WO2016151004A1 - Paper containing synthetic fibres - Google Patents

Paper containing synthetic fibres

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Publication number
WO2016151004A1
WO2016151004A1 PCT/EP2016/056355 EP2016056355W WO2016151004A1 WO 2016151004 A1 WO2016151004 A1 WO 2016151004A1 EP 2016056355 W EP2016056355 W EP 2016056355W WO 2016151004 A1 WO2016151004 A1 WO 2016151004A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
fibers
paper
synthetic
fibrillated
preferably
Prior art date
Application number
PCT/EP2016/056355
Other languages
French (fr)
Inventor
Henri Rosset
Original Assignee
Arjowiggins Security
Priority date (The priority date 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 date listed.)
Filing date
Publication date

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H15/00Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H13/00Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10Organic non-cellulose fibres
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H13/00Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10Organic non-cellulose fibres
    • D21H13/12Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H13/00Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10Organic non-cellulose fibres
    • D21H13/20Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/24Polyesters
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H13/00Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/10Organic non-cellulose fibres
    • D21H13/20Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H13/26Polyamides; Polyimides

Abstract

The present invention relates to a paper containing: - fibrillated synthetic fibres; and - a mixture of non-fibrillated synthetic fibres with different shape factors in cross section, notably a mixture of non-fibrillated synthetic fibres of circular cross section and of flattened cross section.

Description

PAPER WITH FIBERS

The present invention relates to fibrous materials, including secure. The invention relates more particularly but not exclusively to a paper suitable for making security documents and to its manufacturing method.

By "secure document" denotes a security document or value as a means of payment, such as a banknote, a check, a credit card or a restaurant ticket, an identity document, such that an identity card, visa, passport, including the personal data page of a passport, an "inlay" or a driving license, a lottery ticket, a transport ticket or a ticket in cultural or sporting events.

To guard against attempts at tampering or counterfeiting of a secure document, it is known to attach to a substrate of the document security elements eg in the form of fibers, flakes, films, knitted structures or security son. The paper substrate may itself be made of a material difficult to counterfeit, and it is called "security substrate."

The life of security documents are usually critical, security substrates "high sustainability" have been developed.

In the field of sheet in security substrates is known cellulosic substrates, said substrates "composite" plastic substrates and substrates called "hybrid".

Cellulosic substrates are fibrous substrates generally obtained by a papermaking process, also called wet from cellulosic fibers such as hardwood fibers, softwood, annual plants, in particular cotton, or mixtures thereof.

The term "papermaking method" or "wet" denotes a current papermaking process, in particular comprising the following successive steps:

dewatering a fiber suspension can first be refined and optionally comprising fillers and additives conventionally used in papermaking and / or specific security elements,

- pressing the wet sheet obtained, then

drying. Said substrates "composite" are cellulosic substrates, the fibrous composition comprises, in addition to cellulosic fibers, synthetic fibers. Such fibers are generally introduced at rates lower than 20% by dry weight relative to the total weight of the substrate, and their use increases the mechanical strength of the substrate.

The presence of cellulose fibers plays an important role in the tangle and attachment of synthetic fibers, which can reveal the intrinsic potential of synthetic fibers. Indeed, in the development of mechanical performance of a sheet material, the synthetic fibers of polymer performance is important but the fibers ability to interact between them is also decisive. The presence of refined cellulosic fibers greatly favors the bridges between cellulose and polymer synthetic fibers.

The composite substrates have better resistance to traffic as cellulosic substrates. Is meant by the term "flow resistance" combination of the following properties: bending strength, tear resistance and resistance to soiling.

Said substrates "hybrid" comprise at least one cellulosic or composite substrate associated with at least one plastic layer. Relative to cellulosic or composite substrate which composes them, they generally have an equivalent tear resistance and improved folding endurance.

Hybrid substrates used in the field of security substrates are described in WO 2006/066431, WO 2004/028825, EP 1854641, WO 94/29105 and WO 03/054297.

The plastic substrates are conventionally made by extrusion of a polymer. These substrates are typically "high sustainability".

Such plastic substrates are described in applications EP 2225102, WO 99/67093, WO 97/01438 and WO 83/00659. These substrates exhibit good resistance to folding and to soiling, but their resistance to tear propagation is relatively low.

Their security is also more difficult, since these substrates are not compatible with leading security implemented for paper substrates (cellulose, composite or hybrid) such as watermarking and inserting at least partially mass security son of, for example as described in applications EP 0059056, GB 2388377 and GB 2381539.

There are also so-called substrates "nonwovens". A nonwoven substrate is defined in ISO 9092 and EN 29092 as a manufactured sheet, consisting of a fleece or web of fibers oriented directionally or randomly, bonded by friction and / or cohesion and / or adhesion , excluding paper and products obtained by weaving, knitting, tufting or seaming, incorporating son or bonding filaments or felted by wet-milling, whether or not needled.

