WO2020020479A1 - Utilisation d'une composition de peinture durcissable par irradiation, procédé de production de structures micro-optiques ou nano-optiques, structure micro-optique ou nano-optique et support de données - Google Patents

Utilisation d'une composition de peinture durcissable par irradiation, procédé de production de structures micro-optiques ou nano-optiques, structure micro-optique ou nano-optique et support de données Download PDF

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Publication number
WO2020020479A1
WO2020020479A1 PCT/EP2019/000228 EP2019000228W WO2020020479A1 WO 2020020479 A1 WO2020020479 A1 WO 2020020479A1 EP 2019000228 W EP2019000228 W EP 2019000228W WO 2020020479 A1 WO2020020479 A1 WO 2020020479A1
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WO
WIPO (PCT)
Prior art keywords
micro
optical
radiation
diacrylate
nano
Prior art date
Application number
PCT/EP2019/000228
Other languages
German (de)
English (en)
Inventor
Winfried HOFFMÜLLER
Christoph HUNGER
Kai Hermann SCHERER
Original Assignee
Giesecke+Devrient Currency Technology Gmbh
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.)
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Publication date
Application filed by Giesecke+Devrient Currency Technology Gmbh filed Critical Giesecke+Devrient Currency Technology Gmbh
Priority to CN201980045315.9A priority Critical patent/CN112368344B/zh
Priority to EP19749582.3A priority patent/EP3827056A1/fr
Publication of WO2020020479A1 publication Critical patent/WO2020020479A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/004—Reflecting paints; Signal paints
    • 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
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/324—Reliefs
    • 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
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • 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
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/41—Marking using electromagnetic radiation
    • 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
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/425—Marking by deformation, e.g. embossing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/0005—Adaptation of holography to specific applications
    • G03H1/0011—Adaptation of holography to specific applications for security or authentication
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G03H1/024—Hologram nature or properties
    • G03H1/0244—Surface relief holograms
    • 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
    • B41M3/003—Printing processes to produce particular kinds of printed work, e.g. patterns on optical devices, e.g. lens elements; for the production of optical devices

Definitions

  • the present invention relates to the use of a radiation-curable coating composition for the production of micro-optical or nano-optical structures, a method for the production of micro-optical or nano-optical structures, a micro-optical structure, a nano-optical structure and a data carrier, such as a value document, with a micro-optical and / or a nano-optical structure.
  • security elements for security purposes, which allow the authenticity of the data carrier to be checked and which at the same time serve as protection against unauthorized reproduction
  • the security elements can be designed, for example, in the form of a security thread embedded in a banknote, a cover film for a banknote with a hole, an applied security strip or a self-supporting transfer element, such as a label which is applied to the value document after its production
  • security elements can be used which contain optically variable elements which convey a different image impression to the viewer from different viewing angles. Such optically variable elements cannot be reproduced even with high quality color copying machines.
  • the security elements can be equipped with security features in the form of optically diffractive micro- or nanostructures, such as with conventional embossed holograms or other hologram-like diffraction structures, as described, for example, in the publications EP 0 330 733 Al and EP 0 064 067 Al.
  • Microoptical structures are also frequently used, which have retroreflective effects, ie which largely reflect light incident on the microoptical structures, while the self-absorption component is extremely low.
  • the micro-optical structures behave like a kind of mirror and are designed for this purpose in various forms that enhance reflection.
  • US Pat. No. 3,712,706 describes micro-optical structures which compose a relief structure from reflecting tetrahedron elements in the form of cube corners. Such micro-optical structures reflect the incident light in a narrow space
  • a metal master plate with such micro-optical structures is produced, for example, by cutting three sets of parallel, V-shaped furs into a surface of the metal master plate using a diamond tool. The three sets with the parallel, V-shaped grooves intersect at predetermined angles such that the surface of the metal master plate has the micro-optical structures formed from periodically arranged tetrahedral elements.
  • One way of producing micro-optical structures is to use an embossing process.
  • an embossing tool is pressed into a so-called embossing lacquer at a defined pressure and temperature.
  • embossing lacquer In principle, there are two different types of embossing
  • coating compositions curable by radiation, and thus usually by UV light the coating composition shrinks to a certain extent after shaping during curing.
  • the resulting volume shrinkage is comparatively large, which leads to poor quality and poor dimensional accuracy of the micro-optical or nano-optical structures.
  • the shrinkage can be geometrically anisotropic, which additionally leads to reduced shape retention and favors light scattering effects, while light reflection is reduced in the micro-optical structures.
