WO2020126753A1 - Couche adhésive aqueuse - Google Patents

Couche adhésive aqueuse Download PDF

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Publication number
WO2020126753A1
WO2020126753A1 PCT/EP2019/084691 EP2019084691W WO2020126753A1 WO 2020126753 A1 WO2020126753 A1 WO 2020126753A1 EP 2019084691 W EP2019084691 W EP 2019084691W WO 2020126753 A1 WO2020126753 A1 WO 2020126753A1
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WO
WIPO (PCT)
Prior art keywords
adhesive layer
pvdc
support
core
overlay
Prior art date
Application number
PCT/EP2019/084691
Other languages
English (en)
Inventor
Hubertus Van Aert
Jessica MAURIELLO
Nick VALCKX
Original Assignee
Agfa-Gevaert Nv
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 Agfa-Gevaert Nv filed Critical Agfa-Gevaert Nv
Publication of WO2020126753A1 publication Critical patent/WO2020126753A1/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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/04—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09J127/08—Homopolymers or copolymers of vinylidene chloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B42D25/45—Associating two or more layers
    • B42D25/465—Associating two or more layers using chemicals or adhesives
    • B42D25/47—Associating two or more layers using chemicals or adhesives using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2425/00—Cards, e.g. identity cards, credit cards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/08—Vinylidene chloride

Definitions

  • the invention relates to aqueous adhesive layers, in particular aqueous adhesive layers for PVC and PET substrates.
  • Adhesive layers also referred to as primers, are applied on various substrates to improve the adhesion of coatings, foils, sheets, etc. towards that substrate.
  • Security cards such as ID cards, drivers licenses, credit cards, etc. typically consist of an overlay laminated on a core support.
  • the core support may carry visible information, such as alphanumeric information, logos and a picture of the card holder, and optionally also digital information stored in a magnetic strip or in an electronic chip (so-called smart card). Also information, which become visible upon exposure to radiation, UV or IR, may be provided. After lamination of the overlay on the core support, information may also be provided on the overlay.
  • a principal objective of security cards is that they cannot be easily modified or reproduced in such a way that the modification or reproduction is difficult to distinguish from the original.
  • Such modification usually involves de-laminating the overlay from the core support, altering the visible information on the card and relaminating, i.e. closing again, the card.
  • PVC polyvinyl chloride
  • PC polycarbonate
  • TeslinTM and ABS are only suitable for very low-end or single-use cards.
  • PET-G Polyethylene Terephthalate Glycol
  • PET-G Polyethylene Terephthalate Glycol
  • PET-C crystalline polyethylene terephthalate
  • PET-C is a material that is very durable and resistant to mechanical influences (flexion, torsion, scraicnesj, chemical substances, moisture and temperature ranges. Untreated PET-C cannot be sealed or laminated to itself or to other materials, but requires additional adhesive coatings and layers to accomplish this.
  • the overlay is typically laminated onto a core material, which is partly or even completely covered with ink.
  • the adhesion of the overlay to such a core covered with ink may be different compared to the adhesion to a core having no ink on its surface.
  • W02009/063058 discloses an overlay comprising a biaxially oriented polyester substrate and adhesion layer.
  • the adhesion layer includes a polyester, a polyester-urethane or a copolymer of a chlorinated ethylene.
  • overlays adhere well to a PVC, PC and PET-G core, they lose their adhesive properties when the core surface is printed completely or to a large extent with ink. Therefore a need exists to provide overlays based on crystalline polyethylene terephthalate (PET-C) that adhere well to both printed and unprinted PVC, PC and PET-G cores without requiring an extra ink receiving layer on the core body.
  • PET-C crystalline polyethylene terephthalate
  • EP-A 2567812 disclose an overlay comprising an adhesive layer of which the binder is a mixture of a first and a second polymer, wherein the first polymer is a copolymer comprising vinylacetate and vinylchloride and the second polymer is a copolymer of styrene, butadiene and methylmethacrylate or a copolymer of vinyl butyral, vinyl acetate and vinyl alcohol.
  • Aqueous adhesive layers i.e. adhesive layers which are coated from an aqueous composition, are preferred for Health and Safety considerations. Also, drying efficiency of aqueous adhesive layers is typically higher compared to solvent borne adhesive layers. This results in more cost effective manufacturing of such aqueous adhesive layers.
  • Figure 1 shows a schematic representation of an embodiment of a security
  • Figure 2 shows a schematic representation of another embodiment of a security document according to the invention.
