claims description 50
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- LTNZEXKYNRNOGT-UHFFFAOYSA-N dequalinium chloride Chemical compound [Cl-].[Cl-].C1=CC=C2[N+](CCCCCCCCCC[N+]3=C4C=CC=CC4=C(N)C=C3C)=C(C)C=C(N)C2=C1 LTNZEXKYNRNOGT-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
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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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
-
- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
Definitions
- the present invention relates to a wrinkle and crease resistant security sheet, its manufacturing method and a security document comprising the sheet.
- resistant to wrinkling and marked crease means that the sheet hardly undergoes the impact of a wrinkle and crease marked thanks to a controlled stiffening of the cellulosic substrate.
- a disadvantage of the used paper supports is that they resist bad wrinkling and wrinkles. Thus, crumpled or folded areas have marked folds, irreversible, poor resistance to soiling, so that these wrinkled areas are weakened and often give rise to tears.
- the mass treatment of paper is one of the solutions that can be considered to improve the resistance to wrinkling.
- the use of flocculation, before the formation of the sheet makes it possible to form a global fiber-flocculating agent-polymer network via the formation of bonds made possible by the presence of the flocculation agent.
- the flocculation of the polymer takes place directly on the fibers thanks to the presence of the flocculation agent. There is therefore no prior formation of polymer flocculates before contacting the fibers.
- the document WO 2008/152299 discloses safety sheets comprising an anionic polymer having a glass transition temperature above -40 ° C and a cationic flocculation agent having good wrinkling resistance.
- WO 2014/083527 discloses safety sheets comprising a polyurethane having an elongation at break greater than 600%, and a cationic flocculating agent, having good wrinkling resistance as well as good mechanical properties such as tensile strength, including breaking lengths dry and wet, resistance to double-fold or tearing.
- EP 1 466 755 and EP 1 466 756 describe safety sheets whose rigidity is increased on the corners with specific watermarks. However, these processes are not economically very attractive and more importantly, they do not allow to treat the entire cellulosic substrate.
- adding stiffness, for example at least 20%, to the safety sheets would further reduce the mechanical impact of the traffic. (wrinkles, creases ...) on the paper.
- the reduction of the physicochemical impact of the circulation such as soiling, wrinkling or folding marked on the paper, it would reduce the rejection by automatic sorting machines.
- the wrinkling, the marked bending and the soiling of a banknote paper lead to a decrease in its rigidity as well as a large number of rejects in automatic sorting machines.
- an anionic dispersion of at least one polymer having a glass transition temperature greater than 23 ° C. is combined with an effective amount of an agent. cationic flocculation during the manufacture of a security sheet.
- anionic dispersion is meant an aqueous suspension of particles having an anionic surface charge.
- Said surface charge is either intrinsically present in the polymer or is provided by a surfactant compound (or surfactant) used in the formation of said particles.
- the polymer according to the present invention may be anionic or not.
- said surface charge is provided by a surfactant compound (or surfactant) used in the formation of said particles.
- dispersion is here used generically and can therefore also refer to an emulsion.
- Polymer aggregates (s) denotes the flocs formed by bringing into contact with the anionic polymer dispersion (s) with the fibers and the flocculation agent. Flocculation of the anionic dispersion of polymer (s) thus occurs as soon as the anionic dispersion of polymer (s) is mixed with the fibers and the flocculation agent.
- the aggregates are thus preserved within this mixture which is then subjected to the successive common steps of the papermaking process, namely dewatering, pressing and drying. Under the effect of said routine steps of the papermaking process and especially by the disappearance of water, said polymer aggregates (s) are thus dispersed within the network formed by the fibers and the flocculation agent.
- said sheet further comprises an auxiliary cationic flocculating agent, said secondary agent, in an amount of between 0.1% and 0.5% by dry weight relative to the total dry weight of fibers and polymer (s).
- This embodiment is particularly advantageous when the proportion of polymer (s) by dry weight relative to the total weight of the fibers in dry is high, in particular when it exceeds 20% by dry weight relative to the total weight of the fibers, because the presence of the secondary cationic flocculating agent makes it possible to perfect the flocculation of the polymer (s).
- the Applicant has found, as illustrated in the examples below, that the presence of aggregates of polymer (s) having a glass transition temperature greater than 23 ° C and flocculation agent (s) in the composition of the sheet according to the invention significantly improved its rigidity on the entire cellulosic substrate and the resistance to soiling while maintaining good resistance to traction, especially the breaking lengths, dry and wet, wet state and double-fold, and good resistance to creasing and tearing of said sheet.
- the phenomenon of flocculation is chemically reflected by the formation in aqueous medium of electrostatic bonds between a chemical compound having ionized groups, namely in the context of the invention the anionic dispersion of polymer (s) having a glass transition temperature greater than 23 ° C, and an agent of flocculation having ionized groups of charge opposite to that of the chemical compound.
- the flocculation agent forms weak atomic bonds (of the order of 5 kJ / mol) with the chemical compound according to a chemical interaction process taking place under mild conditions (for example, at room temperature) and obligatorily in medium solvated (eg water).
- the anionic dispersion of polymer (s) is introduced last, after having introduced the fibers and the flocculation agent.
- the flocculation results in an inhomogeneous distribution of aggregates of polymers (s) intertwined in the network formed by the fibers and the flocculation agent.
- the flocculation system is used for a mass treatment (by volume) of the sheet and is thus carried out in wet part (period during which the fibers are dispersed in water, then forming a fibrous suspension), before the formation of leaf.
- the aggregates of particles are distributed in the interstices left vacant between the fibers during the formation of the sheet. These interstices are no longer accessible after draining, pressing and drying of the sheet as filled by said aggregates.
- said aggregates preferably have hydrophobic and / or oleophobic properties, so that the penetration of the soil is less and the sheet thus has a better resistance to soiling.
- the sheet according to the invention Before the formation of the sheet according to the invention, there is, in addition to the bonds between the anionic particles of the polymer and the cationic charges of the flocculation agent, formation of bonds between the anionic charges of the cellulose and the cationic charges. flocculation agent. It thus forms a global network (fibers - agent flocculation - polymer) which is preserved during the formation of the paper sheet, which explains the improvement of the rigidity on the totality of the cellulosic substrate.
- the resistance to soiling can also be improved by the chemical nature of the polymer aggregates (s), in particular when they have a hydrophobic and / or oleophobic nature.
- the fibers used when they have a negative surface charge, these can be previously treated to promote the fixing of the cationic flocculation agent. We can then say that we add a preliminary step of "anionization" of the fibers.
- Such fibers may be cotton fibers.
- the cellulosic fibers of wood do not generally have this low negative surface charge. However, they may also be subject to this prior treatment, where appropriate.
- this preliminary step may consist in the addition of cellulose derivatives such as carboxymethylcellulose (CMC).
- CMC carboxymethylcellulose
- Such polymers capable of increasing the negative surface charge of fibers may in any case be chosen from anionic polymers which are soluble in water and have an affinity with cellulose.
- the crosslinking phenomenon is chemically translated by the formation of covalent bonds between two entities: a chemical compound and a crosslinking agent.
- the crosslinking agent composed of reactive groups, forms strong atomic bonds (of the order of 500 kJ / mol) with certain groups of the chemical compound according to a chemical reaction process taking place under specific energy conditions (temperature, pressure, radiation. ..).
- the bonds formed are homogeneously distributed. They are permanent and resistant, which gives the compound / crosslinking mixture rigidity and homogeneous dimensional stability, properties which are the opposite of those sought for a security sheet contemplated by the invention which must be flexible and resistant.
- Flocculation has the advantage of providing stiffness over the entire cellulosic substrate, in particular by virtue of the good distribution of the aggregates of polymer (s) in the substrate. It should also be noted that large amounts of polymer (s) are not necessary to achieve this improvement of the rigidity property.
- the surfacing by the same polymer has the disadvantage of leading to a brittle layer structure, which resists poorly to circulation, including wrinkling.
- such a mass treatment makes it possible to envisage an additional surface treatment, in particular a protective treatment, for example of the antifouling type and / or printing treatment, on the security sheet obtained according to the process of the invention.
- an additional surface treatment in particular a protective treatment, for example of the antifouling type and / or printing treatment
- the surface treatments do not make it so easy to carry out additional surface treatment for obvious reasons of surface affinities between them and modification of the properties provided by the first surface treatment, which must first be taken into account. account.
- the present invention relates to a wrinkle and crease-resistant security sheet comprising fibers, obtained by mass treatment of said fibers by a flocculation system, said flocculation system comprising an anionic dispersion of at least one polymer having a glass transition temperature above 23 ° C and a cationic flocculating agent.
- the invention relates to a wrinkle-resistant security sheet comprising fibers, said fibers comprising en masse aggregates of particles formed following the flocculation of an anionic dispersion of at least one polymer having a glass transition temperature above 23 ° C, and a cationic flocculation agent.
- the security sheet according to the invention comprises fibers.
- total fiber weight should be understood as meaning “ total dry fiber weight " unless otherwise indicated.
- the fibers used in the composition of the sheet comprise natural fibers.
- cellulosic fibers such as wood fibers, for example of eucalyptus, of softwood or their mixture, of cotton, bamboo, viscose, straw, abaca, asperto , hemp, jute, flax, sisal or their mixtures.
- the fibers may be bleached, semi-bleached or unbleached.
- the fibers in the composition of the sheet comprise cellulosic fibers, particularly cotton fibers.
- the fibers comprise fibers previously anionized with polymers capable of increasing the negative surface charge of the fibers such as anionic polymers which are soluble in water and have an affinity with cellulose.
- anionic polymers may be chosen from cellulose derivatives such as carboxymethylcellulose (CMC).
- said cellulosic fibers are present in a proportion greater than 60% by dry weight relative to the total dry weight of fibers and polymer (s), in particular in a proportion of greater than 70%.
- said cellulosic fibers represent at least 70% by dry weight of the total amount of fibers.
- said cellulosic fibers are cotton fibers and represent at least 70% by dry weight of the total amount of 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 Applicant has found that, surprisingly, the use of synthetic fibers, generally used to strengthen the paper, has a synergistic effect with the use according to the invention of a polymer presenting a specific Tg. Indeed, the Applicant has measured that the sheets containing synthetic fibers, while being rigid and retaining resistance to creasing and high soiling, also had a particularly high tear resistance.
- the tear resistance of the sheets according to this particular embodiment of the invention is greater than the tear resistance of the sheets according to the invention without synthetic fibers and the tear resistance of sheets comprising synthetic fibers. but no aggregates of polymer (s).
- the synthetic fibers are in a proportion of between 5% and 30% by dry weight relative to the total dry weight of fibers and polymer (s), and better still between 10% and 15% by weight. %.
- 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 of between 10% and 30% by weight. % by dry weight relative to the total weight of the fibers, the sum total of the cotton fibers and synthetic fibers being equal to 100.
- said synthetic fibers are chosen from polyester, polyamide, rayon and viscose fibers, preferably they are polyamide fibers and / or polyester fibers. It may be, for example, polyamide 6-6 fibers or polyester fibers marketed by Kuraray under the trade name EP133®.
- a security sheet according to the invention further comprises at least polymer aggregates (s) having a glass transition temperature (Tg) greater than 23 ° C.
- the polymer (s) used in the context of the present invention have a glass transition temperature greater than 35 ° C, and more preferably greater than 40 ° C.
- glass transition temperature means the temperature below which the polymer is rigid. As the temperature increases, the polymer passes through a transition state that allows free macromolecular chains amorphous domains to slide relative to each other and the polymer softens.
- the measurement of the glass transition temperature can be carried out by differential scanning calorimetry (" Differential Scanning Calorimetry " or " DSC").
- the polymer (s) may be present in a proportion of between 1% and 40% by dry weight, in in particular between 2% and 25% by dry weight, and preferably between 2% and 15% by dry weight, relative to the total dry weight of fibers and polymer (s).
- the polymer (s) having a glass transition temperature greater than 23 ° C are chosen from polyacrylics, polyacrylates, polyacrylamides, polystyrenes, polyurethanes, polyvinyls, polyethylenes, and mixtures thereof.
- the polymer (s) having a glass transition temperature greater than 23 ° C. are chosen from acrylic (or polyacrylic) polymers, that is to say homopolymers or copolymers comprising at least less an acrylic monomer, namely acrylic homopolymers or acrylic copolymers.
- the polymer (s) having a glass transition temperature greater than 23 ° C. are chosen from acrylic homopolymers.
- the polymer (s) may be non-crosslinkable, crosslinkable with the aid of an external crosslinking agent or else self-crosslinkable.
- the polymer (s) are self-crosslinkable.
- the drying step may lead to crosslinking of the polymers, in a step subsequent to the implementation of the process according to the invention.
- the anionic dispersion of the polymer (s) is monophasic or multiphasic.
- a multiphasic dispersion corresponds in particular to core-shell particles comprising two types of polymers of which at least the most abundant (the core) is a rigid polymer considered according to the invention.
- the other polymer (s) may have a function other than the addition of rigidity, it (s) may (in particular) be used as crosslinking agent and / or binder.
- a security sheet according to the invention further comprises at least an effective amount of a cationic flocculation agent, said main agent.
- the term " effective amount” means the amount of cationic flocculating agent advantageously required to allow the anionic dispersion of the polymer to flocculate. This amount of cationic flocculating agent is to be considered with regard to the associated polymer (s) and may therefore vary from one polymer to another. From his general knowledge, the skilled person is able to adjust the amount of cationic flocculating agent necessary to allow flocculation of the polymer (s).
- the cationic flocculating agent called the main agent
- the main agent is present in an amount of between 0.5% and 5% by dry weight, in particular between 1% and 3% by dry weight, relative to the total dry weight. fiber and polymer (s).
- the cationic flocculating agent, said main agent, present in the security sheet according to the invention is chosen from water-soluble cationic polymers, in particular from polyacrylamides, polyethyleneimines, polyvinylamines and their mixtures.
- the cationic flocculating agent is a cationic resin.
- this resin is a polyamide-amine-epichloridin resin, called PAAE resin.
- the cationic flocculation agent is selected from polyacrylamides, polyethyleneimines, polyvinylamines and mixtures thereof.
- the security sheet comprises, in addition to the cationic flocculating agent, said main agent, described above, a secondary cationic flocculating agent, said secondary agent.
- Such a secondary cationic flocculating agent is present in an amount of between 0.1% and 0.5% by dry weight relative to the total dry weight of fibers and polymer (s).
- said cationic flocculation agent is selected from polyacrylamides, polyethylenimines, polyvinylamines and mixtures thereof.
- the security sheet comprises at least one security element.
- said security element is chosen from optically variable devices (OVD), in particular interference-effect elements, in particular iridescent elements, holograms, liquid crystals and interferential multilayer structures.
- OLED optically variable devices
- interference-effect elements in particular iridescent elements, holograms, liquid crystals and interferential multilayer structures.
- the sheet according to the invention may comprise an RFID device (radio frequency identification device).
- the security sheet comprises at least one at least partially fiber-free zone, also known as a " window " zone .