  • UV embossing lacquers that is to say lacquer compositions which are curable by UV radiation and are applied, for example, to a support, such as a film
  • a lacquer shrinkage may also occur, which is an additional, the quality of the structures and the shape accuracy of the micro-optical structures cause a disadvantageous phenomenon.
  • This is a phenomenon that is also referred to as curl.
  • a tendency to curl is understood to mean the tendency of the wearer to distort under the applied pressure, which is due to the occurrence of internal tensions.
  • the object of the present invention is therefore to avoid the disadvantages of the prior art and to provide a radiation-curable coating composition for the production of micro-optical and nano-optical structures which forms lower internal stresses during curing or these internal stresses before consolidation breaks down, thereby avoiding malformations, distortions and poor quality of the micro- or nano-optical structures formed from the radiation-curable coating composition. It is a particular object of the present invention to provide a use of a radiation-curable lacquer composition for the production of micro-optical or nano-optical structures with very good shape and structure fidelity.
  • micro-optical structures which are distinguished by very good reflection properties owing to their precise structure which is designed with high dimensional accuracy and structural accuracy.
  • a radiation-curable lacquer composition is understood to mean a composition which hardens by exposure to suitable high-energy radiation, such as, for example, UV radiation, X-radiation, electron radiation or IR radiation, and in particular UV radiation cross-linked in the chemical sense, and which thus changes into a solid aggregate state through the formation of bonds between the individual molecules forming the lacquer composition, which is characterized by a lacquer-like or film-like character.
  • suitable high-energy radiation such as, for example, UV radiation, X-radiation, electron radiation or IR radiation, and in particular UV radiation cross-linked in the chemical sense, and which thus changes into a solid aggregate state through the formation of bonds between the individual molecules forming the lacquer composition, which is characterized by a lacquer-like or film-like character.
  • the crosslinking reaction is essentially not restricted and can include radical crosslinking reactions, anionic and cationic crosslinking reactions and addition reactions. Each of these crosslinking reactions produces crosslinked polymeric compounds. Because of the high crosslinking density, radical crosslinking reactions are particularly preferred.
  • the radiation-curable coating composition is in particular in the form of an embossing coating composition. This means that the paint composition can be shaped into desired structures by applying pressure and temperature using an embossing process.
  • micro-optical structure is understood to mean a three-dimensional relief that reflects an incident electromagnetic wave, in particular largely largely independently of the direction of incidence and the orientation of the relief, largely in the direction from which the electromagnetic wave came
  • electromagnetic waves are deflected one after the other at inclined interfaces and thrown back to the source of the electromagnetic wave
  • the radiation source for example the surface of the micro-optical structures can also be mirrored, for example, or the interfaces at which the electromagnetic wave is deflected can differ
  • the surface which is mirrored in the first case can be obtained in particular by providing a metal layer, as is known, for example, from the publication WO 2014/117086 A1.
  • Nano-optical structures are understood here to mean, in particular, sub-wavelength gratings which are suitable for coloring in reflection and also in transmission.
  • Metallic structures which appear in color at a gloss angle and which can additionally be cost-effectively embossed on film are described in the publications WO 2013/053435 A1 , DE 10 2011 101 635 A1 and DE 10 2015 008 655 A1, which can be both one-dimensional and two-dimensional periodic structures, such wavelength grids are suitable for producing true color images, the true color image here being in contrast to hologram grid structures the zeroth diffraction order, i.e. can be seen in the gloss angle.
  • the coating curable by radiation composition at least one radiation-curable compound, at least one chain transfer agent and at least one reactive diluent, selected from dipropylene glycol diacrylate (DPGDA), tricyclodecanedimethanol diacrylate, tricyclodecanedimethanol dimmethacrylate, ester diol diacrylate (EDDA), polyethylene glycol tetraethyl diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol diacrylate, 3-methylene glycol
  • the at least one radiation-curable compound can in particular be selected from monomers or prepolymers, it also being possible to use any mixtures of different monomers and / or prepolymers.
  • a combination of different curable monomers and / or prepolymers of the same chemical compound type that is to say different compounds of one substance class, such as styrene acrylate, methyl methacrylate and the like, can also be used.
  • Any monomer or prepolymer that is curable by radiation and thus crosslinkable is suitable.
  • the reaction of chemically identical radiation-curable compounds of a single compound type leads to the formation of homopolymer.
  • the reaction of chemically different radiation-curable compounds of a single or more compound types leads to the formation of copolymers.
  • the chain transfer agent is used to transfer the activity of a growing polymer chain to the chain transfer agent.
