EP1354097A1 - Paper comprising bodies which comprise at least one biochemical marker - Google Patents

Paper comprising bodies which comprise at least one biochemical marker

Info

Publication number
EP1354097A1
EP1354097A1 EP02712007A EP02712007A EP1354097A1 EP 1354097 A1 EP1354097 A1 EP 1354097A1 EP 02712007 A EP02712007 A EP 02712007A EP 02712007 A EP02712007 A EP 02712007A EP 1354097 A1 EP1354097 A1 EP 1354097A1
Authority
EP
European Patent Office
Prior art keywords
bodies
paper
biochemical marker
fibers
carrying
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.)
Granted
Application number
EP02712007A
Other languages
German (de)
French (fr)
Other versions
EP1354097B1 (en
Inventor
Sandrine Rancien
Sébastien DE LAMBERTERIE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CYPHER SCIENCE
ArjoWiggins Security SAS
Original Assignee
ArjoWiggins Security SAS
Cypher Science SARL
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
Application filed by ArjoWiggins Security SAS, Cypher Science SARL filed Critical ArjoWiggins Security SAS
Publication of EP1354097A1 publication Critical patent/EP1354097A1/en
Application granted granted Critical
Publication of EP1354097B1 publication Critical patent/EP1354097B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath
    • D01F2/10—Addition to the spinning solution or spinning bath of substances which exert their effect equally well in either
    • 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
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/46—Elements suited for chemical verification or impeding chemical tampering, e.g. by use of eradicators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/249933—Fiber embedded in or on the surface of a natural or synthetic rubber matrix
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/249933—Fiber embedded in or on the surface of a natural or synthetic rubber matrix
    • Y10T428/249934—Fibers are aligned substantially parallel
    • Y10T428/249936—Fiber is precoated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/249933—Fiber embedded in or on the surface of a natural or synthetic rubber matrix
    • Y10T428/249937—Fiber is precoated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249942—Fibers are aligned substantially parallel
    • Y10T428/249944—Fiber is precoated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249948—Fiber is precoated

Definitions

  • Paper comprising bodies carrying at least one biochemical marker
  • the present invention relates to a new paper.
  • nucleic acids in particular DNA
  • US Pat. No. 5,763,176 it is known from US Pat. No. 5,763,176, inter alia, to use nucleic acids, in particular DNA, as a means of authentication and / or identification in order to allow authentication and / or identification miscellaneous items.
  • the invention aims in particular to meet this need.
  • the invention thus relates to a new paper, characterized in that it comprises bodies carrying at least one biochemical marker and having a size sufficient to be able to be removed in isolation.
  • the bodies used are preferably bodies having a good affinity with the paper, so as to remain integral with the latter during the usual processing and use of the latter, in particular during printing.
  • the bodies carrying the biochemical marker are advantageously incorporated into the paper fiber mass before the paper is delivered to end users.
  • Extraction of bodies carrying the biochemical marker can be carried out easily, mechanically, without destroying the appearance of the paper, for example using tweezers, under visual control using a microscope if necessary.
  • the largest dimension of said bodies is greater than 100 ⁇ m, and preferably of the order of one to a few mm, for example between 1 and 10 mm.
  • the bodies used can be fibers or agglomerates of fibers, such agglomerates being able to form boards, the fibers being able to be natural, artificial or synthetic.
  • the length of the fibers carrying the biochemical marker can for example be between 3 and 10 mm, being preferably close to 5 mm.
  • the diameter or larger dimension of the boards carrying the biochemical marker can be greater than 2 mm, for example.
  • the latter can be produced in multiple ways, depending on the nature of their main constituent. They can in particular be produced by spinning when they consist essentially of viscose, or by extrusion when they are made of a thermoplastic material such as polyamide or polypropylene.
  • the biochemical marker can be incorporated into bodies intended to carry it in multiple ways, during or after the manufacture of said bodies.
  • the biochemical marker can be incorporated into the material intended to constitute the fibers before the latter are produced by spinning or extrusion, or after their manufacture by a dyeing or other process.
  • the biochemical marker can be deposited on the paper intended to constitute the boards by a surface treatment, in particular using an encoUeuse press or an impregnator.
  • the biochemical marker can also be chemically grafted onto the fibers or other bodies used, with the establishment of a strong chemical bond between the biochemical marker and the fiber or other body.
  • the bodies carrying the biochemical marker may or may not be colored, the coloring being able to facilitate their identification within the fibrous mass of the paper.
  • the bodies carrying the biochemical marker may be colorless but exhibit fluorescence in the infrared or ultraviolet, their sampling then being carried out under adequate lighting.
  • the bodies carrying the biochemical marker can be colorless in appearance but present a fluorescence whose absorption and emission characteristics are between 400 and 800 nm.
  • the revelation of the bodies is obtained under adequate lighting and through an optical filter which selects the emission of fluorescence in a range of wavelengths of the visible.
  • the optical principle of revealing fluorescence in the visible range is described more precisely in patent application PCT / FR01 / 02480, the content of which is incorporated for reference.
  • the bodies carrying the biochemical marker can be incorporated into the paper fiber mass in different ways.
  • the bodies carrying the biochemical marker can be applied in sowing, their distribution in the paper fiber mass then being random, but preferably, they are applied so as to form a relatively narrow band, which has the advantage of reducing the amount of biochemical marker used.
  • the paper may include other security elements in addition to the bodies carrying the biochemical marker, these security elements constituting at least one means of authentication and / or additional identification.
  • the bodies carrying the biochemical marker can have other authentication properties, in particular be radioactive, magnetic, or even have electromagnetic resonance properties at particular frequencies and / or change their appearance depending on the angle of observation or under the action of an excitation source such as radiation.
  • the bodies carrying the biochemical marker can in particular contain microspheres detectable by epifluorescence microscopy, these microspheres being linked or not to the biochemical marker.
  • the microspheres can be mineral particles marked with a specific fluorescence by covalent bond, as described in patent application WO0130936.
  • the bodies carrying the biochemical marker can in particular be fluorescent, thermochromic or photochromic fibers.
  • the density of bodies carrying the biochemical marker can be very low and less, for example, to 10 bodies per dm 2 of paper when the distribution of said bodies is random and extends to the entire paper, or less than 10 bodies per linear dm when the bodies are confined in a strip.
  • Each body can have more than 10 sequences for example.
  • the biochemical marker can be embedded in the material constituting said bodies, as indicated above, or be present on their surface only, or both.
  • the biochemical marker will preferably be embedded in the material constituting the bodies, which makes it possible to protect it against physical attacks, in particular abrasion, or chemical attacks, in particular by falsification products.
  • the biochemical marker When the biochemical marker is provided by a surface treatment, it will preferably be linked to the carrier body by means of a very crosslinked binder in order to protect it, such a binder being able in particular to be a polyurethane crosslinked with an azidine or a crosslinked styrene-acrylate copolymer with a melamine-formaldehyde.
  • biochemical marker preferably single strand sequences of at least 70 nucleotides, for example at least 80 nucleotides, will be used. Preferably, at least 10 5 such sequences will be used per carrier body.
  • Such a biochemical marker offers a large number of coding possibilities and is extremely difficult to detect.
  • telomere sequences from 70 to 110 nucleotides in number less than 10 molecules requires "amplification”.
  • amplification is understood to mean the process which consists in duplicating DNA sequences by a polymerization chain reaction commonly called PCR.
  • the amplification of the sequence requires at least one primer (strand of DNA complementary to one end of the sequence to be amplified)
  • the sequence may include a sequence of nucleotides encoding identification information, in addition to the sequence of nucleotides complementary to the above-mentioned primer.
