CA2194454A1 - Transparent multilayer film and its use for protection of data on documents as well as a tamper-proof label - Google Patents

Transparent multilayer film and its use for protection of data on documents as well as a tamper-proof label

Info

Publication number
CA2194454A1
CA2194454A1 CA002194454A CA2194454A CA2194454A1 CA 2194454 A1 CA2194454 A1 CA 2194454A1 CA 002194454 A CA002194454 A CA 002194454A CA 2194454 A CA2194454 A CA 2194454A CA 2194454 A1 CA2194454 A1 CA 2194454A1
Authority
CA
Canada
Prior art keywords
layer
adhesive
multilayer film
adhesion
film according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002194454A
Other languages
French (fr)
Inventor
Katharina J. Bischof
Luigi Pastore
Wilhelm Kuester
Lynn E. Faykish
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of CA2194454A1 publication Critical patent/CA2194454A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02Forms or constructions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B42BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42DBOOKS; 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
    • B42D25/00Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40Manufacture
    • B42D25/45Associating two or more layers
    • B42D25/465Associating two or more layers using chemicals or adhesives
    • B42D25/47Associating two or more layers using chemicals or adhesives using adhesives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered 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
    • B32B27/08Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/16Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/34Layered products comprising a layer of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B42BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42DBOOKS; 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
    • B42D25/00Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29Laminated material
    • GPHYSICS
    • G09EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09FDISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F3/00Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
    • G09F3/02Forms or constructions
    • G09F3/0291Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
    • G09F3/0292Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time tamper indicating labels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/24All layers being polymeric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00Coating on the layer surface
    • B32B2255/10Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/40Properties of the layers or laminate having particular optical properties
    • B32B2307/412Transparent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554Wear resistance
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582Tearability
    • B32B2307/5825Tear resistant
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/732Dimensional properties
    • B32B2307/734Dimensional stability
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2425/00Cards, e.g. identity cards, credit cards
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2519/00Labels, badges
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered 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
    • B32B7/04Interconnection of layers
    • B32B7/06Interconnection of layers permitting easy separation
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • C09J2423/006Presence of polyolefin in the substrate
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/913Material designed to be responsive to temperature, light, moisture
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/14Layer or component removable to expose adhesive
    • Y10T428/1452Polymer derived only from ethylenically unsaturated monomer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/14Layer or component removable to expose adhesive
    • Y10T428/149Sectional layer removable
    • Y10T428/1495Adhesive is on removable layer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers

Abstract

The invention provides a transparent multilayer film comprising a cover layer, a destructible or irreversibly deformable layer, respectively, a pattern of adhesion-regulating material between the cover layer and the damageable layer, and an adhesive layer for bonding with a substrate. The damageable layer has a thickness of at least 10 µm. The following relationship applies to the cohesive strength as well as the adhesion between the layers: a, d > c > b, whereby a) is the adhesive strength between cover layer (1) and layer (3) in the areas where no adhesion-regulating material (2) is present, b) is the adhesive strength between cover layer (1) and layer (3), in the areas where adhesion-regulating material (2) is present, c) is the cohesive strength of layer (3), and d) is the adhesive strength between layer (3) and adhesive layer (5). The invention also provides for the use of the transparent multilayer film for protection of data on documents, as well as its use as a tamper-proof label. The invention also provides for a tamper-proof document or label, comprising a multilayer film of the present invention.

Description

Transparent Multilayer Film and its Use for Protection of Data on Documents as well as a Tamper-proof Label The present invention concerns a ~ ssparenl multilayer film which has at least one d~m~g~ble layer, in particular an easily destructible layer or an irreversibly d~,-"able layer. The ll anspalelll multilayer film of the invention is especi~lly well-suited for protection of data on doc..ment~ as well as for use as a tamper-proof label, and particularly for durable protection of labels and doc.lment.~
Different types of films and similar constructions are known which are int~n~ledto be used to protect writing, especially data on documentc from attempts at la",l)e,ii,g or to protect labels, such as price tags, from manipulation such as removing and readhering.
A known technology for protection of docl.m~nt~, such as identification cards and driver's licenses, consists of a multilayer film where microspheres are imbedded in a binder in one layer. Directly under the microspheres is a r el, u, ~nective customer-specific printing which can be observed under l ell ol enective conditions. Under this binder layer is a layer of pressure sensitive adhesive or heal-activated adhesive that serves to attach the film to the document. This type of construction, known, forexample, from US 3,801,183, US 4,630,891, US 5,080,463 and US 5,169,707, offers a high degree of protection against ta~,ue~ ing because the technology used in the retlo,t;nective customer-specific printing cannot be imitated with traditional equirm~nt These constructions have the disadvantage, however, in that in order to view the customer-specific printing, equipment for ,el,orenective viewing is necess~y.
DE-C-25 11 367 describes a tamper-proof recording medium comprising several layers where the document is l~min~ted between two films, and where a pattern of adhesion-reducing coating has been applied to either the film or the document, so that very little or no adhesive bond is formed between the film and the document in areas where the adhesion-reducing coating is present. Normally, an attempt to tamper with a construction of this type would result in destruction of the document. In this case as well, however, professional ta~pel el ~ are capable of removing the filmcarefully so that the substrate is not damaged.

The 3M Company brochure "3M ID Security T .~min~te Series 3000" Order No.
75-0500-00377-3 (24.5) IR (1992) from Minnesota Mining and ~n~lf~ctl-ring Company describes a security l~min~te for use when only a certain amount of security is required. The l~min~te consists of two layers, between which lies a customer-5 specific p,il,ling which cannot be photocopied and which is destroyed whend~l~ ..;na~;on is attempted.
Multilayer films for increasing the tamper-reci~t~nce of. docllm~nt$, where the tamper-recict~nce depends on the integrity of an intermediate layer having certain optical propcl lies such as a kinegram or a hologram, are described in EP-A-253 089 and EP-A-401 466. The layer with optical properties is used in combination with a usual film, which itself has only a limited level of tamper-resistance. During an attempt at tampering, the hologram would be destroyed. The film in the area of the hologram is not llanspale~ however, and its extension over the entire document surface is, aside from the expense, not desirable because of the lack of ll ~nspa~ cncy.
US 4,876,123 and US 5,082,702 describe tamper-prooffilms and tapes which are not l.~ns~.drelll. The multilayer constructions are destroyed during attempts at l~lllpel i"g, both sides of the separated film layers showing a color printing which was originally conce~led A l~min~te which works in a similar way is described in US
4,429,015 where fibers are pulled offofthe document when attempts are made to 20 remove the cover film and where the parts cannot be l~min~ted together again without visible damage.
DE-A-28 03 434 describes a self-adhesive clear film having a layer of printed adhesive. When the document is la""~)eled with, this printing remains on the document substrate. When a talllperer desires to exchange a photograph, for example, then the 25 printed pattern must be reproduced on the new photo, a task which is relatively simple for a professional tanll)eler.
FR-A-2 451 081 describes a multilayer safety l~min~te for documPnts which c~,llains an intermediate layer co.~ g ink-filled microcapsules. Upon lalllpe~ii-g, the capsules break and lead to discoloration of the document. This construction has 30 the disadvantage, however, that the microcapsules reduce the ll~ns~,arency ofthe film and that normal use of the document can lead to breakage of the microcapsules.