- the security sheet according to the invention comprises an embedded security thread or strip (e), in particular totally or partially, in said sheet, and preferably appearing in at least one window.
- the security sheet comprises mineral fillers in an amount of 1% to 10% by dry weight relative to the total dry weight of the composition of the sheet.
- said mineral fillers are present in a proportion of between 1% and 5% by dry weight relative to the total dry weight of the composition of the sheet.
- fillers are chosen, for example, from calcium carbonate, kaolin, titanium dioxide or mixtures thereof.
- the security sheet according to the invention may further comprise fillers and additives commonly used in the paper industry.
- the security sheet according to The invention further comprises carboxymethylcellulose (CMC).
- CMC carboxymethylcellulose
- the security sheet may further comprise an additional treatment, in particular an impregnation, an external surfacing layer, a coating or a coating. It can be an external treatment.
- surfacing layers coated on at least one side of a sheet, are well known to those skilled in the art and make it possible, for example for a layer based on a polyvinyl alcohol, to improve the properties of double strength. -plugging and pulling the leaf.
- the security sheet according to the invention may comprise a surfacing layer intended to reinforce its durability properties, such as, for example, a layer whose composition is described in the application EP 1 319 104 and which comprises a transparent or translucent elastomeric binder, such as a polyurethane, and a colloidal silica.
- a surfacing layer intended to reinforce its durability properties, such as, for example, a layer whose composition is described in the application EP 1 319 104 and which comprises a transparent or translucent elastomeric binder, such as a polyurethane, and a colloidal silica.
- the security sheet according to the invention further comprises an outer surfacing layer, preferably based on a polyvinyl alcohol, an acrylic polymer or a transparent or translucent elastomeric binder. , such as a polyurethane, and optionally a colloidal silica.
- the invention also relates to a method of manufacturing the security sheet described above.
- said fibers, said anionic dispersion of at least one polymer having a glass transition temperature greater than 23 ° C and said cationic flocculating agent are advantageously mixed in bulk.
- said polymer aggregates (s) are formed by contacting the anionic dispersion of polymer (s) with the fibers and the flocculation agent.
- said aqueous suspension further comprises an auxiliary cationic flocculating agent, said secondary agent, in an amount of between 0.1% and 0.5% by dry weight relative to the total dry weight fiber and polymer (s).
- the process of the invention makes it possible, by using polymer (s) having a specific Tg and flocculation agent (s), to flocculate the polymer (s) on the fibers and to obtain a very rigid safety sheet with particularly high resistance to creasing and soiling.
- the anionic dispersion of the polymer (s) having a glass transition temperature greater than 23 ° C and the cationic flocculating agent, said main agent are mixed in mass in the fibrous suspension before dewatering .
- said aqueous suspension is obtained from a mixture of fibers and said cationic flocculation agent, said main agent, to which said anionic dispersion of polymer (s) and optionally said cationic flocculation agent, said secondary agent, before proceeding with the formation of said sheet.
- This embodiment has the advantage of bringing the polymer (s) and the flocculation agent into contact in order to facilitate flocculation.
- This embodiment also has the advantage that it can be applied to aqueous suspensions of "standard " fibers used for the manufacture of safety sheets because they include wet strength agents which can also be used as main flocculation in the context of the present invention.
- crosslinking can take place after flocculation.
- the polymers, once flocculated can crosslink under the effect of the high temperature dedicated to drying.
- the method of manufacturing the security sheet comprises a step in which at least one face of said sheet, after dewatering of said suspension is coated with a surfacing layer.
- This surfacing layer may allow, for example, to improve the marked bending and / or tensile strength properties or even the durability properties of said sheet, as described above.
- the invention also relates to a security document comprising the security sheet object of the invention, or as obtained by the method of the invention, described above.
- the invention relates to a means of payment, such as a bank note, a payment card, a check or a restaurant ticket, an identity document, such as an identity card, a visa, a passport or a driving license, a card, including access, a lottery ticket, a ticket or a ticket to cultural or sports events, a loyalty card, a service card, a ticket a membership card, a playing or collectible card, a voucher or a voucher.
- a means of payment such as a bank note, a payment card, a check or a restaurant ticket, an identity document, such as an identity card, a visa, a passport or a driving license, a card, including access, a lottery ticket, a ticket or a ticket to cultural or sports events, a loyalty card, a service card, a ticket a membership card, a playing or collectible card, a voucher or a voucher.
- banknote This is preferably a bank note.
- One of the specificities of banknotes is indeed to be subjected to wrinkles and marked folds, and to have to maintain its rigidity and good resistance to wrinkles and creases marked despite the effects of traffic to minimize rejects in automatic machines and automatic sorting machines.
- a banknote generally has a thickness of between 70 ⁇ m and 170 ⁇ m, for example 100 ⁇ m.
- the grammage measurements can be performed according to ISO 536.
- Thickness measurements can be made according to ISO 534.
- compositions are prepared for making the measurements.
- the first composition is prepared from the weight proportions indicated in Table 1 below: ⁇ i> ⁇ u> Table 1 ⁇ / u> ⁇ /i> compounds Weight (g) Distilled water 500 NaCl 5 Lactic acid 5 Urea 0.5 Histidine hydrochloride 0.5 Water Qs 1000
- the second composition is prepared from the weight proportions indicated in Table 2 below: ⁇ i> ⁇ u> Table 2 ⁇ / u> ⁇ /i> compounds Weight (g) Yellow iron oxide marketed by Lanxess under the name Bayferrox® 420 0.833 Brown iron oxide marketed by Lanxess under the name Bayferrox® 610 0.833 Carbon black sold by the company BASF under the name Black Microlite CK 0.083 Vermiculite 2D marketed by EFISOL 248.25
- the compounds of Table 2 are mixed using a Turbula mixer for 30 minutes in a plastic bottle with six large 20 mm diameter ceramic beads.
- the third composition is prepared from the weight proportions indicated in Table 3 below: ⁇ i> ⁇ u> Table 3 ⁇ / u> ⁇ /i> compounds Weight (g) Lanolin marketed by Lanolines de la Tossée under the name Lanoline Lanor TEC 200 Ethoxylated tridecyl alcohol marketed by the company Nopco under the name Disponil® TD 0785 20
- the mixture of the two compounds of Table 3 is homogenized until the lanolin melts. 28 g of water are then added with stirring, followed by 16 g of ethoxylated ether of behenic alcohol (sold by the company Nopco under the name Eumulgin® BA 10). The whole is mixed by heating until a homogeneous preparation.
- the mixture is then allowed to cool to room temperature and then 24 g of water are then added by mixing for 15 minutes. 190 g of water are then added, incorporating it very slowly at the beginning.
- Each sample is crumpled beforehand 4 times with an IGT creasing device.
- the samples (75 mm x 140 mm) are mounted on wooden blocks (60 mm x 35 mm x 35 mm), around which they are held with three exposed faces.
- composition A 90 ml of composition A, 10 g of composition B, 20 g of composition C and 25 ceramic beads with a maximum diameter of 20 mm are placed in a plastic jar of 2 L.
- the ceramic beads may be alumina beads, they must not weigh less than 300 g. They are packaged before use by placing them in the Turbula mixer with an abrasive cream and a little water for 1 hour and 30 minutes.
- the mixture is agitated then the four wooden blocks, dry, on which the samples were placed are introduced.
- the jar is closed and stirred with a Turbula mixer at 67 rpm for 20 minutes.
- the samples are then rinsed with running water and dried using two blotters. They are then put in the oven at 60 ° C for 3 minutes.
- the samples are then calendered one by one with one passage per side, at 15 bar pressure, at minimum speed.
- the whiteness is an average value of three measurements according to the NF ISO 2470-2 6167 standard and the degree of yellowing is an average value of three measurements, which are well known to those skilled in the art (measurements carried out with the Datacolor Elrepho 3000 apparatus of the company Lorentzen & Wettre).
- flexural strength in Newton
- rigidity measurements can be made according to the ISO 2493-1 standard, in particular with a Taber stiffener (Model 150-B) or with a Franck rigidimeter ( Model 58565).
- the index of flexural strength (Nm 6 / Kg 3 ) is determined by taking into account the basis weight of the paper.
- the sheets according to the invention advantageously have a stiffness gain of at least 15%, or even at least 20%, with respect to the rigidity of a sheet comprising 100% cotton fibers.
- the double-fold resistance measurements can be carried out according to the ISO 5626 standard.
- Tear resistance measurements can be made according to ISO 1974.
- the tear index is obtained by dividing the tear strength by the basis weight.
- BENDTSEN porosity measurements can be made before and after creasing.
- the wrinkling operation causes, because of the folds formed, more or less pronounced alteration of the surface of the paper, leading to an increase in its porosity and therefore its fragility. Comparing the value of the porosity of the paper before and after creasing can therefore be evaluated the crease resistance of the latter. The less the increase in porosity between the initial sheet and the crumpled sheet, the less the paper is wrinkle resistant. The goal is therefore to obtain values of porosity after crumpling the lowest possible.
- the wrinkle test therefore makes it possible to determine the wrinkle resistance of papers such as bank note papers and wrapping papers.
- the apparatus used corresponds to that described by the National Bureau Of Standards ( Carson, FT Shaw, MB Wearing quality of experimental currency type papers, J. Research NBS 36, 256-257 (1946) RP 1701 ).
- the crumpling force is adjusted by the position of the weight on the arm of the lever, so that the pressure on the piston is 10 kg / cm 2 ⁇ 0.1 kg / cm 2 .
- Sampling and conditioning of the specimens are done in accordance with standards NFQ 03-009 and NFQ 03-010.
- the specimens can be measured as such. Since the specimen is constantly handled, it is necessary, in order to avoid moisture exchange with the operator, that the operator wears gloves of a moisture-barrier material during the preparation of the specimens and the run the test.
- test pieces are cut using a template. The running direction is marked on each specimen.
- the tube, closed lid, is then slid in continuity with the sleeve and the rolled test piece is transferred there by a return movement of the fork.
- the tube held by the lid with one hand, is then placed in a vertical position on the piston.
- the crumpling is done by pressing on the cover until the end of the long arm of the lever is raised above its rest position. It is important that the pressure exerted is sufficient to lift the weight, but neither too strong nor too fast for the lever to come into abutment.
- One way to control the effort is to use both hands on each other to press the lid.
- the lid is open and the test piece is crumpled in the shape of a small accordion, and out of the tube. It is put flat by carefully straightening the hand: acting too abruptly could produce notches on the side that would lead to tearing of the specimen.
- the straightened specimen is presented again for rolling in front of the slot of the sleeve but rotated 90 ° with respect to the first introduction; the complete cycle is repeated.
- the air permeability of each specimen is measured before and after wrinkling using a BENDTSEN porosimeter according to ISO 5636-3.
- the porosity is measured as follows: each specimen is straightened until it is reasonably flat. This can easily be done by holding between thumb and forefinger, the test piece by two opposite sides and then stretching it in three or four places. This operation is repeated by the other two sides; to do this operation in all four times is usually sufficient to obtain a sufficiently flat specimen.
- each specimen is introduced between the jaws of the clamping device of a brightness meter and is applied during two seconds enough pressure to mark the paper. Porosity is measured by ensuring that the BENDTSEN porosimeter head is centered on the surface squeezed to the brightnessometer.
- test pieces to be tested depends on the sample studied.
- the reproducibility of the test is such that a sample per sample sheet is sufficient.
- the porosity of the sheets according to the invention after creasing can vary from 1 to 20 ml / min, in particular from 1 to 12 ml / min.
- the sheets A to F, and 1 to 3, tested below, are prepared according to the standard paper-making process, that is to say, in particular by draining, pressing and then drying aqueous suspensions whose compositions in dry weight are given in the tables. 1 to 3 below.
- PAAE resin polyamide-amine-epichloridrine resin
- a flocculation step is carried out in Examples B, C and 1 to 3.
- the PAAE resin has a role of cationic flocculation agent and also resistance to corrosion. wet state.
- Said sheets then undergo, according to a common practice in the paper industry, an external surfacing, as described above, deposited at a rate of 5 g / m 2 / face. Said surfacing is carried out by impregnation.
- the sheets A to C are impregnated with a layer based on a polyvinyl alcohol (PVA).
- Sheets D and E and 1 to 3 are impregnated with a layer based on a polyvinyl alcohol (PVA).
- As for the sheet C it is impregnated with a layer based on an acrylic polymer having a Tg of 38 ° C.
- the sheets E, F and 3 have, before surfacing, a basis weight of 85 g / m 2 .
- Comparative Example A relates to standard, untreated paper.
- Comparative Example B relates to a sheet obtained according to the process as described in document WO 2008/152299 .
- Comparative example C relates to a sheet obtained according to the process as described in the document WO 2014/083527 .
- the sheets of Examples 1 and 2 according to the invention have a clear rigidity gain compared to the sheet of Comparative Example D.
- sheets of Examples 1 and 2 show an improvement in the soiling index of 4 to 5 points.
- the sheet of Example 3 according to the invention has a much higher rigidity than that of Comparative Example E, while exhibiting values of tensile strength, tear strength and double-fold comparable to those of Comparative Example E, which shows that the use of the polymers according to the invention does not degrade the properties of tensile strength, tear and double-fold.
- Example F Comparison of Example F with Example 3 makes it possible to show that the surfacing of a rigid acrylic polymer does not improve the rigidity of the substrate, despite the large amount of polymer supplied (6 g / m 2 against 1.5 g / m 2 of PVA).
Description
La présente invention concerne une feuille de sécurité résistante au froissement et au pli marqué, son procédé de fabrication et un document de sécurité comprenant cette feuille. Au sens de l'invention « résistante au froissement et au pli marqué » signifie que la feuille ne subit quasiment pas l'impact d'un froissement et d'un pli marqué grâce à une rigidification contrôlée du substrat cellulosique.The present invention relates to a wrinkle and crease resistant security sheet, its manufacturing method and a security document comprising the sheet. For the purposes of the invention "resistant to wrinkling and marked crease" means that the sheet hardly undergoes the impact of a wrinkle and crease marked thanks to a controlled stiffening of the cellulosic substrate.
Actuellement, de nombreux documents de sécurité, tels que des billets de banque ou des documents d'identité, comprennent des supports en papier ou substrats cellulosiques.Currently, many security documents, such as banknotes or identity documents, include paper supports or cellulosic substrates.
Un inconvénient des supports en papiers utilisés est qu'ils résistent mal au froissement et aux plis marqués. Ainsi, les zones froissées ou pliées présentent des plis marqués, irréversibles, qui résistent mal à la salissure, de sorte que ces zones froissées sont affaiblies et donnent souvent lieu à des déchirures.A disadvantage of the used paper supports is that they resist bad wrinkling and wrinkles. Thus, crumpled or folded areas have marked folds, irreversible, poor resistance to soiling, so that these wrinkled areas are weakened and often give rise to tears.