  • a means of DNA authentication can advantageously be the use of specific fluorimetric probes which, by hybridization with a central region of the sequences duplicated by PCR, emit a fluorescent signal which can be measured by a laser. The intensity of the fluorescent signal is correlated with a number of amplified sequences.
  • sequences of at least 70 nucleotides use will preferably be made of sequences produced according to the teachings of patent application WO00 / 61799 so that they can be amplified and detected by quantitative PCR.
  • Other biochemical markers can be used, in particular natural double-stranded DNA or molecular semaphores.
  • the subject of the invention is also a method of manufacturing paper, characterized in that it comprises the step consisting in incorporating bodies, in particular fibers, carrying at least one biochemical marker into the papermaking fibrous mass.
  • the bodies carrying the biochemical marker can be introduced en masse or by surface treatment.
  • Said bodies can in particular be mixed with a bath, in particular an impregnation bath, a coating press or a coating press, used during the treatment of the paper fiber mass.
  • the bodies can be distributed over the entire width or only over a part thereof.
  • the biochemical marker is advantageously introduced into a masterbatch used during their extrusion.
  • the subject of the invention is also a method of authenticating and / or identifying a paper into which the bodies carrying at least one biochemical marker have been incorporated during the process of making paper. to identify and take from the paper at least one body carrying the biochemical marker.
  • the method may further comprise the step of separating the sequences from the matrix of the body to which they are attached or incorporated, the matrix of the body being the constituent material of the body. The step of separating the matrix and the DNA sequences is called the DNA extraction and purification step.
  • the extraction of the marker can go through a step of dissolving the body matrix using one or more suitable solvents.
  • the method may include the step of authenticating the DNA by a PCR reaction using specific primers.
  • this amplification can be followed by an analysis, for example by sequencing, in order to identify the DNA sequence which has been introduced into the paper.
  • the subject of the invention is also fibers or boards comprising at least one biochemical marker, preferably at least one nucleotide sequence, advantageously single-stranded and comprising at least 70 nucleotides, in particular at least 80 nucleotides.
  • FIG. 1 is a schematic front view of a paper according to a first example of implementation of the invention
  • - Figure 2 is a schematic front view of a paper according to a second example of implementation of the invention
  • - Figure 3 is a schematic and partial front view of a paper comprising boards coated with a biochemical marker
  • FIGS. 4 and 5 are cross sections of two examples of fibers each carrying a biochemical marker
  • FIG. 6 schematically represents a nucleotide sequence serving as a biochemical marker
  • FIG. 7 is a block diagram schematically illustrating different steps of an identification method.
  • a sheet of paper 1 comprising a paper fiber mass 2, consisting essentially of cellulose fibers for example, and a plurality of bodies 3, each carrying a biochemical marker specific, as will be explained below.
  • the bodies 3 are formed in Figures 1 and 2 by fibers and in Figure 3 by boards.
  • the average length of the fibers 3 is 5 mm, their diameter is 25 ⁇ m, and their specific volume close to 1.
  • the fibers 3 are confined in a limited zone of the width in the example of FIG. 2, thus forming a relatively narrow strip 4.
  • the fibers 3 can be produced by spinning, mainly from viscose for example, or by extrusion of polypropylene for example, other materials and other manufacturing processes being of course usable.
  • the biochemical marker consists, in the example illustrated, of nucleotide sequences.
  • sequences 5 can be dispersed in the mass of the body 3, on its surface or both.
  • Each body 3 comprises in the example described between approximately 10 5 and 10 8 sequences, each sequence 5 being constituted by a single strand of DNA preferably comprising between 70 and 110 nucleotides, for example between 80 and 100 nucleotides.
  • nucleotide sequence 5 comprises in a manner known per se a series of bases chosen for example from the following list: adenine A, cytosine C, guanine G, thymine T, the latter being able to be replaced by uracil, other compounds and nucleotide derivatives which can still be used, if necessary.
  • FIG. 6 shows schematically a sequence 5 which comprises end regions 7 and 8 each composed by a predetermined series of bases and a central region 9 constituting the sequence carrying the identification information.
  • the extreme regions 7 and 8 are intended to recognize complementary primers during the amplification by PCR, and comprise for example between 20 and 25 bases each.
  • the central region 9 comprises for example between 30 and 60 bases, part of which is intended to be recognized by specific fluorimetric probes. Only six bases have been represented for the sake of simplification.
  • the bodies 3 can be incorporated into the paper in various ways, depending on the distribution of the bodies 3 that are desired on the surface of the paper.
  • a bath used during the papermaking process for example an impregnation bath, a coating press or a coating bath.
  • This sample can be taken with or without a microscope, using tweezers for example, without altering the appearance of the paper.
  • the number of bodies 3 removed can be very low and be equal to ten for example.
  • the matrix is dissolved in step 11 in order to extract the biochemical marker therefrom.
  • the bodies 3 taken consist of viscose fibers
  • they can be placed in an ethyl acetate bath which is slightly heated.
  • solvent is added until the fibers are completely dissolved.
  • a mixture of water and ethanol intended to precipitate the DNA is added.
  • the bodies 3 sampled consist of polypropylene fibers, they are placed for example in an extraction cartridge of a Soxhlet extractor sold for example by the company MERCK and which is operated with xylene.
  • the product of the dissolution is then purified for example using a kit “DNeasy” brand purification solution marketed by QIAGEN.
  • the purification procedure can consist in separating the biochemical marker from the dissolved matrix.
  • a quantitative amplification by PCR is carried out in step 12 using specific primers and specific fluorimetric probes.
  • the specific primers allow the amplification of the 5 sequences, while the fluorimetric probes make it possible to measure in real time the quantity of amplified DNA.
  • Amplification by PCR requires the use of specific primers. Thus, only a person having these specific primers is capable of carrying out the amplification.
  • sequence 5 can be carried out according to the characteristics described in patent application WO00 / 61799, which makes it possible to carry out a quantitative PCR.
  • the loop recognizes on a strand of DNA the complementary sequence, it opens and becomes fluorescent, and if not it remains folded and does not emit light. It is also possible to use, as biochemical marker, natural double-stranded DNA.
  • the amplification can be carried out without specific primer.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Paper (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
  • Credit Cards Or The Like (AREA)

Abstract

The invention relates to paper (1) characterised in that it comprises bodies (3) which comprise at least one biochemical marker and are of a sufficient size so that they can be removed individually.

Description

Papier comportant des corps porteurs d'au moins un marqueur biochimique Paper comprising bodies carrying at least one biochemical marker
La présente invention concerne un nouveau papier.The present invention relates to a new paper.
Il est connu par le brevet US 5 763 176, entre autres, d'utiliser des acides nucléiques, notamment de l'ADN, comme moyen d'authentification et/ou d'identification afin de permettre l'authentification et/ou l'identification d'articles divers.It is known from US Pat. No. 5,763,176, inter alia, to use nucleic acids, in particular DNA, as a means of authentication and / or identification in order to allow authentication and / or identification miscellaneous items.
Il est notamment connu d'incorporer à une encre destinée à l'impression d'un objet des microsphères de 0,01 μm à 5 μm environ de diamètre, porteuses chacune d'au moins une séquence de nucléotides. Pour identifier l'objet, il est alors nécessaire dans un premier temps de repérer les microsphères à l'aide d'un microscope adéquat, puis de prélever dans la zone des microsphères repérée un échantillon d'encre et de le purifier afin d'extraire la séquence de nucléotides, puis d'amplifier cette dernière par PCR (Polymerase Chain Reaction) jusqu'à l'obtention de la quantité nécessaire pour l'analyse, l'amplification et l'analyse étant effectuées au moyen d'amorces spécifiques. L'encre est généralement prélevée par grattage, ce qui présente l'inconvénient d'endommager l'objet.It is notably known to incorporate into an ink intended for the printing of an object microspheres of 0.01 μm to approximately 5 μm in diameter, each carrying at least one nucleotide sequence. To identify the object, it is first necessary to locate the microspheres using an appropriate microscope, then to take an ink sample from the identified microsphere area and to purify it in order to extract the nucleotide sequence, then amplify the latter by PCR (Polymerase Chain Reaction) until the quantity necessary for analysis is obtained, amplification and analysis being carried out using specific primers. The ink is generally removed by scraping, which has the disadvantage of damaging the object.