  • support and“foil”, as used in disclosing the present invention, mean a self-supporting polymer-based sheet, which may be associated with one or more subbing layers. Supports and foils are usually manufactured through (co-)extrusion of polymer(s).
  • the term“layer”, as used in disclosing the present invention, is considered not to be self-supporting and is manufactured by coating it on a support or a foil.
  • the term“lamella”, as used in disclosing the present invention, includes one or more foils and one or more layers.
  • PET is an abbreviation for polyethylene terephthalate.
  • PET-G is an abbreviation for polyethylene terephthalate glycol, the glycol
  • glycol modifiers which are incorporated to minimize brittleness and premature aging that occur if unmodified amorphous polyethylene terephthalate (APET) would be used in the production of cards.
  • APET amorphous polyethylene terephthalate
  • PET-C is an abbreviation for crystalline PET, i.e. an oriented polyethylene
  • the adhesive layer according to the present invention is an aqueous adhesive layer comprising a first and a second binder, characterized in that the first binder is polyvinylidene (PVDC) and the second binder is an acrylate having a glass transition temperature (Tg) between 25°C and 100°C.
  • PVDC polyvinylidene
  • Tg glass transition temperature
  • An aqueous adhesive layer is an adhesive layer provided from an aqueous
  • An aqueous composition includes water as main solvent.
  • composition preferably contains at least 70 wt% of water, more preferably at least 80 wt%, most preferably at least 90 wt% of water relative to the total weight of all solvents of the composition.
  • the PVDC and acrylate are preferably provided to the composition as a latex.
  • a latex as used herein is an aqueous dispersion of a polymer particle.
  • the adhesive layer may further comprise other ingredients as long as it does not deteriorate its adhesion properties. Such ingredients include, for example surfactants to enhance the quality of the coating or colorants to provide an aesthetical or functional purpose.
  • the adhesive layer may also comprise colloidal particles preferably being inorganic or organic colloidal particles. Preferred inorganic colloidal particles are colloidal silica particles. Suitable organic particles are crosslinked polystyrene or polymethylmethacrylate particles.
  • the adhesive layer may also comprise UV blocking agents, thickeners, antistatic agents, biocides, light stabilizers, other binders, solvents, etc.
  • the aqueous composition may comprise other solvents.
  • a particularly preferred solvent is 2,5,7,10 T etraoxaundecane (TOU). It has been observed that the addition of TOU may improve the adhesion.
  • TOU 2,5,7,10 T etraoxaundecane
  • the ratio of the amounts of water and TOU is preferably 85wt%/15wt%, more preferably 90wt%/1 Owt%, most preferably 95wt%/5wt% all relative to the total weight of the solvents.
  • the adhesive layer is preferably provided on a support by coating.
  • adhesive layer may also be provided on a support using a spraying or a jetting device, such as an inkjet print head.
  • a jetting device such as an inkjet print head.
  • an inkjet print head allows the composition to be provided according to a pattern or image.
  • the composition may also be provided using a screen printing device.
  • the coated adhesive layer is then preferably dried to remove water and other solvents from the layer.
  • heat is supplied to evaporate the water from the coated layer. Also, when the drying temperature is above the film forming temperature of the latex particles, these will coalesce to form a
  • the drying temperature may be optimized to obtain maximal adhesion properties.
  • Preferred drying temperatures are between 40 °C and 160 °C.
  • the adhesive layer can be applied inline or offline.
  • a stretching of the support including the adhesive layer For example, when the support is a biaxially stretched PET film (BOPET film), the adhesive layer may be applied after a first stretching, preferably the longitudinal stretching, but before the second stretching, preferably the transversally stretching.
  • BOPET film biaxially stretched PET film
  • the adhesive layer may also be applied inline after biaxially stretching the
  • the dry coating weight of the adhesive layer is preferably between 1 g/m 2 and 30 g/m 2 .
  • the dry coating weight is preferably between 5 and 30 g/m 2
  • the dry coating weight is preferably between 1 and 10 g/m 2 .
  • PVDC Polyvinylidenechloride
  • vinylidenechloride but is preferably a copolymer of vinylidenechloride with another monomer.
  • PVDC may be susceptible to yellowing upon exposure to daylight and/or UV light.
  • Crystalline PVDC is preferably used because it is less susceptible to yellowing when compared to more amorphous PVDC.