Ceci est particulièrement désavantageux dans le cas de documents qui, lors de leur manipulation, sont fréquemment pliés ou froissés, comme par exemple des billets de banque, la présence de plis marqués les fragilisant et réduisant leur durée de vie, et rendant leur traitement automatisé malaisé, par exemple lors des vérifications d'authenticité ou d'usure sur machine de tri.This is particularly disadvantageous in the case of documents which, during their handling, are frequently folded or wrinkled, such as for example banknotes, the presence of marked folds weakening and reducing their life, and making their automated processing difficult. , for example during verifications of authenticity or wear on a sorting machine.
On connaît du document
En outre, il existe un besoin pour améliorer la résistance des feuilles produites par le procédé décrit dans ce document aux effets de la circulation et en particulier, leurs résistances au froissement, au pli marqué et à la salissure.In addition, there is a need to improve the resistance of the sheets produced by the method described herein to the effects of the circulation and in particular, their resistance to wrinkling, marked crease and soiling.
Le traitement en masse du papier est une des solutions qui peut être envisagée pour améliorer la résistance au froissement.The mass treatment of paper is one of the solutions that can be considered to improve the resistance to wrinkling.
En effet, comme détaillé ci-après, l'emploi de la floculation, avant la formation de la feuille, permet de former un réseau global fibres - agent de floculation - polymère via la formation de liaisons rendues possible grâce à la présence de l'agent de floculation. Autrement dit, la floculation du polymère a lieu directement sur les fibres grâce à la présence de l'agent de floculation. Il n'y a donc pas de formation préalable de floculats de polymères avant la mise en contact avec les fibres.Indeed, as detailed below, the use of flocculation, before the formation of the sheet, makes it possible to form a global fiber-flocculating agent-polymer network via the formation of bonds made possible by the presence of the flocculation agent. In other words, the flocculation of the polymer takes place directly on the fibers thanks to the presence of the flocculation agent. There is therefore no prior formation of polymer flocculates before contacting the fibers.
Ainsi, le document
Or, il a pu être constaté que la floculation de dispersions polymériques anioniques telle que proposée dans
Le document
Toutefois, l'amélioration des propriétés mécaniques de ces feuilles de sécurité, notamment celles décrites dans les demandes
Certains procédés sont par ailleurs connus pour augmenter la rigidité des feuilles de sécurité. Par exemple,
Il existe donc un besoin de fournir une feuille de sécurité qui présente une amélioration de sa rigidité sur la totalité du substrat cellulosique et de sa résistance à la salissure tout en conservant ses propriétés mécaniques telles que la résistance aux tractions, notamment les longueurs de rupture, sèches et humides et la résistance au double-pli, et une bonne résistance au froissement.There is therefore a need to provide a security sheet which exhibits an improvement in its rigidity on the totality of the cellulosic substrate and its resistance to soiling while retaining its mechanical properties such as tensile strength, especially the breaking lengths, dry and wet and double-fold resistance, and good resistance to wrinkling.
En effet, un apport de rigidité, par exemple d'au moins 20 %, aux feuilles de sécurité permettrait de diminuer encore plus l'impact mécanique de la circulation (froissements, plis...) sur le papier. Quant à la diminution de l'impact physico-chimique de la circulation tel que la salissure, le froissement ou le pliage marqué sur le papier, elle permettrait de réduire le rejet par les machines automatiques de tri. En effet, le froissement, le pliage marqué et la prise de salissure d'un papier billet de banque entrainent une baisse de sa rigidité ainsi qu'un grand nombre de rejets en machines automatiques de tri. En effet, des études montrent que la principale cause de rejet des billets de banque en début de circulation, notamment jusqu'aux trente premiers pourcents de la durée de vie d'un billet de banque, avant la salissure et les déchirures, est la présence de plis marqués qui perturbent les capteurs et peuvent donc être interprétés comme des déchirures ou perforations, devant la salissure et les déchirures.In fact, adding stiffness, for example at least 20%, to the safety sheets would further reduce the mechanical impact of the traffic. (wrinkles, creases ...) on the paper. As for the reduction of the physicochemical impact of the circulation such as soiling, wrinkling or folding marked on the paper, it would reduce the rejection by automatic sorting machines. In fact, the wrinkling, the marked bending and the soiling of a banknote paper lead to a decrease in its rigidity as well as a large number of rejects in automatic sorting machines. Indeed, studies show that the main reason for rejecting banknotes at the beginning of circulation, especially up to the first thirty percent of the life of a bank note, before the stains and tears, is the presence marked wrinkles that disturb the sensors and can therefore be interpreted as tears or perforations, in front of dirt and tears.
De manière inattendue, les inventeurs ont constaté qu'un tel objectif pouvait être atteint sous réserve d'associer une dispersion anionique d'au moins un polymère présentant une température de transition vitreuse supérieure à 23 °C, et une quantité efficace d'un agent de floculation cationique lors de la fabrication d'une feuille de sécurité.Unexpectedly, the inventors have found that such an objective could be achieved provided that an anionic dispersion of at least one polymer having a glass transition temperature greater than 23 ° C. is combined with an effective amount of an agent. cationic flocculation during the manufacture of a security sheet.
Par « dispersion anionique », on entend une suspension aqueuse de particules présentant une charge de surface anionique. Ladite charge de surface est soit intrinsèquement présente dans le polymère, soit est apportée par un composé tensioactif (ou surfactant) utilisé lors de la formation desdites particules. Ainsi, le polymère selon la présente invention peut être anionique ou non. De préférence, ladite charge de surface est apportée par un composé tensioactif (ou surfactant) utilisé lors de la formation desdites particules. Le terme « dispersion » est ici utilisé de façon générique et peut donc également désigner une émulsion.By " anionic dispersion " is meant an aqueous suspension of particles having an anionic surface charge. Said surface charge is either intrinsically present in the polymer or is provided by a surfactant compound (or surfactant) used in the formation of said particles. Thus, the polymer according to the present invention may be anionic or not. Preferably, said surface charge is provided by a surfactant compound (or surfactant) used in the formation of said particles. The term " dispersion " is here used generically and can therefore also refer to an emulsion.
Ainsi, la présente invention décrit une feuille de sécurité résistante au froissement comprenant au moins :
- des fibres,
- des agrégats de polymère(s) présentant une température de transition vitreuse supérieure à 0 °C, et
- une quantité efficace d'un agent de floculation cationique, dit agent principal.
- fibers,
- aggregates of polymer (s) having a glass transition temperature above 0 ° C, and
- an effective amount of a cationic flocculation agent, said main agent.
En particulier, la présente invention concerne une feuille de sécurité résistante au froissement comprenant au moins :
- des fibres,
- des agrégats de polymère(s) présentant une température de transition vitreuse supérieure à 23 °C, et
- une quantité efficace d'un agent de floculation cationique, dit agent principal.
- fibers,
- aggregates of polymer (s) having a glass transition temperature greater than 23 ° C, and
- an effective amount of a cationic flocculation agent, said main agent.
Par « agrégats de polymère(s) », on désigne les flocs formés par la mise au contact de la dispersion anionique de polymère(s) avec les fibres et l'agent de floculation. La floculation de la dispersion anionique de polymère(s) se produit ainsi dès le mélange de la dispersion anionique de polymère(s) avec les fibres et l'agent de floculation. Les agrégats sont ainsi conservés au sein de ce mélange à qui on fait ensuite subir les étapes successives courantes du procédé papetier, à savoir l'égouttage, le pressage et le séchage. Sous l'effet desdites étapes courantes du procédé papetier et notamment par la disparition de l'eau, lesdits agrégats de polymère(s) sont ainsi dispersés au sein du réseau formé par les fibres et l'agent de floculation. "Polymer aggregates (s)" denotes the flocs formed by bringing into contact with the anionic polymer dispersion (s) with the fibers and the flocculation agent. Flocculation of the anionic dispersion of polymer (s) thus occurs as soon as the anionic dispersion of polymer (s) is mixed with the fibers and the flocculation agent. The aggregates are thus preserved within this mixture which is then subjected to the successive common steps of the papermaking process, namely dewatering, pressing and drying. Under the effect of said routine steps of the papermaking process and especially by the disappearance of water, said polymer aggregates (s) are thus dispersed within the network formed by the fibers and the flocculation agent.
Ainsi, la présente invention décrit une feuille de sécurité résistante au froissement comprenant au moins :
- des fibres,
- des agrégats de polymère(s) présentant une température de transition vitreuse supérieure à 5 °C, et
- une quantité efficace d'un agent de floculation cationique, dit agent principal, lesdits agrégats de polymère(s) étant répartis au sein du réseau formé par les fibres et l'agent de floculation.
- fibers,
- aggregates of polymer (s) having a glass transition temperature above 5 ° C, and
- an effective amount of a cationic flocculating agent, said main agent, said polymer aggregates (s) being distributed within the network formed by the fibers and the flocculation agent.
Plus particulièrement, la présente invention décrit une feuille de sécurité résistante au froissement comprenant au moins :
- des fibres,
- des agrégats de polymère(s) présentant une température de transition vitreuse supérieure à 23 °C, et
- une quantité efficace d'un agent de floculation cationique, dit agent principal, lesdits agrégats de polymère(s) étant répartis au sein du réseau formé par les fibres et l'agent de floculation.
- fibers,
- aggregates of polymer (s) having a glass transition temperature greater than 23 ° C, and
- an effective amount of a cationic flocculating agent, said main agent, said polymer aggregates (s) being distributed within the network formed by the fibers and the flocculation agent.
Selon un mode de réalisation de l'invention, ladite feuille comprend en outre un agent de floculation cationique annexe, dit agent secondaire, en une quantité comprise entre 0,1 % et 0,5 % en poids sec par rapport au poids sec total en fibres et polymère(s).According to one embodiment of the invention, said sheet further comprises an auxiliary cationic flocculating agent, said secondary agent, in an amount of between 0.1% and 0.5% by dry weight relative to the total dry weight of fibers and polymer (s).
Ce mode de réalisation est particulièrement avantageux lorsque la proportion en polymère(s) en poids sec par rapport au poids total des fibres en sec est élevée, en particulier lorsqu'elle dépasse 20 % en poids sec par rapport au poids total des fibres, car la présence de l'agent de floculation cationique secondaire permet de parfaire la floculation du ou des polymère(s).This embodiment is particularly advantageous when the proportion of polymer (s) by dry weight relative to the total weight of the fibers in dry is high, in particular when it exceeds 20% by dry weight relative to the total weight of the fibers, because the presence of the secondary cationic flocculating agent makes it possible to perfect the flocculation of the polymer (s).
Plus particulièrement, la présente invention concerne une feuille de sécurité
résistante au froissement et au pli marqué comprenant au moins :
- des fibres,
- des agrégats de polymère(s) présentant une température de transition vitreuse supérieure à 23 °C, dans une proportion comprise entre 1 % et 40 % en poids sec, par rapport au poids sec total en fibres et polymère(s), et
- un agent de floculation cationique, dans une proportion comprise entre 0,5 % et 5 % en poids sec, par rapport au poids sec total en fibres et polymère(s).
crease-resistant and marked-pleat material comprising at least:
- fibers,
- aggregates of polymer (s) having a glass transition temperature greater than 23 ° C, in a proportion of between 1% and 40% by dry weight, relative to the total dry weight of fibers and polymer (s), and
- a cationic flocculating agent, in a proportion of between 0.5% and 5% by dry weight, relative to the total dry weight of fibers and polymer (s).
La Demanderesse a trouvé, comme illustré dans les exemples ci-après, que la présence d'agrégats de polymère(s) présentant une température de transition vitreuse supérieure à 23 °C et d'agent(s) de floculation dans la composition de la feuille selon l'invention permettait d'améliorer de façon significative sa rigidité sur la totalité du substrat cellulosique et la résistance à la salissure tout en conservant une bonne résistance aux tractions, notamment aux longueurs de rupture, sèches et humides, à l'état humide et au double-pli, et une bonne résistance au froissement et à la déchirure de ladite feuille.The Applicant has found, as illustrated in the examples below, that the presence of aggregates of polymer (s) having a glass transition temperature greater than 23 ° C and flocculation agent (s) in the composition of the sheet according to the invention significantly improved its rigidity on the entire cellulosic substrate and the resistance to soiling while maintaining good resistance to traction, especially the breaking lengths, dry and wet, wet state and double-fold, and good resistance to creasing and tearing of said sheet.
Au cours des expériences qu'elle a menées, la Demanderesse a trouvé que seules les feuilles comportant des agrégats de polymère(s) présentant une température de transition vitreuse supérieure à 23 °C présentaient une bonne rigidité et une résistance à la salissure tout en conservant d'excellentes caractéristiques de résistance au froissement, aux tractions sèches et humides et au double-pli.In our experiments, we found that only sheets with aggregates of polymer (s) having a glass transition temperature greater than 23 ° C had good rigidity and resistance to soiling while retaining excellent resistance to wrinkling, dry and wet pulls and double-fold.
En vue de mettre en lumière l'intérêt de la floculation, telle que mise en oeuvre dans le cadre de la présente invention, une description de ce phénomène est présentée ci-dessous, sans que celle-ci ne lie les inventeurs à cette théorie.In order to highlight the interest of flocculation, as used in the context of the present invention, a description of this phenomenon is presented below, without it linking the inventors to this theory.
Le phénomène de floculation se traduit chimiquement par la formation en milieu aqueux de liaisons électrostatiques entre un composé chimique présentant des groupements ionisés, à savoir dans le cadre de l'invention la dispersion anionique de polymère(s) présentant une température de transition vitreuse supérieure à 23 °C, et un agent de floculation présentant des groupements ionisés de charge opposée à celle du composé chimique. L'agent de floculation forme des liaisons atomiques faibles (de l'ordre de 5 kJ/mol) avec le composé chimique selon un processus d'interactions chimiques se déroulant dans des conditions douces (par exemple, à température ambiante) et obligatoirement en milieu solvaté (par exemple l'eau).The phenomenon of flocculation is chemically reflected by the formation in aqueous medium of electrostatic bonds between a chemical compound having ionized groups, namely in the context of the invention the anionic dispersion of polymer (s) having a glass transition temperature greater than 23 ° C, and an agent of flocculation having ionized groups of charge opposite to that of the chemical compound. The flocculation agent forms weak atomic bonds (of the order of 5 kJ / mol) with the chemical compound according to a chemical interaction process taking place under mild conditions (for example, at room temperature) and obligatorily in medium solvated (eg water).
Dans le cadre de la présente invention, à savoir mettant en oeuvre une dispersion anionique de polymère(s) et un agent de floculation cationique, la floculation se déroule en trois étapes :
- adsorption de l'agent de floculation sur les charges anioniques des fibres,
- adsorption d'une partie des particules anioniques formant la dispersion anionique de polymère(s) sur les charges cationiques de l'agent de floculation, puis
- agrégation des particules par coalescence due à la diminution des charges anioniques de surface des particules et l'apparition de liaisons de Van der Waals lors des étapes courantes du procédé papetier, à savoir l'égouttage, le pressage et le séchage.