The combination of non-woven industry (or INDA) defines them as "a sheet or a veil of natural fibers and / or fibers or filaments manufactured, excluding paper, that have not been forged and can be linked together in different ways. "

These substrates and their manufacture are described in more detail in the files "nonwovens" (Gerard Coste, 25 June 2004) and "Material Science & Engineering 554 - Nonwovens science and technology II" (Larry C. Wadsworth, Spring 2004 ) available on the Internet at the following respective addresses:

http://cerig.efpg.inpg.fr/tutoriel/non-tisse/sommaire.htm and http://web.utk.edu/~mse/Textiles/index.html.

Nonwovens are described as being used as security substrates in WO 2002/38368 and FR 2 447 995. These substrates generally consist of long non-cellulosic fibers, for example of length between 3 and 25 mm , and have a specific volume and a high porosity, that confer low resistance to soiling.

The nonwovens are manufactured by various methods, including dry, for example by carding or aerodynamic method (also called "airlaid"), melt route, in particular by extrusion (also called "Spunbond") or extrusion blow molding (also called "Meltblown") in wet (also called "wetlaid") according to a method similar to the papermaking process, or by other routes including dissolution in a solvent (also called "Flash spinning").

Nonwovens made wet generally comprise cellulosic fibers, for example at least 10%, in particular to ensure better cohesion to the obtained substrate. Furthermore, where the proportion of cellulosic fiber in non-woven fabrics in wet is low or zero, the hydrogen bonds formed between these fibers do not ensure sufficient cohesion to the substrate and so it is necessary to work at least one bonding step. Such binding may be carried out by impregnating, spraying or coating of latex, by thermo fixation, by needling or by water jet bonding (also known as "spunlace").

An example of a nonwoven substrate having little or no cellulose fibers is described in application EP 2,438,599.

The mechanical properties of a paper can further be improved by the introduction in the mass thereof from reinforcing fibers. These reinforcing fibers are generally introduced at a rate of more than 3% by dry weight, based on the total weight dry weight of the paper fibers and are usually based on synthetic polymers such polyamide 6.6 (PA 6.6) or polyethylene terephthalate (PET) for the mechanical strength that these polymers impart and for economic reasons, manufacturing and good interaction with the cellulosic fibers of the paper.

By "synthetic fibers" should be understood fibers made with one or more synthetic polymers which are polymers obtained from chemical synthesis, in particular by a monomer polymerization reaction, linked or not to a crosslinking reaction.

Preferably, the non-fibrillated synthetic fibers have an average length of between 0.5 and 8 mm, preferably 2 and 8mm, more preferably 4 and 6.5mm.

By way of information, the table below gives the orders of magnitude of the tensile strength and bending strength of the substrates discussed above.

The tear strength is determined according to ISO 1974 "Paper - Determination of tear strength - Elmendorf method" standard and the bending resistance according to ISO 5626 "Paper standard; determination of the bending resistance ". Substrates Substrates Substrates

cellulosic substrates

plastic hybrid composites

Strength

800 1100 800 250 tear (mN)

resistance

2500 5000> 5000> 50000 fold

In order to obtain new substrates having improved mechanical strength properties, particularly tear strength and improved resistance to bending, in particular a tear strength greater than that of the security paper substrates in the art anterior and a bending resistance at least equivalent to that of plastic substrates, the Applicant has developed internally a paper, comprising:

synthetic fibers fibrillated; and

synthetic fibers non-fibrillated.

Such paper is also compatible with the main guarding implemented for papers, including watermarking and inserting at least partially by weight, Security son.

We have found that the fibrillated synthetic fibers, although having a significant contribution in terms of the sheet formation and rendering watermark, have a limited contribution in terms of improved strength properties.

We have also found that non-fibrillated synthetic fibers, although having a significant contribution in terms of improved strength properties, have a negative effect in terms of the hand (specific volume) and paper rendering the watermark.

It thus remains a need to further improve the mechanical strength properties, including tensile strength and resistance to bending without compromising unduly the sheet formation and rendering any watermark.

The invention aims to meet that need, and it is achieved through a paper, including:

- fibrillated synthetic fibers, non-fibrillated synthetic fiber section having a first shape factor, and

non-fibrillated synthetic fiber section having a second aspect ratio higher than the first.

The presence of synthetic fibers non-fibrillated different form factors can further improve the characteristics of paper, as detailed below.

The two factors of different shape preferably by a factor of at least two. The first form factor may be close to 1, which corresponds to substantially circular cross-section fibers. The second form factor may be greater than 2, more than 3, more preferably 5 to 10, which corresponds to the flattened cross-section fibers, especially substantially rectangular.

The substrate according to the invention is paper, which means it is obtained by a papermaking process, in particular according to a method table inclined flat table and / or round shape. This is preferably a round shape process, for example so as to obtain a better definition of watermark or incorporate at least part by mass, a security thread.

