Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—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
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
  • D21H17/24—Polysaccharides
  • D21H17/25—Cellulose
  • D21H17/26—Ethers thereof
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/63—Inorganic compounds
  • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
  • D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/63—Inorganic compounds
  • D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
• • 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
  • D21H21/28—Colorants ; Pigments or opacifying agents
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/28—Colorants ; Pigments or opacifying agents
  • D21H21/285—Colorants ; Pigments or opacifying agents insoluble
• • 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

Definitions

• the invention relates to a security paper tamper-proof vis-à-vis solvents.
• Documents such as checks, vouchers, passports, certain gift vouchers, identity documents and other documents such as medical prescriptions, title deeds and other vital documents contain personalized information that may be modified by counterfeiters.
• the changes involve using clearing agents to remove variable data from documents and to post new information, a new recipient, or another amount on a check, for example.
• the erasing agents used by counterfeiters are all those likely to be found commercially, it is particularly used bleach, acids, bases, redox combinations, solvents and very generally all products likely to erase inks such as for example hairsprays, white spirit, brake fluid, liquid stain removers etc.
• the paper processing method according to this mode of operation is a printing method. Solubilization by operation of dyes that are insoluble in water but soluble in solvents, these "organo-soluble" dyes being in a finely dispersed form in the mass of the paper, the particles being typically less than 20 ⁇ .
• the paper treatment method according to this mode of operation is a papermaking process, the particles being introduced into the paper pulp before the production of the sheet and therefore distributed in its volume.
• the unfalsifiable paper according to the invention being made mainly by paper means it is necessary to describe in more detail the technique known to date and its limitations.
• the concept of tampering with the current treatment relies on the introduction of organosolvent dyes into the entire sheet finely dispersed so that the individual particles of dyes are imperceptible to the eye and do not stain the paper because they are insoluble in water, these dyes solubilize under the action of the deleting agents containing solvents, producing a discolouration which is perceptible to the eye.
• the dye diffuses into the fibrous network and covers a larger surface than that of the individual particles, thereby developing a coloration.
• This paper processing is suitable enough when the paper is protected on the surface by a security film that hinders counterfeiters but in the case of unprotected paper surface, for example checks, tickets and the vast majority of security papers, counterfeiters found an effective response to this treatment by washing the paper by dipping or by successive application of the solvents so as to extract the dyes completely from the paper.
• the current solution of paper protection is no longer an appropriate response to the problem posed by counterfeiters.
• the invention therefore aims to treat the paper so that the solvents applied by counterfeiters lead to a coloration of the paper that is final, irreversible.
• the tamperproof security paper vis-à-vis tampering attempts with non-aqueous solvents is characterized in that it comprises on its surface and / or in its mass clusters formed of elementary particles amalgamated with a agglomerating agent insoluble in water but almost instantaneously soluble in at least one non-aqueous solvent, which elementary particles are both insoluble in water and in solvents and preferably have sizes smaller than 20 ⁇ , and more preferably still less than 10 ⁇ , they are colored and are advantageously intense pigment dyes such as those used to make inks or paints.
• the principle of operation of the coloration developed by the solvents in the tamperproof paper according to the invention is as follows: the clusters distributed throughout the volume of the sheet are broken by the presence of the solvent and the colored pigment particles are dispersed around the position of each cluster producing a colored dot, the dispersion of the particles is irreversibly by diffusion in the interstices of the fibrous network in a limited manner in the immediate vicinity of the cluster.
• the elementary particles are insoluble in the solvents, said particles will remain trapped in the fibrous network, in the same manner as the mineral fillers introduced into the paper. Once the sintering agent has been removed, the particles can not be extracted by multiple washings with the solvents and the color remains fixed in the paper as a trace of forgery.
• the clusters as described are distinguished from the particles or granules conventionally introduced into papers for authentication purposes, such as those described in patents EP 219 713, EP 226 367, EP 1 074 599, EP 1,342,768 or JP2000303388 in that the agglomerating agent is almost instantaneously soluble in the solvents, due in addition to the choice of said agent, as well as by the choice of incorporated particles, also also, for some of the patents mentioned, by the fact that the pigment particles colored are distributed throughout the entire volume of the cluster and not only on its surface.
• the known clusters that can be used for authentication purposes include binders that are crosslinked under the action of heat during drying of the paper, which makes them insoluble in solvents within the meaning of the invention and according to the definition of solubility indicated later in this description.
• the known agglomerates are unsuitable for releasing the particles contained in the clusters in a time acceptable for the development of a possible coloration, which is not usually possible because the particles in question are expected to be invisible in daylight and luminescent for paper authentication.
• Authentication and falsifiability of papers are two different areas even if tamper-proofs have been used for authentication purposes, the first is to provide proof that a document is authentic, original, the second aim to prevent the modification of the variable data affixed to the documents, tamper-proof reagents intended to produce a visible coloration, generally without apparatus, during an attempted fraud.