  • the crystallinity can be measured by Differential Scanning Calorimetry (DSC) or Fourier Transform Infrared
  • the crystallinity of PVDC may also be characterized by a so-called Crystallinity Index as described in WO2017/157963 paragraph [0024]
  • Such a Crystallinity Index (C.l.) of the PVDC latex is preferably higher than 1 .1 , more preferably at least 1.2, most preferably at least 1 .3.
  • a more crystalline PVDC typically has less chain imperfections, which may
  • tertiary chlorine atoms causes chain branching, and therefore a lower amount of tertiary chlorine atoms.
  • a lower amount of tertiary chlorine atoms may lead to less dehydrochlorination and therefore less double bond formation, which may be the reason for yellowing.
  • the susceptibility towards yellowing is therefore in most cases linked to a so- called dehydrochlorination constant, for example measured according to
  • the PVDC preferably has a high glass transition temperature (Tg) because a higher Tg may result in less mobility of the polymer and therefore a lower susceptibility towards yellowing.
  • the PVDC preferably has a Tg of at least 12°C, more preferably from 13 to 28°C, most preferably from 17 to 20°C.
  • the yellowing of PVDC based coatings may also be influenced by the PVDC copolymer composition.
  • the copolymer composition may influence, for example, the water uptake and oxygen barrier properties of the coatings, both of which may influence the formation of double bonds and therefore the yellowing.
  • the yellowing of PVDC copolymers may be influenced by many parameters, such as crystallinity, glass transition temperature and copolymer composition. Moreover, these parameters may influence each other.
  • the presence of a comonomer may decrease the crystallinity of the polymer dependent on the copolymerisation parameters of the comonomer with vinylidene chloride.
  • a comonomer, which forms a more random or statistical distribution with the vinylidene chloride segments, give generally shorter segments of polyviny!idene chloride resulting in a lower crystallinity.
  • a comonomer which gives a more blocky or sequential structure will resun in a higher crystallinity.
  • the PVDC used in the present invention is preferably a copolymer comprising, besides a vinylidenechloride monomer, another monomer selected from the group consisting of an acrylate (for example methyl acrylate, methyl
  • the PVDC is more preferably a copolymer comprising a vinylidenechloride monomer and methylacrylate.
  • PVDC latexes examples include the Daran® and Serfene® latexes from Owensboro Specialty Polymers, PVDC Latex grades from Asahi Kasei, Diofan® latexes from Solvay Speciality Polymers and
  • the adhesion properties of the aqueous adhesion layer is of major importance.
  • PVDC properties that have a positive influence on yellowing may have a negative influence on the adhesion properties.
  • the adhesion properties of more crystalline PVDC is typically worse than those of more amorphous PVDC, probably due to a higher chain mobility of more amorphous PVDC.
  • Tg glass transition temperature
  • the acrylate has a glass transition temperature from 25°C to 120°C, more
  • the acrylate is preferably an ethyl acrylate - methyl methacrylate copolymer.
  • copolymer may be optimized to fall in the 25°C to 100°C region.
  • a preferred acrylate is a ethyl acrylate - methyl methacrylate copolymer wherein the ratio of methyl acrylate to ethyl acrylate is at least 50wt%/50wt%, more preferably at least 60wt%/40wt%, most preferably 70wt%/30wt%.
  • the acrylate is preferably prepared by emulsion polymerization using anionic and/or non-ionic surfactants.
  • anionic and/or non-ionic surfactants also referred to as surfmers
  • surfmers copolymerizable monomeric surfactants
  • An advantage of an acrylate is its good UV stability, its low cost and its ease to apply.
  • polyurethane copolymers may also be used to slow down the crystallization speed of the PVDC in a coating.
  • the adhesive layer may further include so called stabilizers, which slow down the PVDC dehydrochlorination reaction described above.
  • Preferred stabilizers are those disclosed in“PVC Degradation and Stabilization”, George Wypych, 3rd Edition (ISBN9781895198850).
  • Laser marking i.e. writing information with a laser, is often used to provide
  • security information on a security card Preferably the information is laser marked inside the security card making it more difficult to counterfeit.
  • marking may be carried out in the adhesive layer.
  • the adhesion layer may contain a laser additive, which renders the security document more sensitive to laser radiation.
  • a preferred laser radiation used to laser mark is infrared radiation, more preferably near infrared laser radiation.
  • Suitable laser additives include antimony metal, antimony oxide, carbon black, mica (sheet silicate) coated with metal oxides and tin-antimony mixed oxides.