The techniques typically used to secure papers can thus be used to secure the substrate of the invention. In addition, the substrate according to the invention has improved properties relative to cellulosic papers, including the upper tear resistance.

fibrillated synthetic fibers

The fibrillated fibers are fibers having fibrils, that is to say packages which deviate from the body of the fiber. The fibrillated fibers may be in particular fibers whose at least one wall has been partially broken, causing the partial release of fibrils.

Such fibers are branched by the fibrils, the section is much less than that of the fiber as a whole, which increases the interaction of these fibers with other fibers, in particular synthetic, and limits the ability of the fibers to slip relative to each other. Such fibers are described for example in FR1317778 and FR2199015 document.

The split fibers play an important role in the cohesion of a paper according to the invention, including the effects of entanglement. The paper according to the invention may comprise fibrillated synthetic fibers are polyamide fibers (PA), polyethylene (PE), polypropylene (PP), poly (ethylene terephthalate) (PET, also referred to as polyester), polyvinyl alcohol (PVA), aromatic polyester (e.g., Vectran ® sold by Kuraray), polyamide imide, polyolefin, and preferably polyacrylic fibers, for example such as those marketed by the company under the reference Sterling SBB 111-2. Preferably, the material of the fibrillated synthetic fibers having a tensile strength between 300 and 600 MPa.

The presence of fibrillated synthetic fibers in the invention overcomes the lack of or the least amount of cellulose fibers, and allows to obtain the desired mechanical performance in terms of tensile strength and bending.

According to a preferred variant of the invention, the paper comprises fibrillated fibers of polyethylene, including high density polyethylene. Indeed, in addition to ease of implementation, these fibers allow to get a good rendering watermark. The proportion of fibrillated fibers of polyethylene is preferably greater than 50% by dry weight relative to the total dry weight of the fibers. The average length of fibrillated fibers of polyethylene is preferably between 0.5 and 2 mm.

Particularly when the fibrous paper composition comprises at least 20%, preferably at least 50%, by dry weight of fibrillated fibers of polyethylene, it is also possible:

- to create links by heat sealing, particularly to strengthen the paper,

- create translucent motifs and / or embossed, in particular by embossing, compression and / or thermo forming, and / or

- recycling paper by melting at the melting temperature of polyethylene, the other components of paper generally having melting temperatures higher than the latter.

Preferably, fibrillated synthetic fibers have an average length between 0.5 mm and 8 mm, preferably between 2 mm and 8 mm and more preferably between 4 and 6.5 mm.

The surface area of fibrillated synthetic fibers according to the invention is preferably between 35 and 75 m 2 / g, more preferably from about 50 m 2 / g. It is measured according to ISO 9277 "Determination of specific surface area (surface area) of solids by gas adsorption - BET method."

Preferably the paper according to the invention comprises more than 5% by dry weight, more preferably more than 10% by dry weight and more preferably more than 20% by dry weight, fibrillated synthetic fibers based on the total weight of the paper. Alternatively the paper according to the invention comprises more than 50% by dry weight of fibrillated synthetic fibers based on the total weight of the paper

The fibrillated synthetic fibers may be white or colored, in particular a color that can be the same or different from the one (s) of other synthetic fibers.

The level of fibrillation of the fibers may be between 5 and 700 mL and preferably between 5 and 100 mL according to the CSF standard.

The fibers may contain at least one tracer, said tracer for identifying the fibers determined by a means, in particular by exposure to UV and / or IR and / or by exposure to a chemical developer. This tracer can thus be a luminescent tracer, including fluorescent under UV or IR.

The split fibers may not all have the same wording.

synthetic fibers non-fibrillated form factor first section, including substantially circular section

Preferably, the form factor of these fibers is less than 1.5, more preferably less than or equal to 1.3, more preferably to 1.1, which corresponds to a substantially circular section.

The shape factor is defined as the ratio of the largest external cross-sectional dimension than the smallest external dimension in the same section. A perfectly circular cross-section fiber has a form factor equal to 1. A fiber oval section of small eccentricity could have a form factor close to 1. In the case of a rectangular cross section, the shape factor is equal to ratio of the width of the section to its thickness. In the case of a square section, the shape factor is 2 1/2.

Synthetic fibers non-fibrillated first form factor, particularly of circular section, are preferably chosen from polyamide fibers (PA), polyacrylic, polypropylene (PP), poly (ethylene terephthalate) (PET, also called polyester), polyvinyl alcohol (PVA), aromatic polyester (e.g., Vectran sold by Kuraray), polyamide imide, of ethylene vinyl alcohol copolymer (EVOH), of polyolefin, preferably polyethylene (PE ).

These non-fibrillated synthetic fibers are preferably polyamide fibers, including thermoplastic fibers.

The paper according to the invention preferably comprises less than 95% by dry weight, preferably less than 90% by dry weight and more preferably less than 80%> by dry weight of such non-fibrillated synthetic fibers of the first form factor, including of circular cross-section, relative to the total weight of the paper.