• the colored pigmented particles are insoluble in solvents which makes it possible to avoid the paper washing phenomenon and loss of falsifiability, thus the security of the papers is reinforced, - currently there are very few organo-soluble dyes available for use on the market, these dyes are essentially known in two or three colors, the use of clusters according to the invention allows the use of a variety of pigment dyes, including red, purple, pink, green, or yellow dyes, and therefore very different color reactions from what is possible today,
• the elemental pigments used in the clusters can be very varied because the insolubility criteria, both in solvents and in water, are frequently encountered, it can thus be used very inexpensive products, such as black carbon or inexpensive dyes to replace the more expensive organosoluble dyes, which represents a certain economic advantage given the tonnage of paper manufactured with these products in the world.
• the invention relates to a paper treated in its mass or surface to be tamper-proof with solvents which comprises clusters of elementary particles, which particles are both insoluble in water and in solvents.
• Clusters within the meaning of the invention are agglomerates of pigmentary particles with a binding agent, the particles of small sizes, advantageously less than 20 ⁇ , are distributed throughout the entire volume of the cluster in a more or less homogeneous manner, the cement between the particles being the sintering agent.
• the clusters can be obtained in different ways, according to several physical processes of agglomeration, it can for example be envisaged to make clusters by solubilization of a wax in a solvent, dispersion of the pigment particles in the wax, production of an emulsion in water and precipitation of the clusters, it may also be envisaged to incorporate an agglomeration additive during the manufacture of the pigment particles themselves so as to produce pigment aggregates intended to be ground to the desired size, or Various other techniques can be employed to form particle agglomerates with a binder.
• the elementary pigmentary particles have sizes conventionally developed for the production of inks and paints, that is to say particle sizes preferably less than 20 ⁇ , and even more preferably less than 10 ⁇ , sizes less than 1 ⁇ usually found in dyes and colored pigments.
• it will be chosen from the clusters of pigment particles having a high coloring power such as, for example, carbon black, phthalocyanine derivatives such as Pigment Blue 15: 3, or the pigments defined by the references of the Color Index Pigment Yellow 93 or Pigment Yellow 83.
• the clusters preferably have sizes of less than 500 ⁇ m and more preferentially smaller than 200 ⁇ m, advantageously the clusters are greater than 20 ⁇ m and more preferably still greater than 50 ⁇ m.
• the choice of the maximum size of the clusters is related on the one hand to the desired effect and on the other hand to the category of elementary pigmentary particles used.
• the clusters will advantageously be small so as to be poorly visible to the eye, typically less than 100 ⁇ and more preferably still less than 70 ⁇ .
• the sizes may be larger and up to, for example, 300 ⁇ , so as to possibly provide a means to show that the paper has been treated or to provide a background shade effect. to paper if the amount of clusters is very important.
• the minimum size of the clusters must be greater than 20 ⁇ so that there is no coloring of the paper.
• the clusters are constituted by water insoluble particles and in all types of solvents amalgamated by an agglomeration agent also insoluble in water but soluble almost instantaneously in at least one non-aqueous solvent of to release said elementary particles into the paper.
• agglomeration agent also insoluble in water but soluble almost instantaneously in at least one non-aqueous solvent of to release said elementary particles into the paper.
• binders comprising latexes or polymerized resins do not solubilize in any way under the same conditions and therefore can not be used as agglomerating agent within the meaning of the invention.
• Such binders are generally not solubilized by a soaking operation of the paper as may be practiced by counterfeiters.
• the sintering agent is very precisely selected so as to be able to solubilize very rapidly in solvents, according to the invention the sintering agent is soluble in polar solvents such as, for example, alcohol or acetone, for this it is possible to use a product such as ethyl cellulose as agglomerating agent, in a small proportion relative to the elementary particles.
• polar solvents such as, for example, alcohol or acetone
• the agglomeration agent is soluble in apolar solvents such as for example toluene or hydrocarbons, in this option it is conceivable to use as agglomerating agent a vinyl copolymer resin.
• apolar solvents such as for example toluene or hydrocarbons
• the agglomeration agent is practically not soluble in polar solvents and the clusters do not develop a coloration with all types of solvents.
• the agglomeration agent is soluble in the products used by forgers to erase inks such as hairsprays, household stain removers, essences and, more generally, the products found in the trade which contain a proportion of solvent in the composition.
• the agglomerating agent is soluble in both apolar and polar solvents as well as in commercial products containing a proportion of solvent in the composition.
• the agglomerating agent is advantageously a compound of the family of ethylcelluloses.
• Elementary particles agglomerated in an ethylcellulose matrix which correspond fairly well to the object of the invention are, for example, those of the MICROLITH®-A range of the company CIBA, these very coarse aggregates whose particle size is very heterogeneous require to be crushed and sieved to produce cluster sizes suitable for producing the unfalsifiable papers according to the invention.
• these clusters are crushed and sieved so as to obtain a particle size of less than 100 ⁇ .
• the agglomeration agent is in a small proportion in the cluster with respect to the pigment particles, according to the preparation method this proportion can vary from 2-3% to 30-40% by dry weight, the particles elementary still being the majority in the cluster. In order that the color developed is as intense and as fast as possible, the highest possible ratio between the elementary particles and the agglomeration agent is sought. In practice less the amount of sintering agent is important plus the dispersion of the elementary particles in the paper is fast.
