EP0488902A1 - Sicherheitsdokument mit einem Farbenphotographischen Sicherheitselement - Google Patents

Sicherheitsdokument mit einem Farbenphotographischen Sicherheitselement Download PDF

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Publication number
EP0488902A1
EP0488902A1 EP91403247A EP91403247A EP0488902A1 EP 0488902 A1 EP0488902 A1 EP 0488902A1 EP 91403247 A EP91403247 A EP 91403247A EP 91403247 A EP91403247 A EP 91403247A EP 0488902 A1 EP0488902 A1 EP 0488902A1
Authority
EP
European Patent Office
Prior art keywords
security document
security
photochromic compound
document according
electromagnetic radiation
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.)
Withdrawn
Application number
EP91403247A
Other languages
English (en)
French (fr)
Inventor
Michel Camus
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.)
ArjoWiggins SAS
Original Assignee
ArjoWiggins SAS
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 SAS filed Critical ArjoWiggins SAS
Publication of EP0488902A1 publication Critical patent/EP0488902A1/de
Withdrawn legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/40Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48Elements suited for physical verification, e.g. by irradiation
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/40Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/42Ribbons or strips

Definitions

  • the invention relates to a security document comprising at least one security element reacting to radiation. It relates more particularly to a security document comprising a security element having photochromic properties, that is to say that this element changes color reversibly as a function of the presence or absence of at least one electromagnetic radiation.
  • This security element can for example be in the form of a fiber, a wire, a strip or boards.
  • photochromic products are colorless or almost colorless in the absence of certain radiations, in particular ultraviolet rays or infrared rays, and become colored under the action of these radiations.
  • security documents for example papers for banknotes or for checks or any other security of value, include chemical or physical means of authentication and / or indicators of falsification.
  • falsification indicator means react for example to acids (hydrochloric, citric, acetic, sulfuric, etc.), bases (especially soda), oxidants (bleach), reducers and solvents.
  • inorganic compounds mention may be made of silver halides, transition metal salts, tungsten and vanadium acids, optionally doped metal oxides, etc.
  • fulgides derivatives of succinic anhydride
  • fulgimides derivatives of succinimide
  • stilbene derivatives pyran derivatives
  • spiropyranes spirobenzo (or naphtho) pyranes
  • spiroxazines hydrazones
  • oxazones etc.
  • Such compounds are usually used for (mineral or organic) lenses of sunglasses, as described for example in documents FR-A-2 290 401, EP-A-246 114, FR-A-2 467 182, FR -A-2 450 469. These compounds give the glasses the property of darkening when exposed to full sunlight (containing UV rays) and of lightening in the shade.
  • Photochromic compounds are also used to manufacture security inks as described in documents EP-A-327,788, EP-A-248,631 or WO-A-88 01 288 and WO-A-83 00 568
  • the use of these inks can be used in particular to authenticate the document on which they are applied.
  • the safety device is a woven material containing one or more threads made up of photochromic fibers. This woven material is used as a label which is placed on an authentic item, such as a garment, bag, fabric, etc.
  • the authentication process consists in illuminating the label using a UV lamp to reveal the color of the photochrome.
  • the recognition process will be carried out at the time of the sale or resale of a well-known brand object, and this to avoid counterfeiting of luxury objects.
  • the authentication process will be carried out at most two to five times. To make such a label, it is sufficient for the photochrome to have a maximum number of transition cycles of 10.
  • Patent application JP-A-61 179 399 describes the manufacture of cellulose fibers dyed with photochromic compounds. These fibers are then used as basic fibers to make a document. Therefore, the entire document is photochromic. Such a document is very expensive, because the fibers require for their dyeing a particular compound and large quantities of photochromic compound.
  • An object of the invention is therefore to provide a security document which is not woven and which comprises at least one security element containing a photochromic compound, this compound being such that the transition from the non-activated form to the activated form is reversible and the number of transition cycles is very large.
  • this security element is intended for the manufacture, for example, of banknotes, checks, restaurant vouchers, credit cards, identity cards, passport sheets, etc. It can therefore be used very often, for example several times a day and capable of being subjected to an authentication process at least once a week and even at least once a day.
  • Another object of the invention is to provide a security document which comprises at least one security element containing a photochromic compound which changes from its non-activated form to its activated form (photo) very quickly.
  • the reverse transition from its activated form to its non-activated form will be fairly rapid.
  • the security document according to the invention is intended to be authenticated more particularly by the man in the street or for example by a cashier in a payment center. If the number of documents to be authenticated is large, the user will want the color change to be rapid. In addition, the man in the street will immediately prefer the color change to be rapid when he uses the security document as a means of payment.
  • the security document could constitute, for example, a passport or identity card sheet and here again, when verifying the identity of many people, the cycle of color change should be quick.
  • a third object of the invention is to provide a security document which comprises a security element containing a photochromic compound and which is introduced during the production of the document, the security element forming an integral part of the document. This is particularly important, because if the element is an integral part of the document it will be very difficult for counterfeiters to reproduce this document.
  • the invention therefore aims to provide a security document which is not woven integrally comprising at least one security element comprising at least one photochromic compound, the security element having a long service life and being easy to authenticate. .
  • the total reversibility time period is less than one minute.
  • the photochrome will be found on and / or in the security element in dissolved form in individual microdroplets within the material.
  • confinement has the advantage of protecting the photochrome from the chemical agents to which it could be subjected and also of isolating it from the compounds of the document with which it could interact in a harmful manner.
  • microdroplets may be found individualized in microcapsules.
  • microcapsules have walls at least partially transparent to active electromagnetic radiation. They must also have the highest possible resistance to pressure. To better protect the microcapsules against bursting under the effect of pressure, they can be used in admixture with protective elements such as glass microbeads.
  • polyurethane As base material for the walls of the microcapsules, polyurethane, melamine-formaldehyde or urea-formaldehyde resins may be used.