The amount by dry weight of non-fibrillated fibers of the first form factor, based on the total weight of the paper is preferably greater than or equal to 5%.

Preferably, the synthetic fiber non-fibrillated first form factor have a mean length of between 3 and 6 mm, and a count of between 0.3 and 1.7 dtex.

Preferably, the synthetic fiber non-fibrillated first form factor have a lower titration to 2 dtex, more preferably less than 1 dtex, more preferably less than 0.5 dtex. The non-fibrillated first form factor are synthetic fibers such as fibers sold under the reference mini Eslon by Woongjin society and are PET fibers 0.3 dtex, or for example the fibers sold under the reference EP023 by Kuraray and are PET fibers of 0.33 dtex. In particular, synthetic fibers, non-fibrillated first form factor, particularly of circular section, may be polyamide fibers 6.6 l, 7dTex 4mm marketed by Rhodia or fibers of poly (ethylene terephthalate) sold by Kuraray under the reference EP023 5mm.

The non-fibrillated first form factor synthetic fibers may have the same color as the fibrillated fibers or a different color.

synthetic fibers non-fibrillated second form factor, including flattened section, in particular rectangular

These fibers are preferably cross-section fibers "flat", that is to say, the synthetic fibers to which the section has a width greater than or equal to three times, preferably five times, and more preferably 10 times, the thickness of this same section. Thus the form factor of these fibers is preferably greater than or equal to 3, more preferably greater than or equal to 5, more preferably greater than or equal to 10. The width of the section of the synthetic fiber non-fibrillated second form factor section including shape factor of at least 3, is preferably between 5 and 25 μιη, more preferably between 10 and 20 μιη.

The thickness of the section of the synthetic non-fibrillated second form factor fibers, in particular higher shape factor or equal to 3, is preferably between 0.5 and 10 μιη, more preferably between 1 and 5 μιη.

Preferably, the synthetic fiber non-fibrillated second form factor, including higher shape factor or equal to 3, are chosen from polyamide fibers (PA), polyacrylic, polypropylene (PP), poly (terephthalate terephthalate) (PET, also referred to as polyester), polyvinyl alcohol (PVA), aromatic polyester (e.g., Vectran ® sold by Kuraray) imide polyamide, ethylene vinyl alcohol copolymer (EVOH) of polyolefin, preferably poly ethylene (PE).

Synthetic fibers non-fibrillated second form factor, including higher shape factor or equal to 3, are more preferably polyamide fibers and / or polyester.

In particular, synthetic fibers, non-fibrillated second form factor, including higher shape factor or equal to 3, can be polyester fibers and polyamide mixture sold by Kuraray, for example under the reference Wramp W101, or polyester fibers sold by Teijin company, for example under the reference 14N TA.

The paper according to the invention comprises preferably more than 10% by dry weight, preferably more than 15% by dry weight and more preferably more than 25% by dry weight of non-fibrillated synthetic fibers of the second form factor, especially factor greater than or equal to 3 form, relative to the total weight of the paper.

The paper according to the invention preferably comprises less than 60% by dry weight, preferably less than 50% by dry weight and more preferably less than 40% by dry weight of non-fibrillated synthetic fibers of the second form factor, especially factor greater than or equal to 3 form, relative to the total weight of the paper.

Preferably, the synthetic fiber non-fibrillated second form factor, including higher shape factor or equal to 3, have an average length of between 2 and 10 mm, preferably between 3 and 7 mm and more preferably between 5 and 6 mm, and a coverage of from 0.2 to 3 dtex.

Synthetic fibers non-fibrillated second form factor, including higher shape factor or equal to 3, can have the same color as the fibrillated fibers or a different color.

Synthetic fibers non-fibrillated second form factor, including higher shape factor or equal to 3, are preferably obtained from multi-component primary fibers ( "splittable fibers" in English), preferably bi-component. These primary fibers may be in the form of segmented ribbon, segmented cross, or may have a multi-lobed section, in particular trilobal, or a segmented circular sectional areas, hollow or non Examples of such fibers are shown in Figures 1-6 described below.

Primary bicomponent fibers 1 shown in these figures comprises a first component 2 and a second component 3. It is for example polyester and polyamide respectively.

Figure 1 represents a primary bicomponent fiber 1 in section segmented into sectors, called "pie share" ( "pie wedge fiber" in English). Sectors of one component alternate with those of the other component, about the axis of the fiber. The sectors are separated in the pulp during papermaking as by stirring of the pulp suspension. In order to enable this separation (or cleavage), the areas can be linked together by a soluble adhesive. Such fibers are produced by extrusion.

2 shows a primary bicomponent fiber 1 to said section "segmented ribbon" ( "segmented ribbon fiber" in English).

3 shows a primary bicomponent fiber 1 to said section "hollow piece of pie" ( "hollow pie wedge fiber" in English).

4 shows a primary bicomponent fiber 1 to said section "segmented cross" ( "segmented cross fiber" in English).

