Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
  • B41M3/14—Security printing
  • B41M3/142—Security printing using chemical colour-formers or chemical reactions, e.g. leuco-dye/acid, photochromes
• • 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
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B44—DECORATIVE ARTS
  • B44F—SPECIAL DESIGNS OR PICTURES
  • B44F1/00—Designs or pictures characterised by special or unusual light effects
  • B44F1/08—Designs or pictures characterised by special or unusual light effects characterised by colour effects
  • B44F1/10—Changing, amusing, or secret pictures
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
  • B41M5/286—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating using compounds undergoing unimolecular fragmentation to obtain colour shift, e.g. bleachable dyes
• • B42D2035/24—

Definitions

• the present invention relates to a document, in particular fiduciary, which has on the surface at least one security sign with variable visual perception.
• security sign means a mark of whatever form (text, numbers, drawings, grid lines, etc.) that has or has no meaning, and the nature and / or manner of which affixing to the document was made to make the reproduction of the document particularly complex, if not impossible.
• variable visual perception is meant that this security sign is perceived by the observer, according to the conditions implemented for this observation, at least in two different ways.
• an optical variable ink (Optical Variable Ink) meets this qualification because, depending on the viewing angle, at least two different color perceptions are possible.
• fiducial printing inks intended to obtain safe visual effects are mixtures of substances that are difficult to obtain and / or whose formulation is complex.
• EP-A-0 327 788 describes the use of compounds of the family spiropyrans, fulgides and spiro-indolizines in the manufacture of photochromic inks for application in the fiduciary field.
• JP-A-2004 / 277,968 describes the use of a photochromic compound of the diarylethene family in the manufacture of a photochromic ink which, initially colorless, turns blue when exposed to light. of the sun.
• JP-A-2004 / 277,969 describes the use of a photochromic compound of the diarylethene family in the manufacture of a photochromic ink which, initially pink, becomes violet when exposed to light. of the sun.
• the main purpose of the present invention is to further improve the security of documents, in particular fiduciary documents, which have on the surface at least one security sign with variable visual perception.
• Another aim is to propose a document whose authenticity and, conversely, falsification, is easily controllable by means of simple, inexpensive and widespread devices.
• the invention relates to a document, in particular a fiduciary document, which comprises on the surface a security mark with variable visual perception, characterized in that said mark consists of a material which includes a part possessing properties photochromes and another part having photothermochromic properties.
• the security level of the document is raised compared to a document incorporating only a photochromic material.
• the material contains a first photochromic substance and a second photothermochromic substance.
• said first and second substances are mixed within said material
• said first and second substances form distinct and superimposed layers within said material
• Said second substance returns to its initial state when it is subjected to a heat treatment;
• Said first substance returns to its initial state when it is subjected to a light of wavelength ⁇ 2 , K 2 being different from ⁇ i;
• R 1 and R 2 identical or different, independently of one another represent an alkyl radical substituted or not with heteroatomic groups;
• the X and Y groups which may be identical or different, represent, independently of one another, heteroatoms or methylenes substituted or unsubstituted by alkyl, cycloalkyl or aromatic rings, or heteroatoms.
• the group Z represents a heteroatom or a methylene group which may or may not be substituted by electron donor or acceptor groups.
• the group R is a hydrogen or a halogen
• R 1 and R 2 identical or different, independently of one another represent an alkyl radical substituted or not with heteroatomic groups
• R 3 and R 4 identical or different, represent independently of each other electron donor or acceptor groups
• X and Y are heteroatoms or methylenes substituted or unsubstituted by alkyl radicals, cycloalkyl radicals, aromatic rings, or heteroatoms.
• said first substance replies, in the initial colorless state, to the following formula (UIa):
• R 1, R 3 and R 4 which may be identical or different, represent, independently of one another, alkyl, cycloalkyl, aromatic or heteroaromatic rings, which may or may not be substituted by heteroatomic groups.
• R 1, R 3, R 4, R 5 and R 6, which may be identical or different, represent, independently of one another, alkyl, cycloalkyl, an aromatic ring or a heteroaromatic ring, which may or may not be substituted by heteroatomic groups.