  • the chain transfer agent has at least a weak bond to an element or a substituent group, usually an abstractable hydrogen atom.
  • the element abstracted from the chain transfer agent for example a hydrogen atom, or the substituent group saturates the polymer chain that has grown during the curing process. What remains is a relatively stable chain transfer agent radical that starts a new polymer chain and is therefore found at one end of the new polymer chain.
  • the radiation-curable coating composition contains at least one reactive thinner which is selected from dipropylene glycol diacrylate (DPGDA), tricyclodecandimethanoldiacry lat, tricyclodecanedimethanoldimethacry lat, ester diol- diacrylate (EDDA), polyethylene glycol diacrylate, tetraethylene glycol diacrylate, 3-methyl-l, 5-pentanediol diacrylate, decanediol diacrylate, 1,6-hexanediol diacrylate, T r imethy lolpr opantriacry lat, T ripr opy rengylated derivative, these reagent and ethylenated derivative , By adding one or more of these reactive diluents, the running of the hardened polymer film forming the micro-optical or nano-optical structures can be improved, so that the surface of the micro-optical
  • the reactive diluent can also act as a solvent, for example for prepolymers, and thus reduce the volume shrinkage.
  • the addition of reactive diluents contributes to improving the shape retention by delaying the reaching of the gel point of the curable coating composition, so that the viscosity only increases at a late point in time.
  • the reactive diluent can in particular react with the components of the radiation-curable coating composition according to the invention and is therefore at least partially also contained in its crosslinked form in the micro-optical structure or the nano-optical structure according to the present invention. This makes it possible to influence the subsequent properties, such as the solubility of the hardened coating composition, in the desired manner by selecting a suitable reactive diluent.
  • the gel point is later reached during the curing of the coating composition by radiation. Without being bound by theory, it is believed that this is due to the fact that numerous short polymer chains are formed in the initial phase of the curing reaction. This short zen polymer chains are more flexible than long polymer chains.
  • the paint composition consequently remains fluid for a long time.
  • the gel point is only reached with a significantly higher conversion of compounds curable by radiation. This is particularly favored by the addition of reactive diluents.
  • very long internal stresses can be reduced and thus avoided.
  • the degree of crosslinking that can ultimately be achieved remains the same, despite the addition of chain transfer agent, but the resulting polymer network is characterized by very low internal stresses.
  • the shrinkage also remains almost the same. However, since no internal tension forces can be built up by the crosslinking lacquer composition due to the flow behavior before the gel point is reached, the shrinkage which conventionally acts in all directions essentially only has a vertical effect on the polymer network which forms. This can prevent rolling phenomena.
  • the state of low internal stresses also ensures that the micro-optical or nano-optical structures to be produced from the lacquer composition can be produced with very high precision, very good quality or very high structural and shape accuracy.
  • the flowability of the radiation-curable coating composition is further improved according to the invention in that the viscosity of the radiation-curable coating composition at a temperature of 20 ° C., measured in accordance with EN ISO 3219: 1994, is less than 1000 mPa s.
  • This also allows, for example, reflow into a mold, such as an embossing mold, provided that the coating composition according to the invention is advantageously designed as an embossing coating composition.
  • the reactive diluent used according to the invention has ner also found to be advantageous because it contributes to lowering the viscosity of the radiation-curable coating composition and thus facilitates the embossing process.
  • micro-optical or nano-optical structures resulting from the use of the radiation-curable lacquer composition according to the invention thus have a specifically designed relief structure which enables a double or multiple reflection of incident electromagnetic waves with a very small spread of the reflected waves.
  • the radiation-curable coating composition can contain, in addition to the essential ingredients described above, other additives, such as stabilizers (e.g. the commercially available products Irgastab 22 from BASF), additives for viscosity control, additives for flow or release, waxes, defoamers or thinners. Other optional additives are coloring additives and / or additives that increase the refractive index.
  • the radiation-curable coating composition can be solvent-based or solvent-free. Solvent-free coating compositions are preferred insofar as their composition does not change even after a longer exposure time. In the absence of a solvent, no solvent can evaporate.
  • the radiation-curable compound is not specifically limited and can be selected accordingly depending on the desired property profile of the polymer network obtained therefrom.
  • the radiation-curable compound is preferably selected from epoxides, unsaturated esters, melamine, episulfides, urethanes, isocyanates and olefinically unsaturated compounds since allow these compounds to be cured very easily and with a high degree of polymerization or degree of crosslinking and a stable polymer network is available.