  • the invention more particularly provides a security document characterized in that the photochromic compound is present with at least one of its solvents in microcapsules with walls at least partially transparent to electromagnetic radiation.
  • the average size of the microcapsules is between 3 to 12 ⁇ m, preferably between 4 and 10 ⁇ m.
  • the photochromic compound can be present in the form of microdroplets dispersed within a varnish or a crosslinked binder and at least partially transparent to active electromagnetic radiation.
  • the varnish or the binder can, for example, be crosslinked by UV radiation or by heat.
  • the photochromic compound is resistant to a temperature of up to 120 ° C.
  • resistant is meant that the photochromic compound does not lose its qualities of passage from the non-activated state to the photoactivated state and vice versa, when it is not subjected or subjected to electromagnetic radiation.
  • the photochromic compound optionally after confinement, is chemically resistant to oxidizing agents and / or reducing agents such as hydrogen peroxide, sodium hypochlorite, or other hypohalides of alkali metals, to strong or weak acids, by example acetic, citric acid, with strong or weak bases.
  • oxidizing agents and / or reducing agents such as hydrogen peroxide, sodium hypochlorite, or other hypohalides of alkali metals, to strong or weak acids, by example acetic, citric acid, with strong or weak bases.
  • the security element is arranged at least partially between the two faces of the security document. It can be located completely on the surface of the document, or it can be placed in windows made in the document. Such windows are produced in a manner known from the prior art as described in document EP-A-059 056.
  • the security element can also be completely included between the two faces of the security document, but then it must be located at a depth allowing electromagnetic radiation to reach it to induce coloring of the photochromic compound.
  • the security element may for example be a wire, a fiber, a board made of synthetic and / or natural material comprising a photochromic compound (possibly encapsulated) in mass or on the surface, uniformly or not.
  • the security element may include the photochromic compound in the form of a bar code, for example it may be a wire printed using an ink comprising a photochromic compound, the printing being under form of bars perpendicular to the longitudinal axis of the wire. It can also be provided that the printing is done in the form of alphanumeric characters.
  • An embodiment of the invention may consist in using mixtures of photochromic compounds, or different photochromic compounds for certain parts of the security element, these compounds giving different colors for a given radiation or reacting to radiation of lengths. different wave.
  • the photochromic compound (s) can be incorporated into the bulk security element or be deposited on the surface on at least one face of the element, for example by coating or printing.
  • the photochromic compound can be deposited using a binder.
  • a binder As transparent binder, it is possible to use, for example, a polyvinyl alcohol (PVA), a polyvinyl acetate, an acrylic latex, especially when the photochromic is encapsulated.
  • PVA polyvinyl alcohol
  • acrylic latex especially when the photochromic is encapsulated.
  • the electromagnetic radiation to which the safety document according to the invention is subjected is preferably radiation whose wavelength spectrum corresponds to that of the solar spectrum.
  • the security document is preferably obtained by the wet method by producing an aqueous suspension of a mixture of natural and / or synthetic and / or mineral fibers, binders, flocculants and then by draining this suspension on a canvas, for example of a flat table of a fourdrinier machine or a canvas of a round shape and finally by pressing and drying the sheet obtained.
  • a mixture of polycarbonate and of a photochromic compound of the spiro (or naphtho) pyran type is extruded comprising, as a substituent, an adamantane ring in position 2 of the spiropyran ring (as described in patent application EP-A-246,114).
  • the film is biaxially stretched until a film with a thickness of 30 ⁇ m is obtained.
  • a colorless film is obtained.
  • This film is cut into strips 1 mm wide.
  • the strip is incorporated into a sheet of paper according to the technique described in patent application EP-A-059 056.
  • the sheet obtained is cut to make security documents.
  • the security document obtained according to the invention is illuminated in full sunlight, the security document becomes very dark immediately. As soon as you put the security document in a dimly lit area, the security document clears up very quickly.
  • a security document is produced as in Example 1, but a polymethacrylate is used in place of polycarbonate and as photochromic a stabilized fatigue-resistant spiroxazine is used, as described in patent application FR-A-2 523 593 .
  • a 38 g / m2 paper is printed with a photochromic gravure ink containing a spiroindolinonaphtoxazine.
  • a photochromic gravure ink containing a spiroindolinonaphtoxazine was cut in the form of boards. These boards are introduced into a sheet of paper during its manufacture and so as to obtain a finished sheet comprising in large quantity of boards flush with the faces of the sheet. We transform this sheet into security documents.
  • the security elements By irradiating a document obtained at a wavelength of 366 nanometers, the security elements quickly color blue. They discolor very quickly if the document is placed in a non-irradiated place.
  • a security document is produced by incorporating during its manufacture photochromic organic fibers, such as for example polyamide fibers (NYLON) described in US Pat. No. 3,578,389.
  • photochromic organic fibers such as for example polyamide fibers (NYLON) described in US Pat. No. 3,578,389.
  • a security document is produced as in Example 4, but glass mineral fibers having a high zirconia content and whose photochromic compound is a silver halide with copper oxide are used as photochromic fibers. Zirconia increases the speed of photochromic reversibility.
  • the photochromic fibers can, for example, be obtained from mineral glass described in patent application FR-A-2 290 401.
  • a photochromic compound with a solvent is encapsulated, according to a known encapsulation technique.
  • the walls of the capsules are for example made of melamine-formaldehyde; they are transparent.
  • the photochromic compound is a spirooxazine (VARIACROL sold by ENICHEM) dissolved at 1.2% in the solvent EXSOL D100 (sold by EXXON).
  • an additive can be added to facilitate its dissolution.
  • the capsules have an average diameter of 4 ⁇ m.
  • capsules are deposited in mixture with a transparent binder, for example a polyvinyl alcohol (PVA) on a sheet of paper or on a plastic film (for example of polyester) using a MEYER bar.
  • a transparent binder for example a polyvinyl alcohol (PVA) on a sheet of paper or on a plastic film (for example of polyester) using a MEYER bar.
  • PVA polyvinyl alcohol
  • the capsule / binder mixture is in a 50/50 ratio by dry weight.
  • the dry weight of deposited capsules is 10 g / m2.
  • the sheet or film thus obtained are cut into threads or strips or boards which are then incorporated into a paper during its manufacture.
  • Such paper is printable by conventional printing methods in the field of security papers.
  • glass microbeads (10 to 20% compared to the capsules) having an average size of 20 ⁇ m can be added to the binder-capsule mixture.