Il existe un besoin pour authentifier et/ou identifier un objet sans réaliser d'analyse destructive de l'objet.There is a need to authenticate and / or identify an object without carrying out a destructive analysis of the object.
Un tel besoin d'authentification et/ou d'identification existe notamment pour les papiers destinés à des utilisations diverses, en particulier les papiers destinés à servir de support à des œuvres d'art ou les papiers utilisés pour la fabrication de documents de sécurité, de documents de valeur ou de vignettes, par exemple des passeports, des billets de banque ou des étiquettes destinées à être apposées sur des articles ou des emballages.Such a need for authentication and / or identification exists in particular for papers intended for various uses, in particular papers intended to serve as a support for works of art or papers used for the manufacture of security documents, valuable documents or labels, for example passports, banknotes or labels to be affixed to articles or packaging.
L'invention vise notamment à répondre à ce besoin.The invention aims in particular to meet this need.
L'invention a ainsi pour objet un nouveau papier, caractérisé par le fait qu'il comporte des corps porteurs d'au moins un marqueur biochimique et présentant une taille suffisante pour pouvoir être prélevés isolément.The invention thus relates to a new paper, characterized in that it comprises bodies carrying at least one biochemical marker and having a size sufficient to be able to be removed in isolation.
Les corps utilisés sont de préférence des corps ayant une bonne affinité avec le papier, de manière à rester solidaires de ce dernier lors des procédés de transformation et d'utilisation usuels de celui-ci, notamment lors de l'impression. Les corps porteurs du marqueur biochimique sont avantageusement incorporés à la masse fibreuse papetière avant que le papier ne soit livré aux utilisateurs finaux.The bodies used are preferably bodies having a good affinity with the paper, so as to remain integral with the latter during the usual processing and use of the latter, in particular during printing. The bodies carrying the biochemical marker are advantageously incorporated into the paper fiber mass before the paper is delivered to end users.
L'extraction des corps porteurs du marqueur biochimique peut s'effectuer facilement, de manière mécanique, sans détruire l'aspect du papier, par exemple à l'aide de brucelles, sous contrôle visuel à l'aide d'un microscope éventuellement.Extraction of bodies carrying the biochemical marker can be carried out easily, mechanically, without destroying the appearance of the paper, for example using tweezers, under visual control using a microscope if necessary.
De préférence, pour faciliter leur enlèvement, la plus grande dimension desdits corps est supérieure à 100 μm, et de préférence de l'ordre d'un à quelques mm, par exemple comprise entre 1 et 10 mm.Preferably, to facilitate their removal, the largest dimension of said bodies is greater than 100 μm, and preferably of the order of one to a few mm, for example between 1 and 10 mm.
Les corps utilisés peuvent être des fibres ou agglomérats de fibres, de tels agglomérats pouvant former des planchettes, les fibres pouvant être naturelles, artificielles ou synthétiques.The bodies used can be fibers or agglomerates of fibers, such agglomerates being able to form boards, the fibers being able to be natural, artificial or synthetic.
La longueur des fibres porteuses du marqueur biochimique peut être par exemple comprise entre 3 et 10 mm, étant préférentiellement voisine de 5 mm.The length of the fibers carrying the biochemical marker can for example be between 3 and 10 mm, being preferably close to 5 mm.
Le diamètre ou plus grande dimension des planchettes porteuses du marqueur biochimique peut être supérieur à 2 mm, par exemple.The diameter or larger dimension of the boards carrying the biochemical marker can be greater than 2 mm, for example.
Lorsque des fibres sont utilisées, ces dernières peuvent être réalisées de multiples manières, selon la nature de leur constituant principal. On peut notamment les réaliser par filage lorsqu'elles sont constituées de viscose essentiellement, ou par extrusion lorsqu'elles sont réalisées dans une matière thermoplastique telle que le polyamide ou le polypropylène.When fibers are used, the latter can be produced in multiple ways, depending on the nature of their main constituent. They can in particular be produced by spinning when they consist essentially of viscose, or by extrusion when they are made of a thermoplastic material such as polyamide or polypropylene.
Le marqueur biochimique peut être incorporé aux corps destinés à le porter de multiples manières, pendant ou après la fabrication desdits corps. Lorsque lesdits corps sont des fibres, le marqueur biochimique peut être incorporé à la matière destinée à constituer les fibres avant l'élaboration de ces dernières par filage ou extrusion, ou après leur fabrication par un procédé de teinture ou autre.The biochemical marker can be incorporated into bodies intended to carry it in multiple ways, during or after the manufacture of said bodies. When said bodies are fibers, the biochemical marker can be incorporated into the material intended to constitute the fibers before the latter are produced by spinning or extrusion, or after their manufacture by a dyeing or other process.
Lorsque les corps sont des agglomérats de fibres tels que des planchettes, le marqueur biochimique peut être déposé sur le papier destiné à constituer les planchettes par un traitement de surface, notamment à l'aide d'une presse encoUeuse ou d'une imprégnatrice.When the bodies are agglomerates of fibers such as boards, the biochemical marker can be deposited on the paper intended to constitute the boards by a surface treatment, in particular using an encoUeuse press or an impregnator.
Le marqueur biochimique peut encore être greffé chimiquement sur les fibres ou autres corps utilisés, avec établissement d'une liaison chimique forte entre le marqueur biochimique et la fibre ou autre corps. Les corps porteurs du marqueur biochimique peuvent être colorés ou non, la coloration pouvant faciliter leur repérage au sein de la masse fibreuse du papier.The biochemical marker can also be chemically grafted onto the fibers or other bodies used, with the establishment of a strong chemical bond between the biochemical marker and the fiber or other body. The bodies carrying the biochemical marker may or may not be colored, the coloring being able to facilitate their identification within the fibrous mass of the paper.
Les corps porteurs du marqueur biochimique peuvent être incolores mais présenter une fluorescence dans l'infrarouge ou l'ultraviolet, leur prélèvement s'effectuant alors sous un éclairage adéquat.The bodies carrying the biochemical marker may be colorless but exhibit fluorescence in the infrared or ultraviolet, their sampling then being carried out under adequate lighting.
Les corps porteurs du marqueur biochimique peuvent être incolores en apparence mais présenter une fluorescence dont les caractéristiques d'absorption et d'émission sont comprises entre 400 et 800 nm. La révélation des corps est obtenue sous éclairage adéquat et à travers un filtre optique qui sélectionne l'émission de fluorescence dans une plage de longueurs d'ondes du visible. Le principe optique de révélation des fluorescences du domaine du visible est décrit plus précisément dans la demande de brevet PCT/FR01/02480 dont le contenu est incorporé pour référence. Les corps porteurs du marqueur biochimique peuvent être incorporés à la masse fibreuse papetière de différentes façons.The bodies carrying the biochemical marker can be colorless in appearance but present a fluorescence whose absorption and emission characteristics are between 400 and 800 nm. The revelation of the bodies is obtained under adequate lighting and through an optical filter which selects the emission of fluorescence in a range of wavelengths of the visible. The optical principle of revealing fluorescence in the visible range is described more precisely in patent application PCT / FR01 / 02480, the content of which is incorporated for reference. The bodies carrying the biochemical marker can be incorporated into the paper fiber mass in different ways.