  • olefinically unsaturated compounds acrylates, alkenes, allyl ethers, vinyl acetate, alkyl vinyl ethers, conjugated dienes and styrene are particularly preferred.
  • the radiation-curable compounds mentioned above can also be used in any mixtures thereof.
  • Particularly preferred compounds curable by radiation are, for example, acrylates which can polymerize via their unsaturated bonds, or epoxides which can polymerize via their epoxy groups, or also episulfides which polymerize via their episulfide groups and can thus cure.
  • Acrylates, epoxides and episulfides, each with a functionality of greater than 1, are self-crosslinking compounds that harden through radiation.
  • Preferred acrylates are, for example, phenylthioethyl acrylate (PTEA) with a refractive index of 1.557, available from BIMAX and bis (4-methacryloylthiophenyl sulfide (MPSMA), available from Sumitomo Seika Co. (Japan). Also preferred is bis (4-vinylthiophenyl) sulfide (MPV) with a refractive index of 1.695, available from Sumitomo Seika Co. (Japan). Further preferred acrylates are pentabromophenyl methacrylate or 2,6-dichlorostyrene.
  • CN104 bisphenol-A-epoxy-diacrylate
  • CN111 silica
  • CN550 amine-modified polyether acrylate
  • CN9200 aliphatic urethane diacrylate
  • Ebecryl 8402 aliphatic urethane diac- rylate
  • Ebecryl 270 aliphatic urethane diacrylate
  • a preferred epoxy is bis [4- (2,3-epoxypropylthio) phenyl] sulfide (MPG) with a refractive index of 1.669.
  • Preferred episulfides are disulfides as disclosed in U.S. Patent No. 6,709,107.
  • the addition of one or more curing agents may be necessary or at least advantageous.
  • Preferred radiation-curable compounds which contain a curing agent for crosslinking contain, for example, isocyanates, olefinically unsaturated compounds, epoxides or episulfides as further compounds.
  • Preferred olefinically unsaturated compounds include, for example, simple alkenes, allyl ethers, vinyl acetate, alkyl vinyl ethers, conjugated dienes, styrene and acrylates.
  • Isocyanates, olefinically unsaturated compounds, epoxides and episulfides are advantageously crosslinked with polythiols as hardeners.
  • Polythiols lead to particularly rapid curing in the case of epoxides and episulfides as well as in isocyanates and in the case of unsaturated monomers / oligomers / prepolymers.
  • the crosslinking reactions can be initiated both with UV light and with electron beams.
  • the hardness of the resulting polymer material and thus the degree of crosslinking can be adjusted via the functionality of the components.
  • the radiation-curable coating composition is further advantageously characterized in that the chain transfer agent is selected from: vinyl sulfonate esters, silanes, thiol compounds, acetaldehyde and isopropanol.
  • the above-mentioned chain transfer reagents can be used individually or in any combination.
  • Vinyl sulfonate esters, silanes and thiol compounds in particular have been found to be particularly advantageous since they have easily abstractable hydrogen atoms and, after the hydrogen atom has been abstracted, a relatively stable radical remains, which can generate a polymer chain as a further starting radical.
  • Bis (trimethylsilyl) silane should be mentioned as particularly advantageous, while the particularly preferred thiol compound is dodecyl mercaptan and the following commercially available thiol compounds: the Thiocure series from the manufacturer BrunoBock, such as e.g. TMPMP (CAS 33007-83- 9), i.e. Trimethylolpropane tris (3-mercaptopropionate), PETMP (CAS 7575-23-7), i.e. Pentaerythritol tetrakis (3-mercaptopropionate), ETTMP 700 (CAS 674786-5), i.e.
  • TMPMP CAS 33007-83- 9
  • Trimethylolpropane tris 3-mercaptopropionate
  • PETMP CAS 7575-23-7
  • Pentaerythritol tetrakis 3-mercaptopropionate
  • ETTMP 700 CAS 674786-5
  • PETMP CAS 7575-23-7
  • TMP (EO) 3TA CAS 28961-43-5
  • EO trimethlylolpropane
  • Miramer ES110 PETMP (CAS 7575-23-7), ie pentaerythritol tetrakis (3-mercaptopropionate)
  • TMPTA CAS 15625-89-5
  • Ebecryl LED 02 PETMP (CAS 7575-23-7), ie pentaerythritol tetrakis (3-mercaptopropionate
  • TMP (EO) 3TA CAS 28961-43-5
  • Ebecryl 375 PETMP (CAS 7575-23-7)
  • the total mass of chain transfer agent based on the total mass of the radiation-curable lacquer composition, is 1 to 20% by mass, in particular 1 is up to 10 mass% and in particular 1.5 to 4 mass%.