- adsorption of the flocculation agent on the anionic charges of the fibers,
- adsorption of a portion of the anionic particles forming the anionic dispersion of polymer (s) on the cationic charges of the flocculation agent, then
- aggregation of particles by coalescence due to the decrease of the anionic surface charges of the particles and the appearance of van der Waals bonds during the common steps of the paper process, namely dewatering, pressing and drying.
Selon un mode de réalisation particulier, on introduit la dispersion anionique de polymère(s) en dernier lieu, après avoir introduit les fibres et l'agent de floculation.According to a particular embodiment, the anionic dispersion of polymer (s) is introduced last, after having introduced the fibers and the flocculation agent.
Ainsi, la floculation aboutit à une répartition inhomogène d'agrégats de polymères(s) entrelacés dans le réseau formé par les fibres et l'agent de floculation. Le système de floculation est employé pour un traitement en masse (en volume) de la feuille et s'effectue donc en partie humide (période pendant laquelle les fibres sont dispersées dans l'eau, formant alors une suspension fibreuse), avant la formation de la feuille.Thus, the flocculation results in an inhomogeneous distribution of aggregates of polymers (s) intertwined in the network formed by the fibers and the flocculation agent. The flocculation system is used for a mass treatment (by volume) of the sheet and is thus carried out in wet part (period during which the fibers are dispersed in water, then forming a fibrous suspension), before the formation of leaf.
Ainsi, les agrégats de particules sont répartis dans les interstices laissés vacants entre les fibres durant la formation de la feuille. Ces interstices n'étant plus accessibles après égouttage, pressage et séchage de la feuille car comblés par lesdits agrégats. Selon un mode de réalisation particulier, lesdits agrégats ont de préférence des propriétés hydrophobes et/ou oléophobes, de sorte que la pénétration de la salissure est moindre et que la feuille présente donc une meilleure résistance à la salissure.Thus, the aggregates of particles are distributed in the interstices left vacant between the fibers during the formation of the sheet. These interstices are no longer accessible after draining, pressing and drying of the sheet as filled by said aggregates. According to a particular embodiment, said aggregates preferably have hydrophobic and / or oleophobic properties, so that the penetration of the soil is less and the sheet thus has a better resistance to soiling.
Avant la formation de la feuille selon l'invention, il y a, en plus des liaisons entre les particules anioniques du polymère et les charges cationiques de l'agent de floculation, formation de liaisons entre les charges anioniques de la cellulose et les charges cationiques de l'agent de floculation. Il se forme ainsi un réseau global (fibres - agent de floculation - polymère) qui est conservé lors de la formation de la feuille de papier, ce qui explique l'amélioration de la rigidité sur la totalité du substrat cellulosique.Before the formation of the sheet according to the invention, there is, in addition to the bonds between the anionic particles of the polymer and the cationic charges of the flocculation agent, formation of bonds between the anionic charges of the cellulose and the cationic charges. flocculation agent. It thus forms a global network (fibers - agent flocculation - polymer) which is preserved during the formation of the paper sheet, which explains the improvement of the rigidity on the totality of the cellulosic substrate.
Par ailleurs, comme évoqué ci-dessus, la résistance à la salissure peut également être améliorée de par la nature chimique des agrégats de polymère(s), en particulier lorsqu'ils présentent un caractère hydrophobe et/ou oléophobe.Moreover, as mentioned above, the resistance to soiling can also be improved by the chemical nature of the polymer aggregates (s), in particular when they have a hydrophobic and / or oleophobic nature.
Selon une variante de la présente invention, lorsque les fibres mises en oeuvre présentent une charge négative de surface faible, ces dernières peuvent être préalablement traitées pour favoriser la fixation de l'agent de floculation cationique. On peut alors dire que l'on ajoute une étape préalable d'« anionisation » des fibres. De telles fibres peuvent être des fibres de coton. A titre indicatif, les fibres cellulosiques de bois ne présentent pas en général cette faible charge négative de surface. Elles peuvent toutefois également faire l'objet de ce traitement préalable, le cas échéant.According to a variant of the present invention, when the fibers used have a negative surface charge, these can be previously treated to promote the fixing of the cationic flocculation agent. We can then say that we add a preliminary step of "anionization" of the fibers. Such fibers may be cotton fibers. As an indication, the cellulosic fibers of wood do not generally have this low negative surface charge. However, they may also be subject to this prior treatment, where appropriate.
Selon cette variante, cette étape préalable peut consister en l'ajout de dérivés cellulosiques comme la carboxyméthylcellulose (CMC). De tels polymères aptes à augmenter la charge négative de surface de fibres peuvent être en tout état de cause choisis parmi des polymères anioniques solubles dans l'eau et présentant une affinité avec la cellulose.According to this variant, this preliminary step may consist in the addition of cellulose derivatives such as carboxymethylcellulose (CMC). Such polymers capable of increasing the negative surface charge of fibers may in any case be chosen from anionic polymers which are soluble in water and have an affinity with cellulose.
Ainsi, selon cette variante, la floculation se déroule en quatre étapes :
- adsorption sur les fibres d'un polymère anionique, ayant une affinité avec les fibres, tel que la CMC,
- adsorption de l'agent de floculation sur les charges anioniques des fibres,
- adsorption d'une partie des particules anioniques formant la dispersion anionique de polymère(s) sur les charges cationiques de l'agent de floculation, puis
- agrégation des particules par coalescence due à la diminution des charges anioniques de surface des particules et l'apparition de liaisons de Van der Waals lors des étapes courantes du procédé papetier, à savoir l'égouttage, le pressage et le séchage.
- adsorption on the fibers of an anionic polymer, having an affinity with the fibers, such as CMC,
- adsorption of the flocculation agent on the anionic charges of the fibers,
- adsorption of a portion of the anionic particles forming the anionic dispersion of polymer (s) on the cationic charges of the flocculation agent, then
- aggregation of particles by coalescence due to the decrease of the anionic surface charges of the particles and the appearance of van der Waals bonds during the common steps of the paper process, namely dewatering, pressing and drying.
En vue de bien distinguer ce phénomène de floculation de la réticulation, qui intervient notamment lors d'un procédé de couchage, la Demanderesse a jugé utile de décrire ci-après le phénomène de réticulation.In order to clearly distinguish this phenomenon of flocculation from the crosslinking, which occurs especially during a coating process, the Applicant has found it useful to describe hereinafter the crosslinking phenomenon.
Contrairement au phénomène de floculation, le phénomène de réticulation se traduit chimiquement par la formation de liaisons covalentes entre deux entités : un composé chimique et un réticulant.Unlike the phenomenon of flocculation, the crosslinking phenomenon is chemically translated by the formation of covalent bonds between two entities: a chemical compound and a crosslinking agent.
Le réticulant, composé de groupements réactifs, forme des liaisons atomiques fortes (de l'ordre de 500 kJ/mol) avec certains groupements du composé chimique selon un processus de réaction chimique se déroulant sous des conditions énergétiques spécifiques (température, pression, radiation...). Les liaisons formées sont réparties de façon homogène. Elles sont permanentes et résistantes ce qui confère au mélange composé/réticulant de la rigidité et une stabilité dimensionnelle homogène, propriétés qui sont à l'opposé de celles recherchées pour une feuille de sécurité visée par l'invention qui doit être souple et résistante.The crosslinking agent, composed of reactive groups, forms strong atomic bonds (of the order of 500 kJ / mol) with certain groups of the chemical compound according to a chemical reaction process taking place under specific energy conditions (temperature, pressure, radiation. ..). The bonds formed are homogeneously distributed. They are permanent and resistant, which gives the compound / crosslinking mixture rigidity and homogeneous dimensional stability, properties which are the opposite of those sought for a security sheet contemplated by the invention which must be flexible and resistant.
La floculation présente l'avantage d'apporter de la rigidité sur la totalité du substrat cellulosique, en particulier grâce à la bonne répartition des agrégats de polymère(s) dans le substrat. Il est d'ailleurs à noter que de grandes quantités de polymère(s) ne sont pas nécessaires pour atteindre cette amélioration de la propriété de rigidité.Flocculation has the advantage of providing stiffness over the entire cellulosic substrate, in particular by virtue of the good distribution of the aggregates of polymer (s) in the substrate. It should also be noted that large amounts of polymer (s) are not necessary to achieve this improvement of the rigidity property.
A titre comparatif, le surfaçage par un même polymère, présente quant à lui l'inconvénient de conduire à une structure en couche cassante, qui résiste mal à la circulation, notamment au froissement.For comparison, the surfacing by the same polymer, has the disadvantage of leading to a brittle layer structure, which resists poorly to circulation, including wrinkling.
De plus, un tel traitement en masse permet d'envisager un traitement additionnel en surface, notamment un traitement protecteur, par exemple de type anti-salissure et/ou traitement par impression, sur la feuille de sécurité obtenue selon le procédé de l'invention. Par contraste, les traitements de surface ne permettent pas aussi facilement de procéder à un traitement additionnel en surface pour des raisons évidentes d'affinités des surfaces entre elles et de modification des propriétés apportées par le premier traitement de surface, qui doivent être préalablement prises en compte.In addition, such a mass treatment makes it possible to envisage an additional surface treatment, in particular a protective treatment, for example of the antifouling type and / or printing treatment, on the security sheet obtained according to the process of the invention. . By contrast, the surface treatments do not make it so easy to carry out additional surface treatment for obvious reasons of surface affinities between them and modification of the properties provided by the first surface treatment, which must first be taken into account. account.
Selon un autre de ses aspects, la présente invention décrit un procédé de fabrication consistant à former ladite feuille par voie humide à partir d'une suspension aqueuse comprenant au moins :
- des fibres,
- une dispersion anionique d'au moins un polymère présentant une température de transition vitreuse supérieure à 0 °C, de préférence supérieure à 5 °C, et
- une quantité efficace d'un agent de floculation cationique, dit agent principal, puis à égoutter, presser et sécher ladite feuille.
- fibers,
- an anionic dispersion of at least one polymer having a glass transition temperature greater than 0 ° C, preferably greater than 5 ° C, and
- an effective amount of a cationic flocculating agent, said main agent, and then to drain, squeeze and dry said sheet.
Ainsi, la présente invention concerne un procédé de fabrication consistant à former ladite feuille par voie humide à partir d'une suspension aqueuse comprenant au moins :
- des fibres,
- une dispersion anionique d'au moins un polymère présentant une température de transition vitreuse supérieure à 23 °C, et
- une quantité efficace d'un agent de floculation cationique, dit agent principal, puis à égoutter, presser et sécher ladite feuille.
- fibers,
- an anionic dispersion of at least one polymer having a glass transition temperature above 23 ° C, and
- an effective amount of a cationic flocculating agent, said main agent, and then to drain, squeeze and dry said sheet.
Selon encore un autre de ses aspects, la présente invention concerne une feuille de sécurité résistante au froissement et au pli marqué comprenant des fibres, obtenue par traitement en masse desdites fibres par un système de floculation, ledit système de floculation comprenant une dispersion anionique d'au moins un polymère présentant une température de transition vitreuse supérieure à 23 °C et un agent de floculation cationique.According to yet another of its aspects, the present invention relates to a wrinkle and crease-resistant security sheet comprising fibers, obtained by mass treatment of said fibers by a flocculation system, said flocculation system comprising an anionic dispersion of at least one polymer having a glass transition temperature above 23 ° C and a cationic flocculating agent.
Selon encore un autre de ses aspects, l'invention concerne une feuille de sécurité résistante au froissement comprenant des fibres, lesdites fibres comprenant en masse des agrégats de particules formés suite à la floculation d'une dispersion anionique d'au moins un polymère présentant une température de transition vitreuse supérieure à 23 °C, et d'un agent de floculation cationique.According to yet another of its aspects, the invention relates to a wrinkle-resistant security sheet comprising fibers, said fibers comprising en masse aggregates of particles formed following the flocculation of an anionic dispersion of at least one polymer having a glass transition temperature above 23 ° C, and a cationic flocculation agent.
Comme précisé ci-dessus, la feuille de sécurité selon l'invention comprend des fibres.As stated above, the security sheet according to the invention comprises fibers.
Dans la présente demande, l'expression « poids total des fibres » doit être comprise comme signifiant « poids total des fibres en sec », sauf indication contraire.In the present application, the expression " total fiber weight " should be understood as meaning " total dry fiber weight " unless otherwise indicated.
Selon un mode de réalisation de l'invention, les fibres entrant dans la composition de la feuille comprennent des fibres naturelles.According to one embodiment of the invention, the fibers used in the composition of the sheet comprise natural fibers.
Parmi les fibres naturelles, on peut citer les fibres cellulosiques, telles que les fibres de bois, par exemple d'eucalyptus, de résineux ou leur mélange, de coton, de bambou, de viscose, de paille, d'abaca, d'asperto, de chanvre, de jute, de lin, de sisal ou leurs mélanges.Among the natural fibers, mention may be made of cellulosic fibers, such as wood fibers, for example of eucalyptus, of softwood or their mixture, of cotton, bamboo, viscose, straw, abaca, asperto , hemp, jute, flax, sisal or their mixtures.
Les fibres peuvent être blanchies, semi-blanchies ou non blanchies.The fibers may be bleached, semi-bleached or unbleached.
De préférence, les fibres entrant dans la composition de la feuille comprennent des fibres cellulosiques, en particulier des fibres de coton.Preferably, the fibers in the composition of the sheet comprise cellulosic fibers, particularly cotton fibers.
Selon une variante, les fibres comprennent des fibres préalablement anionisées par des polymères aptes à augmenter la charge négative de surface des fibres tels que des polymères anioniques solubles dans l'eau et présentant une affinité avec la cellulose. Selon cette variante, de tels polymères anioniques peuvent être choisis parmi des dérivés cellulosiques comme la carboxyméthylcellulose (CMC).According to one variant, the fibers comprise fibers previously anionized with polymers capable of increasing the negative surface charge of the fibers such as anionic polymers which are soluble in water and have an affinity with cellulose. According to this variant, such anionic polymers may be chosen from cellulose derivatives such as carboxymethylcellulose (CMC).
En particulier, lesdites fibres cellulosiques sont présentes en une proportion supérieure à 60 % en poids sec par rapport au poids sec total en fibres et polymère(s), en particulier en une proportion supérieure à 70 %.In particular, said cellulosic fibers are present in a proportion greater than 60% by dry weight relative to the total dry weight of fibers and polymer (s), in particular in a proportion of greater than 70%.
Selon un mode de réalisation particulier de l'invention, lesdites fibres cellulosiques représentent au moins 70 % en poids sec de la quantité totale de fibres.According to a particular embodiment of the invention, said cellulosic fibers represent at least 70% by dry weight of the total amount of fibers.
En particulier, lesdites fibres cellulosiques sont des fibres de coton et représentent au moins 70 % en poids sec de la quantité totale de fibres.In particular, said cellulosic fibers are cotton fibers and represent at least 70% by dry weight of the total amount of fibers.
De préférence, selon un autre mode de réalisation de l'invention, les fibres entrant dans la composition de la feuille peuvent comprendre des fibres synthétiques.Preferably, according to another embodiment of the invention, the fibers used in the composition of the sheet may comprise synthetic fibers.