Les corps porteurs du marqueur biochimique peuvent être appliqués en semis, leur répartition dans la masse fibreuse papetière étant alors aléatoire, mais de préférence, ils sont appliqués de manière à former une bande relativement étroite, ce qui présente l'avantage de réduire la quantité de marqueur biochimique utilisée.The bodies carrying the biochemical marker can be applied in sowing, their distribution in the paper fiber mass then being random, but preferably, they are applied so as to form a relatively narrow band, which has the advantage of reducing the amount of biochemical marker used.
Le papier peut comporter d'autres éléments de sécurité en plus des corps porteurs du marqueur biochimique, ces éléments de sécurité constituant au moins un moyen d'authentification et/ou d'identification supplémentaire.The paper may include other security elements in addition to the bodies carrying the biochemical marker, these security elements constituting at least one means of authentication and / or additional identification.
Les corps porteurs du marqueur biochimique peuvent présenter d'autres propriétés d'authentification, notamment être radioactifs, magnétiques, ou encore présenter des propriétés de résonance électromagnétique à des fréquences particulières et/ou changer d'aspect selon l'angle d'observation ou sous l'action d'une source d'excitation tel qu'un rayonnement.The bodies carrying the biochemical marker can have other authentication properties, in particular be radioactive, magnetic, or even have electromagnetic resonance properties at particular frequencies and / or change their appearance depending on the angle of observation or under the action of an excitation source such as radiation.
Les corps porteurs du marqueur biochimique peuvent notamment contenir des microsphères détectables par microscopie à épifluorescence, ces microsphères étant liées ou non au marqueur biochimique. Les microsphères peuvent être des particules minérales marquées d'une fluorescence spécifique par liaison covalente, comme décrit dans la demande de brevet WO0130936.The bodies carrying the biochemical marker can in particular contain microspheres detectable by epifluorescence microscopy, these microspheres being linked or not to the biochemical marker. The microspheres can be mineral particles marked with a specific fluorescence by covalent bond, as described in patent application WO0130936.
Les corps porteurs du marqueur biochimique peuvent être notamment des fibres fluorescentes, thermochromes ou photochromes.The bodies carrying the biochemical marker can in particular be fluorescent, thermochromic or photochromic fibers.
La densité de corps porteurs du marqueur biochimique peut être très faible et inférieure par exemple à 10 corps par dm2 de papier lorsque la répartition desdits corps est aléatoire et s'étend à l'ensemble du papier, ou inférieure à 10 corps par dm linéaire lorsque les corps sont confinés dans une bande. Chaque corps peut comporter plus de 10 séquences par exemple.The density of bodies carrying the biochemical marker can be very low and less, for example, to 10 bodies per dm 2 of paper when the distribution of said bodies is random and extends to the entire paper, or less than 10 bodies per linear dm when the bodies are confined in a strip. Each body can have more than 10 sequences for example.
Le marqueur biochimique peut être noyé dans la matière constituant lesdits corps, comme indiqué plus haut, ou être présent à leur surface uniquement, ou les deux.The biochemical marker can be embedded in the material constituting said bodies, as indicated above, or be present on their surface only, or both.
Le marqueur biochimique sera préférentiellement noyé dans la matière constituant les corps, ce qui permet de le protéger contre les attaques physiques, notamment l'abrasion, ou chimiques, notamment par les produits de falsification.The biochemical marker will preferably be embedded in the material constituting the bodies, which makes it possible to protect it against physical attacks, in particular abrasion, or chemical attacks, in particular by falsification products.
Lorsque le marqueur biochimique est apporté par un traitement de surface, il sera de préférence lié au corps porteur grâce à un liant très réticulé afin de le protéger, un tel liant pouvant être notamment un polyuréthane réticulé par une azidine ou un copolymère styrène-acrylate réticulé avec une mélamine-formol.When the biochemical marker is provided by a surface treatment, it will preferably be linked to the carrier body by means of a very crosslinked binder in order to protect it, such a binder being able in particular to be a polyurethane crosslinked with an azidine or a crosslinked styrene-acrylate copolymer with a melamine-formaldehyde.
Comme marqueur biochimique, on utilisera de préférence des séquences monobrin d'au moins 70 nucléotides, par exemple au moins 80 nucléotides. On utilisera de préférence au moins 105 de telles séquences par corps porteur.As biochemical marker, preferably single strand sequences of at least 70 nucleotides, for example at least 80 nucleotides, will be used. Preferably, at least 10 5 such sequences will be used per carrier body.
Un tel marqueur biochimique offre un grand nombre de possibilités de codage et s'avère extrêmement difficile à détecter.Such a biochemical marker offers a large number of coding possibilities and is extremely difficult to detect.
La détection de séquence d'ADN de 70 à 110 nucléotides en nombre inférieur à 10 molécules nécessite une « amplification ». On entend par « amplification » le processus qui consiste à dupliquer des séquences d'ADN par une réaction de polymérisation en chaîne appelée communément PCR.Detection of DNA sequences from 70 to 110 nucleotides in number less than 10 molecules requires "amplification". The term “amplification” is understood to mean the process which consists in duplicating DNA sequences by a polymerization chain reaction commonly called PCR.
La réalisation de l'amplification de la séquence nécessite au moins une amorce (brin d'ADN complémentaire d'une extrémité de la séquence à amplifier)The amplification of the sequence requires at least one primer (strand of DNA complementary to one end of the sequence to be amplified)
En l'absence d'une telle amorce, l'amplification ne peut avoir lieu, ce qui offre déjà un moyen permettant de limiter l'accès à la détection de la séquence d'ADN.In the absence of such a primer, amplification cannot take place, which already offers a means of limiting access to the detection of the DNA sequence.
La séquence peut comporter une suite de nucléotides codant des informations d'identification, en plus de la suite de nucléotides complémentaire de l'amorce précitée.The sequence may include a sequence of nucleotides encoding identification information, in addition to the sequence of nucleotides complementary to the above-mentioned primer.
Un moyen d'authentification de l'ADN peut être avantageusement l'utilisation de sondes fluorimétriques spécifiques qui par hybridation avec une région centrale des séquences dupliquées par PCR émettent un signal fluorescent qui peut être mesuré par un laser. L'intensité du signal fluorescent est corrélée à un nombre de séquences amplifiées.A means of DNA authentication can advantageously be the use of specific fluorimetric probes which, by hybridization with a central region of the sequences duplicated by PCR, emit a fluorescent signal which can be measured by a laser. The intensity of the fluorescent signal is correlated with a number of amplified sequences.
L'avantage de cette technique est qu'elle permet de valider en temps réel une amplification appelée alors amplification quantitative.The advantage of this technique is that it validates an amplification in real time then called quantitative amplification.
Comme séquences monobrin d'au moins 70 nucléotides, on utilisera de préférence des séquences réalisées selon les enseignements de la demande de brevet WO00/61799 de manière à pouvoir être amplifiées et détectées par PCR quantitative. D'autres marqueurs biochimiques sont utilisables, notamment de l'ADN naturel double brin ou des sémaphores moléculaires.As single strand sequences of at least 70 nucleotides, use will preferably be made of sequences produced according to the teachings of patent application WO00 / 61799 so that they can be amplified and detected by quantitative PCR. Other biochemical markers can be used, in particular natural double-stranded DNA or molecular semaphores.
L'invention a encore pour objet un procédé de fabrication de papier, caractérisé par le fait qu'il comporte l'étape consistant à incorporer à la masse fibreuse papetière des corps, notamment des fibres, porteurs d'au moins un marqueur biochimique. Les corps porteurs du marqueur biochimique peuvent être introduits en masse ou par un traitement de surface.The subject of the invention is also a method of manufacturing paper, characterized in that it comprises the step consisting in incorporating bodies, in particular fibers, carrying at least one biochemical marker into the papermaking fibrous mass. The bodies carrying the biochemical marker can be introduced en masse or by surface treatment.