5 shows a primary bicomponent fiber 1 to said section "trilobal to tapered tip" ( "tipped trilobal fiber" in English). 6 shows a primary bicomponent fiber 1 to multilayer section whose components alternate from one side of the section to the opposite side, called the "conjugate" ( "conjugated fiber" in English).

Preferably the components of such primary fibers are separated at their implementation for making a paper according to the invention, so as to obtain said non-fibrillated second form factor section fibers, in particular flattened factor form higher than or equal to 3.

The non-fibrillated rectangular section synthetic fibers are preferably obtained from fibers conjugated bicomponent section.

Preferably, the synthetic fiber non-fibrillated second form factor, including higher shape factor or equal to 3, have a lower titration to 3 dtex. Synthetic non-fibrillated second form factor fibers, in particular higher shape factor or equal to 3, for example the fibers sold under the name TA 14N by Teijin company, and are of polyester fibers, or from e.g. the separation of the fibers sold under the reference Wramp W101 by Kuraray, which are bicomponent conjugate fibers polyester / polyamide 3.3 dtex before cleavage.

The multicomponent primary fibers at their dissociation, may only produce non-fibrillated synthetic fibers of higher shape factors or equal to 3. Alternatively, they produce both shape factor fibers strictly less than 3, particularly 2, more than 1.1, and form factor fiber strictly greater than 3. All non-fibrillated synthetic fibers of the invention, the form factors are different, may originate from the dissociation of the same type of primary fibers. Alternatively, the mixture of synthetic fibers not fibrillated of different form factors, according to the invention comes from both the introduction of fibers having a first shape factor, in particular circular cross-section fibers and primary fibers multicomponent including two-component.

other fibers

The paper according to the invention may comprise less than 5% by dry weight of non-synthetic fibers, such as cellulosic fibers, based on the total weight of the paper, preferably less than 2% by dry weight of non-cellulosic fibers relative to the total weight of the paper, more preferably be free of non-synthetic fibers, such as cellulosic fibers.

In particular, in a preferred embodiment, the paper fibers of the invention are exclusively constituted by synthetic fibers fibrillated and non-fibrillated synthetic fibers.

treatments

It is possible to strengthen the cohesion of a paper according to the invention through the introduction of a polymeric binder such as polyvinyl alcohol (PVA) or a styrene-acrylic copolymer which has a synergy with synthetic fibers allowing surprisingly the development of resistance to bending and also the tear strength. The application of the polymeric binder may be by impregnation, surfacing or coating, preferably the polymeric binder is introduced at least partially by weight.

The composition may comprise an anionic polymer dispersion, including flocculated. Preferably, the composition comprises at least 3% by dry weight of anionic polymer dispersion, including flocculated. Such anionic dispersion polymer improves the wet tensile resistance, cohesion and resistance to folding of the paper.

The latex used is for example the latex sold by Dow Chemicals under the reference 94755.04 or a latex as described in the international application WO2008152299 or WO2014083527 request.

The formulation of paper according to the invention may also include a main cationic flocculation agent, amount between 1 and 5% by dry weight relative to the total weight of the paper, and optionally a secondary cationic flocculation agent, amount of 0.1 and 0.5% by dry weight, selected from a cationic resin, polyacrylamides, polyethyleneimines, polyvinylamines, and mixtures thereof, preferably a cationic resin, and more preferably a polyamide-amine épichloridrine resin.

Other binders can be used, in particular a transparent or translucent elastomer binder, such as polyurethane and colloidal silica, a binder or acrylic or styrene-acrylic copolymer polymer. In order to reinforce the strength of the paper, of the flocs (aggregates) of a polyurethane having an elongation at break large, for example greater than 600%, may be incorporated into paper by anionic dispersion, in particular in a proportion of between 5 and 45 % by dry weight relative to the total weight of the paper.

Other components of the paper

The paper according to the invention can comprise all compounds and adjuvants conventionally used in the manufacture of a paper by a papermaking process, such as fillers, retention agents, sizing agents and / or to the state strength agents wet, including epichlorohydrin resins.

The paper according to the invention may in particular comprise fillers mouth- porantes, including plastics such as vinyl chloride particles (PVC) sold by the company under the Kern One Lacovyl Pb reference 1302. Such fillers include the ability to densify the paper of the invention.

Papermaking

The paper according to the invention can be manufactured according to conventional manufacturing techniques of cellulosic papers, except the steps related specifically to the presence of cellulose fibers if they are absent. In particular, the refining step, particularly energy intensive, can be advantageously suppressed.

The manufacturing process may be adapted to the presence of security elements such as a watermark or a security thread.

The paper preferably has a hand less than or equal to 2.5 cm 3 / g, more preferably a lower hand or equal to 2 cm 3 / g and more preferably less than or equal to 1.5 cm 3 / g.

The paper may have a thickness between 100 and 300 μιη, preferably between 100 and 150 μιη. It is measured according to ISO 534 "Paper and board - Determination of thickness, density and specific volume."