  • WO 2006/042714 the dark coloration of plastics is obtained by the use of additives based on various phosphorus-containing mixed oxides of iron, copper, tin and/or antimony.
  • Suitable commercially available laser additives include mica coated with
  • antimony-doped tin oxide sold under the trade name of LazerflairTM 820 and 825 by MERCK; copper hydroxide phosphate sold under the trade name of
  • FabulaseTM 322 by BUDENHEIM aluminium heptamolybdate sold under the trade name of AOMTM by HC STARCK; and antimony-doped tin oxide pigments such as Engelhard Mark-itTM sold by BASF.
  • the laser additive is carbon black. This avoids the use of heavy metals in manufacturing these security documents. Heavy metals are less desirable from an ecology point of view and may also cause problems for persons having a contact allergy based on heavy metals.
  • Suitable carbon blacks include Special Black 25, Special Black 55, Special Black 250 and FarbrussT M FW2V all available from EVONIK; MonarchTM 1000 and MonarchTM 1300 available from SEPULCHRE; and ConductexTM 975 Ultra Powder available from COLUMBIAN CHEMICALS CO.
  • carbon black pigments as laser additives may lead to an undesired background colouring of the security document precursor.
  • a too high concentration of carbon black in the adhesive layer of the security document having a white core may result in grey security documents.
  • the average particle size of carbon black particles can be determined with a
  • Infrared absorbing dyes having substantial no absorption in the visible region may also be used as laser additives.
  • Such dyes as disclosed in for example WO2014/057018 (Agfa Gevaert), are particular suitable for use with a NIR laser, for example with a 1064 nm laser.
  • the overlay (10) comprises an adhesive layer (100) as described above provided on a support (200).
  • the overlay according to this embodiment is then preferably laminated on a core (300) thereby forming the security card.
  • the overlay may be laminated on one or both sides of the core, as shown in Figure 2.
  • the adhesive layer (100) containing the halogenated co- or homopolymer is coated directly on the core.
  • the coating composition of the adhesive layer can be coated using any conventional coating technique, such as dip coating, knife coating, extrusion coating, spin coating, slide hopper coating and curtain coating on the support.
  • Another layer or foil may then be applied on the coated adhesive layer.
  • the overlay preferably comprises a support ( Figure 2, 100), more preferably a transparent polymeric support.
  • Suitable transparent polymeric supports include cellulose acetate propionate or cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polyimides, polyolefins, polyvinylchlorides, polyvinylacetals, polyethers and polysulphonamides.
  • polyester substrates are based on polyesters like
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • CHDM cyclohexyldimethanol
  • FDCA 5-f u rand icarboxyl ic acid
  • PHA polylactic acid
  • the support is preferably an oriented polyester support. Orienting a polyester support is achieved by stretching the support in a longitudinal direction, a transversal direction or both directions. The highest crystallinity of the polyester support is obtained by biaxially stretching.
  • the polyester is preferably biaxially stretched with a stretching factor of at least 2.0, more preferably at least 3.0 and most preferably a stretching factor of about 3.5.
  • the temperature used during stretching is preferably at least 100°C, more preferably at least 140°C and most preferably about 160°C.
  • the oriented polyester support is preferably a polyethylene terephthalate or a polyethylene napthalate support.
  • the oriented polyester support is a biaxially stretched polyethylene terephthalate support.
  • a polyethylene terephthalate support has excellent properties of dimensional stability and is very durable and resistant to scratches and chemical substances.
  • the biaxially stretched polyethylene terephthalate substrate should be sufficiently thick to be self-supporting, but thin enough to be flexed, folded or creased without cracking.
  • the biaxially stretched polyethylene terephthalate substrate has a thickness of between about 7 pm and about 100 pm, more preferably between about 10 pm and about 90 pm, most preferably between about 25 pm and about 80 pm.
  • polyester foils and supports are well-known in the art of preparing suitable supports for silver halide photographic films.
  • suitable supports for silver halide photographic films for example,
  • GB 81 1066 (ICI) teaches a process to produce biaxially oriented polyethylene terephthalate (BOPET) foils and supports.
  • the support preferably comprises subbing layers to improve the adhesion
  • the support (100) preferably comprises subbing layers to improve the adhesion between the support and layers provided thereon.
  • subbing layers for this purpose are well known in the photographic art and include, for example, polymers of vinylidene chloride such as vinylidene chloride/acrylonitrile/acrylic acid terpolymers or vinylidene chloride/methyl acrylate/itaconic acid terpolymers.