WO 96/02W8 2 ! 9 4 4 5 4 PCT/US95/08191 DE-A-36 08 907 describes an adherable material for labels where an underlying tearable layer is destroyed when a surface layer is manually removed. This material is non-~lans~Jalw~l~ as the easily tearable layer is preferably an aluminum vapor coating which has adhesive on both sides, the adhesives differing in their adhesive slreng~
5 Between the tearable layer and the lower adhesive layer is a pattern of an adhesion-reducing coating. A cover layer can be printed as well and the entire construction used as a tamper-proof tape or safety label. Removal of the tape or label leads to anirreversible destruction of the largely two-dimensional no.,l~an~,al enl metal layer.
Similar multilayer constructions with largely flat, very thin, non-l, a~ spare"l frangible layers are known from US 3,925,584 and EP-A-170 712.
Further descriptions of tamper-proof labels can be found in US 4,121,003 and US 4,184,701. These labels have a transparent cover layer which has a printed pattern on its inner surface. The printed pattern is destroyed when the cover layer is removed.
US 4,721,638 describes a non~ ns~arenl sticking material for preventing 15 restir~ing, having an adhesive layer, a second layer l~min~tçd on one mail surface of the adhesive layer, a peeling agent layer l~min~ted on the second layer anda first layer l~min~ted on the peeling agent layer. The second and first layers are adhered temporarily via the peeling agent layer. The first layer once separated from the second layer cannot be restuck. The non-transparent sticking material is designed to avoid the 20 use of polyester film and met~lli7~tion in the construction.
A method of m~nuf~ctllring tamper-proof docum~nt~ which is related to one of the previously described multilayer films is described in DE-C-29 52 322. In this process, a document is l~min~ted with a polyethylene film which has an adhesive coating comprising a radiation cross-linkable mass of ethylenically unsaturated 25 oligomers or polymers based on urethane-modified polyepoxides. The film is l~min~ted to the document in such a way that the crosslinkable mass comes in contact with the docllm.ont The l~min~te is then exposed to a crosclinking radiation (UVradiation). In this case, the document is provided with a very high level of protection from ta,--~,c,;ng. However, tre~tmPnt of the l~min~te with W radiation is necç~c~ry, 30 which in practice would require undesirable investment in equipment and associated safety measures because every distribution point which issues such doc.lmçnts would need such W-radiation equipment.

wo 96/02048 2 1 ~ 4 4 ~ 4 rcTlusgsl08l9l In summary, none of the numerous solutions to the problem provided by the state-of-the-art, described above, provides a s~ticf~ctory multilayer film whichco",bines an especially high degree oftamper-rçcict~nce with l,~-,s~,a~ency as well as a sirnple, relatively in~ n~ive method of m~n~lf~chlre and none has fulfilled the 5 requi, ~."~ S laid out for protecting the data on docum~ntc and labels.
One object of the invention is thus to provide a new multilayer film, intentled especially for the protection of data on docl~mçntc as well as for tamper-proof labels, which shows a high degree of tamper-resist~nce~ that is, where tal,lpe~i"g can be detected even after alterations have been made by a professional ta",perer, and which 10 in addition is simple and inexpensive to m~nuf~ct~lre.
In solution to the above problem, the invention provides a 1, ~ ,al e"l multilayer film having a cover layer, d~m~g~hle layer, a pattern of adhesion-reg~ ting material between said layers, and a first adhesive layer for bonding with a substrate, said first adhesive layer being present on the surface of the film opposite that of the 15 cover layer, characterized in that the d~m~g~ble layer 3 has a thickness of at least 10 ~m and that the cohesive strength of damagable layer 3 as well as the adhesive "~,lhs between the layers have the following relationship:
a, d>c>b wLeleby a is the adhesive strength between cover layer 1 and d~m~g~ble layer 3 in the areas where no adhesion-reg~ ting material 3 is present, b is the adhesive strength between cover layer 1 and d~m~ble layer 3, in the areas where adhesion-regul~ting material 2 is present, c is the cohesive strength of d~m~g~ble layer 3, and d is the adhesive strength between d~m~g~hle layer 3 and first adhesive layer 5.

A further object of the invention is to provide a method of use of these ~"s~are"l multilayer films for protection of data on documents as well as a method of 30 use as a tamper-proof label.
An additional object of the invention is a tamper-proof document or label, comprising a multilayer film of the present invention bonded by means of the first adhesive layer 5 to a data carrier 6, whereby the adhesive strength f between the adhesive layer 5 and the data carrier 6 is about the same as or larger than the cohesive strength c of the layer 3 and/or the cohesive ~l. englll e of the adhesive layer 5.
The irreversibly d~mag~hle layer of the multilayer film of the present invention5 may be a destructible or an irreversibly deformable layer (hereafter called simply the "d~rn~hle layer") and co".~,. ;ses in one embodiment a hot-melt adhesive (heat-activated adhesive), for example, an ethylene vinyl acetate (EVA) copolymer, an ethylene acrylic acid copolymer, an ethylene methacrylic acid copolymer, a polyester, a polyamide or a polyurethane, or a pressure-sensitive adhesive. The term " destructible"
10 in~ic~tes in the context ofthis application that the layer may be irreversibly d~m~ged, e.g. by brittle fracture or by tearing, so that a continuous layer no longer exists. The term "irreversibly deformable" in~icates in the context of this application that the layer may be irreversibly damaged by deformation, e.g. by plastic extension, whereby the layer need not be completely destroyed.
In a further embodiment, the multilayer film of the present invention can also have an adhesive layer between the cover sheet or pattern of adhesion-re~ tin~
material, les~,e~ ely, and the d~mag~hle layer. In this embodiment, there can be a further pattern of adhesion-regl-lating material between the tl~m~g~ble layer and the substrate-bonding adhesive layer, this second pattern being non-superimposable with 20 the first pattern of adhesion-regnlating material between the d~m~g~hle layer and the cover layer.
In the two latter described embo~lim~nts, the ~l~mag~hle layer need not be adhesive in nature itself; it consists preferably of a non-oriented polypropylene or a linear low density polyethylene (LLDPE), but can also consist of one of the previously-25 mentioned hot-melt adhesives. In one variation of this embodiment, the d~m~g~hle layer can consist of a brittle, frangible material. This material can contain a filler, such as glass microspheres, which increases its brittleness.
The cover layer of the multilayer film of the invention is normally a durable, dimensionally stable, wear, tear and abrasion-resistant polymeric film, such as a 30 polyethylene terephthalate (PET) film, which can be corona-treated or treated with primer.