On peut notamment mélanger lesdits corps à un bain, notamment d'imprégnation, de presse encoUeuse ou de couchage, utilisé lors du traitement de la masse fibreuse papetière. Les corps peuvent être répartis sur toute la laize ou sur une partie seulement de celle-ci.Said bodies can in particular be mixed with a bath, in particular an impregnation bath, a coating press or a coating press, used during the treatment of the paper fiber mass. The bodies can be distributed over the entire width or only over a part thereof.
Concernant la fabrication desdits corps, lorsque ces derniers sont constitués par des fibres extradées, le marqueur biochimique est avantageusement introduit dans un mélange maître utilisé lors de leur extrusion. L'invention a encore pour objet un procédé d'authentification et/ou d'identification d'un papier dans lequel ont été incorporés lors du processus de fabrication du papier des corps porteurs d'au moins un marqueur biochimique, comprenant l'étape consistant à repérer et à prélever dans le papier au moins un corps porteur du marqueur biochimique. Lorsque le marqueur biochimique est une séquence de nucléotides monobrin, le procédé peut comporter en outre l'étape consistant à séparer les séquences de la matrice du corps auquel elles sont rattachées ou incorporées, la matrice du corps étant la matière constituante du corps. On qualifie l'étape de séparation de la matrice et des séquences ADN d'étape d'extraction et de purification d'ADN. Lorsque le marqueur biochimique est incorporé à la matrice du corps, l'extraction du marqueur peut passer par une étape de dissolution de la matrice du corps au moyen d'un ou plusieurs solvants adéquats.As regards the manufacture of said bodies, when the latter consist of extruded fibers, the biochemical marker is advantageously introduced into a masterbatch used during their extrusion. The subject of the invention is also a method of authenticating and / or identifying a paper into which the bodies carrying at least one biochemical marker have been incorporated during the process of making paper. to identify and take from the paper at least one body carrying the biochemical marker. When the biochemical marker is a single-stranded nucleotide sequence, the method may further comprise the step of separating the sequences from the matrix of the body to which they are attached or incorporated, the matrix of the body being the constituent material of the body. The step of separating the matrix and the DNA sequences is called the DNA extraction and purification step. When the biochemical marker is incorporated into the body matrix, the extraction of the marker can go through a step of dissolving the body matrix using one or more suitable solvents.
Lorsque le marqueur biochimique est une séquence de nucléotides monobrin, le procédé peut comporter l'étape d'authentification de l'ADN par une réaction de PCR au moyen d'amorces spécifiques.When the biochemical marker is a single-stranded nucleotide sequence, the method may include the step of authenticating the DNA by a PCR reaction using specific primers.
En réalisant une amplification quantitative au moyen d'amorces spécifiques et de sondes fluorimétriques spécifiques, on peut valider en temps réel l'amplification et identifier l'ADN amplifié. Le papier est alors identifié.By carrying out a quantitative amplification using specific primers and specific fluorimetric probes, it is possible to validate the amplification in real time and identify the amplified DNA. The paper is then identified.
Dans le cas d'amplification par PCR non quantitative, cette amplification peut être suivie d'une analyse par exemple par un séquençage, afin d'identifier la séquence d'ADN qui a été introduite dans le papier.In the case of amplification by non-quantitative PCR, this amplification can be followed by an analysis, for example by sequencing, in order to identify the DNA sequence which has been introduced into the paper.
L'invention a encore pour objet des fibres ou planchettes comprenant au moins un marqueur biochimique, de préférence au moins une séquence de nucléotides, avantageusement monobrin et comprenant au moins 70 nucléotides, notamment au moins 80 nucléotides.The subject of the invention is also fibers or boards comprising at least one biochemical marker, preferably at least one nucleotide sequence, advantageously single-stranded and comprising at least 70 nucleotides, in particular at least 80 nucleotides.
D'autres caractéristiques et avantages de la présente invention ressortiront à la lecture de la description détaillée qui va suivre, d'exemples de mise en œuvre non limitatifs, et à l'examen du dessin annexé, sur lequel :Other characteristics and advantages of the present invention will emerge on reading the detailed description which follows, of nonlimiting examples of implementation, and on examining the appended drawing, in which:
- la figure 1 est une vue schématique de face d'un papier conforme à un premier exemple de mise en œuvre de l'invention,FIG. 1 is a schematic front view of a paper according to a first example of implementation of the invention,
- la figure 2 est une vue schématique de face d'un papier conforme à un deuxième exemple de mise en œuvre de l'invention, - la figure 3 est une vue schématique et partielle de face d'un papier comportant des planchettes revêtues d'un marqueur biochimique,- Figure 2 is a schematic front view of a paper according to a second example of implementation of the invention, - Figure 3 is a schematic and partial front view of a paper comprising boards coated with a biochemical marker,
- les figures 4 et 5 sont des sections transversales de deux exemples de fibres porteuses chacune d'un marqueur biochimique,FIGS. 4 and 5 are cross sections of two examples of fibers each carrying a biochemical marker,
- la figure 6 représente de manière schématique une séquence de nucléotides servant de marqueur biochimique, etFIG. 6 schematically represents a nucleotide sequence serving as a biochemical marker, and
- la figure 7 est un schéma en blocs illustrant de manière schématique différentes étapes d'un procédé d'identification.- Figure 7 is a block diagram schematically illustrating different steps of an identification method.
On a représenté aux figures 1 à 3 une feuille de papier 1 conforme à l'invention, comportant une masse fibreuse papetière 2, constituée essentiellement par des fibres de cellulose par exemple, et une pluralité de corps 3, porteurs chacun d'un marqueur biochimique spécifique, comme cela sera précisé dans la suite.There is shown in Figures 1 to 3 a sheet of paper 1 according to the invention, comprising a paper fiber mass 2, consisting essentially of cellulose fibers for example, and a plurality of bodies 3, each carrying a biochemical marker specific, as will be explained below.
Les corps 3 sont constitués sur les figures 1 et 2 par des fibres et sur la figure 3 par des planchettes.The bodies 3 are formed in Figures 1 and 2 by fibers and in Figure 3 by boards.
Dans l'exemple des figures 1 et 2, la longueur moyenne des fibres 3 est de 5 mm, leur diamètre est de 25 μm, et leur volume spécifique voisin de 1.In the example of FIGS. 1 and 2, the average length of the fibers 3 is 5 mm, their diameter is 25 μm, and their specific volume close to 1.
Leur répartition à la surface de la masse fibreuse papetière 2 est aléatoire dans l'exemple de la figure 1.Their distribution on the surface of the paper fiber mass 2 is random in the example of FIG. 1.
En revanche, les fibres 3 sont confinées dans une zone limitée de la laize dans l'exemple de la figure 2, formant ainsi une bande 4 relativement étroite.On the other hand, the fibers 3 are confined in a limited zone of the width in the example of FIG. 2, thus forming a relatively narrow strip 4.
Les fibres 3 peuvent être réalisées par filage, principalement à partir de viscose par exemple, ou par extrusion de polypropylène par exemple, d'autres matériaux et d'autres procédés de fabrication étant bien entendu utilisables.The fibers 3 can be produced by spinning, mainly from viscose for example, or by extrusion of polypropylene for example, other materials and other manufacturing processes being of course usable.
Le marqueur biochimique est constitué, dans l'exemple illustré, par des séquences 5 de nucléotides.The biochemical marker consists, in the example illustrated, of nucleotide sequences.
Ces séquences 5 ont été représentées à échelle agrandie sur les figures 4 et 5, sans respect des proportions réelles. Elles peuvent être liées, le cas échéant, à des microsphères, comme cela est décrit dans le brevet US 5 763 176.These sequences 5 have been shown on an enlarged scale in FIGS. 4 and 5, without respecting the actual proportions. They can be linked, if necessary, to microspheres, as described in US Pat. No. 5,763,176.