  • At least one photoinitiator may be added to the radiation-curable coating composition.
  • Standard photoinitiators which generate free radicals can be used as initiators, or initiators which release hydrogen can be used.
  • Particularly suitable photoinitiators should preferably be active both in the short-wave UV spectrum and in the long-wave UV spectrum. The activity in the short-wave spectral range is often important for good surface hardening and the activity in the long-wave spectral range is important for good hardening. It is therefore often advisable to use a photoinitiator system consisting of at least two photoinitiators with activities in different spectral ranges.
  • the radiation-curable coating composition can further advantageously contain at least one curing agent.
  • at least one curing agent This applies in particular to non-self-polymerizing compounds curable by radiation or, if desired, to crosslink them for further purposes Increase in crosslink density.
  • curing agents such as those in U.S. Patent No. 4,856,857 may be used.
  • Suitable curing agents for epoxides are, in particular, polyvalent amines, e.g. 1,3-diaminobenzene, and aliphatic amines, such as diethylene triamine. Aliphatic amines cure at room temperature. Alternatively, so-called “acidic curing agents” can also be used, which often comprise dicarboxylic acid anhydrides such as hexahydrophthalic anhydride. Here, the curing reaction takes place at higher temperatures, for example in the range between 120 ° C. to 160 ° C. The reactive epoxy rings react in addition reactions with the functional groups of the curing agent.
  • such a radiation-curable lacquer composition comprising at least one radiation-curable compound, at least one chain transfer agent and at least one reactive diluent selected from dipropylene glycol diacrylate (DPGDA), tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol diol EDDA acrylate , Polyethylene glycol diacrylate, tetraethylene glycol diacrylate, 3-methyl-l, 5-pentanediol diacrylate, decanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, and the respective ethoxylated derivatives of these, one of which contains a reactive and thinned derivative of this temperature 20 ° C, measured according to EN ISO 3219: 1994, which is less than 1000 mPa s, for the production of micro-optical structures that have at least two times reflection,
  • DPGDA dipropylene glycol
  • a coating composition which comprises at least one radiation-curable compound, which is in particular an acrylate, at least one thiol compound, such as, in particular, special dodecyl mercaptan or one of the following commercially available thiol compounds
  • Chain transfer agent the series Thiocure from the manufacturer BrunoBock, such as TMPMP (CAS 33007-83-9), ie trimethylolpropane-tris (3-mercaptopropionate), PETMP (CAS 7575-23-7), ie pentaerythritol-tetrakis (3-mercaptopropionate) , ETTMP 700 (CAS 674786-5), ie ethoxylated trimethylolpropane tri (3-mercaptopropionate), GDMP (CA522504-50-3), ie glycol-di (3-mercaptopropionate), TEMPIC (CAS 36196- 44-8), ie
  • TMPMP CAS 33007-83-9
  • thiols as a chain transfer agent, and in particular the use of dodecyl mercaptan or a thiol compound selected from the following commercially available thiol compounds: TMPMP (CAS 33007-83-9), ie trimethylolpropane tris (3-mercaptopropionate), PETMP (CAS 7575-23-7), ie pentaerythritol tetrakis (3-mercaptopropionate), ETTMP 700 (CAS 674786-5), ie ethoxylated trimethylolpropane tri (3-mercaptopropionate), GDMP (CA522504-50-3), ie glycol- di (3-mercaptopropionate), TEMPIC (CAS 36196- 44-8), ie tris [2- (3-mercaptopropionyloxy) ethyl isocyanurate, leads to a particularly high structural and shape fidelity of the micro-optical or nano-optical structures to be produced.
  • the addition of reactive diluents is particularly advantageous here because it has been shown that the addition of thiols as chain transfer agent results in an increase in viscosity of the coating composition.
  • the reactive diluents used according to the invention prevent this undesirable increase in viscosity effectively, so that premature gelation of the coating composition is particularly easily prevented and thus the low viscosity is maintained for a relatively long time, so that the desired micro-optical or nano-optical structures with high shape retention and structure accuracy are formed to let.
  • micro-optical or nano-optical structures are, in particular, as already trained for the use according to the invention of the radiation-curable coating composition disclosed. In this regard, reference is therefore made additionally to the use according to the invention of the radiation-curable coating composition.
  • a carrier is coated with at least one layer of a radiation-curable coating composition.
  • the coating process can be carried out as desired, for example by spraying, rolling, knife coating or the like.
  • a suitable coating process can be selected depending on the micro-optical or nano-optical structures to be produced.