• the elementary particles are colored pigments and are preferably intense pigment dyes such as those used to make inks or paints, which pigment dyes are advantageously temperature and light stable.
• luminescent pigments that is to say fluorescent or phosphorescent pigments, or those sensitive to infrared, Anti-Stokes or containing various authenticatable markers, in the clusters. likely to function according to the same principle of diffusion as the pigment dyes when the clusters are split up.
• which luminescent pigments can be used in combination with the colored pigment particles to simultaneously provide the tamperproof appearance with an authenticatable appearance.
• each individual cluster contains colored pigment particles, short or long UV fluorescent pigments, anti-Stokes pigment particles, and other types of markers having complete insolubility properties in water. and solvents.
• Such clusters exhibit tamper-proof properties with regard to solvents and authentication properties which make them very secure products that can be used for passports in particular, and for documents requiring both the protection of personal data vis-à-vis the falsifications and to be authenticated.
• the clusters contain, in addition to the colored pigment particles, different categories of other pigment particles, each unit cluster may comprise, alone or in combination, luminescent pigment particles under suitable lighting such as fluorescent particles, phosphorescent, anti-Stokes, infrared, X-ray opaque, DNA markers, and generally markers known to authenticate documents that are insoluble in water and solvents or that are feasible in a form having such properties.
• luminescent pigment particles under suitable lighting such as fluorescent particles, phosphorescent, anti-Stokes, infrared, X-ray opaque, DNA markers, and generally markers known to authenticate documents that are insoluble in water and solvents or that are feasible in a form having such properties.
• it may be considered to place markers in polymer matrices of small sizes, typically less than 10 ⁇ , which matrices are insensitive to water and solvents and therefore usable for the agglomeration process.
• the invention corresponds to a tamper-resistant security paper vis-à-vis non-aqueous solvents comprising in the entire volume of the sheet clusters of less than 100 ⁇ and more than 50 ⁇ formed particles colored pigments of sizes smaller than 10 ⁇ amalgamated with a water-insoluble agglomerating agent soluble in polar and apolar solvents, in a manner that is almost instantaneous so as to release the color-producing particles of a color indicating the falsification, of
• the agglomerating agent is a compound of the family of ethylcelluloses whose proportion in clusters is less than 40% by dry weight, which clusters advantageously correspond to the MICROLITH® Black CA reference of the company CIBA which have have been crushed and sieved, or other references of the Microlith® range.
• the invention also relates to a process for making a tamper-proof paper vis-à-vis polar and / or apolar solvents characterized in that introduced into the pulp, before making the sheet, clusters of sizes less than 500 ⁇ formed of small elementary pigment particles of reduced size both insoluble in water and in solvents, preferably less than 20 ⁇ , and more preferably still less than 10 ⁇ , amalgamated with an agglomerating agent of the ethyl family -celluloses also insoluble in water but soluble in at least one solvent almost instantaneously.
• the clusters according to the invention are introduced into the pulp at a rate of 1 to 20 kg per ton of paper, and preferably from 1 to 5 kg per ton of paper for clusters of sizes less than 100 ⁇ and for a weight dry of clusters. For larger clusters and depending on the desired effect the quantities may increase.
• the clusters may be envisaged to prepare the clusters in the aqueous phase and to use them in a dispersed form easier to manage in the production of the paper.
• this variant of implementation does not affect the infalsifiability result of the paper and how the clusters burst under the effect of a solvent. Because of their size the clusters are well retained in the paper during the process of dewatering the dough during the formation of the sheet, whether it is a Fourdrinier type table or a form round usable to carry out passports.
• a coating apparatus for example a curtain system
• a printing process in particular screen printing
• paper should be understood as a flexible porous network, advantageously fibrous, printable and usable for making secure documents, it is preferably a paper machine paper, but the term also encompasses non-woven products that can be made by a non-papermaking route and carton materials or various fibrous agglomerates.

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• 2011
  • 2011-01-25 FR FR1100211A patent/FR2970716B1/fr active Active
  • 2011-12-01 EP EP11811554.2A patent/EP2668335B1/de active Active
  • 2011-12-01 RU RU2013139436/05A patent/RU2013139436A/ru not_active Application Discontinuation
  • 2011-12-01 ES ES11811554.2T patent/ES2539163T3/es active Active
  • 2011-12-01 BR BR112013018554A patent/BR112013018554B8/pt active IP Right Grant
  • 2011-12-01 MX MX2013007873A patent/MX2013007873A/es active IP Right Grant
  • 2011-12-01 WO PCT/FR2011/000630 patent/WO2012101334A1/fr active Application Filing
  • 2011-12-01 CA CA2824673A patent/CA2824673C/fr active Active
• 2013
  • 2013-07-10 ZA ZA2013/05205A patent/ZA201305205B/en unknown
  • 2013-07-18 US US13/945,507 patent/US9057159B2/en active Active

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