Ce mode de réalisation est particulièrement avantageux, car il permet d'améliorer encore les propriétés de résistance à la déchirure de la feuille selon l'invention.This embodiment is particularly advantageous because it makes it possible to further improve the tear-resistance properties of the sheet according to the invention.
En effet, au cours de ses recherches, la Demanderesse a trouvé que, de façon surprenante, l'utilisation de fibres synthétiques, généralement utilisées afin de renforcer le papier, présentait un effet synergique avec l'utilisation selon l'invention d'un polymère présentant une Tg spécifique. En effet, la Demanderesse a mesuré que les feuilles contenant des fibres synthétiques, tout en étant rigide et en conservant une résistance au froissement et à la salissure élevée, présentaient de plus une résistance à la déchirure particulièrement élevée. La résistance à la déchirure des feuilles selon ce mode de réalisation particulier de l'invention est supérieure à la résistance à la déchirure des feuilles selon l'invention dépourvues de fibres synthétiques ainsi qu'à la résistance à la déchirure de feuilles comprenant des fibres synthétiques mais pas d'agrégats de polymère(s).Indeed, in the course of its research, the Applicant has found that, surprisingly, the use of synthetic fibers, generally used to strengthen the paper, has a synergistic effect with the use according to the invention of a polymer presenting a specific Tg. Indeed, the Applicant has measured that the sheets containing synthetic fibers, while being rigid and retaining resistance to creasing and high soiling, also had a particularly high tear resistance. The tear resistance of the sheets according to this particular embodiment of the invention is greater than the tear resistance of the sheets according to the invention without synthetic fibers and the tear resistance of sheets comprising synthetic fibers. but no aggregates of polymer (s).
Selon un mode de réalisation préféré de l'invention, les fibres synthétiques sont en une proportion comprise entre 5 % et 30 % en poids sec par rapport au poids sec total en fibres et polymère(s), et mieux comprise entre 10 % et 15 %.According to a preferred embodiment of the invention, the synthetic fibers are in a proportion of between 5% and 30% by dry weight relative to the total dry weight of fibers and polymer (s), and better still between 10% and 15% by weight. %.
Selon un mode de réalisation particulier de l'invention, la feuille comprend des fibres de coton en une proportion d'au moins 70 % en poids sec par rapport au poids total des fibres et des fibres synthétiques en une proportion comprise entre 10 % et 30 % en poids sec par rapport au poids total des fibres, la somme totale des fibres de coton et des fibres synthétiques étant égale à 100.According to a particular embodiment of the invention, 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 of between 10% and 30% by weight. % by dry weight relative to the total weight of the fibers, the sum total of the cotton fibers and synthetic fibers being equal to 100.
Selon un mode de réalisation préféré de l'invention, lesdites fibres synthétiques sont choisies parmi les fibres de polyester, de polyamide, de rayonne et de viscose, de préférence ce sont des fibres de polyamide et/ou des fibres de polyester. Il peut s'agir, par exemple de fibres de polyamide 6-6 ou de fibres de polyester commercialisées par la société Kuraray sous le nom commercial EP133®.According to a preferred embodiment of the invention, said synthetic fibers are chosen from polyester, polyamide, rayon and viscose fibers, preferably they are polyamide fibers and / or polyester fibers. It may be, for example, polyamide 6-6 fibers or polyester fibers marketed by Kuraray under the trade name EP133®.
Une feuille de sécurité selon l'invention comprend en outre au moins des agrégats de polymère(s) présentant une température de transition vitreuse (Tg) supérieure à 23 °C.A security sheet according to the invention further comprises at least polymer aggregates (s) having a glass transition temperature (Tg) greater than 23 ° C.
Selon un mode de réalisation préféré de l'invention, le ou les polymère(s) utilisé(s) dans le cadre de la présente invention présentent une température de transition vitreuse supérieure à 35 °C, et mieux supérieure à 40 °C.According to a preferred embodiment of the invention, the polymer (s) used in the context of the present invention have a glass transition temperature greater than 35 ° C, and more preferably greater than 40 ° C.
Ces polymères sont qualifiés de « rigides » dans le cadre de la présente invention.These polymers are described as "rigid" in the context of the present invention.
On entend par « température de transition vitreuse », la température au-dessous de laquelle le polymère est rigide. Lorsque la température augmente, le polymère passe par un état de transition qui permet aux chaînes macromoléculaires libres des domaines amorphes de glisser les unes par rapport aux autres et le polymère se ramollit.The term " glass transition temperature " means the temperature below which the polymer is rigid. As the temperature increases, the polymer passes through a transition state that allows free macromolecular chains amorphous domains to slide relative to each other and the polymer softens.
La mesure de la température de transition vitreuse peut être effectuée par calorimétrie différentielle à balayage (« Differential Scanning Calorimetry » en anglais, ou « DSC »).The measurement of the glass transition temperature can be carried out by differential scanning calorimetry (" Differential Scanning Calorimetry " or " DSC ").
Selon un mode de réalisation particulier de l'invention, le ou les polymère(s) peuvent être présents en une proportion comprise entre 1 % et 40 % en poids sec, en particulier entre 2 % et 25 % en poids sec, et de préférence entre 2 % et 15 % en poids sec, par rapport au poids sec total en fibres et polymère(s).According to one particular embodiment of the invention, the polymer (s) may be present in a proportion of between 1% and 40% by dry weight, in in particular between 2% and 25% by dry weight, and preferably between 2% and 15% by dry weight, relative to the total dry weight of fibers and polymer (s).
En particulier, le ou les polymère(s) présentant une température de transition vitreuse supérieure à 23 °C sont choisis parmi les polyacryliques, les polyacrylates, les polyacrylamides, les polystyrènes, les polyuréthanes, les polyvinyliques, les polyéthylènes, et leurs mélanges.In particular, the polymer (s) having a glass transition temperature greater than 23 ° C are chosen from polyacrylics, polyacrylates, polyacrylamides, polystyrenes, polyurethanes, polyvinyls, polyethylenes, and mixtures thereof.
Selon un mode de réalisation préféré, le ou les polymère(s) présentant une température de transition vitreuse supérieure à 23 °C sont choisis parmi les polymères acryliques (ou polyacryliques), c'est-à-dire les homopolymères ou les copolymères comprenant au moins un monomère acrylique, à savoir les homopolymères acryliques ou les copolymères acryliques.According to a preferred embodiment, the polymer (s) having a glass transition temperature greater than 23 ° C. are chosen from acrylic (or polyacrylic) polymers, that is to say homopolymers or copolymers comprising at least less an acrylic monomer, namely acrylic homopolymers or acrylic copolymers.
A titre de copolymères acryliques, peuvent notamment être cités :
- les vinyl-acryliques, par exemple le produit Orgal VA-HP commercialisé par la société Organik Kimya (Tg = +41 °C),
- les styrène-acryliques, par exemple le produit Acronal DS2416 commercialisé par la société BASF (Tg = +38 °C), et
- les polyuréthane-acryliques, par exemple le produit Joncryl U6336 commercialisé par la société BASF (Tg = +40 °C).
- vinyl acrylics, for example the Orgal VA-HP product marketed by the company Organik Kimya (Tg = +41 ° C.),
- styrene-acrylics, for example the product Acronal DS2416 sold by the company BASF (Tg = + 38 ° C.), and
- polyurethane-acrylics, for example the Joncryl U6336 product marketed by BASF (Tg = + 40 ° C.).
De préférence, le ou les polymère(s) présentant une température de transition vitreuse supérieure à 23 °C sont choisis parmi les homopolymères acryliques.Preferably, the polymer (s) having a glass transition temperature greater than 23 ° C. are chosen from acrylic homopolymers.
De tels polymères sont disponibles en dispersion anionique, par exemple :
- auprès de la société Tanatex Chemicals, sous la dénomination Edolan AH (Tg = +36 °C),
- auprès de la société Organik Kimya, sous la dénomination Orgal NA 302 (Tg = +26 °C),
- auprès de la société Icap Sira, sous la dénomination Acrilem 7105 (Tg = +50 °C), et
- auprès de la société BASF, sous la dénomination Acronal DS 2416 (Tg = +38 °C).
- from Tanatex Chemicals, under the name Edolan AH (Tg = + 36 ° C.),
- from the company Organik Kimya, under the name Orgal NA 302 (Tg = + 26 ° C),
- from Icap Sira under the name Acrilem 7105 (Tg = + 50 ° C), and
- from BASF under the name Acronal DS 2416 (Tg = + 38 ° C.).
Le ou les polymère(s) peuvent être non réticulables, réticulables à l'aide d'un réticulant externe ou encore auto-réticulables.The polymer (s) may be non-crosslinkable, crosslinkable with the aid of an external crosslinking agent or else self-crosslinkable.
Selon un mode de réalisation particulier, le ou les polymère(s) sont auto-réticulables. Ainsi, comme cela ressort ci-après en lien avec la description du procédé, l'étape de séchage peut conduire à une réticulation des polymères, dans une étape ultérieure à la mise en oeuvre du procédé selon l'invention.According to a particular embodiment, the polymer (s) are self-crosslinkable. Thus, as is apparent hereinafter in connection with the description of the process, the drying step may lead to crosslinking of the polymers, in a step subsequent to the implementation of the process according to the invention.
Selon l'invention, la dispersion anionique du ou des polymère(s) est monophasique ou multiphasique. Une dispersion multiphasique correspond notamment à des particules coeur-écorce (« core-shell ») comprenant deux types de polymères dont au moins le plus abondant (le coeur) est un polymère rigide considéré selon l'invention. Le ou les autre(s) polymère(s) peut (peuvent) avoir une autre fonctionnalité que l'apport de rigidité, il(s) peut (peuvent) notamment être utilisé(s) en tant que réticulant et/ou liant.According to the invention, the anionic dispersion of the polymer (s) is monophasic or multiphasic. A multiphasic dispersion corresponds in particular to core-shell particles comprising two types of polymers of which at least the most abundant (the core) is a rigid polymer considered according to the invention. The other polymer (s) may have a function other than the addition of rigidity, it (s) may (in particular) be used as crosslinking agent and / or binder.
Une feuille de sécurité selon l'invention comprend en outre au moins une quantité efficace d'un agent de floculation cationique, dit agent principal.A security sheet according to the invention further comprises at least an effective amount of a cationic flocculation agent, said main agent.
Au sens de la présente invention, on entend par « quantité efficace », la quantité en agent de floculation cationique avantageusement nécessaire pour permettre à la dispersion anionique du polymère de floculer. Cette quantité en agent de floculation cationique est à considérer au regard du ou des polymère(s) associé(s) et peut par conséquent varier d'un polymère à un autre. A partir de ses connaissances générales, l'homme du métier est apte à ajuster la quantité en agent de floculation cationique nécessaire pour permettre la floculation du ou des polymère(s).For the purposes of the present invention, the term " effective amount " means the amount of cationic flocculating agent advantageously required to allow the anionic dispersion of the polymer to flocculate. This amount of cationic flocculating agent is to be considered with regard to the associated polymer (s) and may therefore vary from one polymer to another. From his general knowledge, the skilled person is able to adjust the amount of cationic flocculating agent necessary to allow flocculation of the polymer (s).
De préférence, l'agent de floculation cationique, dit agent principal, est présent en une quantité comprise entre 0,5 % et 5 % en poids sec, en particulier entre 1 % et 3 % en poids sec, par rapport au poids sec total en fibres et polymère(s).Preferably, the cationic flocculating agent, called the main agent, is present in an amount of between 0.5% and 5% by dry weight, in particular between 1% and 3% by dry weight, relative to the total dry weight. fiber and polymer (s).
L'agent de floculation cationique, dit agent principal, présent dans la feuille de sécurité selon l'invention est choisi parmi les polymères cationiques solubles dans l'eau, notamment parmi les polyacrylamides, les polyéthylèneimines, les polyvinylamines et leurs mélanges.The cationic flocculating agent, said main agent, present in the security sheet according to the invention is chosen from water-soluble cationic polymers, in particular from polyacrylamides, polyethyleneimines, polyvinylamines and their mixtures.
Selon un mode de réalisation préféré de l'invention, l'agent de floculation cationique, dit agent principal, est une résine cationique. En particulier, cette résine est une résine polyamide-amine-épichloridrine, dite résine PAAE.According to a preferred embodiment of the invention, the cationic flocculating agent, said main agent, is a cationic resin. In particular, this resin is a polyamide-amine-epichloridin resin, called PAAE resin.
Selon un autre mode de réalisation de l'invention, l'agent de floculation cationique, dit agent principal, est choisi parmi les polyacrylamides, les polyéthylèneimines, les polyvinylamines et leurs mélanges.According to another embodiment of the invention, the cationic flocculation agent, said main agent, is selected from polyacrylamides, polyethyleneimines, polyvinylamines and mixtures thereof.
Selon un mode particulier de réalisation de l'invention, la feuille de sécurité comprend, outre l'agent de floculation cationique, dit agent principal, décrit ci-dessus, un agent de floculation cationique annexe, dit agent secondaire.According to a particular embodiment of the invention, the security sheet comprises, in addition to the cationic flocculating agent, said main agent, described above, a secondary cationic flocculating agent, said secondary agent.
Un tel agent de floculation cationique secondaire est présent en une quantité comprise entre 0,1 % et 0,5 % en poids sec par rapport au poids sec total en fibres et polymère(s).Such a secondary cationic flocculating agent is present in an amount of between 0.1% and 0.5% by dry weight relative to the total dry weight of fibers and polymer (s).
De façon préférée, ledit agent de floculation cationique, dit agent secondaire, est choisi parmi les polyacrylamides, les polyéthylènimines, les polyvinylamines et leurs mélanges.Preferably, said cationic flocculation agent, said secondary agent, is selected from polyacrylamides, polyethylenimines, polyvinylamines and mixtures thereof.
Selon un mode de réalisation de l'invention, la feuille de sécurité comprend au moins un élément de sécurité.According to one embodiment of the invention, the security sheet comprises at least one security element.
En particulier, ledit élément de sécurité est choisi parmi les dispositifs optiquement variables (OVD), notamment les éléments à effet interférentiel, en particulier les éléments iridescents, les hologrammes, les cristaux liquides et les structures multicouches interférentielles. Ces éléments de sécurité peuvent être apposés sur des fils de sécurité, des foils, des patchs, des planchettes, des pigments ou fibres luminescents et/ou magnétiques et/ou métalliques, et leurs combinaisons. A titre d'autre élément de sécurité, on peut également citer les filigranes.In particular, said security element is chosen from optically variable devices (OVD), in particular interference-effect elements, in particular iridescent elements, holograms, liquid crystals and interferential multilayer structures. These security elements may be affixed to security threads, foils, patches, boards, pigments or luminescent fibers and / or magnetic and / or metal, and their combinations. As another element of security, one can also mention the watermarks.