  • Suitable vinylidene chloride copolymers include: the copolymer of vinylidene chloride, N-tert.-butylacrylamide, n-buty! acrylate, and N-vinyl pyrrolidone
  • the support is provided with a subbing layer inciuamg a copolymer selected from the group consisting of a hydroxyl-functional, partially- hydrolyzed vinyl chloride/vinyl acetate copolymer and a polyester-urethane.
  • the support is provided with a subbing layer including a binder based on a polyester-urethane copolymer.
  • the polyester-urethane copolymer is an ionomer type polyester urethane, preferably using polyester segments based on terephthalic acid and ethylene glycol and hexamethylene diisocyanate.
  • Suitable polyester-urethane copolymers are Hydran APX101 H, Hydran AP40N and Hydran AP20, all from DIC Europe GmbH or mixtures of different polyester- urethanes or mixtures of polyester-urethanes with other polymers.
  • subbing layers are well-known in the art of manufacturing
  • polyester supports for silver halide photographic films for silver halide photographic films.
  • subbing layers for silver halide photographic films.
  • AGFA GB 1441591
  • the subbing layer has a dry thickness of no more than 2 pm or preferably no more than 200 mg/m2.
  • EP-A 2374602 an EP-A 2567812 both from Agfa Gevaert.
  • a preferred method comprises the steps of a) stretching a polyester substrate in either a longitudinal or a transversal direction; b) coating and drying a subbing layer on the stretched polyester substrate ; c) stretching the coated polyester substrate in the longitudinal or transversal direction not selected in step a) in order to obtain a coated biaxially stretched polyester substrate having a subbing layer.
  • the overlay may also comprise an outer layer provided at a side of the support opposite to the side of the support upon which the adhesive layer is provided.
  • Such an outer layer is preferably an ink receiving layer or a receiver layer for Dye Diffusion Thermal Transfer (D2T2) printing.
  • D2T2 Dye Diffusion Thermal Transfer
  • an additional laser markable layer may be provided.
  • Such a laser markable layer is preferably provided on the adhesive layer.
  • Any laser markable composition may be used to form the laser markable layer.
  • the laser markable layer is capable of forming a black colour upon exposure to infrared radiation by carbonization of ingredients, typically the binder, of the laser markable layer.
  • Such a laser markable layer preferably comprises polymers selected from polycarbonate (PC), polybutylene
  • PBT polyvinyl chloride
  • PS polystyrene
  • copolymers thereof such as e.g. aromatic polyester-carbonate and acrylonitrile butadiene styrene (ABS).
  • An optothermal converting agent which absorbs infrared radiation and converts that radiation into heat, may be added to the laser markable layer to increase the marking density upon exposure to such infrared radiation.
  • laser markable compositions that may be used are those disclosed in for example W02002/074548, comprising a binder and an oxyanion of a multivalent metal, such as ammonium octamolybdate (AOM), which may be laser marked using a CO2 laser; W02006/018640 and WO2012/114121 , both comprising a diacetylene compound and which may be laser marked using a UV laser;
  • AOM ammonium octamolybdate
  • WO2007/141522 comprising a marking component, for example AOM, and a metal salt, for example reduced indium oxide, that absorbs laser irradiation at 780 to 2500 nm and may be laser marked using a NIR laser.
  • a marking component for example AOM
  • a metal salt for example reduced indium oxide
  • Preferred laser markable compositions include a leuco dye.
  • a leuco dye is a substantially colourless compound, which may react with for example a colour developing agent to form a coloured dye. The reaction may be triggered by exposure to laser irradiation. Depending on the type of leuco dyes, or mixture of leuco dyes, any colour may be obtained.
  • the colour laser markable layers may comprise an optothermal converting agent such as an infrared absorbing dye (IR dye) or an infrared absorbing pigment (IR pigment), both absorbing the IR radiation and converting it into heat.
  • an optothermal converting agent such as an infrared absorbing dye (IR dye) or an infrared absorbing pigment (IR pigment), both absorbing the IR radiation and converting it into heat.
  • Preferred laser markable compositions comprises a leucodye, an optothermal converting agent and a colour developing agent or colour developing agent precursor.
  • the composition may further comprise an acid scavenger and a UV absorber.
  • Aqueous laser markable compositions, compared to solvent based compositions, are preferred for health and safety reasons.
  • Aqueous laser markable compositions are disclosed in for example for example W02006/052842, W02008/030428 and WO2014/124052.