  • the radiation-curable lacquer composition which is in particular in the form of an embossing lacquer composition, contains at least one radiation-curable compound, at least one chain transfer agent and at least one reactive diluent which is selected from dipropylene glycol diacrylate (DPGDA), tricyclodecanedimethanol diacrylate, tricyclodecanedimethanediol dimethacrylate, and ester diol EDDA ), Polyethylene glycol diacrylate, tetraethylene glycol diacrylate, 3-methyl-l, 5-pentanediol diacrylate, decanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, and the respective ethoxylated derivatives of these reactive diluents.
  • DPGDA dipropylene glycol diacrylate
  • tricyclodecanedimethanol diacrylate tricyclodecan
  • the radiation-curable compound, the chain transfer agent and the at least one reactive diluent can be designed as disclosed above for the coating composition according to the invention. This enables the paint composition to flow very well with a late gel point, which is also supported by the fact that the viscosity of the radiation-curable paint composition at a temperature of 20 ° C, measured in accordance with EN ISO 3219: 1994, is less than 1000 mPa s, and is therefore relatively low viscosity and flowable.
  • the radiation-curable coating composition can be prepared, for example, by simply mixing the corresponding compounds, for example with stirring or homogenization with a suitable mixing element or homogenizer.
  • the structural fidelity of the micro-optical or nano-optical structures to be produced can be improved by using the coating composition according to the invention. This can also be done during the current process by adding appropriate amounts of chain transfer reagent, for example by measuring the reflective properties of the micro-optical or nano-optical structures after production and optimizing the amount of chain transfer reagent in ongoing production based on the result. The angular deviation of the micro-optical or nano-optical structures can thus also be continuously reduced to an optimum by adapting the amount of chain transfer agent.
  • the carrier to which the lacquer composition is applied is not restricted in an individual, but is advantageously in the form of a carrier film.
  • a transparent plastic film is preferably used as the carrier, in particular a PET film, a PVC film, a polyurethane film or any combination of these plastic films, layer thicknesses of the respective films between about 6 mhi and 80 pm being preferred.
  • Composite films obtained from a combination of several of these plastic films can be used with layer thicknesses of up to approximately 100 ⁇ m.
  • the paint composition adheres to this sufficiently well and, if desired, is also available from the artist removable fabric foil. If it is desired to detach the micro-optical or nano-optical structures obtained from the support, the support can be coated with a non-stick coating. If the micro-optical or nano-optical structures are to remain permanently on the carrier, the material of the carrier is preferably selected such that there is a high level of adhesion between the carrier and the micro-optical / nano-optical structures. To adjust the adhesive properties of the carrier, the carrier can be treated with a primer.
  • a micro-optical or nano-optical structure is formed in the radiation-curable lacquer composition.
  • the micro-optical or nano-optical structures get their three-dimensional structure.
  • This can preferably be achieved by performing an embossing process in the radiation-curable coating composition. As a result, even small-sized micro-optical or nano-optical structures can be manufactured with high precision.
  • Suitable radiations include UV radiation, X-rays, electron radiation and IR radiation, UV radiation preferably being used as high-energy radiation.
  • UV radiation preferably being used as high-energy radiation.
  • the three-dimensional structure of the micro-optical or nano-optical structures is permanently fixed and stabilized by the exposure process.
  • the paint composition cures by crosslinking the contained compounds.
  • the combination of at least one radiation-curable compound with at least one chain transfer agent results in In the initial phase of the curing reaction triggered and possibly promoted by exposure, numerous short-chain polymer chains were formed, which are characterized by high mobility. This is supported by the addition of at least one reactive diluent.
  • the coating composition thus remains flowable over a long period of time and the gel point is only reached when the radiation-curable compound has a higher conversion. This means that internal tensions in the hardening paint composition can be reduced and thus reduced or even avoided, although the absolute shrinkage in volume remains essentially the same. If the coating composition is applied to a film-based carrier, curling phenomena and distortions can also be prevented.
  • the shape and structure fidelity of the micro-optical or nano-optical structures formed is thus particularly high, which means that, in particular in the case of micro-optical structures, very good reflection properties can be obtained, in particular a retroreflection of electromagnetic radiation radiating onto the micro-optical structures through an at least double reflection , and especially by multiple reflection on the surfaces of the micro-optical structures, in the direction of the radiation source with particularly low scattering of the electromagnetic radiation.
  • the process is easy to implement without high technical effort.