Pour chaque corps 3, les séquences 5 peuvent être dispersées dans la masse du corps 3, à sa surface ou les deux.For each body 3, the sequences 5 can be dispersed in the mass of the body 3, on its surface or both.
Chaque corps 3 comporte dans l'exemple décrit entre environ 105 et 108 séquences, chaque séquence 5 étant constituée par un simple brin d'ADN comprenant de préférence entre 70 et 110 nucléotides, par exemple entre 80 et 100 nucléotides.Each body 3 comprises in the example described between approximately 10 5 and 10 8 sequences, each sequence 5 being constituted by a single strand of DNA preferably comprising between 70 and 110 nucleotides, for example between 80 and 100 nucleotides.
Des exemples de marqueurs biochimiques comprenant des séquences de nucléotides sont donnés dans le brevet US 5 763 176 et dans la les demandes internationales WO94/04918 et WO00/61799, auxquels on se référera utilement, de tels marqueurs étant commercialisés par la société CYPHER SCIENCE notamment. La séquence 5 de nucléotides comporte de façon connue en soi une suite de bases choisies par exemple dans la liste suivante : adénine A, cytosine C, guanine G, thymine T, cette dernière pouvant être remplacée par de l'uracile, d'autres composés et dérivés de nucléotides pouvant être encore utilisés, le cas échéant.Examples of biochemical markers comprising nucleotide sequences are given in US Pat. . The nucleotide sequence 5 comprises in a manner known per se a series of bases chosen for example from the following list: adenine A, cytosine C, guanine G, thymine T, the latter being able to be replaced by uracil, other compounds and nucleotide derivatives which can still be used, if necessary.
On a représenté à la figure 6, de manière schématique, une séquence 5 qui comporte des régions extrêmes 7 et 8 composées chacune par une suite prédéterminée de bases et une région centrale 9 constituant la séquence porteuse de l'information d'identification. Les régions extrêmes 7 et 8 sont destinées à reconnaître des amorces complémentaires lors de l'amplification par PCR, et comportent par exemple entre 20 et 25 bases chacune.FIG. 6 shows schematically a sequence 5 which comprises end regions 7 and 8 each composed by a predetermined series of bases and a central region 9 constituting the sequence carrying the identification information. The extreme regions 7 and 8 are intended to recognize complementary primers during the amplification by PCR, and comprise for example between 20 and 25 bases each.
Seules trois ou quatre bases ont été représentées à la figure 6 dans un souci de clarté du dessin.Only three or four bases have been shown in Figure 6 for the sake of clarity of the drawing.
La région centrale 9 comporte par exemple entre 30 et 60 bases dont une partie est destinée à être reconnue par des sondes fluorimétriques spécifiques. Seules six bases ont été représentées dans un souci de simplification.The central region 9 comprises for example between 30 and 60 bases, part of which is intended to be recognized by specific fluorimetric probes. Only six bases have been represented for the sake of simplification.
Les corps 3 peuvent être incorporés au papier de diverses manières, selon la répartition des corps 3 que l'on souhaite à la surface du papier.The bodies 3 can be incorporated into the paper in various ways, depending on the distribution of the bodies 3 that are desired on the surface of the paper.
Ils peuvent être mélangés à un bain utilisé lors du processus de fabrication du papier, par exemple un bain d'imprégnation, de presse encoUeuse ou de couchage.They can be mixed with a bath used during the papermaking process, for example an impregnation bath, a coating press or a coating bath.
Ils peuvent encore être pulvérisés à la surface du papier.They can still be sprayed onto the surface of the paper.
Pour authentifier et/ou identifier un papier conforme à l'invention, on commence par repérer les corps 3 et on procède ensuite à leur prélèvement à l'étape 10, comme illustré à la figure 7.To authenticate and / or identify a paper in accordance with the invention, we start by locating the bodies 3 and then we collect them in step 10, as illustrated in FIG. 7.
Ce prélèvement peut s'effectuer à l'aide ou non d'un microscope, au moyen de brucelles par exemple, sans altérer l'aspect du papier.This sample can be taken with or without a microscope, using tweezers for example, without altering the appearance of the paper.
Le nombre de corps 3 prélevés peut être très faible et être égal à dix par exemple.The number of bodies 3 removed can be very low and be equal to ten for example.
Une fois les corps 3 prélevés, on en dissout la matrice à l'étape 11 afin d'en extraire le marqueur biochimique.Once the bodies 3 have been removed, the matrix is dissolved in step 11 in order to extract the biochemical marker therefrom.
Lorsque les corps 3 prélevés sont constitués par des fibres de viscose, on peut les placer dans un bain d'acétate d'éthyle que l'on chauffe légèrement. Au fur et à mesure que l'acétate d'éthyle s'évapore, on rajoute du solvant jusqu'à dissolution complète des fibres. On ajoute en fin de dissolution un mélange d'eau et d'éthanol destiné à précipiter l'ADN.When the bodies 3 taken consist of viscose fibers, they can be placed in an ethyl acetate bath which is slightly heated. As the ethyl acetate evaporates, solvent is added until the fibers are completely dissolved. At the end of dissolution, a mixture of water and ethanol intended to precipitate the DNA is added.
Lorsque les corps 3 prélevés sont constitués par des fibres de polypropylène, on les place par exemple dans une cartouche d'extraction d'un extracteur Soxhlet commercialisé par exemple par la société MERCK et que l'on fait fonctionner avec du xylène.When the bodies 3 sampled consist of polypropylene fibers, they are placed for example in an extraction cartridge of a Soxhlet extractor sold for example by the company MERCK and which is operated with xylene.
Le produit de la dissolution est ensuite purifié par exemple en utilisant un kit de purification de marque « DNeasy » et commercialisé par la société QIAGEN. La procédure de purification peut consister à séparer le marqueur biochimique de la matrice dissoute.The product of the dissolution is then purified for example using a kit “DNeasy” brand purification solution marketed by QIAGEN. The purification procedure can consist in separating the biochemical marker from the dissolved matrix.
Une fois les séquences 5 de nucléotides extraites et purifiées, on effectue à l'étape 12 une amplification quantitative par PCR à l'aide d'amorces spécifiques et de sondes fluorimétriques spécifiques. Les amorces spécifiques permettent l'amplification des séquences 5, tandis que les sondes fluorimétriques permettent de mesurer en temps réel la quantité d'ADN amplifiée.Once the nucleotide sequences 5 have been extracted and purified, a quantitative amplification by PCR is carried out in step 12 using specific primers and specific fluorimetric probes. The specific primers allow the amplification of the 5 sequences, while the fluorimetric probes make it possible to measure in real time the quantity of amplified DNA.
L'amplification par PCR nécessite l'utilisation d'amorces spécifiques. Ainsi, seule une personne disposant de ces amorces spécifiques est capable de procéder à l'amplification.Amplification by PCR requires the use of specific primers. Thus, only a person having these specific primers is capable of carrying out the amplification.
La séquence 5 peut être réalisée selon les caractéristiques décrites dans la demande de brevet WO00/61799, ce qui permet de réaliser une PCR quantitative.The sequence 5 can be carried out according to the characteristics described in patent application WO00 / 61799, which makes it possible to carry out a quantitative PCR.
Bien entendu, l'invention n'est pas limitée aux exemples qui viennent d'être donnés.Of course, the invention is not limited to the examples which have just been given.