  • the security document comprises a core.
  • the core can be transparent, translucent or opaque.
  • the core is preferably opaque.
  • the advantage of an opaque core, preferably of a white colour, is that any information of the security document is more easily readable and that a colour image is more appealing by having a white
  • Suitable polymers for the core of the security document include cellulose acetate propionate or cellulose acetate butyrate, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamides, polycarbonates, polyimides, polyolefins, polyvinyl chlorides, polyvinylacetals, polyethers and polysulphonamides.
  • Preferred polymeric cores are based on polycarbonate (PC), polyvinylchloride (PVC), and polyethylene terephthalate (PET).
  • PC polycarbonate
  • PVC polyvinylchloride
  • PET polyethylene terephthalate
  • the core may also be based on paper, such as polyethylene or propylene coated paper.
  • the core may be a single component extrudate, but can also be co-extrudate.
  • Examples of suitable co-extrudates are PET/PETG and PET/PC.
  • an opacifying layer can be coated onto a transparent support.
  • Such opacifying layer preferably contains a white pigment with a refractive index greater than 1.60, preferably greater than 2.00, and most preferably greater than 2.60.
  • the white pigments may be employed singly or in combination. Suitable white pigments include C.l. Pigment White 1 , 3, 4, 5, 6, 7, 10, 1 1 , 12, 14, 17, 18, 19, 21 , 24, 25, 27, 28 and 32.
  • Preferably titanium dioxide is used as pigment with a refractive index greater than 1.60. Titanium oxide occurs in the crystalline forms of anatase type, rutile type and brookite type. In the present invention the rutile type is preferred because it has a very high refractive index, exhibiting a high covering power.
  • Preferred security documents are security cards, which are widely used for
  • ID cards identification purposes
  • financial transfers credit cards
  • the security document may include an electronic chip and optionally an antenna.
  • the security document is a so-called radio frequency identification card or RFID-card.
  • the security document may contain various security features, such as anti-copy patterns, guilloches, endless text, miniprint, microprint, nanoprint, rainbow colouring, 1 D-barcode, 2D-barcode, coloured fibres, fluorescent fibres and planchettes, fluorescent pigments, kinegramsTM, overprint, relief embossing, perforations, metallic pigments, magnetic material, Metamora colours, microchips, RFID chips, images made with OVI (Optically Variable Ink) such as iridescent and photochromic ink, images made with thermochromic ink, phosphorescent pigments and dyes, OVD’s, watermarks including duotone and multitone watermarks, ghost images and security threads
  • OVI Optically Variable Ink
  • a combination with one of the above security features increases the difficulty for falsifying a security document.
  • DIOFAN® P530 is a PVDC latex available from Solvay.
  • DARAN® SL159 is a PVDC latex based on vinylidene chloride and methyl
  • Tivida® FL2500 is a fluorosurfactant available from Merck.
  • TOU is 2,5,7,10 Tetraoxaundecane, a solvent available from Lambiotte.
  • Chemfac PB133 is an alkyl ether phosphate surfactant from Chemax Inc. Preparation of subbed polyester PET-1
  • a coating composition SUB-1 was prepared by mixing the components according to Table 1 using a dissolver.
  • the coating composition SUB-1 was coated onto the longitudinally stretched PET and dried.
  • the coated longitudinally stretched PET was then transversally stretched to produce a 63 pm thick transparent and glossy subbed biaxially stretched polyethylene terephthaiate substrate PET-1.
  • the dry thickness of the subbing layer coated from SUB-1 was 211 mg/m 2 .
  • the acrylate latexes LX-01 to LX-03 include a methyl methacrylate (MM A) - ethyl acrylate copolymer having a varying methyl methylacrylate - ethyl acrylate ratio.
  • the remaining part of the monomer (124.1 1 g of ethylacrylate and 53.19 g of MM A) was added during 180 minutes to the reaction mixture simultaneously with the remaining part of initiator solution (29.7 gr of the 2% sodium persulfate solution in water).
  • reaction mixture was kept at 80°C for 60 minutes. Then, the residual monomer was removed by distillation under reduced pressure during 90 minutes where the pressure is gradually reduced to 400 mBar. After cooling to room temperature, the reaction mixture was filtered over a coarse S & S paper.
  • the resulting latex had a concentration of 21.45 wt% and a particle size of 46 nm (measured with a Malvern Zetasizer Nano S).