The paper weight can be between 70 g / m 2 and 150 g / m 2 and preferably between 90 g / m 2 and 110 g / m 2. It is measured according to ISO 536 "Paper and board - Determination of grammage." Watermark

The paper according to the invention may include a watermark. This watermark can be formed of round or flat table.

The watermark can be of any known type, for example light and / or dark, possibly multitone or multitone effect, for example as described in EP 1122360, EP 2350384 and EP 2550395.

Security thread

The paper according to the invention may comprise a security thread introduced in bulk or between two plies of paper according to the invention linked in the wet phase. The security thread may be at least partially inserted into the paper.

The paper may comprise a fibrous tape, particularly a cellulosic fibrous tape as described in WO2008043965 application, a plastic band or a knitted tape, especially as described in the application WO2006016088.

The wire may be plated and / or hologram and / or an interference effect and / or provided with optical structures, such as lenses or mirrors.

multijet paper

The paper according to the invention may be single ply or multi-ply.

In the case of a multi-ply structure, the jets may or may not have the same fibrous composition. In particular, the paper may comprise firstly a jet of synthetic fibers according to the invention, and secondly a jet of cellulosic fibers, assembled in the wet phase, the jet according to the invention thus constituting a reinforcing jet.

Alternatively, the paper may comprise firstly a jet of synthetic fibers, in particular watermark according to the invention whose fiber content promotes the formation of the sheet, including look-through, and rendering the watermark, and the other share a jet of synthetic fibers according to the invention whose fiber content promotes the mechanical strength properties, said jets being assembled in the wet phase.

The jets can be the same color or not.

properties

The Bendsten porosity of the paper may range from 0 ml / min to 10,000 ml / min, more preferably between 1 mL / min and 7000 mL / min. It is measured according to ISO 5636-3 "Paper and cardboard; determination of the air permeability (mean value); Part 3: Bendtsen method "Preferably, the resistance to double-fold folding Schopper paper according to the invention is greater than 5000, preferably greater than 20000, more preferably greater than 50000. It is measured according to ISO 5626" Paper standard; determination of the bending resistance ".

Preferably, the tear strength of the paper (measured according to standard

ISO 1974) is higher than 1000 mN, more than 2000 mN, more preferably greater than 3000 mN. It is measured according to ISO 1974 "Paper - Determination of tearing resistance - Elmendorf method"

The invention allows to obtain a synthetic paper having mechanical properties, particularly bending strength and tear strength, are superior to those of a conventional paper, while allowing if it is sought to achieve quality watermarks and satisfactory resolution.

The use of synthetic fibers, non-wettable and less sensitive to water as cellulosic fibers, provides a substrate with durability, including naturally more resistant to attack by molds.

security and secure document Elements

The paper according to the invention preferably comprises a security element, especially a watermark or a security thread, for example a wire inserted window (s) as mentioned above.

The invention further relates to a security document comprising a paper according to the invention.

In a preferred embodiment of the invention, the security document is a banknote. The secure document can also be a different type of payment method such as a check or a restaurant ticket, an identity document such as an identity card, visa, passport, including the personal data page a passport, a secure label, shrink secure sleeve, a "Prelam" insert or "inlay" for passport or card, including smart card, or a driver's license, a lottery ticket, a ticket, a ticket entry to cultural or sporting events, a playing card or a trading card. An insert is a layer supporting a contactless communication device, preferably radio frequency. The paper according to the invention and / or the secure document produced with the paper of the invention may include one or more additional security elements as defined below.

Among the additional security elements, some are detectable to the eye, in daylight or in artificial light, without using a particular device. These security elements comprise, for example colored fibers or flakes. These security elements are said first level.

Other types of additional security elements are detectable only using a relatively simple device, such as a lamp emitting in the ultraviolet (UV) or infrared (IR). These security elements comprise, for example, fibers, planchettes or particles. These security elements may be visible to the naked eye or not, being, for example luminescent under a Wood light lamp emitting a wavelength of 365 nm. These security elements are said second level.

Other types of additional security features require for their detection a more sophisticated detection equipment. These security elements are, for example capable of generating a specific signal when they are subjected, simultaneously or not, to one or more sources of external excitation. Automatic detection of the signal is used to authenticate, if applicable, the document. These security elements comprise, for example tracers in the form of active materials, particles or fibers, capable of generating a specific signal when these markers are subjected to an optronic excitation, electrical, magnetic or electromagnetic. These security elements are said third level.

The one or more additional security elements present in the paper according to the invention or security document according to the invention may have first security features, second or third level.

In the case where the formulation of the synthetic fiber composition comprises fibers of a thermoplastic material, in particular polyethylene, hot melt, or the additional security elements may be attached to the document by simply heating, thereby avoiding the use of a heat-activatable adhesive. comparative tests

Several trials were conducted to demonstrate the advantageous properties of a paper according to the invention.

