EP1354097A1 - Papier, mit elementen die mindestens einen biochemischen marker enthalten - Google Patents

Papier, mit elementen die mindestens einen biochemischen marker enthalten

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
English (en)
French (fr)
Other versions
EP1354097B1 (de
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/de
Application granted granted Critical
Publication of EP1354097B1 publication Critical patent/EP1354097B1/de
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)
EP02712007A 2001-01-22 2002-01-18 Papier, mit elementen die mindestens einen biochemischen marker enthalten Expired - Lifetime EP1354097B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0100805A FR2819831A1 (fr) 2001-01-22 2001-01-22 Papier comportant des corps porteurs d'au moins un marqueur biochimique
FR0100805 2001-01-22
PCT/FR2002/000209 WO2002057548A1 (fr) 2001-01-22 2002-01-18 Papier comportant des corps porteurs d'au moins un marqueur biochimique

Publications (2)

Publication Number Publication Date
EP1354097A1 true EP1354097A1 (de) 2003-10-22
EP1354097B1 EP1354097B1 (de) 2012-01-11

Family

ID=8859078

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02712007A Expired - Lifetime EP1354097B1 (de) 2001-01-22 2002-01-18 Papier, mit elementen die mindestens einen biochemischen marker enthalten

Country Status (6)

Country Link
US (1) US7235289B2 (de)
EP (1) EP1354097B1 (de)
AT (1) ATE541091T1 (de)
BR (1) BRPI0206645B1 (de)
FR (1) FR2819831A1 (de)
WO (1) WO2002057548A1 (de)

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US5869160A (en) * 1996-06-07 1999-02-09 Avery Dennison Corporation Release coated liners and security labels containing such release coated liners
FR2818672B1 (fr) * 2000-12-22 2003-02-21 Arjo Wiggins Sa Papier de securite comportant une zone reagissant aux solvants apolaires
FR2838228B1 (fr) * 2002-04-03 2005-03-25 Arjo Wiggins Document de securite avec marqueur

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Also Published As

Publication number Publication date
BRPI0206645B1 (pt) 2015-03-17
US20040063117A1 (en) 2004-04-01
WO2002057548A1 (fr) 2002-07-25
ATE541091T1 (de) 2012-01-15
EP1354097B1 (de) 2012-01-11
BR0206645A (pt) 2004-02-25
US7235289B2 (en) 2007-06-26
FR2819831A1 (fr) 2002-07-26

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