  • LX-02 was prepared using the same method as for LX-01 but with different
  • the resulting latex LX-02 had a concentration of 23.06 wt% and a particle size of 44 nm (measured with a Malvern Zetasizer Nano S).
  • LX-03 was prepared using the same method as for LX-01 but with different
  • the resulting latex LX-03 had a concentration of 23.25 wt% and a particle size of 42 nm (measured with a Malvern Zetasizer Nano S).
  • An overlay (OL) was prepared by hand coating an adhesive layer at 45°C onto the subbed polyester PET-1 at a wet coating thickness of 30 mih. The coating was subsequently dried at 130°C during 15 minutes.
  • the overlay was then laminated onto a PVC or PETG core (thickness 350 pm) using an Oasys laminator or a Lauffer laminator.
  • the lamination times, pressures and temperatures were optimized for the different cores and overlays.
  • Both plain or preprinted cores using UV waterless offset printer and Supra UV WL Process Inks) were used.
  • Dry adhesion was tested through a simple knife resistance test: a pen knife was used to slice the overlay and to attempt to peel away the overlay from the core material. If this was successfully removed with no, or very little resistance a quantitative analysis of 0 would be given to the dry adhesion of that product. Should the overlay not be able to be detached or damaged, a grade of 1 would be awarded to the dry adhesion. A scale ranging from 0 to 1 was applied for those cards with some resistance or minor detachment.
  • Crystallinity Index (C.l.) of the PVDC latex was determined by the method disclosed in WO2017/157963 paragraph [0024]. The C.l. was determined after annealing the spincoated samples at 48 hours for 45°C.
  • DSC Differential Scanning Calorimetry

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une couche adhésive aqueuse comprenant un premier et un second liant, caractérisée en ce que le premier liant comprend un PVDC et le second liant comprend un acrylate ayant une température de transition vitreuse comprise entre 25°C et 120°C.
PCT/EP2019/084691 2018-12-18 2019-12-11 Couche adhésive aqueuse WO2020126753A1 (fr)

Applications Claiming Priority (2)

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EP18213711.7 2018-12-18
EP18213711 2018-12-18

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WO2020126753A1 true WO2020126753A1 (fr) 2020-06-25

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GB811066A (en) 1956-05-18 1959-03-25 Ici Ltd Biaxially oriented films
US3649336A (en) 1967-09-28 1972-03-14 Agfa Gevaert Nv Plural coated sheet material
GB1441591A (en) 1972-07-17 1976-07-07 Agfa Gevaert Process for adhering hydrophilic layers to dimensionally stable polyester film support
EP0119698A1 (fr) * 1983-02-21 1984-09-26 Imperial Chemical Industries Plc Composition aqueuse d'un latex du copolymère de chlorure de vinylidène
EP0185464A1 (fr) * 1984-12-06 1986-06-25 Imperial Chemical Industries Plc Compositions aqueuses d'un latex de copolymères
WO2002074548A2 (fr) 2001-03-16 2002-09-26 Sherwood Technology Ltd. Compositions pouvant etre marquees au laser
WO2006018640A1 (fr) 2004-08-20 2006-02-23 Datalase Ltd. Impression polychrome
WO2006042714A1 (fr) 2004-10-15 2006-04-27 Ticona Gmbh Matieres moulables marquables au laser ; produits obtenus a partir de ces matieres et procede de marquage au laser
WO2006052842A2 (fr) 2004-11-09 2006-05-18 The Trustees Of The University Of Pennsylvania Methodes de diagnostic de syndromes myelodysplasiques (mds)
WO2007141522A1 (fr) 2006-06-08 2007-12-13 Datalase Ltd. Marquage laser
WO2008030428A2 (fr) 2006-09-05 2008-03-13 Fujifilm Hunt Chemicals U.S.A., Inc. Compositions destinées à la formation d'un revêtement marquable par laser et matériau marquable par laser contenant des additifs organiques favorisant l'absorption
US20080238086A1 (en) 2007-03-27 2008-10-02 Ingrid Geuens Security document with a transparent pattern and a process for producing a security document with a transparent pattern