On peut notamment utiliser d'autres marqueurs biochimiques que ceux décrits dans la les demandes internationales O94/04918 et WO00/61799 et notamment des sémaphores moléculaires tels que décrits dans la revue "Sciences & Avenir" de juillet 2000, pages 60-61. De tels sémaphores comportent une boucle d'ADN aux extrémités de laquelle sont greffées une molécule fluorescente et une molécule cache.One can in particular use other biochemical markers than those described in the international applications O94 / 04918 and WO00 / 61799 and in particular molecular semaphores such as described in the review "Sciences & Avenir" of July 2000, pages 60-61. Such semaphores have a DNA loop at the ends of which are grafted a fluorescent molecule and a hidden molecule.
Si la boucle reconnaît sur un brin d'ADN la séquence complémentaire, elle s'ouvre et devient fluorescente, et dans la négative elle reste repliée et n'émet pas de lumière. On peut encore utiliser comme marqueur biochimique de l'ADN naturel double brin.If the loop recognizes on a strand of DNA the complementary sequence, it opens and becomes fluorescent, and if not it remains folded and does not emit light. It is also possible to use, as biochemical marker, natural double-stranded DNA.
Dans ce cas, l'amplification peut s'effectuer sans amorce spécifique. In this case, the amplification can be carried out without specific primer.

Claims

REVENDICATIONS
1. Papier (1) caractérisé par le fait qu'il comporte des corps (3) porteurs d'au moins un marqueur biochimique (5) et présentant une taille suffisante pour pouvoir être prélevés isolément.1. Paper (1) characterized in that it comprises bodies (3) carrying at least one biochemical marker (5) and having a size sufficient to be able to be removed in isolation.
2. Papier selon la revendication 1, caractérisé par le fait que la plus grande dimension desdits corps (3) est supérieure à 100 μm et de préférence comprise entre 1 et 10 mm.2. Paper according to claim 1, characterized in that the largest dimension of said bodies (3) is greater than 100 microns and preferably between 1 and 10 mm.
3. Papier selon la revendication 1 ou 2, caractérisé par le fait que les corps (3) sont des fibres ou agglomérats de fibres.3. Paper according to claim 1 or 2, characterized in that the bodies (3) are fibers or fiber agglomerates.
4. Papier selon la revendication 3, les corps étant des fibres, caractérisé par le fait que la longueur des fibres (3) est comprise entre 3 et 10 mm, étant de préférence voisine de 5 mm.4. Paper according to claim 3, the bodies being fibers, characterized in that the length of the fibers (3) is between 3 and 10 mm, preferably being close to 5 mm.
5. Papier selon la revendication 3 ou 4, les corps étant des agglomérats de fibres constituant des planchettes, caractérisé par le fait que le diamètre des planchettes est supérieur à 2 mm.5. Paper according to claim 3 or 4, the bodies being agglomerates of fibers constituting boards, characterized in that the diameter of the boards is greater than 2 mm.
6. Papier selon la revendication 3 ou 4, caractérisé par le fait que les corps sont des fibres extradées, le marqueur biochimique étant mélangé à un constituant des fibres avant l'extrusion. 6. Paper according to claim 3 or 4, characterized in that the bodies are extruded fibers, the biochemical marker being mixed with a constituent of the fibers before extrusion.
7. Papier selon la revendication 3 ou 4, les corps étant des fibres, caractérisé par le fait que les fibres (3) sont à base de viscose.7. Paper according to claim 3 or 4, the bodies being fibers, characterized in that the fibers (3) are based on viscose.
8. Papier selon l'une quelconque des revendications précédentes, caractérisé par le fait que les corps (3) porteurs du marqueur biochimique (5) sont colorés.8. Paper according to any one of the preceding claims, characterized in that the bodies (3) carrying the biochemical marker (5) are colored.
9. Papier selon l'une quelconque des revendications précédentes, caractérisé par le fait que les corps (3) porteurs du marqueur biochimique (5) présentent une fluorescence dans l'infrarouge ou l'ultraviolet.9. Paper according to any one of the preceding claims, characterized in that the bodies (3) carrying the biochemical marker (5) have a fluorescence in the infrared or ultraviolet.
10. Papier selon l'une quelconque des revendications 1 à 8, caractérisé par le fait que les corps (3) porteurs du marqueur biochimique (5) présentent une fluorescence du domaine du visible qui s'observe sous excitation spécifique à travers un filtre. 10. Paper according to any one of claims 1 to 8, characterized in that the bodies (3) carrying the biochemical marker (5) have a fluorescence of the visible range which is observed under specific excitation through a filter.
11. Papier selon l'une quelconque des revendications précédentes, caractérisé par le fait que les corps (3) porteurs du marqueur biochimique (5) contiennent aussi des microsphères fluorescentes, notamment à base minérale. 11. Paper according to any one of the preceding claims, characterized in that the bodies (3) carrying the biochemical marker (5) also contain fluorescent microspheres, in particular mineral-based.
12. Papier selon l'une quelconque des revendications précédentes, caractérisé par le fait que les corps (3) porteurs du marqueur biochimique présentent d'autres propriétés d'authentification, notamment sont radioactifs, magnétiques ou présentent des propriétés de résonance électromagnétique à des fréquences particulières et/ou changent d'aspect selon l'angle d'observation ou sous l'action d'une source d'excitation tel qu'un rayonnement, les corps (3) porteurs du marqueur biochimique pouvant être notamment des fibres fluorescentes, thermochromes ou photochromes.12. Paper according to any one of the preceding claims, characterized in that the bodies (3) carrying the biochemical marker have other authentication properties, in particular are radioactive, magnetic or have properties of electromagnetic resonance at frequencies particular and / or change in appearance depending on the angle of observation or under the action of a source of excitation such as radiation, the bodies (3) carrying the biochemical marker can be in particular fluorescent fibers, thermochromes or photochromic.
13. Papier selon l'une quelconque des revendications précédentes, caractérisé par le fait que la répartition des corps (3) porteurs du marqueur biochimique (5) dans la masse papetière (2) est aléatoire.13. Paper according to any one of the preceding claims, characterized in that the distribution of the bodies (3) carrying the biochemical marker (5) in the paper mass (2) is random.
14. Papier selon l'une quelconque des revendications 1 à 12, caractérisé par le fait que les corps (3) porteurs du marqueur biochimique (5) sont confinés selon une bande (4).14. Paper according to any one of claims 1 to 12, characterized in that the bodies (3) carrying the biochemical marker (5) are confined in a strip (4).
15. Papier selon l'une quelconque des revendications précédentes, caractérisé par le fait que la densité de corps (3) porteurs du marqueur biochimique (5) est inférieure à15. Paper according to any one of the preceding claims, characterized in that the density of bodies (3) carrying the biochemical marker (5) is less than
10 corps par dm2 de papier lorsque la répartition des corps est aléatoire et s'étend à l'ensemble du papier, ou inférieure à 10 corps par dm linéaire lorsque les corps sont confinés dans une bande.10 bodies per dm 2 of paper when the distribution of the bodies is random and extends to the whole of the paper, or less than 10 bodies per linear dm when the bodies are confined in a strip.
16. Papier selon l'une quelconque des revendications précédentes, caractérisé par le fait que le marqueur biochimique est composé de séquences de nucléotides, de préférence d'au moins 105 séquences (5) de nucléotides.16. Paper according to any one of the preceding claims, characterized in that the biochemical marker is composed of nucleotide sequences, preferably at least 10 5 nucleotide sequences (5).
17. Papier selon la revendication 16, caractérisé par le fait que chaque corps (3) comporte plus de 107 séquences.17. Paper according to claim 16, characterized in that each body (3) has more than 10 7 sequences.
18. Papier selon la revendication 15 ou 16, caractérisé par le fait que chaque séquence est monobrin et comporte de préférence entre 70 et 110 nucléotides.18. Paper according to claim 15 or 16, characterized in that each sequence is single-strand and preferably comprises between 70 and 110 nucleotides.
