EP0243285A1 - Durch Thermochromie fälschungssicheres und/oder auf seine Echtheit zu prüfendes Sicherheitspapier und sein Herstellungsverfahren - Google Patents

Durch Thermochromie fälschungssicheres und/oder auf seine Echtheit zu prüfendes Sicherheitspapier und sein Herstellungsverfahren Download PDF

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Publication number
EP0243285A1
EP0243285A1 EP87420103A EP87420103A EP0243285A1 EP 0243285 A1 EP0243285 A1 EP 0243285A1 EP 87420103 A EP87420103 A EP 87420103A EP 87420103 A EP87420103 A EP 87420103A EP 0243285 A1 EP0243285 A1 EP 0243285A1
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EP
European Patent Office
Prior art keywords
paper
papers
proof
acid
compound
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
EP87420103A
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English (en)
French (fr)
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EP0243285B1 (de
Inventor
André Honnorat
Claude Riou
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.)
Aussedat Rey SA
Original Assignee
Aussedat Rey SA
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 Aussedat Rey SA filed Critical Aussedat Rey SA
Publication of EP0243285A1 publication Critical patent/EP0243285A1/de
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Publication of EP0243285B1 publication Critical patent/EP0243285B1/de
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—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
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • 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 present invention relates to a security paper that cannot be forged and / or authenticated by thermochromy. It also relates to its preparation process.
  • thermochromy for the authentication of security papers has already been developed in the German patent 1 228 972 and the Austrian patent 362 658. However, these described methods used uncommon, expensive and used products delicate paper mill.
  • thermochromy in security papers from thermochromic and thermomagnetic substances as well as sophisticated test equipment. This process is not easy to use.
  • thermochromic compositions containing violet lactone crystal have been patented: in Japanese patents 75 40 475 and 77 140 483, the co-reactants ensuring the reversibility of the reaction are different from those developed in the present invention, - other compositions associating the lactone violet crystal with Bisphenol A have been filed: Japanese patent 72 53 649 (German patent: 2 327 723), 74 78 682, 80 167 134 (German patent 3 147 146) and 57 123 283.
  • patent GB-1 507 454 relating to a document authentication method, as well as a combination of a document to be authenticated and an authentication composition.
  • the document is printed on a security paper consisting of a base paper coated with a leuco-dye precursor dye, an inert filler and a binder.
  • This document is authenticated by marking with an authentication composition comprising a mixture of a dark pigmented ink and a solution of the acid material which reacts with the dye precursor leuco-dye.
  • This method has the drawback of giving rise to an irreversible coloring reaction carried out in a liquid medium, without the intervention of heat.
  • the security document is characterized in that it comprises a substrate, a first substance incorporated into the substrate or applied to it , this first substance being able to participate in a toning reaction, and a second substance applied to the substrate and capable of participating in a different toning reaction, so that, during document verification by application of at least one reagent, first and second substances change color as a result of the toning reactions.
  • the proposed technique involves the implementation, little practical, of a liquid reagent to be applied and leads to an irreversible coloring.
  • an invention is described making it possible to overcome the various technical and economic difficulties encountered in the use of known systems for obtaining papers which can be authenticated by thermochromy and in the implementation of the systems already proposed for making the papers tamper-proof.
  • the implementation of the present invention is easily adaptable to the production techniques of the various types of paper and it makes it possible to obtain, at will, either authentifiable papers, or tamper-proof papers, or papers being simultaneously authentifiable and tamper-proof.
  • the objective of the invention is to provide a new security and / or authenticated paper, by simple temperature rise developing a reversible coloring making it possible to restore the paper in its original and falsifiable state, by irreversible colored reaction, by reaction with erasable felts, bases or reducing products.
  • the invention is characterized in that a water-soluble association of crystal violet lactone ( I ) and an aliphatic organic acid with a short hydrocarbon chain ( II ) is introduced into the paper.
  • the lactone violet crystal (compound I ) is a known product of formula: it is commonly used in stationery, especially in carbonless papers.
  • aliphatic organic acid with a short hydrocarbon chain ( II ) is meant acids having up to 6 carbon atoms, saturated or unsaturated, comprising one or more acid functions and, optionally, other substituents which may be: hydroxyl group, halogen ketone function ...
  • oxalic acid the preferred is oxalic acid but mention may also be made of:
  • the quantities of crystal violet ( I ) and acid ( II ) to be used may, as we will see later, vary in large proportions, giving rise to different effects, generally, the amount of crystal violet can be of the order of 0.01 to 0.2 g / m2 of paper surface and the weight ratio of II to I can be between about 3 and about 20.