De plus, la feuille selon l'invention peut comporter un dispositif RFID (dispositif d'identification radio fréquence).In addition, the sheet according to the invention may comprise an RFID device (radio frequency identification device).
Selon un autre mode de réalisation de l'invention, la feuille de sécurité comprend au moins une zone dépourvue de fibres au moins partiellement, zone également appelée « fenêtre ». According to another embodiment of the invention, the security sheet comprises at least one at least partially fiber-free zone, also known as a " window " zone .
Selon un autre mode de réalisation, la feuille de sécurité selon l'invention comprend un fil ou une bande de sécurité incorporé(e), notamment totalement ou partiellement, dans ladite feuille, et de préférence apparaissant dans au moins une fenêtre.According to another embodiment, the security sheet according to the invention comprises an embedded security thread or strip (e), in particular totally or partially, in said sheet, and preferably appearing in at least one window.
Selon un mode de réalisation de l'invention, la feuille de sécurité comprend des charges minérales en une quantité de 1 % à 10 % en poids sec par rapport au poids sec total de la composition de la feuille.According to one embodiment of the invention, the security sheet comprises mineral fillers in an amount of 1% to 10% by dry weight relative to the total dry weight of the composition of the sheet.
En particulier, lesdites charges minérales sont présentes dans une proportion comprise entre 1 % et 5 % en poids sec par rapport au poids sec total de la composition de la feuille.In particular, said mineral fillers are present in a proportion of between 1% and 5% by dry weight relative to the total dry weight of the composition of the sheet.
Ces charges sont choisies, par exemple, parmi le carbonate de calcium, le kaolin, le dioxyde de titane ou leurs mélanges.These fillers are chosen, for example, from calcium carbonate, kaolin, titanium dioxide or mixtures thereof.
La feuille de sécurité selon l'invention peut comprendre en outre des charges et adjuvants couramment utilisés dans le domaine papetier.The security sheet according to the invention may further comprise fillers and additives commonly used in the paper industry.
Il s'agit en particulier de charges synthétiques, d'agents de rétention et/ou d'agents de résistance à l'état humide.These are in particular synthetic fillers, retention agents and / or wet strength agents.
Selon le mode de réalisation particulier exposé ci-dessus relatif à l'utilisation d'une composition fibreuse présentant une charge négative surfacique peu importante, notamment dans le cas d'une composition fibreuse comprenant des fibres de coton, la feuille de sécurité selon l'invention comprend en outre de la carboxyméthylcellulose (CMC).According to the particular embodiment described above relating to the use of a fibrous composition having a small negative surface charge, particularly in the case of a fibrous composition comprising cotton fibers, the security sheet according to The invention further comprises carboxymethylcellulose (CMC).
Selon un autre mode de réalisation de l'invention, la feuille de sécurité peut comprendre en outre un traitement supplémentaire, notamment une imprégnation, une couche de surfaçage externe, une enduction ou un couchage. Il peut s'agir d'un traitement externe.According to another embodiment of the invention, the security sheet may further comprise an additional treatment, in particular an impregnation, an external surfacing layer, a coating or a coating. It can be an external treatment.
Ces couches de surfaçage, revêtues sur au moins une face d'une feuille, sont bien connues de l'homme du métier et permettent, par exemple pour une couche à base d'un alcool polyvinylique, d'améliorer les propriétés de résistance au double-pli et à la traction de la feuille.These surfacing layers, coated on at least one side of a sheet, are well known to those skilled in the art and make it possible, for example for a layer based on a polyvinyl alcohol, to improve the properties of double strength. -plugging and pulling the leaf.
Selon un autre exemple, la feuille de sécurité selon l'invention peut comprendre une couche de surfaçage destinée à renforcer ses propriétés de durabilité, telle que par exemple une couche dont la composition est décrite dans la demande
Ainsi, selon un mode de réalisation particulier, la feuille de sécurité selon l'invention comprend en outre une couche de surfaçage externe, de préférence à base d'un alcool polyvinylique, d'un polymère acrylique ou d'un liant élastomère transparent ou translucide, tel qu'un polyuréthane, et éventuellement une silice colloïdale.Thus, according to a particular embodiment, the security sheet according to the invention further comprises an outer surfacing layer, preferably based on a polyvinyl alcohol, an acrylic polymer or a transparent or translucent elastomeric binder. , such as a polyurethane, and optionally a colloidal silica.
L'invention concerne également un procédé de fabrication de la feuille de sécurité décrite ci-dessus.The invention also relates to a method of manufacturing the security sheet described above.
Selon l'invention, le procédé de fabrication consiste à former ladite feuille par voie humide à partir d'une suspension aqueuse comprenant au moins :
- des fibres,
- une dispersion anionique d'au moins un polymère présentant une température de transition vitreuse supérieure à 23 °C, et
- une quantité efficace d'un agent de floculation cationique, dit agent principal, puis à égoutter, presser et sécher ladite feuille.
- fibers,
- an anionic dispersion of at least one polymer having a glass transition temperature above 23 ° C, and
- an effective amount of a cationic flocculating agent, said main agent, and then to drain, squeeze and dry said sheet.
Selon l'invention, lesdites fibres, ladite dispersion anionique d'au moins un polymère présentant une température de transition vitreuse supérieure à 23 °C et ledit agent de floculation cationique, sont avantageusement mélangés en masse.According to the invention, said fibers, said anionic dispersion of at least one polymer having a glass transition temperature greater than 23 ° C and said cationic flocculating agent, are advantageously mixed in bulk.
En particulier, lesdits agrégats de polymère(s) se forment par la mise au contact de la dispersion anionique de polymère(s) avec les fibres et l'agent de floculation.In particular, said polymer aggregates (s) are formed by contacting the anionic dispersion of polymer (s) with the fibers and the flocculation agent.
Autrement dit, la présente invention est relative à un procédé de fabrication d'une feuille de sécurité résistante au froissement et au pli marqué comprenant au moins les étapes :
- (i) de mise en contact d'une dispersion anionique d'au moins un polymère présentant une température de transition vitreuse supérieure à 23 °C, avec des fibres et une quantité efficace d'un agent de floculation cationique pour former des agrégats de polymère(s) répartis sur lesdites fibres, puis
- (ii) d'égouttage, de pressage et de séchage.
- (i) contacting an anionic dispersion of at least one polymer having a glass transition temperature above 23 ° C with fibers and an effective amount of a cationic flocculating agent to form polymer aggregates (s) distributed on said fibers, then
- (ii) dewatering, pressing and drying.
Selon un mode de réalisation de l'invention, ladite suspension aqueuse comprend en outre un agent de floculation cationique annexe, dit agent secondaire, en une quantité comprise entre 0,1 % et 0,5 % en poids sec par rapport au poids sec total en fibres et polymère(s).According to one embodiment of the invention, said aqueous suspension further comprises an auxiliary cationic flocculating agent, said secondary agent, in an amount of between 0.1% and 0.5% by dry weight relative to the total dry weight fiber and polymer (s).
Le procédé de l'invention permet, grâce à l'utilisation de polymère(s) possédant une Tg particulière et d'agent(s) de floculation, de faire floculer le ou les polymère(s) sur les fibres et d'obtenir une feuille de sécurité très rigide présentant des propriétés de résistance au froissement et à la salissure particulièrement élevées.The process of the invention makes it possible, by using polymer (s) having a specific Tg and flocculation agent (s), to flocculate the polymer (s) on the fibers and to obtain a very rigid safety sheet with particularly high resistance to creasing and soiling.
Selon l'invention, la dispersion anionique du ou des polymère(s) présentant une température de transition vitreuse supérieure à 23 °C et l'agent de floculation cationique, dit agent principal, sont mélangés en masse dans la suspension fibreuse avant l'égouttage.According to the invention, the anionic dispersion of the polymer (s) having a glass transition temperature greater than 23 ° C and the cationic flocculating agent, said main agent, are mixed in mass in the fibrous suspension before dewatering .
Ce procédé se distingue clairement d'un procédé de couchage.This process is clearly distinguishable from a coating process.
Ainsi, selon un mode de réalisation particulier de l'invention, ladite suspension aqueuse est obtenue à partir d'un mélange de fibres et dudit agent de floculation cationique, dit agent principal, auquel on ajoute ladite dispersion anionique de polymère(s) et éventuellement ledit agent de floculation cationique, dit agent secondaire, avant de procéder à la formation de ladite feuille.Thus, according to a particular embodiment of the invention, said aqueous suspension is obtained from a mixture of fibers and said cationic flocculation agent, said main agent, to which said anionic dispersion of polymer (s) and optionally said cationic flocculation agent, said secondary agent, before proceeding with the formation of said sheet.
Ce mode de réalisation présente l'avantage de mettre en contact le ou les polymère(s) et l'agent de floculation afin de faciliter la floculation.This embodiment has the advantage of bringing the polymer (s) and the flocculation agent into contact in order to facilitate flocculation.
Ce mode de réalisation présente également l'avantage de pouvoir être appliqué à des suspensions aqueuses de fibres « standard » utilisées pour la fabrication des feuilles de sécurité car elles comprennent des agents de résistance à l'état humide qui peuvent également être utilisés comme agents de floculation principaux dans le cadre de la présente invention.This embodiment also has the advantage that it can be applied to aqueous suspensions of " standard " fibers used for the manufacture of safety sheets because they include wet strength agents which can also be used as main flocculation in the context of the present invention.
Selon un cas particulier du procédé, on ajoute ladite dispersion anionique de polymère(s) avant ledit agent de floculation dit agent secondaire.According to a particular case of the process, adding said anionic dispersion of polymer (s) before said flocculating agent said secondary agent.
Selon un mode de réalisation de l'invention, une réticulation peut avoir lieu après la floculation. Ainsi, les polymères, une fois floculés, peuvent réticuler, sous l'effet de la haute température dédiée au séchage.According to one embodiment of the invention, crosslinking can take place after flocculation. Thus, the polymers, once flocculated, can crosslink under the effect of the high temperature dedicated to drying.
Selon un mode de réalisation de l'invention, le procédé de fabrication de la feuille de sécurité comprend une étape dans laquelle au moins une face de ladite feuille, après égouttage de ladite suspension est revêtue d'une couche de surfaçage.According to one embodiment of the invention, the method of manufacturing the security sheet comprises a step in which at least one face of said sheet, after dewatering of said suspension is coated with a surfacing layer.
Cette couche de surfaçage peut permettre, par exemple, d'améliorer les propriétés de résistance au pliage marqué et/ou à la traction ou bien encore les propriétés de durabilité de ladite feuille, comme décrit ci-dessus.This surfacing layer may allow, for example, to improve the marked bending and / or tensile strength properties or even the durability properties of said sheet, as described above.
L'invention concerne également un document de sécurité comprenant la feuille de sécurité objet de l'invention, ou telle qu'obtenue par le procédé objet de l'invention, décrit ci-dessus.The invention also relates to a security document comprising the security sheet object of the invention, or as obtained by the method of the invention, described above.
En particulier, l'invention concerne un moyen de paiement, tel qu'un billet de banque, une carte de paiement, un chèque ou un ticket restaurant, un document d'identité, tel qu'une carte d'identité, un visa, un passeport ou un permis de conduire, une carte, notamment d'accès, un ticket de loterie, un titre de transport ou encore un ticket d'entrée à des manifestations culturelles ou sportives, une carte de fidélité, une carte de prestation, une carte d'abonnement, une carte à jouer ou à collectionner, un bon d'achat ou un voucher.In particular, the invention relates to a means of payment, such as a bank note, a payment card, a check or a restaurant ticket, an identity document, such as an identity card, a visa, a passport or a driving license, a card, including access, a lottery ticket, a ticket or a ticket to cultural or sports events, a loyalty card, a service card, a ticket a membership card, a playing or collectible card, a voucher or a voucher.
Il s'agit de préférence d'un billet de banque. Une des spécificités des billets de banque est en effet d'être soumis à des froissements et des plis marqués, et de devoir conserver sa rigidité ainsi qu'une bonne résistance aux froissements et aux plis marqués malgré les effets de la circulation afin de minimiser les rejets dans les automates et machines automatiques de tri. Un billet de banque présente généralement une épaisseur comprise entre 70 µm et 170 µm, par exemple 100 µm.This is preferably a bank note. One of the specificities of banknotes is indeed to be subjected to wrinkles and marked folds, and to have to maintain its rigidity and good resistance to wrinkles and creases marked despite the effects of traffic to minimize rejects in automatic machines and automatic sorting machines. A banknote generally has a thickness of between 70 μm and 170 μm, for example 100 μm.
Les mesures de grammage peuvent être effectuées selon la norme ISO 536.The grammage measurements can be performed according to ISO 536.
Les mesures d'épaisseur peuvent être effectuées selon la norme ISO 534.Thickness measurements can be made according to ISO 534.
Afin d'évaluer la résistance à la salissure de la feuille de sécurité, on peut évaluer des indices de salissures IS.In order to evaluate the resistance to soiling of the security sheet, it is possible to evaluate IS dirt indices.
Trois compositions sont préparées, pour effectuer les mesures.Three compositions are prepared for making the measurements.
La première composition, dite composition de sueur artificielle A, est préparée à partir des proportions pondérales indiquées dans le tableau 1 ci-dessous :
La deuxième composition, dite composition colorée pulvérulente B, est préparée à partir des proportions pondérales indiquées dans le tableau 2 ci-dessous :
Les composés du tableau 2 sont mélangés en utilisant un mélangeur Turbula pendant 30 minutes, dans une bouteille en plastique avec six grosses billes en céramique de 20 mm de diamètre.The compounds of Table 2 are mixed using a Turbula mixer for 30 minutes in a plastic bottle with six large 20 mm diameter ceramic beads.
La troisième composition, dite composition grasse C, est préparée à partir des proportions pondérales indiquées dans le tableau 3 ci-dessous :
Le mélange des deux composés du tableau 3 est mis à homogénéiser jusqu'à ce que la lanoline fonde. 28 g d'eau sont ensuite ajoutées sous agitation, puis 16 g d'éther éthoxylé d'alcool béhénique (commercialisé par la société Nopco, sous la dénomination Eumulgin® BA 10). Le tout est mélangé en chauffant jusqu'à obtenir une préparation homogène.The mixture of the two compounds of Table 3 is homogenized until the lanolin melts. 28 g of water are then added with stirring, followed by 16 g of ethoxylated ether of behenic alcohol (sold by the company Nopco under the name Eumulgin® BA 10). The whole is mixed by heating until a homogeneous preparation.
Le mélange est ensuite laissé à refroidir à température ambiante, puis 24 g d'eau sont ensuite ajoutées en mélangeant pendant 15 minutes. 190 g d'eau sont ensuite encore ajoutées, en l'incorporant très lentement au début.The mixture is then allowed to cool to room temperature and then 24 g of water are then added by mixing for 15 minutes. 190 g of water are then added, incorporating it very slowly at the beginning.
Une émulsion à 42 % de lanoline est obtenue.An emulsion containing 42% lanolin is obtained.
Chaque échantillon est froissé au préalable 4 fois avec un appareil de froissement IGT.Each sample is crumpled beforehand 4 times with an IGT creasing device.