WO 96/02048 L~ I 9 4 4 5 4 PCr/US95/08191 The adhesion-reg ll~ting material can be an adhesion-reducing or an adhesive repellent material, applied in a pattern located between the d~m~g~ble layer and the cover layer and can be located as well between the d~m~g~hle layer and the substrate-bonding adhesive layer, in cases where the adhesive layer is present.
The adhesive layers, which may be found on both sides of the d~m~g~hle layer, col.lplise preferably a layer of pressure sensitive adhesive (PSA) or hot-melt adhesive.
In a further embodiment, the d~m~g~hle layer is treated, for example, by corona discharge, on the side facing the cover layer or on both sides, in order to improve adhesion to ~dj~cPnt layers.
In a prefelled embodiment ofthe invention, a verification marking, for example a customer-specific printing, is present within the multilayer film. The verification marking is preferably present on the d~m~g~hle layer, namely between the d~m~g~ble layer and the adhesive layer which bonds, the multilayer film to the substrate, or between the bonding adhesive layer and the substrate, or between the adhesion re~ ting material/cover layer and the d~m~g~hle layer. It is preferred if the verification marking is irreversibly damaged when the d~m~g~hle layer is d~m~ged by e~ g.
The l-~nsparent multilayer film of the invention comprises a cover layer, a d~m~g~ble layer, a pattern of an adhesion-regul~ting material between the d~m~g~hle layer and the cover layer, and an adhesive layer which bonds the film to the substrate.
These elements are described hereafter in detail.
The upper layer of the ll ~ns~a~ e..l multilayer film of the present invention is a cover layer made of an abrasion resistant, preferably, a durable, wear and tear resistant material. A material which is p.e~..ed for this purpose is durable, abrasion resistant 25 film, for çY~ml le a polyethylene terephthalate (PET) polymeric film which normally has good ~1imPn~ional stability, mech~nical properties and solvent reci~t~nce. The abrasion resistant cover layer protects the underlying layers of the l~min~te and the document itself from wear, moisture and other undesirable influences during the length of its entire life. Such documents intçnded for long-term use include driver's licenses, 30 pas~,uol ls and personal identification papers. The film seals the document, thus protecting it from undesirable changes which can occur due to constant use. In order to provide the laminate and the document, respectively, with sufficient stiffnec~ and WO 96/02048 2 1 9 4 4 ~4 PCT/US95/08191 recict~nce to folding, the cover layer preferably has a thickness of from 10 to 200 ,um.
Especially pre~e"ed is a thickness from about 15 to about 150 ~m. In order to improve adhesion to the underlying layer, and to provide the adhesive strength pl es-"ibed by the present invention, the film is treated with corona discharge or treated with a primer.
5 The primer can be applied in the customary manner, for example with a coating rod, at a usual thicl ..esses of up to about 1 llm.
On the inner side of the cover layer of the l~ ~nspal enl multilayer film of thepresent invention is a pattern of adhesion-reg~ ting material. This adhesion reducing or adhesive repellent coating, applied in a non-continuous fashion, covers only part of 10 the surface and can generate differing surfaces on the inner side of the construction.
These differing surfaces also have differing adhesion characteristics. While theadhesive ~,e,lglll is high between the cover layer and the adjacent d~m~g~ble layer (in one embodiment an adhesive layer provided between the two layers) in the areas where adhesion-re~ ting material is absent, the adhesive strength is less than the cohesive 15 strength ofthe damagable layer, preferably substantially less, for example, about 1/10 or less, in areas where the adhesion-regulating material is present. In these areas, there is often practically no adhesion between said layers.
Several materials can be used as adhesion-reducing or adhesive repellent substances, in order to create this pattern. Examples of these materials include20 ca~l,A...rtes like polyvinyl octadecyl carbamate, available under the name "Kalle release coat K" from Hoechst AG, Germany, or "Escoat P 20" from Anderson Development Company, U.S.A. Further suitable materials include silicone systems like W-curable free-radical silicone-acrylate release coatings, silicone addition systems, silicone cond~n.c~tion systems and cationically-curing silicone systems. The pattern of this 25 material is applied to the inner side of the cover layer, preferably after the cover layer has been corona-treated or primed as mentioned. A more complete description of both the silicone and non-silicone based adhesion-regulating materials and their use to create patterns can be found in US 5,061,535. The type of pattern used in the present invention is not critical. Every pattern such as crossed lines, dot patterns, 30 checkerboard patterns or diamond-shaped patterns can be used. The pattern covers prerelably 5 to 80% of the surface of the cover layer. Especially pr~re~, ed is 20 to 60% of the surface of the cover layer.