  • the papers obtained can have any fibrous composition, purely cellulosic or partly synthetic, to which can be added the conventional stationery additives, namely mineral fillers, various resistance agents, binders, resins, shading dyes, bonding products, alumina sulfate for acid bonding or pH adjustment, etc.
  • the conventional stationery additives namely mineral fillers, various resistance agents, binders, resins, shading dyes, bonding products, alumina sulfate for acid bonding or pH adjustment, etc.
  • These papers may also contain, in their mass, in the dispersed pigmentary state, one or more dyes insoluble in water but organo-soluble, so as to preserve the writings or expressions made on these papers vis-à-vis attempts to falsify using organic solvents.
  • these papers can be watermarked or contain various devices intended to ensure recognition, such as fibers, pellets, colored and / or fluorescent particles.
  • sensitizing reagents analogous to those already used today in security papers, for example, products ensuring a modification of the appearance of the paper by contact of the latter with oxidizing reagents. These products are introduced either in aqueous solution, in which case it is necessary to ensure their retention on the fibers by direct bonding or by means of fixing agents, or in the microdispersed or pigmented precipitated state.
  • Aqueous solutions containing violet crystal ( I ) and an acid ( II ) are deposited on the surface of a paper in varying concentrations and proportions. Different effects are then obtained, according to said concentrations and proportions, which have been represented in FIGS. 1, 2 and 3.
  • the compound report is plotted on the abscissa II / compound I of the weights of II and I deposited on the paper and expressed in g / m2 of paper, and the amount of compound I (in g / m2) deposited is plotted on the ordinate.
  • the paper obtained has a blue background which is all the more pronounced as the concentration coordinates place the point in the middle part between curves 1 and 2 .
  • the coloring of the paper can be accentuated by heating, that is to say that the paper is authentifiable, the return to the initial blue background takes place fairly quickly after stopping the heat source. Due to the background coloring, the paper is not sensitive to ink erasers, bases and reducers.
  • zone B the paper is white or very slightly bluish, authenticity by heat is preserved and the reaction to the ink erasing felts, bases and reducers, is clearly perceptible.
  • the paper is authentifiable and forgery-proof.
  • the paper In area C , the paper is white and less reactive to heat. Authentication requires a higher temperature. On the other hand, the reaction to the ink erasing felts, bases and reducers, is very intense.
  • the formulation comprises a coating binder which may be, by way of indication, synthetic or natural polymers with compatible hydroxy terminations, such as starch, polyvinyl alcohol and cellulose derivatives.
  • activators can be added to this composition.
  • activators can be added to this composition.
  • stabilizers can be added to this composition.
  • the authentication of the document can be carried out by thermochromy, that is to say by the appearance of a blue coloration when the paper is placed in the presence of any heating source making it possible to bring its temperature between 70 ° C. and 170 ° C in a short time (a few seconds maximum), then by the very rapid weakening (a few minutes) of the color formed when the document is brought to room temperature. The initial whiteness is then restored more slowly.
  • thermochromy that is to say by the appearance of a blue coloration when the paper is placed in the presence of any heating source making it possible to bring its temperature between 70 ° C. and 170 ° C in a short time (a few seconds maximum), then by the very rapid weakening (a few minutes) of the color formed when the document is brought to room temperature. The initial whiteness is then restored more slowly.
  • thermochromy that is to say by the appearance of a blue coloration when the paper is placed in the presence of any heating source making it possible to bring its temperature between 70 ° C. and 170 ° C in a short
  • thermochromy can be carried out manually by contact with a heating element or infrared radiation and visual recognition of the color obtained, or else using an automatic apparatus adapted to this authentication.
  • the document whose authenticity is to be checked is introduced into a machine which causes, using an appropriate device, the thermochromy of the paper: contact heating (regulated heating plate) or non-contact (hot air, IR radiation). ..).
  • the coloration obtained is read using an optical device (densitometer equipped with suitable filters), which makes it possible to reject documents which do not have the hue and the coloration density corresponding to an authentic document.
  • the white paper obtained is colored blue with the erasable felts, the reducers and the bases.
  • a clearly visible blue coloration forms, then quickly loses its intensity: in 10 minutes, 75% of the initial coloration has disappeared.
  • Instant coloring obtained with pencils ink erasers, reducers and bases, is cyan blue.
  • the bleach leads to a brown coloring, the solvents to variable coloring depending on the solvent and the dye introduced into the mass.
  • the paper turns blue with the temperature, when it is above 80 ° C (contact time of at least 3 seconds).
  • the preferred test apparatus consists of a fan pulsing hot air at a temperature of 100 to 140 ° C to reveal the color, then blowing cold air (or ambient air) to accelerate the return to the initial whiteness of the paper.
  • the colors obtained are, for the ink erasers, the reducers, the bases and the increase in temperature of the blue, and for the bleach of the beige-brown.
  • Solvents give variable colors depending on the dyes introduced into the mass and the solvents used.
  • the paper is white and not fluorescent after facing.