  • the reflection properties of the micro-optical structures produced by the method according to the invention can advantageously be improved by producing the micro-optical structures with a structure depth of 5 pm to 90 pm, in particular from 20 pm to 80 pm and particularly preferably from 25 pm to 60 pm.
  • Such structure depths are also advantageous in terms of the reproducibility of the micro-optical structures with high quality and precision.
  • Very good reflection properties of the micro-optical structures can be obtained by arranging or forming the reflection surfaces at an angle to one another.
  • Structures with mutually inclined reflection surfaces include, for example, pyramidal structures, tetrahedron structures, structures in the form of cube corners and prismatic structures.
  • Very good multiple reflections can be achieved by providing structures in the form of cube corners and prisms, whereby any structure shapes can also be combined with one another.
  • micro-optical structures with mutually inclined reflection surfaces e.g. reference is made to EP 1 469 325 A2.
  • a reflective layer in particular a metallic layer
  • the metallic layer can thus be applied as the top layer of the micro-optical or nano-optical structures.
  • the metallic layer with a protective layer in particular with one or more layers, by the radiation-curable lacquer composition be formed, is covered.
  • the metal of the metallic layer is not specifically limited. Particularly suitable metals include aluminum, silver, chrome, gold, copper and tellurium. Corresponding alloys can also be used. Suitable metals are disclosed, for example, in U.S. Patent No. 4,856,857.
  • the metallic layer can be applied by a suitable method.
  • Layer thicknesses of the metallic layer are preferably in a range from 10 nm to 150 nm, which can be achieved particularly well by means of PVD (physical vapor deposition).
  • a micro-optical structure is also described which is produced by the method disclosed above. Due to the use of the method according to the invention, the micro-optical structure is distinguished by a precisely formed structure, a high degree of shape retention and thus very good quality. This means that distortions or structure induced by shrinkage and tendency to curl are avoided, as a result of which very good reflection properties of the micro-optical structures can be achieved.
  • a micro-optical structure which comprises at least one compound hardened by radiation with at least one terminal residue of a chain transfer agent and at least one reactive diluent selected from dipropylene glycol diacrylate
  • the micro-optical structure is through a radiation-hardened lacquer is formed in such a way that a double reflection or multiple reflection on surfaces of the micro-optical structure is possible.
  • the cured coating can be obtained, for example, by curing the radiation-curable coating composition of the invention disclosed above by exposure.
  • DPGDA dipropylene glycol diacrylate
  • EDDA ester diol diacrylate
  • Decanediol diacrylate 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, and the respective ethoxylated derivatives of these
  • the micro-optical structure according to the invention has a precise structure which is designed with high dimensional accuracy and very good quality, without distortions, malformations, defects and structural irregularities.
  • the micro-optical structure according to the invention shows a double or multiple reflection with very good reflection properties and low scatter of the reflected electromagnetic radiation.
  • the micro-optical structure can be produced in particular by the method according to the invention for producing micro-optical structures. Accordingly, the advantages, advantageous effects and further training are mutually applied.
  • the terminal radical is advantageously a radical which consists of a vinyl sulfonate ester radical, a silane radical, such as, in particular, bis (trimethylsilyl) silyl, a thiol radical, such as, in particular, dodecyl mercaptyl or a thiol radical of TMPMP, PETMP, ETTMP, GDMP, TEMPIC,
  • CH3C 0 and (CH3) 2CHO is selected.
  • a chain reagent which is selected from: vinyl sulfonate esters, silanes, such as in particular bis (trimethylsilyl) silane, thiol compounds, such as in particular dodecyl mercaptan or thiol compounds of the following commercially available products: TMPMP (CAS 33007-83-9), i.e. Trimethylolpropane tris (3-mercaptopropionate), PETMP (CAS 7575-23-7), i.e. Pentaerythritol tetrakis (3-mercaptopropionate), ETTMP 700 (CAS 674786-5), i.e.
  • chain transfer reagents have very easily abstractable hydrogen atoms. After abstraction of the hydrogen atoms, a terminal residue as defined above remains, which serves as the starting compound for a further curing or crosslinking reaction.
  • One or more chain transfer reagents can be used in combination to produce the micro-optical structure according to the invention, so that several of the terminal chain transfer agent residues mentioned above can also be present.
  • the micro-optical structure according to the invention is, in particular, an embossed micro-optical structure, since even very fine structures can be produced precisely and reproducibly by the embossing process.
  • the micro-optical structure according to the present invention can in principle have any three-dimensional shape or structure that enables at least a double reflection of electromagnetic radiation from a radiation source, so that the electromagnetic radiation irradiated onto the micro-optical structure is finally reflected back in the direction of the radiation source. Cube structures and prismatic structures have proven to be particularly suitable with regard to high reflectance values. Incident electromagnetic radiation is successively deflected at the inclined interfaces by approximately 45 ° and reflected back to the radiation source.