W096/02048 2 1 94 ~ 54 PCT/US95/08191 An important element of the transparent multilayer film of the invention is the destructible or irreversibly deformable layer which lies under the cover layer and under the pattern of adhesion-re~llatin~ material. In one embodiment of the invention, this layer comprises a hot-melt adhesive or a pressure-sensitive adhesive. Especially5 suitable examples of the heat-activated adhesive include ethylene vinyl acetate. (EVA) copolymers, ethylene acrylic acid copolymers, ethylene methacrylic acid copolymers, polyesters, polyamides and polyureth~nes. A special example of a pressure-sensitive adhesive is an adhesive based on copolymers of acrylic acid esters. P~ efel, ed for this embodiment is an ethylene vinyl acetate (EVA) copolymer with an ethylene to vinyl acetate ratio of about 85:15, for example, the commercially available Guttacoll PE 90 or Elvax 550. It is most practical if the material is corona treated for improved adhesion to adjac~nt layers.
Adhesives suitable for use as the adhesive layer on the surface of the rl~m~g~hle layer opposite that adjacent to the cover layer and which forms the bond to the 15 substrate, include the usual, well-known pressure-sensitive, hot-melt (heat activatable) or reactive adhesives. P~e~"ed are pressure-sensitive adhesives (PSA), for example, those based on acrylates which can be tackified optionally by known methods. These adhesive layers can be introduced into the multilayer film as a transfer tape, using methods which in themselves are known, or can be coated from organic solution or20 aqueous dispersion on adjac~nt layers. A high adhesion of the d~m~g~ble layer to the adhesive layer is also essçnti~l to the present invention.
In one embodiment, a further layer of adhesive may be placed between the d~m~ hle layer and the cover layer or the pattern of adhesion-regul~ting material, les~.e~ ely. This layer can be made of the same adhesive which is used to bond the 25 d~m~g~hle layer to the substrate, or of another adhesive.
When layers of adhesive are provided both above and below the d~m~g~ble layer, then other materials can be used, in addition to the hot-melt adhesives or ples~u,e-sensitive adhesives mentioned previously, which themselves are not adhesive.
Examples are layers made of non-oriented polypropylene or linear low density 30 polyethylene (LLDPE).
Within the context of the present invention, it is of great significance that the d~mag~hle layer has a limited cohesive strength, this cohesive strength being less than WO 96/02048 2 1 9 4 4 ~ 4 PCT/US9~/08191 the adhesion of this layer to the cover layer in areas where no adhesion-regl-l~ting-material is present, and also less than the adhesion to the adhesive layer present on its opposite surface. The cl~m~hle layer has a lower cohesive strength than the durable cover layer. The d~m~g~ble layer is thus the weakest point in the multilayer film and, 5 thus, is the predetermined failure point of the film. The layer is easily deformed, mP~ning that it is stretched in an irreversible, non-elastic manner when ~ttempts are made to remove the film from a substrate (a data carrier or document), so that manipulation is visually easy to recognize. An irreversibly deformable layer has the advantage that inadvertant damage by flexing of the document can be reduced.
10 Further, rein~t~tçment of the irreversibly deformed layer is practically impossible.
In a further embodim~nt, the damagable layer comprises a brittle, frangible material which breaks as a results of ta---pel ing attempts. Examples of materials suitable for this embodiment of the invention include acrylic resins which are self-crosslinked through acrylamide groups, for example the commercially available 15 products Jagotex SV 21 1 and Jagotex SV 212 from Ernst Jager GmbH, Germany. Allanspalenl filler which further increases the brittleness, such as glass microspheres, can be built into this layer. The glass microspheres result in an inhomogeneous layer and increase its tendency to break easily when forces are applied, especially tPn~ili7ing forces.
The d~m~g~ble layer is preferably pretreated on its side facing the cover layer,or on both sides, to improve bonding to adjacent layers. Suitable prel,e~l,..e~
processes include corona discharge ll eal",el~t or L~ eallllenl with primers.
Further, for the purpose of increasing the adhesion differences, a second pattern of adhesion-re~ ting material can be provided between the d~m~g~hle layer 25 and the adhesive layer Iying under it, this second pattern being arranged so that it is non-supe,i"")osable with the pattern of adhesion-reglll~ting material between the d~m~g~hle layer and the cover layer.
The d~m~g~ble layer of the multilayer film of the present invention is a pronounced three-dimensional transparent layer in contrast to many constructions30 known in the state-of-the art, especially in the case of labels where the d~m~g~ble layer is largely flat (two-dimensional), examples being a vapor-coated metal layer or a printed layer, hologram, kh~e~l~lll or the like. The use of a L~n~arelll d~m~g~hle WO 96/02048 ~ 1 9 4 4 5 4 PCI/US9~/08191 layer makes transparency of the entire l~min~te possible. The damagable layer in the l51Jarelll multilayer film of the present invention has a thickness of at least 10 ~m, whereby the thickness ranges from 10 llm to 500 llm, preferably 15 ~m to 100 llmand, ecperi~lly preferred, 20 llm to 60 llm. The three-dimensional nature ofthe 5 d~m~g~ble layer is responsible for the superior tamper-proof properties of themultilayer film of the invention. In the first embodiment of this layer described, the layer undergoes an irreversible stretching when tall,pe.ing attempts are made. Alalll?elillg attempt can be easily recognized because the layer is stretched dirrelelilly in di~l ~ areas, these being prescribed by the pattern of adhesion-regul~ing material.
10 The stretching of the d~m~ble layer cannot be reversed and remains easily visible as uneven waves after the film has been reapplied to the substrate.
If attempts to remove the laminate continue and the stretching of the d~m~g~ble layer continues, the l~min~te finally breaks. This occurs at its weakest point. Before the stretching began, the ~l~m~g~ble layer had the lowest strength within 15 the multilayer film, so that the break would occur within this -layer. The cohesive strength of this material can increase, however, as a result of stretching and ~im~lt~neous orientation of the macromolecules in the d~m~g~ble layer, so that one or more other areas of the film have similar or less cohesive strength than the d~m~e~hle layer. For this reason, the film can tear, for example, through the d~m~ ~ble layer and 20 the adhesive layer (whose cohesive strength can be similar to that of the stretched ci~...,.g~ble layer). It can also fail by partially separating from the substrate (document) after the ~i~m~g~ble layer has been stretched. The substrate itself can also del~min~te when its cohesive strength is low.
In the case of the brittle frangible layer, instead of an irreversible stretching of 25 the previously described embodiment, an irregularly broken edge remains, the parts of which cannot be perfectly fit together again, thus rendering this embodiment also ill~pal~bly destroyed.
In a pl e~ll ed embodiment of the invention, a verification marking is present within the multilayer film, preferably immediately beneath the d~m~g~ble layer, or 30 alternatively between the lower adhesive layer and the document, or above thed~m~g~ble layer. This can be a customer-specific verification marking, made, forexample, using ink, thus creating a logo or a specific pattern such as the eagle symbol w096/02048 ~ 1 9 4 4 54 Pcr/uss5/08191 ,11 of the Federal Republic of Germany. The ink can be applied, for example, by screen p"nling or flexographic printing techniques. The verification marking can be a frame-like pattern or can be a pattern of transparent lines. The verification marking can be such that it is visible with the naked eye or with the assistance of a W lamp.
The verification marking serves with respect to the current invention primarily ~ as a means of recognizing authPnticity of the film. It can also repl ese,ll an element contributing to the tamper-proof nature of the film. This is being primarily provided in the present invention by the d~m~g~ble layer, however.
The multilayer film of the invention can be provided with a removable release paper before use so that the film can be stored in stacks or roll form.
The invention is described as follows with reference to the attached drawings.
These are:
Fig. 1 a security laminate described in the state-of-the-art (Basic construction accordil.g to DE-A-36 08 907) in intact condition Fig. 2 the l~min~te of Fig. 1 after a tampering attempt Fig. 3 an embodiment of the l.~nspare.. l multilayer film of the present invention in intact condition Fig. 4-8 embodiments of the transparent multilayer film of the present invention after a tampering attempt The figures, which are not drawn to scale, are provided to further elucid~te theinvention, but are not intended to restrict the invention in any manner to the embodimçnts l~plesellled therein.
In Fig. 1, showing the security laminate of the prior art, 1 is the cover layer,25 made of polyethylene terephthalate for example, which can be printed with ,.alion, like a price, for example, when the l~min~te is used as a label. Under this layer is a pattern 2 of adhesion-re~ ting material which bonds the cover layer to the ~...agPble layer 3. This layer 3 is thin and is created by ahlmimlm vapor coating, for example. It can also be made of a brittle resin layer coated with W ink or it can be a 30 layer of only ink. In this case, this layer also fulfills the characteristics desirable for the verification marking 4. Under this flat two-dimensional layer is an adhesive layer 5, which serves to bond the laminate to the substrate 6.