Les échantillons (75 mm x 140 mm) sont montés sur des cales en bois (60 mm x 35 mm x 35 mm), autour desquelles ils sont maintenus avec trois faces exposées.The samples (75 mm x 140 mm) are mounted on wooden blocks (60 mm x 35 mm x 35 mm), around which they are held with three exposed faces.
90 mL de composition A, 10 g de composition B, 20 g de composition C et 25 billes de céramiques de diamètre 20 mm maximum sont disposées dans un bocal en plastique de 2 L. Les billes de céramiques peuvent être des billes d'alumine, elles ne doivent pas peser moins de 300 g. Elles sont conditionnées avant usage en les plaçant dans le mélangeur Turbula avec une crème abrasive et un peu d'eau pendant 1 heure et 30 minutes.90 ml of composition A, 10 g of composition B, 20 g of composition C and 25 ceramic beads with a maximum diameter of 20 mm are placed in a plastic jar of 2 L. The ceramic beads may be alumina beads, they must not weigh less than 300 g. They are packaged before use by placing them in the Turbula mixer with an abrasive cream and a little water for 1 hour and 30 minutes.
Le mélange est agité puis les quatre cales en bois, sèches, sur lesquelles les échantillons ont été placés sont introduits. Le bocal est fermé puis agité à l'aide d'un mélangeur Turbula à 67 rpm pendant 20 minutes.The mixture is agitated then the four wooden blocks, dry, on which the samples were placed are introduced. The jar is closed and stirred with a Turbula mixer at 67 rpm for 20 minutes.
Les échantillons sont ensuite rincés à l'eau courante, puis séchés en utilisant deux buvards. Ils sont ensuite mis au four à 60 °C pendant 3 minutes.The samples are then rinsed with running water and dried using two blotters. They are then put in the oven at 60 ° C for 3 minutes.
Les échantillons sont ensuite calandrés un par un avec un passage par côté, à 15 bars de pression, à vitesse minimale.The samples are then calendered one by one with one passage per side, at 15 bar pressure, at minimum speed.
Les indices de salissure IS sont ensuite évalués, grâce à la formule :
- B1 est la blancheur mesurée sur les échantillons après le test,
- B0 est la blancheur avant le test,
- J1 est le degré de jaunissement après le test, et
- J0 est le degré de jaunissement avant le test.
- B 1 is the whiteness measured on the samples after the test,
- B 0 is the whiteness before the test,
- J 1 is the degree of yellowing after the test, and
- J 0 is the degree of yellowing before the test.
La blancheur est une valeur moyenne de trois mesures selon la norme NF ISO 2470-2 6167 et le degré de jaunissement est une valeur moyenne de trois mesures, bien connues de l'homme du métier (mesures effectuées avec l'appareil Datacolor Elrepho 3000 de la société Lorentzen & Wettre).The whiteness is an average value of three measurements according to the NF ISO 2470-2 6167 standard and the degree of yellowing is an average value of three measurements, which are well known to those skilled in the art (measurements carried out with the Datacolor Elrepho 3000 apparatus of the company Lorentzen & Wettre).
Afin d'évaluer la résistance à la flexion (en Newton), et notamment la rigidité, des mesures peuvent être effectuées selon la norme ISO 2493-1, notamment avec un rigidimètre Taber (Modèle 150-B) ou encore avec un rigidimètre Franck (Modèle 58565). L'indice de résistance à la flexion (N.m6/Kg3) est déterminé en prenant en compte le grammage du papier.In order to evaluate the flexural strength (in Newton), and in particular the rigidity, measurements can be made according to the ISO 2493-1 standard, in particular with a Taber stiffener (Model 150-B) or with a Franck rigidimeter ( Model 58565). The index of flexural strength (Nm 6 / Kg 3 ) is determined by taking into account the basis weight of the paper.
Selon cette méthode, les feuilles selon l'invention présentent avantageusement un gain de rigidité d'au moins 15 %, voire d'au moins 20 %, par rapport à la rigidité d'une feuille comprenant 100 % de fibres de coton.According to this method, the sheets according to the invention advantageously have a stiffness gain of at least 15%, or even at least 20%, with respect to the rigidity of a sheet comprising 100% cotton fibers.
Les mesures de résistance au double-pli peuvent être effectuées selon la norme ISO 5626.The double-fold resistance measurements can be carried out according to the ISO 5626 standard.
Les mesures de résistance à la déchirure peuvent être effectuées selon la norme ISO 1974. L'indice de déchirure est obtenu en divisant la résistance à la déchirure par le grammage.Tear resistance measurements can be made according to ISO 1974. The tear index is obtained by dividing the tear strength by the basis weight.
Afin d'évaluer la résistance à la traction, notamment la longueur de rupture, à l'état sec, on peut mesurer la longueur à laquelle les feuilles cassent sous l'effet de leur propre poids selon la norme ISO 1924-2.In order to evaluate the tensile strength, especially the breaking length, in the dry state, it is possible to measure the length at which the sheets break under the effect of their own weight according to the ISO 1924-2 standard.
Afin d'évaluer la résistance à la traction, notamment la longueur de rupture, à l'état humide, on peut mesurer la longueur à laquelle les feuilles cassent sous l'effet de leur propre poids selon la norme NF Q03-056.In order to evaluate the tensile strength, especially the breaking length, in the wet state, it is possible to measure the length at which the sheets break under the effect of their own weight according to standard NF Q03-056.
Afin d'évaluer la résistance au froissement de la feuille de sécurité, on peut effectuer des mesures de la porosité BENDTSEN avant et après froissement.In order to evaluate the crease resistance of the security sheet, BENDTSEN porosity measurements can be made before and after creasing.
En effet, l'opération de froissement provoque, du fait des plis formés, une altération plus ou moins prononcée de la surface du papier, conduisant à une augmentation de sa porosité et donc de sa fragilité. En comparant la valeur de la porosité du papier avant et après froissement on peut donc évaluer la résistance au froissement de ce dernier. Moins l'augmentation de la porosité entre la feuille initiale et la feuille froissée est marquée, moins le papier est résistant au froissement. Le but est donc d'obtenir des valeurs de porosité après froissement les plus basses possibles.Indeed, the wrinkling operation causes, because of the folds formed, more or less pronounced alteration of the surface of the paper, leading to an increase in its porosity and therefore its fragility. Comparing the value of the porosity of the paper before and after creasing can therefore be evaluated the crease resistance of the latter. The less the increase in porosity between the initial sheet and the crumpled sheet, the less the paper is wrinkle resistant. The goal is therefore to obtain values of porosity after crumpling the lowest possible.
Le test de froissement permet donc de déterminer la résistance au froissement des papiers tels que les papiers à billets de banque et les papiers d'emballage.The wrinkle test therefore makes it possible to determine the wrinkle resistance of papers such as bank note papers and wrapping papers.
L'appareil utilisé correspond à celui décrit par le National Bureau Of Standards (
L'appareil comprend :
- a) un dispositif pour rouler l'éprouvette de papier en un cylindre. Ce dispositif est constitué d'un manchon fendu à l'intérieur duquel est placée une fourche mobile à deux dents.
- b) un tube dont l'une des extrémités est pourvue d'un couvercle mobile.
- c) un guide cylindre glissant à l'intérieur du tube.
- d) un guide cylindrique permettant de maintenir à l'intérieur et en position verticale le piston dont la base inférieure repose à l'extrémité d'un levier. Le guide cylindrique est conçu de telle manière que le tube peut coulisser entre ce guide et le piston.
- e) un levier monté sur un pivot.
- f) un poids à l'extrémité du bras long du levier, opposée à celle du bras court qui supporte le piston.
- 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 with one end provided with a movable lid.
- c) a sliding cylinder guide inside the tube.
- d) a cylindrical guide for maintaining inside and in vertical position the piston whose lower base rests at the end of a lever. The cylindrical guide is designed such that the tube can slide between this guide and the piston.
- e) a lever mounted on a pivot.
- f) a weight at the end of the long arm of the lever, opposite to that of the short arm which supports the piston.
La force de froissement est réglée par la position du poids sur le bras du levier, de manière à ce que la pression sur le piston soit de 10 kg/cm2 ± 0,1 kg/cm2.The crumpling force is adjusted by the position of the weight on the arm of the lever, so that the pressure on the piston is 10 kg / cm 2 ± 0.1 kg / cm 2 .
Les différentes pièces cylindriques : guide, tube, piston doivent pouvoir coulisser librement et notamment glisser sous leur poids.The various cylindrical parts: guide, tube, piston must be able to slide freely and in particular slide under their weight.
Tube et piston étant en place dans le guide, le piston doit tomber ou se lever selon que l'on soulève ou que l'on rabaisse le poids à l'extrémité du levier.Tube and piston being in place in the guide, the piston must fall or rise as one raises or lowers the weight at the end of the lever.
L'échantillonnage et le conditionnement des éprouvettes se font selon les normes NFQ 03-009 et NFQ 03-010. Dans un but particulier, les éprouvettes peuvent être mesurées telles quelles. Etant donné que l'éprouvette est constamment manipulée, il est nécessaire, pour éviter des échanges d'humidité avec l'opérateur, que ce dernier porte des gants d'un matériau barrière à l'humidité, pendant la préparation des éprouvettes et l'exécution du test.Sampling and conditioning of the specimens are done in accordance with standards NFQ 03-009 and NFQ 03-010. For a particular purpose, the specimens can be measured as such. Since the specimen is constantly handled, it is necessary, in order to avoid moisture exchange with the operator, that the operator wears gloves of a moisture-barrier material during the preparation of the specimens and the run the test.
Des éprouvettes de 67 mm de côté sont découpées en utilisant un gabarit. Le sens marche est repéré sur chaque éprouvette.67 mm test pieces are cut using a template. The running direction is marked on each specimen.
L'entrefourche et les deux fentes du manchon étant alignées, introduire l'éprouvette selon le sens marche jusqu'à sa moitié, puis la rouler par rotation de la fourche.With the fork and the two slots of the sleeve aligned, introduce the test tube in the direction of travel up to its half, then roll it by rotation of the fork.
Le tube, couvercle fermé, est alors glissé en continuité du manchon et l'éprouvette roulée y est transférée par un mouvement aller-retour de la fourche.The tube, closed lid, is then slid in continuity with the sleeve and the rolled test piece is transferred there by a return movement of the fork.
Le tube, tenu par le couvercle avec une main, est alors placé en position verticale sur le piston. Le froissement est effectué en pressant sur le couvercle jusqu'à ce que l'extrémité du bras long du levier se soulève au-dessus de sa position de repos. Il est important que la pression exercée soit suffisante pour lever le poids, mais ni trop forte ni trop rapide pour que le levier vienne en butée. Un moyen de contrôler l'effort est d'utiliser les deux mains l'une sur l'autre pour appuyer sur le couvercle.The tube, held by the lid with one hand, is then placed in a vertical position on the piston. The crumpling is done by pressing on the cover until the end of the long arm of the lever is raised above its rest position. It is important that the pressure exerted is sufficient to lift the weight, but neither too strong nor too fast for the lever to come into abutment. One way to control the effort is to use both hands on each other to press the lid.
Le couvercle est ouvert et l'éprouvette est froissée en forme de petit accordéon, et sortie du tube. Elle est remise plane en effectuant de la main de prudents étirements : agir trop brutalement pourrait produire, sur le côté, des entailles qui conduiraient à la déchirure de l'éprouvette.The lid is open and the test piece is crumpled in the shape of a small accordion, and out of the tube. It is put flat by carefully straightening the hand: acting too abruptly could produce notches on the side that would lead to tearing of the specimen.
L'éprouvette redressée est présentée à nouveau pour roulage devant la fente du manchon mais tournée de 90° par rapport à la première introduction ; le cycle complet est répété.The straightened specimen is presented again for rolling in front of the slot of the sleeve but rotated 90 ° with respect to the first introduction; the complete cycle is repeated.
On effectue ainsi huit cycles, avec rotation à chaque fois de 90°, et en retournant l'éprouvette après la quatrième fois.This is done eight cycles, with rotation each time 90 °, and returning the specimen after the fourth time.
On peut en particulier attendre un certain temps entre chaque cycle, par exemple trente minutes, pour permettre au matériau auto-réparant de se restructurer. Cela permet de se rapprocher des conditions de circulation réelles que cherche à reproduire le test de résistance au froissement. En effet, lors de la circulation des supports d'information, les contraintes sont appliquées de façon répétée mais épisodiquement.In particular, it is possible to wait a certain time between each cycle, for example thirty minutes, to allow the self-repairing material to restructure itself. This allows to get closer to the actual traffic conditions that the wrinkle resistance test is trying to reproduce. Indeed, during the circulation of the information media, the constraints are applied repeatedly but episodically.
La perméabilité à l'air de chaque éprouvette est mesurée avant et après froissement à l'aide d'un porosimètre BENDTSEN selon la norme ISO 5636-3.The air permeability of each specimen is measured before and after wrinkling using a BENDTSEN porosimeter according to ISO 5636-3.
La mesure devant être faite dans les mêmes conditions avant et après froissement, il est nécessaire dans les deux cas d'enlever la butée de la tête du porosimètre si la course normale est insuffisante pour pouvoir glisser l'éprouvette froissée.The measurement to be made under the same conditions before and after wrinkling, it is necessary in both cases to remove the stopper of the head of the porosimeter if the normal stroke is insufficient to be able to slide the wrinkled specimen.
Après froissement, la porosité est mesurée comme suit : chaque éprouvette est redressée jusqu'à ce qu'elle soit raisonnablement plane. Ceci peut-être facilement réalisé en tenant entre le pouce et l'index, l'éprouvette par deux côtés opposés puis en l'étirant en trois ou quatre endroits. Cette opération est répétée par les deux autres côtés ; faire cette opération en tout quatre fois est généralement suffisant pour obtenir une éprouvette suffisamment plane.After wrinkling, the porosity is measured as follows: each specimen is straightened until it is reasonably flat. This can easily be done by holding between thumb and forefinger, the test piece by two opposite sides and then stretching it in three or four places. This operation is repeated by the other two sides; to do this operation in all four times is usually sufficient to obtain a sufficiently flat specimen.
Afin de former sur l'éprouvette une surface circulaire dont la planéité soit telle que les fuites de surface soient négligeables face à la mesure de porosité, chaque éprouvette est introduite entre les mâchoires du dispositif de serrage d'un éclatomètre et l'on applique durant deux secondes une pression suffisante pour marquer le papier. La porosité est mesurée en s'assurant que la tête du porosimètre BENDTSEN est centrée sur la surface pressée à l'éclatomètre.In order to form on the test specimen a circular surface whose flatness is such that surface leakage is negligible with respect to the porosity measurement, each specimen is introduced between the jaws of the clamping device of a brightness meter and is applied during two seconds enough pressure to mark the paper. Porosity is measured by ensuring that the BENDTSEN porosimeter head is centered on the surface squeezed to the brightnessometer.