In the following :

- the tear strength is measured according to ISO 1974

- bending strength (or at said double-fold "Schopper folding") is measured according to ISO 5626,

- the weight is measured according to ISO 536,

- the thickness is measured according to ISO 534 standard, and provides the hand (or specific volume) which is equal to the thickness divided by the basis weight,

- the quality of the watermark is visually assessed by a score from 1 (bad) to 6 (very good).

Crude substrates, that is to say free of any treatment as defined hereinabove, and the surfaced substrates, that is to say impregnated by means of a polyvinyl alcohol composition or a composition styrene-acrylic copolymer, are tested.

The properties of a substrate whose fiber content is composed only of synthetic fibers fibrillated and non-fibrillated synthetic fibers of circular cross section (Example 1) were compared to those of a substrate having a fibrous composition corresponds to that of the example 1 apart from the fact that part of non-fibrillated synthetic fibers of circular section is replaced by non-fibrillated synthetic fibers of rectangular cross section (example 2).

The results, shown in Table below, reflect the fact that the mixture of non-fibrillated synthetic fibers of different sections and of different form factors, in this case circular and rectangular sections, allow to increase the resistance to tearing and bending strength without degrading also measures the quality of the watermark. Satisfactory properties are then obtained, in particular good resistance to tearing. Example 1 Example 2

polyethylene fibers fibrillated SWP E400 66% 66%

polyamide 6,6 fibers to non-circular section

30% 10% 1.7 dtex fibrillated Rhodia mid-mate 4 mm

Fibers not fibrillated rectangular section

20% polyamide / polyester Wramp W101

substrate blanks

Grammage g / m 2 88.2 85.5

Tear resistance mN 511 1518

Quality Watermark Rating 3.0 2.8

surfaced substrate

Grammage g / m 2 105.7 115.9

Main cm 3 / g 1.40 1.37

Tear resistance mN 1884 2005

folding endurance number of folds 8033 23787

The proportions are by weight.

The properties of a substrate whose fiber content is composed of fibrillated synthetic fibers and synthetic fibers fibrillated non circular section (Example 3) were compared to those of a substrate having a fibrous composition corresponds to that of Example 3 except that the fibrillated synthetic fiber non-circular cross section are replaced entirely by synthetic fibers non-fibrillated rectangular section (example 4).

The results, shown in Table below, reflect the fact that replacing wholly synthetic fibers fibrillated non-circular cross-section by non-fibrillated synthetic fibers of rectangular cross section does not allow to increase significantly the tensile strength and the bending resistance, and degrades the quality of the watermark. As demonstrated by the comparison examples, it is therefore the combination of synthetic non-fibrillated fibers different form factors, i.e. circular cross-section fibers and rectangular cross-section fibers in the examples considered, thereby increasing the tear resistance and resistance to bending without unduly degrade the quality of the watermark. Example 3 Example 4

Polyacrylic fibers fibrillated SBB 111-2 10% 10%

polyethylene fibers fibrillated SWP E400 76% 76%

polyamide 6,6 fibers fibrillated non-circular section

10%

Rhodia 1.7 dtex mid-mate 4 mm

Polyamide fibers rectangular / polyester Wramp

10%

W101

substrate blanks

Grammage g / m 2 88.2 86.4

Tear resistance mN 702856

Quality Watermark Note 6 4.5

surfaced substrate

Grammage g / m 2 92.8 96.6

Main cm 3 / g 1.41 1.45

Tear resistance mN number of 1082 701

folding endurance 1387 254 double pleats

The proportions are by weight.

Depending on the intended application, it may be important to get a little dense and porous substrate, such as for achieving a quality watermark.

The properties of a substrate whose fiber content is composed of 76%> of fibrillated synthetic fibers, fibrillated synthetic fibers non-circular cross section and 10% of non-fibrillated synthetic fibers of rectangular cross section (Example

5) were compared:

- firstly to those of a substrate whose fiber content is composed of 56%> of fibrillated synthetic fibers, fibrillated synthetic fibers non-circular cross section and 30% of non-fibrillated synthetic fibers of rectangular cross section (Example

6), and

- secondly to those of a substrate whose fiber content is composed of 56%> of fibrillated synthetic fibers, fibrillated synthetic fibers non-circular cross section and 30%> of a mixture of non-fibrillated synthetic fibers rectangular section (example 5) (example 7).

The results, reported in the table below, reflect the fact that the fiber compositions of examples 6 and 7 achieve, after surfacing, the resistance performance to tearing and resistance to very high bending. Note also that Wramp W101 fibers enable a better tear resistance that Teijin TA 14N fiber, which highlights the value of using primary fibers multicomponent.

Figure imgf000022_0001

The proportions are by weight.

The term "comprising a" should be understood as being synonymous with "comprising at least one" and "between" means inclusive, unless otherwise specified.