19. Papier selon l'une quelconque des revendications précédentes, caractérisé par le fait que le marqueur biochimique est lié à un liant, notamment un liant tel qu'un polyméthane réticulé par un azidine ou un copolymère styrène-acrylate réticulé avec une mélamine-formol. 19. Paper according to any one of the preceding claims, characterized in that the biochemical marker is linked to a binder, in particular a binder such as a polymethane crosslinked with an azidine or a styrene-acrylate copolymer crosslinked with a melamine-formaldehyde .
20. Procédé de fabrication de papier, caractérisé par le fait qu'il comporte l'étape consistant à incorporer à la masse fibreuse papetière (2) lors du processus de fabrication du papier des corps, de préférence des fibres (3) ou agglomérats de fibres, porteurs d'au moins un marqueur biochimique (5).20. A method of manufacturing paper, characterized in that it comprises the step of incorporating into the paper fiber mass (2) during the paper manufacturing process bodies, preferably fibers (3) or agglomerates of fibers, carrying at least one biochemical marker (5).
21. Procédé selon la revendication précédente, caractérisé par le fait que les corps porteurs du marqueur biochimique (5) sont mélangés à un bain utilisé lors du traitement de la masse papetière. 21. Method according to the preceding claim, characterized in that the bodies carrying the biochemical marker (5) are mixed with a bath used during the treatment of the paper mass.
22. Procédé selon l'une des deux revendications immédiatement précédentes, caractérisé par le fait que le marqueur biochimique (5) a été préalablement introduit dans un mélange maître utilisé pour fabriquer par extrusion les fibres (3).22. Method according to one of the two immediately preceding claims, characterized in that the biochemical marker (5) has been previously introduced into a masterbatch used to manufacture the fibers (3) by extrusion.
23. Procédé selon l'une des revendications 20 ou 21, caractérisé par le fait que les fibres (3) sont réalisées par filage de viscose. 23. Method according to one of claims 20 or 21, characterized in that the fibers (3) are made by viscose spinning.
24. Procédé selon la revendication 22, caractérisé par le fait que les fibres (3) sont réalisées par extrusion de polypropylène.24. The method of claim 22, characterized in that the fibers (3) are made by extruding polypropylene.
25. Procédé d'authentification et ou d'identification d'un papier dans lequel ont été incorporés lors du processus de fabrication du papier des corps, de préférence des fibres (3) ou agglomérats de fibres, porteurs d'au moins un marqueur biochimique, comprenant l'étape consistant à repérer et à prélever dans le papier au moins un corps (3) porteur du marqueur biochimique.25. Method for authenticating and / or identifying a paper in which bodies, preferably fibers (3) or fiber agglomerates, carrying at least one biochemical marker, have been incorporated during the process of making paper , comprising the step of identifying and removing from the paper at least one body (3) carrying the biochemical marker.
26. Procédé selon la revendication précédente, caractérisé par le fait que le marqueur biochimique est extrait du corps par dissolution de la matrice dudit corps et par purification du produit de la dissolution. 26. Method according to the preceding claim, characterized in that the biochemical marker is extracted from the body by dissolution of the matrix of said body and by purification of the product of the dissolution.
27. Procédé selon la revendication 25, caractérisé par le fait que le marqueur biochimique comporte au moins une séquence (5) de nucléotides monobrin, et par le fait que l'on effectue une amplification par PCR au moyen d'amorces spécifiques.27. The method of claim 25, characterized in that the biochemical marker comprises at least one sequence (5) of single-stranded nucleotides, and in that an amplification is carried out by PCR using specific primers.
28. Procédé selon la revendication précédente, caractérisé par le fait que l'ADN est identifié en temps réel et quantitativement par l'occurrence de la réaction de PCR.28. Method according to the preceding claim, characterized in that the DNA is identified in real time and quantitatively by the occurrence of the PCR reaction.
29. Fibre ou planchette (3) comprenant au moins un marqueur biochimique, de préférence au moins une séquence (5) de nucléotides monobrin comprenant au moins 70 nucléotides.29. Fiber or planchette (3) comprising at least one biochemical marker, preferably at least one sequence (5) of single-stranded nucleotides comprising at least 70 nucleotides.
30. Fibre ou planchette selon la revendication 29, caractérisée par le fait que la plus grande dimension de la fibre ou planchette est supérieure à 100 μm et de préférence comprise entre 1 et 10 mm.30. Fiber or board according to claim 29, characterized in that the largest dimension of the fiber or board is greater than 100 μm and preferably between 1 and 10 mm.
31. Fibre selon la revendication 30, caractérisée par le fait que la longueur de la fibre est comprise entre 3 et 10 mm.31. Fiber according to claim 30, characterized in that the length of the fiber is between 3 and 10 mm.
32. Planchette selon la revendication 30, caractérisée par le fait qu'elle présente un diamètre supérieur à 2 mm.32. Plate according to claim 30, characterized in that it has a diameter greater than 2 mm.
33. Fibre selon la revendication 29, caractérisée par le fait qu'elle comporte une matrice extradée.33. Fiber according to claim 29, characterized in that it comprises an extruded matrix.
34. Fibre selon la revendication 29, caractérisée par le fait qu'elle est à base de viscose.34. Fiber according to claim 29, characterized in that it is based on viscose.
35. Fibre ou planchette selon la revendication 29, caractérisée par le fait qu'elle présente une fluorescence dans l'infrarouge ou l'ultraviolet. 35. Fiber or board according to claim 29, characterized in that it exhibits fluorescence in the infrared or ultraviolet.
36. Fibre ou planchette selon la revendication 29, caractérisée par le fait qu'elle présente une fluorescence du domaine du visible qui s'observe sous excitation spécifique à travers un filtre.36. Fiber or board according to claim 29, characterized in that it exhibits a fluorescence of the visible range which is observed under specific excitation through a filter.
37. Fibre ou planchette selon la revendication 29, caractérisée par le fait qu'elle comporte au moins une microsphère fluorescente, notamment une microsphère à buse minérale.37. Fiber or board according to claim 29, characterized in that it comprises at least one fluorescent microsphere, in particular a microsphere with mineral nozzle.
38. Fibre ou planchette selon la revendication 29, caractérisée par le fait qu'elle comporte d'autres propriétés d'authentification, notamment par le fait qu'elle est radioactive, magnétique ou présente des propriétés de résonance électromagnétiques à des fréquences particulières et/ou change d'aspect selon l'angle d'observation ou sous l'action d'une source d'excitation tel qu'un rayonnement.38. Fiber or board according to claim 29, characterized in that it has other authentication properties, in particular in that it is radioactive, magnetic or has electromagnetic resonance properties at particular frequencies and / or changes its appearance depending on the angle of observation or under the action of an excitation source such as radiation.
39. Fibre ou planchette selon la revendication 29, caractérisée par le fait qu'elle comporte plus de 107 séquences. 39. Fiber or board according to claim 29, characterized in that it comprises more than 10 7 sequences.
EP02712007A 2001-01-22 2002-01-18 Paper comprising bodies which comprise at least one biochemical marker Expired - Lifetime EP1354097B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0100805A FR2819831A1 (en) 2001-01-22 2001-01-22 PAPER COMPRISING BODIES CARRYING AT LEAST ONE BIOCHEMICAL MARKER
FR0100805 2001-01-22
PCT/FR2002/000209 WO2002057548A1 (en) 2001-01-22 2002-01-18 Paper comprising bodies which comprise at least one biochemical marker

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WO2002057548A1 (en) 2002-07-25
US20040063117A1 (en) 2004-04-01
US7235289B2 (en) 2007-06-26
BR0206645A (en) 2004-02-25
ATE541091T1 (en) 2012-01-15
BRPI0206645B1 (en) 2015-03-17
FR2819831A1 (en) 2002-07-26

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