Le nombre d'éprouvettes à tester est fonction de l'échantillonnage étudié. La reproductibilité du test est telle qu'une éprouvette par feuille-échantillon est suffisante.The number of test pieces to be tested depends on the sample studied. The reproducibility of the test is such that a sample per sample sheet is sufficient.
Selon cette méthode, la porosité des feuilles selon l'invention après froissement peut varier de 1 à 20 ml/min, en particulier de 1 à 12 ml/min.According to this method, the porosity of the sheets according to the invention after creasing can vary from 1 to 20 ml / min, in particular from 1 to 12 ml / min.
Dans toute la description, y compris les revendications, l'expression « comportant un » doit être comprise comme étant synonyme de « comportant au moins un », sauf si le contraire est spécifié.Throughout the description, including the claims, the phrase " having one " should be understood as being synonymous with " having at least one ", unless the opposite is specified.
Les expressions « compris entre ... et ... », « allant de ... à ... » et « variant de ... à ... », doivent se comprendre bornes incluses, sauf si le contraire est spécifié.Expressions " between ... and ...", " ranging from ... to ..." and " varying from ... to ...", must be understood inclusive, unless otherwise specified .
Dans le texte, les expressions « supérieur(e) à ... » et « inférieur(e) à ... » entendent signifier que les bornes ne sont pas incluses, sauf mention contraire.In the text, the expressions " greater than ..." and " less than ..." mean that the terminals are not included, unless otherwise indicated.
L'invention est illustrée plus en détail par les exemples présentés ci-après, à titre illustratif et non limitatif du domaine de l'invention.The invention is illustrated in more detail by the examples presented below, by way of illustration and without being limiting to the scope of the invention.
Les feuilles A à F, et 1 à 3 testées ci-après sont préparées selon le procédé papetier courant, c'est-à-dire notamment par égouttage, pressage puis séchage de suspensions aqueuses dont les compositions en poids sec sont données dans les tableaux 1 à 3 ci-dessous.The sheets A to F, and 1 to 3, tested below, are prepared according to the standard paper-making process, that is to say, in particular by draining, pressing and then drying aqueous suspensions whose compositions in dry weight are given in the tables. 1 to 3 below.
La quantité de résine polyamide-amine-épichloridrine (résine PAAE), est fixée à 2,5 % en poids sec par rapport au poids sec total en fibres et polymère(s).The amount of polyamide-amine-epichloridrine resin (PAAE resin) is set at 2.5% by dry weight relative to the total dry weight of fibers and polymer (s).
Aucune étape de floculation n'est mise en oeuvre dans les exemples comparatifs A, D, E et F. La résine PAAE joue ainsi un rôle d'agent de résistance à l'état humide dans les exemples comparatifs A, D, E et F.No flocculation step is carried out in comparative examples A, D, E and F. The PAAE resin thus plays a role of wet strength agent in Comparative Examples A, D, E and F .
Une étape de floculation est mise en oeuvre dans les exemples B, C et 1 à 3. Ainsi, dans les exemples B, C et 1 à 3, la résine PAAE a un rôle d'agent de floculation cationique et également de résistance à l'état humide.A flocculation step is carried out in Examples B, C and 1 to 3. Thus, in Examples B, C and 1 to 3, the PAAE resin has a role of cationic flocculation agent and also resistance to corrosion. wet state.
Trois types de fibres cellulosiques ont été mis en oeuvre. Il s'agit de fibres de coton de différentes provenances et/ou à différents degrés de raffinage.Three types of cellulosic fibers have been used. These are cotton fibers of different origins and / or different degrees of refining.
Lesdites feuilles subissent ensuite, selon une pratique courante dans le domaine papetier, un surfaçage externe, comme décrit précédemment, déposé à raison de 5 g/m2/face. Ledit surfaçage est réalisé par imprégnation.Said sheets then undergo, according to a common practice in the paper industry, an external surfacing, as described above, deposited at a rate of 5 g / m 2 / face. Said surfacing is carried out by impregnation.
Ainsi, les feuilles A à C sont imprégnées d'une couche à base d'un alcool polyvinylique (PVA). Les feuilles D et E et 1 à 3 sont imprégnées d'une couche à base d'un alcool polyvinylique (PVA). Quant à la feuille C, elle est imprégnée d'une couche à base d'un polymère acrylique possédant une Tg de 38 °C.Thus, the sheets A to C are impregnated with a layer based on a polyvinyl alcohol (PVA). Sheets D and E and 1 to 3 are impregnated with a layer based on a polyvinyl alcohol (PVA). As for the sheet C, it is impregnated with a layer based on an acrylic polymer having a Tg of 38 ° C.
Les feuilles E, F et 3 possèdent, avant surfaçage, un grammage de 85 g/m2.The sheets E, F and 3 have, before surfacing, a basis weight of 85 g / m 2 .
Les feuilles A à F, et 1 à 3 ainsi obtenues, correspondant respectivement aux exemples comparatifs A à F et aux exemples 1 à 3 selon l'invention, ont été soumises aux tests décrits précédemment.The sheets A to F, and 1 to 3 thus obtained, respectively corresponding to Comparative Examples A to F and Examples 1 to 3 according to the invention, were subjected to the tests described above.
L'exemple comparatif A est relatif à un papier standard, n'ayant pas subi de traitement.Comparative Example A relates to standard, untreated paper.
L'exemple comparatif B est relatif à une feuille obtenue selon le procédé tel que décrit dans le document
L'exemple comparatif C est relatif à une feuille obtenue selon le procédé tel que décrit dans le document
Comme le montre le tableau 1 des résultats, par rapport à une feuille comprenant 100 % de fibres cellulosiques (exemple comparatif A), les feuilles des exemples B et C, reposant également sur des techniques de floculation mais comprenant des polymères non conformes à l'invention, présentent une diminution de leur rigidité.
Comme le montre le tableau 2 des résultats, les feuilles des exemples 1 et 2 selon l'invention présentent un net gain de rigidité par rapport à la feuille de l'exemple comparatif D.As shown in Table 2 of the results, the sheets of Examples 1 and 2 according to the invention have a clear rigidity gain compared to the sheet of Comparative Example D.
En outre, les feuilles des exemples 1 et 2 présentent une amélioration de l'indice de salissure de 4 à 5 points.In addition, the sheets of Examples 1 and 2 show an improvement in the soiling index of 4 to 5 points.
Ainsi, par rapport à une composition fibreuse donnée, les essais ont permis de démontrer l'amélioration de la rigidité et de la résistance à la salisse par la mise en oeuvre de polymère conformément à l'invention.
Comme le montre le tableau 3 des résultats, la feuille de l'exemple 3 selon l'invention présente une rigidité bien supérieure à celle de l'exemple comparatif E, tout en présentant des valeurs de résistance à la traction, à la déchirure et au double-pli comparables à celles de l'exemple comparatif E, ce qui montre que l'utilisation des polymères selon l'invention ne dégrade pas les propriétés de résistance à la traction, à la déchirure et au double-pli.As shown in Table 3 of the results, the sheet of Example 3 according to the invention has a much higher rigidity than that of Comparative Example E, while exhibiting values of tensile strength, tear strength and double-fold comparable to those of Comparative Example E, which shows that the use of the polymers according to the invention does not degrade the properties of tensile strength, tear and double-fold.
Ainsi, par rapport à une composition fibreuse donnée, les essais ont permis de démontrer l'amélioration de la rigidité par la mise en oeuvre d'une dispersion de polymère conformément à l'invention.
La comparaison de l'exemple F avec l'exemple 3 permet de montrer que le surfaçage d'un polymère acrylique rigide n'améliore pas la rigidité du substrat, et ce malgré l'importante quantité de polymère apportée (6 g/m2 contre 1,5 g/m2 de PVA).Comparison of Example F with Example 3 makes it possible to show that the surfacing of a rigid acrylic polymer does not improve the rigidity of the substrate, despite the large amount of polymer supplied (6 g / m 2 against 1.5 g / m 2 of PVA).
Claims (14)
- Security sheet resistant to crumpling and hard creasing comprising at least:- fibres,- aggregates of polymer(s) having a glass transition temperature above 23°C, in a proportion of between 1% and 40% by dry weight, relative to the total dry weight of fibres and polymer(s), and- a cationic flocculating agent, in a proportion of between 0.5% and 5% by dry weight, relative to the total dry weight of fibres and polymer(s).
- Security sheet according to Claim 1, characterized in that the polymer (s) has (have) a glass transition temperature above 35°C, preferably above 40°C.
- Security sheet according to either of the preceding claims, characterized in that the proportion of polymer(s) is between 2% and 25% by dry weight, and preferably between 2% and 15% by dry weight, relative to the total dry weight of fibres and polymer(s).
- Security sheet according to any one of the preceding claims, characterized in that the polymer or polymers are chosen from acrylic polymers, polyacrylates, polyacrylamides, polystyrenes, polyurethanes, polyvinyls, polyethylenes, and mixtures thereof, preferably chosen from acrylic polymers, and more preferentially chosen from acrylic homopolymers.
- Security sheet according to any one of the preceding claims, characterized in that the proportion of cationic flocculating agent is between 1% and 3% by dry weight, relative to the total dry weight of fibres and polymer(s) .
- Security sheet according to any one of the preceding claims, characterized in that the cationic flocculating agent is chosen from water-soluble cationic polymers, in particular from polyacrylamides, polyethyleneimines, polyvinylamines and mixtures thereof, preferably a cationic resin, and better still a polyamide-amine-epichlorohydrin resin.
- Security sheet according to any one of the preceding claims, characterized in that said fibres comprise cellulosic fibres, in particular cotton fibres, and preferably cotton fibres previously anionized by polymers capable of increasing the negative surface charge of the fibres such as anionic polymers that are water-soluble and that have an affinity with cellulose, in particular chosen from cellulosic derivatives such as carboxymethyl cellulose (CMC), said cellulosic fibres preferably being present in a proportion of greater than 60% by dry weight relative to the total dry weight of fibres and polymer(s), in particular in a proportion of greater than 70%.
- Security sheet according to any one of the preceding claims, characterized in that said fibres comprise synthetic fibres, in particular chosen from polyamide fibres and/or polyester fibres, said synthetic fibres preferably being present in an amount of between 5% and 30% relative to the total dry weight of fibres and polymer(s), and better still between 10% and 15%.
- Security sheet according to any one of the preceding claims, characterized in that said sheet comprises an extra cationic flocculating agent, referred to as secondary cationic flocculating agent, chosen from polyacrylamides, polyethyleneimines, polyvinylamines and mixtures thereof, in an amount which may be between 0.1% and 0.5% by dry weight relative to the total dry weight of fibres and polymer(s).
- Security sheet according to any one of the preceding claims, characterized in that said sheet comprises at least one security element, in particular chosen from watermarks or optically variable devices (OVDs), especially elements having an interference effect, in particular iridescent elements, holograms, liquid crystals and multilayer interference structures, said optically variable devices possibly being affixed to security threads, foils, patches, planchettes, luminescent and/or magnetic and/or metallic pigments or fibres and combinations thereof, and/or comprises an RFID device.
- Security sheet according to any one of the preceding claims, characterized in that said sheet comprises an outer external surfacing layer, preferably based on a polyvinyl alcohol, on an acrylic polymer or on a transparent or translucent elastomer binder, such as a polyurethane, and a colloidal silica.
- Process for manufacturing a security sheet as described in any one of Claims 1 to 11, consisting in forming said sheet via a wet route from an aqueous suspension comprising at least:- fibres,- an anionic dispersion of at least one polymer having a glass transition temperature above 23°C, and- an effective amount of a cationic flocculating agent, then draining, pressing and drying said sheet.
- Process according to Claim 12, characterized in that said fibres, said anionic dispersion of at least one polymer having a glass transition temperature above 23°C and said cationic flocculating agent are mixed in bulk.
- Security document, characterized in that it comprises a security sheet as described in any one of Claims 1 to 11 or obtained according to the process as defined in either of Claims 12 and 13, said security document preferably being a means of payment, such as a banknote, a payment card, a cheque or a restaurant voucher, an identity document, such as an identity card, a visa, a passport or a driving licence, a card, in particular an access card, a lottery ticket, a transport pass or else an entrance ticket to cultural or sporting events, a loyalty card, a benefit card, a season ticket, a playing or trading card, a gift token or a voucher, and more preferentially is a banknote.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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SI201530704T SI3172379T1 (en) | 2014-07-25 | 2015-07-21 | Security sheet resistant to crumpling and hard creasing |
PL15741536T PL3172379T3 (en) | 2014-07-25 | 2015-07-21 | Security sheet resistant to crumpling and hard creasing |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1457239A FR3024165B1 (en) | 2014-07-25 | 2014-07-25 | SAFETY SHEET RESISTANT TO GROWTH AND PLI BRAND |
PCT/EP2015/066668 WO2016012461A1 (en) | 2014-07-25 | 2015-07-21 | Security sheet resistant to crumpling and hard creasing |
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Publication Number | Publication Date |
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EP3172379A1 EP3172379A1 (en) | 2017-05-31 |
EP3172379B1 true EP3172379B1 (en) | 2019-01-30 |
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EP15741536.5A Active EP3172379B1 (en) | 2014-07-25 | 2015-07-21 | Security sheet resistant to crumpling and hard creasing |
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EP (1) | EP3172379B1 (en) |
ES (1) | ES2720251T3 (en) |
FR (1) | FR3024165B1 (en) |
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PL (1) | PL3172379T3 (en) |
SI (1) | SI3172379T1 (en) |
WO (1) | WO2016012461A1 (en) |
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FR2916768B1 (en) * | 2007-05-31 | 2009-07-24 | Arjowiggins Licensing Soc Par | CRISIS RESISTANT SECURITY SHEET, METHOD FOR MANUFACTURING SAME, AND SAFETY DOCUMENT COMPRISING SAME |
FR2998588B1 (en) * | 2012-11-29 | 2015-01-30 | Arjowiggins Security | FACTOR RESISTANT SAFETY SHEET, PROCESS FOR PRODUCING THE SAME, AND SAFETY DOCUMENT COMPRISING THE SAME. |
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2014
- 2014-07-25 FR FR1457239A patent/FR3024165B1/en active Active
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2015
- 2015-07-21 HU HUE15741536A patent/HUE042649T2/en unknown
- 2015-07-21 WO PCT/EP2015/066668 patent/WO2016012461A1/en active Application Filing
- 2015-07-21 PL PL15741536T patent/PL3172379T3/en unknown
- 2015-07-21 EP EP15741536.5A patent/EP3172379B1/en active Active
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Also Published As
Publication number | Publication date |
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ES2720251T3 (en) | 2019-07-19 |
WO2016012461A1 (en) | 2016-01-28 |
SI3172379T1 (en) | 2019-05-31 |
FR3024165B1 (en) | 2017-05-19 |
FR3024165A1 (en) | 2016-01-29 |
EP3172379A1 (en) | 2017-05-31 |
PL3172379T3 (en) | 2019-08-30 |
HUE042649T2 (en) | 2019-07-29 |
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