• R 1 , R 2 which may be identical or different, represent, independently of one another, electron donor or acceptor groups;
• the groups R 3 , R 4 and R 5 which may be identical or different, represent, independently of one another, electron donor or acceptor groups;
• the groups X, Y and Z which may be identical or different, represent, independently of one another, a heteroatom or a methylene group which may or may not be substituted by alkyl or cycloalkyl radicals.
• said second substance in its initial colorless state, corresponds to the following formula (VIII):
• R 2 identical or different, represent independently of each other electron donor or acceptor groups; the groups R 3 , R 4 , R 5 , R 6 and R 7, which may be identical or different, represent, independently of one another, alkyl or cycloalkyl radicals, which may or may not be substituted by heteroatomic groups.
• said second substance replies, in the initial colorless state, to the following formulas (Xa) and (Xb):
• said material contains a single substance which has both photochromic and photothermochromic properties.
• n being an integer from 1 to 20.
• FIG. 2 shows the successive states of a molecule that can be used in the context of the invention.
• the sign of the document according to the invention is applied to the latter by any suitable known printing method.
• the active substance (s) will be incorporated in a printable vehicle such as an ink, a colorless varnish, for example used in flexographic printing.
• the surface layer has a substance density assayed such that the visual effect perceived by the observer results from the combination of the visual effect of each layer.
• the upper layer is not sufficiently thick and / or dense to mask the substance of the lower layer.
• the two active substances are initially colorless and are able to change color in the same wavelength range ( ⁇ i ⁇ 50 nm).
• the active substance belonging to the class of photothermochromes can return colorless to room temperature in a relatively short time (for example of the order of 10 minutes).
• the other active substance, belonging to the photochromic class becomes colorless only by irradiation at a known wavelength A 2 , generally much greater than ⁇ i.
• P photochromic active substance
• P ' modified state of P.
• T photothermochrome active substance
• T ' modified state of T.
• T.A ambient temperature.
• Color means a color itself, but also a shade. Thus, if the colors Cp and CT are respectively blue and red, the perceived color under A 1 will be purple. However, it is conceivable that the colors of Cp and CT are vermilion red and dark red, the perceived color being dark red. However, when the photothermochrome substance becomes colorless again, the perceived color will be vermilion red.
• the goal is to raise the security level of a color transition from a simple photochromic, which is binary in nature, to a ternary or even higher level where the return to the initial state passes through an intermediate color shade perfectly distinguishable from the initial state and the final state.
• the stimulus that makes it possible to obtain this intermediate color is of a different nature (thermal energy supply) from that which makes it possible to obtain the final shade (irradiation under UV) as well as that which allows the return to the initial state (irradiation at a monochromatic wavelength in the visible spectrum).
• thermal energy supply thermal energy supply
• the reversibility of the changes is controlled on two levels: the speed of obtaining the intermediate color depends on the amount of thermal energy brought and the locking on this intermediate color can only be unlocked under irradiation at a specific monochromatic wavelength in the visible spectrum (this also works with sunlight).
• the photochromic substance belongs to the family of diarylethenes and corresponds to formula (Ia) below.
• R 1 and R 2 represent, independently of one another, an alkyl radical which may or may not be substituted by heteroatomic groups.
• the X and Y groups represent, independently of one another, heteroatoms or methylenes which may or may not be substituted by aromatic rings or heteroatoms.
• the group Z represents a heteroatom or a methylene group optionally substituted by electron donor or acceptor groups.
• the reverse reaction is known to be able to be carried out by irradiation at a wavelength ⁇ 2 generally greater than 500 nm.
• the photochromic family of diarylethenes corresponds to formula (II).
• R 1 and R 2 which are identical or different, represent, independently of one another, an alkyl radical which may or may not be substituted by heteroatomic groups
• R 3 and R 4 which may be identical or different , represent independently of each other electron donor or acceptor moieties.
• X and Y are methylenic groups or heteroatoms. Even more advantageously, the photochromic of the family of diarylethenes corresponds to formula (IIIa).
• This compound is known to change color according to the transformation below.
• the photochromic substance preferentially belongs to the fulgid family and corresponds to the generic formula (IVa).