WO 96/02048 2 1 9 4 4 ~ 4 PCI/US95/08191 On attempts to remove the laminate or label, the adhesive layer 5 remains completely on the substrate 6, while the d~m~g~ble layer/verification marking 3/4 divides itself between the substrate and the cover layer 1, depending on the p, esence or absence of the adhesion-regul~ting material, as shown in Fig 2. Due to the S llans~Jarency of the cover layer, which in the case of a price tag carries the info",laLion to be tampered with, the parts ofthe non-transparent d~m~g~ble layer 3/4 re~Ainil~g on the substrate render the manipulation visible. The tamperer has largely a problem which is two-dimensional and purely optical. This means that by simply removing the residues of the non-l~ pal e"~ d~m~g~hle layer from the substrate or by application of 10 a suitable ink on the substrate or cover layer, the la",pe~ing can be concealed. Because of the limited thickness of the damagable layer, a manually detectable change in the surface of the laminate is not present.
Fig. 3 shows an embodiment of the transparent multilayer film of the present invention in intact form. As in the previous figures, 1 is a transparent cover layer 15 which is bonded--over a pattern of adhesion-re~ tin~ material 2 to a d~m~g~ble layer 3. This layer shows a definite three-dimensional structure with a thickness of at least 10 ,um. Beneath the damagable layer 3 is a verification marking 4. Then the adhesive layer 5 and the substrate 6 follow.
In case of a tampering attempt, information which is under the security 20 l~min~t~, namely on the document 6, is manipulated or replaced and then the altered document 6 is rel~l..;n~ted to the protective multilayer film. This is prevented, however, by the multilayer film of the invention because the l~min~te cannot be removed from the substrate without being destroyed. If attempts are made to remove the film from the document, then the d~m~g~ble layer 3 stretches irreversibly in a 25 manner prescribed by the pattern-coating of adhesion-regnl~ting material 2. If removal forces continue to be applied, then the film breaks at its weakest point and the layer 3 is either divided between the document 6 and the cover layer 1 or remains on the cover layer 1 in the form of a waved sheet, the waves being caused by irreversible stretching of layer 3 . This behavior results from the good adhesion of the layer 3 to the adhesive 30 layer 5 and to the cover layer 1 in the areas where no adhesive repellent coating is present. As shown in Figures 4 through 6, the d~m~g~ble layer 3 separates from the cover layer in areas where the adhesion-regulating pattern 2 is present, but remains WO 96/02W8 2 1 q 4 4 5 4 PCT/US95/08191 adhered to the cover layer in all other areas. When attempts are made to remove the cover layer 1, the d~m~g~hle layer is stretched irreversibly. Upon further pulling, the break occurs in di~erenl .,.am e.~ depending upon the respective cohesive strengths.
The break can thus occur, for example, directly through the layer 3 and 5 acco...l-a~-ied 5 by portions of the substrate 6 (See Figure 4), through the layers 3 and 5 with partial separation from the substrate 6 (See Figure 5), where in both cases the verification ".a.Lng is also destroyed, or by complete separation from the substrate when theadhesive strength f of layer 5 to the substrate 6 is less than the cohesive strength c' of the stretched layer 3 and e of the layer 5.
During attempts to remove the multilayer film of the invention from the doc~-mPnt7 the tamperer is not only conrl onled with partial destruction of a two-dimensional ink/verification marking 3/4 as in the state-of-the-art, but also with a three-dimensional problem because the d~m~g~ble layer 3 (and the adhesive layer 5) is excessively stretched and waved and fr~gmentc of it 9 (and the adhesive layer 5) are 15 present on both the cover layer 1 and the document 6. These residues must be removed before the document and l~min~te are pressed together again, because otherwise adocument with a surface unevenness which can be felt by the hand will result. Because the verification marking 4, as shown in Figs 4 and 5, is destroyed as well, simple application of a new transparent film is not effective. The complete removal of the 20 residues of the d~m~g~hle layer with a solvent would in certain embodiments also completely remove the verification marking 4.
Fig. 7 shows an embodiment of the 1. ~ns~,ale..l multilayer film of the invention where adhesive layers 5 and 51 and a pattern of adhesion-reg~ ting material 2 and 21 are provided on both sides of the d~m~g~kle layer 3 . Tampering attempts result in a 25 behavior similar to that depicted in Figures 4-6. The d~m~g~hle layer 3 and, in this case, the upper adhesive layer 5' are completely destroyed as a result of the irreversible extension of the d~m~g~hle layer 3.
Fig. 8 shows a further embodiment of the invention where the d~m~g~hle layer 3 comprises a brittle, frangible material cont~ining a transparent filler (glass30 microspheres) which contributes further to brittleness. In this embodiment as well, the d~m~g~ble layer 3 and the upper adhesive layer 5' distribute themselves between the w096/02048 ~ 1 9 4 4 5 4 Pcr/uss5/08191 cover layer and the substrate in a pattern prescribed by the pattern of adhesion-re~ ting material 2 and are irreversibly destroyed.
An i".~,o, la"L advantage of the transparent multilayer film of the present invention exists in that lifting of the film from the document without damage to the 5 d~m~ble layer, performed by applying a support to the film in advance, is impossible even for professional talllpCltl:i because the d~m~g~kle layer is present in the interior of the l~min~te and is strongly adhered to adjacent layers. Reconstruction of the tallli)ered document is made substantially more difficult or impossible because the d~m~g~ble layer in the preferred embodiment of the invention is irreversibly deÇo""ed 10 before it finally breaks. The transparent multilayer film of the invention is espeçi~lly suitable for this reason as a highly tamper-proof laminate for protection of data on docllm~ntc and as a tamper-proof label.
This suitability for use on documents or as a label is further increased by the high transparency of the film. Thus the substrates covered by the film are still machine lS readable as there are no surface irregularities to cause light scattering.
The following examples serve to illustrate the invention, without limiting it inscope.
Example I
A ~ al ell~ multilayer film, as shown in Fig. 3, is prepared in the following 20 manner. A dot pattern 2 of a mixture of a silicone-acrylate mixture [Th. Goldsçhmidt AG: RC 726/KN. 7060 = 70/30 weight per cent] together with 3 weight per cent 2-hydroxy-2-methyl-1-phenyl-propane-1-one as photoinitiator [Merck: Darocure 1173] is applied to a 50 llm thick corona discharge treated polyester film (PET) 1 using a suitably embossed roll built into a 5-roll coating system. The pattern coating 2 covers 25 25% ofthe surface ofthe film and the diameter ofthe dots is 0.5 cm. The coating is then cured using a high pressure mercury lamp under inert gas conditions. The coating weight is 5 g/m2.
A 40 llm thick ethylene vinyl acetate film 3 (hot-melt adhesive) [Guttacoll:
PE90/40; ethylene/vinyl acetate = 82/18] which is corona discharge treated on both 30 sides is then l~min~ted to the printed side of the PET film 1 using a commercially available heat l~min~tor at 130~C. Then a 50 llm thick layer of acrylate-based pressure-sensitive adhesive 5 (tackified with resin; 3M Transfer Tape # 9482, modified by w096/02048 2~94~4 PCT/USg5/08191 omission of glass fibers, referred to hereafter as "PSA 1 ") in the form of a transfer film on a release paper 6 is laminated to the layer of hot-melt adhesive at room tt.,.i~c.~ re.
The release paper 6 is then removed and the l~min~te pressed onto a docum~nt 5 6 (Papierfabrik T ~hnctein Neobond] using a commercially available l~ or at room te---l,e-al-lre. After 24 hours aging, the laminate is carefully removed by hand from the docl-mPnt In the areas of the dot pattern 2, the PET film 1 separates from the ethylene vinyl acetate 3, while in the re...~ areas it continues to adhere. Thus the ethylene vinyl acetate layer stretches until it finally breaks. The layer of pressure-sensitive adhesive 5 stretched as well and is destroyed, whereby the surface ofthe docl~ment 6 is damaged as well. Compare with Fig. 4 (with no verification .,.a~ing 4) and Table I. After the complete removal of the l~min~te from the documPnt 6, dot-shaped residues of ethylene vinyl acetate layer 3 and adhesive 5 remain on the surface of the document, these dot-shapes being missing from the l~min~te which has beenremoved. Portions ofthe document paper are also adhered to the adhesive rem~inin~
on the l~min~te. Due to the non-elastic de~ ation of the ethylene vinyl acetate layer 3, the residues are not regular and even, so that on attempt to rPl~min~te an uneven surface is obtained and air bubbles rem~ined entrapped in the l~min~te Example 2 Example 1 is repeated, with the exception that a 25 llm thick acrylate-based adhesive layer 5 (tackified with resin; 3M Transfer Tape # 9458; lefe"ed to hereafter as "PSA 2").
When the l~min~te is removed from the document, it is stretched and destroyed in a manner similar to that described in Example 1, as shown in Table I.
Example 3 Example 1 is repeated, with the exception that an ethylene vinyl acetate film 3 (corona treated on only the side towards the PET) is laminated to the PET film 1.
When the laminate is removed from the document, it is stretched and destroyed in a manner similar to that described in Example 1, as shown in Table I.
Example 4 Example 2 is repeated with the ethylene vinyl acetate film described in Example 3 (corona-treated on one side).