  • the micro-optical structure particularly advantageously has a structure depth of 5 pm to 90 square meters, in particular from 20 pm to 80 pm and in particular from 25 pm to 60 square meters. This makes it possible to achieve three-dimensional structures with very high reflectivity from electromagnetic radiation, which can also be used for objects with a low total layer thickness, such as Banknotes and the like are suitable.
  • a nano-optical structure which comprises at least one compound hardened by radiation with at least one terminal residue of a chain transfer agent and at least one reactive diluent selected from dipropylene glycol diacylate (DPGDA), tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dole methacrylate, ester diol diacrylate, ester diol diacrylate, ester diol diacrylate, ester diol doldiacrylate, ester diol diacrylate, Tetraethylene glycol diacrylate, 3-methyl-l, 5-pentanediol diacrylate, decanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tripropylene glycol diacrylate, and the respective ethoxylated derivatives of these reactive diluents.
  • DPGDA dipropylene glycol diacylate
  • the terminal residue of the chain transfer agent is advantageously selected from a vinyl sulfonate ester residue, a silane residue, such as in particular bis (trimethylsilyl) silyl, a thiol residue, such as especially dodecyl mercaptyl or a thiol residue of the following commercially available thiol compounds: TMPMP (CAS 33007-83-9), ie trimethylolpropane-tris (3-mercaptopropionate), PETMP ( CAS 7575-23-7), ie pentaerythritol tetrakis (3-mercaptopropionate), ETTMP 700 (CAS 674786-5), ie ethoxylated trimethylolpropane tri (3-mercaptopropionate), GDMP (CA522504-50-3), ie glycol di ( 3-mercaptopropionate), TEMPIC (CAS 36196-44-8), ie tris [2- (3-mercaptopropionyloxy
  • the invention also describes a data carrier which comprises at least one micro-optical and / or nano-optical structure as disclosed above.
  • value or ID documents are used as data carriers.
  • Valuable documents can include banknotes in particular.
  • the data carrier according to the invention is distinguished by a very high quality and very good properties reflecting electromagnetic radiation.
  • the data carrier can be equipped with security features or identification features.

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Abstract

L'invention concerne une utilisation d'une composition de peinture durcissable par irradiation pour produire des structures micro-optiques, qui contient i) au moins un composé durcissable par irradiation, ii) au moins un réactif de transfert de chaîne et iii) au moins un diluant réactif, choisi parmi le diacrylate de dipropylène glycol, le diacrylate de tricyclodécanediméthanol, le diméthacrylate de tricyclodécanediméthanol, le diacrylate d'esterdiol, le diacrylate de polyéthylène glycol, le diacrylate de tétraéthylène glycol, le diacrylate de 3-méthyl-1,5-pentanediol, le diacrylate de décanediol, le diacrylate de 1,6-hexanediol, le triacrylate de triméthylolpropane, le diacrylate de tripropylène glycol et des dérivés éthoxylés des diluants réactifs susmentionnés, la viscosité de la composition de peinture durcissable par irradiation, à une température de 20 °C, mesurée selon la norme EN ISO 3219:1994, étant inférieure à 1000 mPa⋅s, pour produire des structures micro-optiques ou nano-optiques.
PCT/EP2019/000228 2018-07-25 2019-07-25 Utilisation d'une composition de peinture durcissable par irradiation, procédé de production de structures micro-optiques ou nano-optiques, structure micro-optique ou nano-optique et support de données WO2020020479A1 (fr)

Priority Applications (2)

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CN201980045315.9A CN112368344B (zh) 2018-07-25 2019-07-25 通过辐射可固化的涂料组合物的用途、制造微光学或纳光学结构的方法、微光学或纳光学结构和数据载体
EP19749582.3A EP3827056A1 (fr) 2018-07-25 2019-07-25 Utilisation d'une composition de peinture durcissable par irradiation, procédé de production de structures micro-optiques ou nano-optiques, structure micro-optique ou nano-optique et support de données

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DE102018005872.8A DE102018005872A1 (de) 2018-07-25 2018-07-25 Verwendung einer durch Strahlung härtbaren Lackzusammensetzung, Verfahren zur Herstellung von mikrooptischen Strukturen, mikrooptische Struktur und Datenträger
DE102018005872.8 2018-07-25

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CN112368344B (zh) 2022-08-23

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