Claims

1. Paper, including:
synthetic fibers fibrillated
- synthetic fibers non-fibrillated first form factor section, and
synthetic fibers non-fibrillated second form factor section, greater than the first.
2. Paper according to claim 1, synthetic fibers not fibrillated first form factor having a lower shape factor equal to or better 1.3 to 1.1.
3. Paper according to claim 1 or 2, the synthetic fibers not fibrillated second form factor having a larger form factor than or equal to 3, more preferably to 5, more preferably to 10.
4. Paper according to any preceding claim, synthetic fibers not fibrillated first form factor being of circular cross-section fibers.
5. Paper according to any preceding claim, synthetic fibers not fibrillated second form factor being flattened cross-section fibers, more preferably rectangular.
6. Paper according to any preceding claim, the gap between the first and second form factors greater than or equal to 3, more than 5, more preferably to 10.
7. Paper according to any preceding claim, non-fibrillated fibers of the second form factor resulting from the dissociation of multicomponent primary fibers in the pulp used for papermaking, preferably bicomponent fibers, preferably bicomponent fibers polyester / polyamide.
8. Paper according to claim 7, the multicomponent fibers being conjugate fibers, preferably polyester fibers / polyamide
9. Paper according to any preceding claim, the quantity by weight of synthetic fibers not fibrillated second shape factor being greater than that of the first form factor fiber.
10. Paper according to any preceding claim, comprising a security element.
11. Paper according to one of the preceding claims, comprising a watermark.
12. Paper according to any preceding claim, wherein the non-fibrillated synthetic fibers are chosen from polyamide fibers, poly fibers (ethylene terephthalate), polyvinyl alcohol fibers, copolymer fibers ethylene vinyl alcohol copolymer and polyolefin fibers, preferably polyethylene.
13. Paper according to any preceding claim, comprising more than 5% by dry weight, preferably more than 10% by dry weight, and most preferably more than 20% by dry weight, of non-fibrillated compared synthetic fibers the total weight of paper, the amount of synthetic fibers not fibrillated second form factor, including higher shape factor or equal to 3, being greater than or equal to 10% by dry weight, relative to the total weight of the paper.
14. Paper according to any preceding claim, wherein the fibrillated synthetic fibers are fibrillated fibers of polyethylene.
15. Paper according to any preceding claim, wherein the non-fibrillated synthetic fibers have an average length of between 0.5 mm and 8 mm, preferably between 2 mm and 8 mm and more preferably between 4 and 6,5mm.
16. Paper according to any preceding claim comprising less than 95% by dry weight, preferably less than 90% by dry weight, and most preferably less than 80% by dry weight of synthetic fibers fibrillated by weight total paper.
17. Paper according to any preceding claim, comprising a surfacing agent, in particular being impregnated with a surface treatment agent, the surface treatment agent comprising or consisting preferably of polyvinyl alcohol.
18. Paper according to any preceding claim, comprising a latex, particularly flocculated.
19. Paper according to the preceding claim, comprising at least 3% by dry weight of latex, in particular flocculated, relative to the total weight of the paper.
20. Paper according to any preceding claim comprising less than 5% by dry weight of non-synthetic fibers, such as cellulosic fibers, based on the total weight of the paper, preferably less than 2% by dry weight relative to the total weight of the paper, more preferably being free of non-synthetic fibers, such as cellulosic fibers.
21. Paper according to any one of the preceding claims, the paper fibers solely constituted by synthetic fibers fibrillated and non-fibrillated synthetic fibers.
22. Paper according to any preceding claim, having a hand less than or equal to 2.5 cm 3 / g, preferably less than or equal to 2 cm 3 / g.
23. Paper according to any preceding claim, having a basis weight between 70 g / m 2 and 150 g / m 2 and preferably between 90 g / m 2 and
110 g / m 2.
24. Paper according to any preceding claim, having a resistance to double-fold folding Schopper greater than or equal to 5000, preferably greater than or equal to 10,000, more preferably greater than or equal to 25000.
25. Paper according to any one of the preceding claims, having a tear strength measured according to the ISO 1974 standard greater than 1000 mN, preferably greater than 2000 mN, preferably greater than 3000 mN.
26. Paper according to any preceding claim, comprising a security thread, in particular at least partially introduced into the paper.
27. Security document comprising a paper as defined in any one of the preceding claims.
28. Security document according to claim, constituting a means of payment such as a bank note, a check or a restaurant ticket, an identity document such as an identity card, visa, passport, secure label, shrink sleeve safety, insert a card or passport, including smart card, or a driver's license, a lottery ticket, a ticket, a ticket to cultural or sporting events, a playing card or a trading card.
PCT/EP2016/056355 2015-03-23 2016-03-23 Paper containing synthetic fibres WO2016151004A1 (en)

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EP3274502A1 (en) 2018-01-31 application
CN107667198A (en) 2018-02-06 application
FR3034110A1 (en) 2016-09-30 application
FR3034110B1 (en) 2017-04-21 grant

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