When the laminate is removed from the document, it is stretched and destroyed in a manner similar to that described in Example 1, as shown in Table I.
Example 5 Example 1 is repeated, with the exception that a S0 ~m thick film of ethylene vinyl acetate 3 [DuPont Elvax 550, ethylene vinyl acetate = 85/15](corona treated on both sides) is used.
When the l~min~te is removed from the document, it is stretched and destroyed in a manner similar to that described in Example 1, as shown in Table I.
Example 6 Example 2 is repeated using the ethylene vinyl acetate film (corona treated on both sides) described in Example 5.
When the l~min~te is removed from the document paper, it is stretched and destroyed in a manner similar to that described in Example 1, as shown in Table I.
Comparative Example 1 Example 1 is repeated, with the exception that a 25 ~lm thick film ofthe ionomer ethylene methacrylic acid [DuPont: Surlyn 1706] (corona treated on both sides) is used as layer 3.
When the laminate is tested as in Example 1, the cover layer 1 del~min~tes from the d~mag~hle layer 3 together with the adhesion repellent pattern 2, because the adhesive strength (a) is less than the cohesive strength (c). Layers 3 and 5 remain un~m~ed on the document surface. (The cohesive strength (c) at 5% elongation is already greater than the adhesive strength (a); see Table I.) Comparative Example 2 Example 1 is repeated, with the exception that a 50 ~lm thick film of the ionomer ethylene acrylic acid (Dow: Primacor 1410 XT] (corona treated on both sides) is used as layer 3.
When the laminate is tested as in Example 1, the cover layer I del~min~tes from the d~m~g~ble layer 3 together with the-adhesion repellent pattern 2. Layers 3 and 5 remain on the document surface, whereby 3 is stretched slightly upwards, because the adhesive strength (a) is greater than the cohesive strength (c) at 5%
elongation.