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  • Credit Cards Or The Like (AREA)
  • Paper (AREA)
EP91403247A 1990-11-29 1991-11-29 Sicherheitsdokument mit einem Farbenphotographischen Sicherheitselement Withdrawn EP0488902A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9014947 1990-11-29
FR9014947A FR2669948B1 (fr) 1990-11-29 1990-11-29 Document de securite comportant un element de securite ayant des proprietes photochromiques.

Publications (1)

Publication Number Publication Date
EP0488902A1 true EP0488902A1 (de) 1992-06-03

Family

ID=9402728

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91403247A Withdrawn EP0488902A1 (de) 1990-11-29 1991-11-29 Sicherheitsdokument mit einem Farbenphotographischen Sicherheitselement

Country Status (2)

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EP (1) EP0488902A1 (de)
FR (1) FR2669948B1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007144657A2 (en) 2006-06-15 2007-12-21 D. W. Spinks (Embossing) Limited Planchette for use in couterfeit protection
EP2484537B1 (de) 2011-02-02 2016-04-06 Giesecke&Devrient Authentizitätssicherung von Wertdokumenten mittels photochromer Farbstoffe

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115262284A (zh) * 2022-07-27 2022-11-01 华南理工大学 一种智能防水光致变色纸及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0328320A1 (de) * 1988-02-05 1989-08-16 Courtaulds Plc Sicherheitsvorrichtung

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61179399A (ja) * 1985-02-05 1986-08-12 大蔵省印刷局長 ホトクロミツク物質を付着した製紙用繊維

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0328320A1 (de) * 1988-02-05 1989-08-16 Courtaulds Plc Sicherheitsvorrichtung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WORLD PATENTS INDEX LATEST Week 8638, Derwent Publications Ltd., London, GB; AN 86-249926 & JP-A-61 179 399 (OKURASHO INSATSU KY) 12 Août 1986 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007144657A2 (en) 2006-06-15 2007-12-21 D. W. Spinks (Embossing) Limited Planchette for use in couterfeit protection
WO2007144657A3 (en) * 2006-06-15 2008-02-28 Dw Spinks Embossing Ltd Planchette for use in couterfeit protection
EP2484537B1 (de) 2011-02-02 2016-04-06 Giesecke&Devrient Authentizitätssicherung von Wertdokumenten mittels photochromer Farbstoffe

Also Published As

Publication number Publication date
FR2669948B1 (fr) 1993-01-22
FR2669948A1 (fr) 1992-06-05

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