• R 1 , R 3 and R 4 which may be identical or different, represent, independently of each other, alkyl, cycloalkyl, aromatic or heteroaromatic rings, which may or may not be substituted by heteroatomic groups.
• the Ar group is an aromatic ring. This family of compounds is known to change color under the action of a specific wavelength A 1 , between 200 and 400 nm, according to the transformation below.
• the reverse reaction is known to be able to be performed by irradiation at a wavelength h generally greater than 500 nm.
• the photochromic family of fulgids corresponds to formula (V).
• R 1 , R 3 , R 4 , R 5 and R 6 which are identical or different, represent, independently of one another, alkyl, cycloalkyl, aromatic or heteroaromatic rings, substituted or unsubstituted by heteroatomic groups.
• the photochromic of the fulgid family corresponds to the formula (VIa). (Via)
• This compound is known to change color according to the transformation below.
• the photothermochromic substance advantageously belongs to the family of spiropyrans and corresponds to the following formula (VIIa).
• Ri, R ⁇ identical or different, represent
• the groups R 3 , R 4 and R 5 which may be identical or different, represent, independently of each other, alkyl or cycloalkyl radicals, which may or may not be substituted by heteroatomic groups.
• the groups X, Y and Z which may be identical or different, represent, independently of one another, a heteroatom or a methylene group which may or may not be substituted by alkyl or cycloalkyl radicals.
• the reverse reaction is known to be able to be carried out thermally in a range of temperature varying around the ambient temperature in relatively short time. It is accelerated by a supply of thermal energy.
• the photothermochrome of the family of spiropyrans can meet the following formula (VII).
• R 1 , R 2 which may be identical or different, represent, independently of one another, electron donor or acceptor groups.
• the photothermochrome of the family of spiropyrans will have the following formula (IXa).
• This compound is known to change color according to the following transformation.
• the photothermochromic substance preferably belongs to the family of stilbenes and corresponds to the following formula (Xa). (Xa)
• R 1, R 2, R 3, R 4, R 5 and R 6 which may be identical or different, represent, independently of one another, alkyl, cycloalkyl, aromatic or heteroaromatic rings, which may or may not be substituted by heteroatomic groups .
• the group X represents a nitrogen atom or a carbon.
• This family of compounds is known to change color under the action of a specific wavelength A 1 , between 200 and 400 nm, depending on the transformation.
• the reverse reaction is known to be able to be carried out thermally in a range of temperature varying around the ambient temperature in relatively short time. It is accelerated by a supply of thermal energy.
• n being an integer from 1 to 20.
• the starting molecule is colorless, since the spiropyran groups are closed (colorless) and the central diarylethene group is open (colorless),
• the photothermochrome group becomes colorless again in about ten minutes, so that the molecule emits in the blue
• the photochromic and thermophotochromic substances in the case where they are separated, but also in the case where fragments exhibiting these properties are on the same molecule, will for example be advantageously incorporated in an ink, a varnish, printable on a natural support (paper ) or synthetic (polymers) by all existing printing techniques and especially those commonly used in the field of fiduciary printing (offset, intaglio, screen printing, flexography, typography ).
• the formulation containing said substances may also form a layer in an assembly constituting a heat transfer film and be deposited by the same technique.
• a flexographic varnish doped at 1% by weight with the substances mentioned here will be used to print the mark or the desired sign.
• a 365 nm UV lamp irradiates the printed sign, which changes color in a few seconds. Then, either waiting for a natural relaxation of the thermophotochrome or by accelerating the latter by a supply of thermal energy (for example with a device such as a hair dryer), the element changes color and stabilizes on its intermediate color stable. Finally irradiation under a small monospectral lamp centered for example on 588 nm allows the return to the colorless initial state.

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• Business, Economics & Management (AREA)
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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Glass Compositions (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

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• 2008
  • 2008-02-25 FR FR0801008A patent/FR2927840B1/fr not_active Expired - Fee Related
• 2009
  • 2009-02-25 EP EP09719819.6A patent/EP2244884B1/de not_active Not-in-force
  • 2009-02-25 PL PL09719819T patent/PL2244884T3/pl unknown
  • 2009-02-25 WO PCT/FR2009/000203 patent/WO2009112723A2/fr not_active Ceased

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