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Example 7 Example 1 is repeated, with the exception that the ethylene vinyl acetate layer 3 is additionally printed with a security print 4 based on a solvent-co.~ ing screen-printing ink to which a shiny, pearl-like pigment [Merck: Iriodin 235] has been added.
5 The security print is destroyed as well when the l~min~te is removed from the docu~ ,nl 6. See Fig. 4.
Example 8 Example 1 is repeated, with the exception that a hologram 4 is l~min~ted to the adhesive layer 5, before the adhesive layer is laminated to the EVA layer 3. The10 hologram is destroyed when the l~min~te is removed from the document 6.
Example 9 Example 1 is repeated, with the exception that a 50 ~lm thick polyester film ~Guttacoll: PE 52/50] is used as layer 3.
When the laminate is removed from the document, it is stretched and destroyed 15 in a manner similar to that described in Example 1, as shown in Table I.
Example 10 Example 1 is repeated, with the exception that a 50 llm thick polyamide film [Guttacoll: PE 71/50] is used as layer 3.
When the l~min~te is removed from the document, it is stretched and destroyed 20 in a manner similar to that described in Example 1, as shown in Table I.
Example 11 Example 1 is repeated, with the exception that a dot pattern 2 of an aqueous-based silicone system [Dow: 1171] with 3 weight per cent of a catalyst [Dow: 1171A]
is applied with the aid of a patterned roller and cured by drying at 150~C.
Example 12 A checkerboard pattern of an aqueous solution of an adhesion-reducing (to PET) ethylene acrylic acid copolymer [Morton Int.: Adcote 50T49831 is applied to a 125 ~lm thick polyester film (PET) using a flexographic printing system. The coating covers 50% of the surface and the pattern squares are 0.3 cm in length and width. The coated film is then dried in an oven, resulting in a coating weight of 5 g/m2.

._ 19 NeYt, a verification marking comprising a mixture of 65 parts of a water-based polyurethane ink [Miles Inc.: Bayhydrol 123], 5 parts water and 30 parts pearl-like pig",e"l based on tit~ninm dioxide is printed onto the pattern-coated side of the PET
film.
Then the printed side of the PET is corona treated.
~ A 50 ,um thick film 3 of ethylene vinyl acetate (hot melt adhesive) [DuPont:
Elvax 550, ethylene/vinyl acetate = 85/15] (corona-discharge-treated on both sides) is then l~min~ted to the printed, corona treated side of the PET film using a commercially available heat l~ or at 130~C. Finally, a 25 llm thick layer of a pressure-sensitive adhesive 5 (PSA 2) in the form of a transfer film on release paper 6 is laminated to the ethylene vinyl acetate layer 3.
The l~min~te thus obtained is pressed onto a document as described in Example 1.
When the l~min~te is removed from the document, it is stretched and destroyed in a manner similar to that described in Example 1, as shown in Table I.
Example 13 Example 11 is repeated, with the exception that a second adhesive repellent pattern 21 is applied under the ethylene vinyl acetate layer 3, said second pattern 2' not being ~upe~hll?osable with the first adhesive repellent pattern 2.
The l~min3te thus obtained is pressed onto a document as described in F.Y~mple 1.
When the l~min~te is removed from the document paper, it is stretched and destroyed in a manner similar to that described in Example 1, as shown in Table I.
Example 14 A l, ~r,~a~ enl multilayer film of the type shown in Fig. 7 is prepared by the following method A dot pattern of a mixture of an epoxysilicone [General Electric Company.: W9300] and 3% of a photoinitiator [General Electric Co.: W9310 C] is applied to a 50 ,um thick polyester (PET) film 1 (Hoechst: Hostaphan RN 2900]
(primed on one side) using a suitably embossed coating roll built into a 5-roll coating system. The pattern coating covers 25% of the surface of the film and the ~i~met~r of WO 96/02048 ~ I 9 4 4 5 4 PCT/US95108191 the dots is 0.5 cm. The coating is cured using a high pressure mercury lamp. Thecoating weight is 5 g/m2.
A 25 ~m thick film of acrylate-based pressure sensitive adhesive 5 (PSA 2) in the form of a transfer film on a release paper is l~min~ted to the printed side of the PET film at room tel~lperalllre. The release paper is removed and then a 35 ~m thick, non-oriented polyolefin film 3 [Amerplast: Amprop PP 609] is l~min~ted to the adhesive surface at room temperature. The polyolefin film has been corona treated on both sides and then coated on both sides with an adhesion promoter (primer) based on chlorinated polypropylene [Tramaco: Trapylen 822]. The coating weight ofthe primer, applied with a doctor blade, is 0.5 g/m2. Then a second pattern 2' of silicone material is printed on the polyolefin film in the same manner as described previously, except that the second pattern is not directly superimposable over the first silicone pattern 2. Then a further 25 llm thick layer of acrylate-based pressure-sensitive adhesive 5 (PSA 2) in the form of a transfer film on release paper 6 is l~min~ted to the polyolefin film 3 at room temperature.
The l~min~te thus obtained is pressed onto a document 6 as described in Example 1.
When the laminate is removed from the document, it is stretched and de~L. oyed in a manner similar to that described in Example 1, as shown in Table I.
Example 15 Example 13 is repeated, with the exception that a non-oriented 30 ~lm thick polypropylene film is used as layer 3 [Dickel & Co.: Sarafan PPST 300].
The l~min~te thus obtained is pressed onto a document 6 as described in Example 1.
When the l~min~te is removed from the document, it is stretched and destroyed in a manner similar to that described in Example 1, as shown in Table I.
Example 16 A llanspal el,l multilayer film of the type shown in Fig. 7 is prepared by the following method. A dot pattern of a solvent-based silicone addition system [Wacker Chemie GmbH: 100 parts Dehesive 940, 3.6 parts Katalysator OL and 1 part crosslinker V93] is printed onto the primed side of a 19 llm thick polyester film using wo 96/02048 2 ~ 9 4 4 5 4 PCT/USg~/08191 screen printing. The coating covers 25% of the surface of the film and the rli~meter of the dots is 0.5 cm. The coating is then dried and cured in an oven at 100~C. Thecoating weight is S g/m2.
A 25 ~m thick layer of acrylate-based pressure sensitive adhesive 5 (PSA 2) in the form of a transfer film on release paper is l~min~ted to the printed side of the PET
film 1 at room temperature.
The release paper is removed and a 25 llm thick non-oriented polyolefin film 3 [Dow: LLDPE Dowlex 2047] laminated onto the construction. The polyolefin film 3 has been previously corona treated on both sides and primed using a doctor blade(0.5 g/m2) with a primer based on chlorinated polypropylene [Polychimie: polyprime DF20].
Then a second pattern 2' of silicone material is applied to the p~ reàled polyolefin film 3, as in Example 13, in a manner so that the pattern 2' is not superimposable with the first pattern 2.
lS Then a further layer 5 comprising a 25 ~m thick coating of acrylate-based pl~s~ule-sensitive adhesive (PSA 2) in the form of a transfer film on release paper 6 is l~min~ted to the polyolefin film layer at room temperature.
The l~min~te thus obtained is pressed onto a document as described in Example 1.
When the l~min~te is removed from the document, it is stretched and destroyed in a manner similar to that described in Example 1, as shown in Table I.
Example 17 A Llans~alt;ll~ multilayer film ofthe type shown in Figure 8 is prepa-ed by the follo~,ving method. A dot pattern 2 of a solvent-based silicone addition system [Wacker Chemie GmbH: 100 parts Dehesive 940, 3.6 parts Katalysator OL and 1 partcrosslinker V93] is printed onto the primed side of a 19 llm thick polyester film 1 [Hoechst: Hostaphan RN2900] using screen printing techniques. The coating covers25% ofthe surface ofthe film and the ~i~met~r ofthe dots is 0.5 cm. The coating is then dried and cured in an oven at 100~C. The coating weight is 5 g/m2.
A 25 llm thick layer of acrylate-based pressure sensitive adhesive 5' (PSA 2) inthe form of â trânsfer film on release paper is l~min~ted to the printed side of the PET