WO2009063058A1 (fr) 2007-11-15 2009-05-22 Agfa-Gevaert Nv Lamelle de polyester à orientation biaxiale pour laminés de sûreté
EP2335967A2 (fr) 2009-12-19 2011-06-22 Rehau AG + Co Pièce intercalaire pour système de barres conductrices
EP2374602A1 (fr) 2010-04-08 2011-10-12 Agfa-Gevaert Laminés de sécurité à base Pet-C et documents
WO2012114121A2 (fr) 2011-02-24 2012-08-30 Datalase Ltd. Diacétylènes activables de façon réversible et leur utilisation à titre de chromogènes
EP2567812A1 (fr) 2011-09-12 2013-03-13 Agfa-Gevaert Laminés de sécurité à base Pet-C et documents
EP2648920A1 (fr) 2010-12-07 2013-10-16 Agfa-Gevaert Marquage laser couleur d'articles et précurseurs de documents de sécurité
WO2014057018A1 (fr) 2012-10-11 2014-04-17 Agfa-Gevaert Colorants infrarouges pour marquage au laser
WO2014124052A1 (fr) 2013-02-06 2014-08-14 Fujifilm Hunt Chemicals, Inc. Revêtement chimique destiné à un matériau pouvant subir un marquage au laser
WO2017157963A1 (fr) 2016-03-18 2017-09-21 Solvay Sa Composition de revêtement anti-corrosion à base d'eau

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB811066A (en) 1956-05-18 1959-03-25 Ici Ltd Biaxially oriented films
US3649336A (en) 1967-09-28 1972-03-14 Agfa Gevaert Nv Plural coated sheet material
GB1441591A (en) 1972-07-17 1976-07-07 Agfa Gevaert Process for adhering hydrophilic layers to dimensionally stable polyester film support
EP0119698A1 (fr) * 1983-02-21 1984-09-26 Imperial Chemical Industries Plc Composition aqueuse d'un latex du copolymère de chlorure de vinylidène
EP0185464A1 (fr) * 1984-12-06 1986-06-25 Imperial Chemical Industries Plc Compositions aqueuses d'un latex de copolymères
WO2002074548A2 (fr) 2001-03-16 2002-09-26 Sherwood Technology Ltd. Compositions pouvant etre marquees au laser
WO2006018640A1 (fr) 2004-08-20 2006-02-23 Datalase Ltd. Impression polychrome
WO2006042714A1 (fr) 2004-10-15 2006-04-27 Ticona Gmbh Matieres moulables marquables au laser ; produits obtenus a partir de ces matieres et procede de marquage au laser
WO2006052842A2 (fr) 2004-11-09 2006-05-18 The Trustees Of The University Of Pennsylvania Methodes de diagnostic de syndromes myelodysplasiques (mds)
WO2007141522A1 (fr) 2006-06-08 2007-12-13 Datalase Ltd. Marquage laser
WO2008030428A2 (fr) 2006-09-05 2008-03-13 Fujifilm Hunt Chemicals U.S.A., Inc. Compositions destinées à la formation d'un revêtement marquable par laser et matériau marquable par laser contenant des additifs organiques favorisant l'absorption
US20080238086A1 (en) 2007-03-27 2008-10-02 Ingrid Geuens Security document with a transparent pattern and a process for producing a security document with a transparent pattern
WO2009063058A1 (fr) 2007-11-15 2009-05-22 Agfa-Gevaert Nv Lamelle de polyester à orientation biaxiale pour laminés de sûreté
EP2335967A2 (fr) 2009-12-19 2011-06-22 Rehau AG + Co Pièce intercalaire pour système de barres conductrices
EP2374602A1 (fr) 2010-04-08 2011-10-12 Agfa-Gevaert Laminés de sécurité à base Pet-C et documents
EP2648920A1 (fr) 2010-12-07 2013-10-16 Agfa-Gevaert Marquage laser couleur d'articles et précurseurs de documents de sécurité
WO2012114121A2 (fr) 2011-02-24 2012-08-30 Datalase Ltd. Diacétylènes activables de façon réversible et leur utilisation à titre de chromogènes
EP2567812A1 (fr) 2011-09-12 2013-03-13 Agfa-Gevaert Laminés de sécurité à base Pet-C et documents
WO2014057018A1 (fr) 2012-10-11 2014-04-17 Agfa-Gevaert Colorants infrarouges pour marquage au laser
WO2014124052A1 (fr) 2013-02-06 2014-08-14 Fujifilm Hunt Chemicals, Inc. Revêtement chimique destiné à un matériau pouvant subir un marquage au laser
WO2017157963A1 (fr) 2016-03-18 2017-09-21 Solvay Sa Composition de revêtement anti-corrosion à base d'eau

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* Cited by examiner, † Cited by third party
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GEORGE WYPYCH: "PVC Degradation and Stabilization"

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