Landscapes

  • Business, Economics & Management (AREA)
  • Accounting & Taxation (AREA)
  • Finance (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Paper (AREA)
  • Color Printing (AREA)
  • Credit Cards Or The Like (AREA)
  • Printing Methods (AREA)
EP19870420103 1986-04-24 1987-04-21 Durch Thermochromie fälschungssicheres und/oder auf seine Echtheit zu prüfendes Sicherheitspapier und sein Herstellungsverfahren Expired EP0243285B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8606144A FR2597895B1 (fr) 1986-04-24 1986-04-24 Papier de securite infalsifiable et/ou authentifiable par thermochromie et son procede de preparation
FR8606144 1986-04-24

Publications (2)

Publication Number Publication Date
EP0243285A1 true EP0243285A1 (de) 1987-10-28
EP0243285B1 EP0243285B1 (de) 1989-08-16

Family

ID=9334698

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19870420103 Expired EP0243285B1 (de) 1986-04-24 1987-04-21 Durch Thermochromie fälschungssicheres und/oder auf seine Echtheit zu prüfendes Sicherheitspapier und sein Herstellungsverfahren

Country Status (5)

Country Link
EP (1) EP0243285B1 (de)
DE (1) DE3760455D1 (de)
ES (1) ES2012811B3 (de)
FR (1) FR2597895B1 (de)
PT (1) PT84736B (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0608078A1 (de) * 1993-01-20 1994-07-27 Portals (Bathford) Limited Sicherheitsfaden, und ihre Verwendung in Sicherheitspapier
WO1996030811A2 (de) * 1995-03-24 1996-10-03 Drescher Geschäftsdrucke Gmbh Papiererzeugnis
US6159585A (en) * 1997-03-14 2000-12-12 Georgia-Pacific Corporation Security paper
DE102009017444A1 (de) 2009-04-15 2010-10-21 Sension, Biologische Detektions- Und Schnelltestsysteme Gmbh Wärmeempfindliches Aufzeichnungsmaterial mit Sicherheitsmerkmal

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1228972B (de) * 1959-06-06 1966-11-17 Dr Karlheinz Koenig Echtheitskennzeichnung von Wertpapieren
FR2279570A1 (fr) * 1974-04-26 1976-02-20 Portals Ltd Document dont l'authenticite peut etre verifiee avec surete
GB1507454A (en) * 1975-06-19 1978-04-12 Wiggins Teape Ltd Security paper

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1228972B (de) * 1959-06-06 1966-11-17 Dr Karlheinz Koenig Echtheitskennzeichnung von Wertpapieren
FR2279570A1 (fr) * 1974-04-26 1976-02-20 Portals Ltd Document dont l'authenticite peut etre verifiee avec surete
GB1507454A (en) * 1975-06-19 1978-04-12 Wiggins Teape Ltd Security paper

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF IMAGING TECHNOLOGY, vol. 11, no. 5, octobre 1985, pages 224-228, Society of Photographic Scientists and Engineers, Springfield, Virginia, US; J.E. ASSNER: "Leuco color formers, modern imaging materials" *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0608078A1 (de) * 1993-01-20 1994-07-27 Portals (Bathford) Limited Sicherheitsfaden, und ihre Verwendung in Sicherheitspapier
WO1996030811A2 (de) * 1995-03-24 1996-10-03 Drescher Geschäftsdrucke Gmbh Papiererzeugnis
WO1996030811A3 (de) * 1995-03-24 1996-12-12 Drescher Geschaeftsdrucke Papiererzeugnis
US6159585A (en) * 1997-03-14 2000-12-12 Georgia-Pacific Corporation Security paper
DE102009017444A1 (de) 2009-04-15 2010-10-21 Sension, Biologische Detektions- Und Schnelltestsysteme Gmbh Wärmeempfindliches Aufzeichnungsmaterial mit Sicherheitsmerkmal
WO2010119089A1 (de) 2009-04-15 2010-10-21 Sension Biologische Detektions- Und Schnelltestsysteme Gmbh Wärmeempfindliches aufzeichnungsmaterial mit sicherheitsmerkmal

Also Published As

Publication number Publication date
ES2012811B3 (es) 1990-04-16
FR2597895B1 (fr) 1989-07-28
DE3760455D1 (en) 1989-09-21
PT84736B (pt) 1989-12-29
EP0243285B1 (de) 1989-08-16
PT84736A (fr) 1987-05-01
FR2597895A1 (fr) 1987-10-30

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