wo 96/02048 2 1 9 4 ~ 5 4 Pcr/usssl0819l film 1 at room te"")el ~l~re. The release paper is removed and a 75 llm thick layer of a brittle acrylate polymer 3, mounted on release paper as well, is then l~min~ted to the adhesive surface. This material is made by mixing a commercially available solution of an acrylate polymer which crosslinks upon drying (100~C) through amide groups [Ernst Jager GmbH: Jagotex SV211 or SV212] to which 20 weight per cent (based onper cent solids) of glass microspheres (50 ~m ~i~metçr) has been added. After removal of the release paper, a second dot pattern 2' is printed onto the brittle layer 3 in the manner described in Example 13, that is, not directly superimposed over the first pattern 2. Then a second acrylate-based pressure-sensitive adhesive layer 5 (PSA 2) in the form of a transfer film on release paper 6 is laminated to the brittle layer.
The laminate thus obtained is pressed onto a document 6 as described in Example 1. When the laminate is removed from the document, layer 3 stretches andbreaks.
Example 18 F.x~mple 16 was repeated, with the exception that Jagotex SV212 was used instead of Jagotex SV211 and that only 10% glass microspheres were added.
The l~min~te thus obtained is pressed onto a document 6 as described in F- ~ ple 1. When the laminate is removed from the document, layer 3 stretches and breaks.
Testing and Evaluation of the adhesive and cohesive characteristics of the multilayer films 1. Adhesion of the d~m~g~ble layer 3 to the cover layer 1 A 1.27 cm wide-strip of ~luminum was laminated using different types of hot-melt adhesive strips (1.27 cm wide) shown in Table I to PET at 130~C.
The test samples were then subjected to a 180~ peel test. The adhesive strength was measured in N/1.27 cm.
The PET cover layer as well as the hot-melt adhesive layer were tested in both corona-treated and untreated form. As can be seen from the results, corona treatment of both surfaces increases adhesion. In cases where PET and heat-activated adhesive are used, then the anchorage to PET is very good without p,~l,e~l,.,~nt WO 96/02048 2 1 9 4 4 ~ 4 PCT/US95/08191 One t,.~,el h,.ent showed that çh~nging the thickness of the layer of hot-melt adhesive from 40 llm to 60 ~m had no influence on the adhesion.
2. Tensile strength and elongation of the d~m~ble film (3) as a function of thickness and material, measured in N
The tensile strength was measured at 5% and 10% elongation, as well as at the breaking point. The test speed was 300 mm/min. Tests showed that the test speed had no .~ignifiç~nt influence on the values at elongations of S and 10%. Breaking ofthe film occurred at about 500% elongation.
3. Adhesion of the d~m~P~ble layer 3 to adhesive layer 5 A 1.27 cm wide laminate of hot melt adhesive strips 3 and PSA 5 were laminated together at 130~C. between two aluminllm strips and then subjected to a 180~ peel test. The values were recorded in N/1.27 cm.
4. Adhesion of PSA layer 5 to the document 6 Adhesive strength was measured using a paper frequently used for docume~ts [Papierfabrik T ~hn~tein: Neobond]. The removal angle was 90~.
The removal test was condLIcted after the aging 24 hours at 90~C. The test stripes were 1.27 cm wide. Two pressure-sensitive adhesives (PSA 1 and PSA
2) were tested, both acrylate-based materials, whereby the following results were obtained:
PSA 1: 12.2 N/1.27cm PSA 2: 10.5 N/1.27 cm

Claims (22)

C l a i m s
1. Transparent multilayer film, comprising a cover layer, a damagable layer, a pattern of adhesion-regulating material between said layers, and a first adhesive layer on the side of the film opposite that of the cover layer, for bonding with a substrate, characterized in that damagable layer (3) has a thickness of at least 10 µm and that the cohesive strength of the damagable layer (3) and the adhesive strength between the layers obeys the following relationship:
a, d > c > b whereby a is the adhesive strength between cover layer (1) and damagable layer (3) in the areas where no adhesion-regulating material (2) is present, b is the adhesive strength between cover layer (1) and damagable layer (3), in the areas where adhesion-regulating material (2) is present, c is the cohesive strength of damagable layer (3), and d is the adhesive strength between layer (3) and first adhesive layer (5).
2. Multilayer film according to Claim 1, characterized in that the cohesive strength e of the first adhesive layer (5) is about the same as or greater than the cohesive strength c of the damagable layer (3).
3. Multilayer film according to claim 1 or 2, characterized in that said damagable layer (3) is a destructible or an irreversibly deformable layer.
4. Multilayer film according to any of the claims 1 to 3, characterized in that the damagable layer (3) comprises a hot-melt adhesive or a pressure sensitive adhesive.
5. Multilayer film according to claim 4, characterized in that the hot-melt adhesive is an ethylene vinyl acetate that the hot-melt adhesive comprises an (EVA) copolymer, an ethylene acrylic acid copolymer, an ethylene methacrylic acid copolymer, a polyester, a polyurethane or a polyamide.
6. Multilayer film according to any of the claims 1 to 5, characterized in that a second adhesive layer (51) is present between the cover layer (1) or pattern of adhesion-regulating material (2), respectively, and the damagable layer (3), said second adhesive layer behaving like said first adhesive layer (5) with respect to its cohesive strength and adhesion to the damagable layer (3).
7. Multilayer film according to any of the claims 1 to 6, characterized in that a further pattern of adhesion-regulating material (2'), not superimposable with the first pattern of adhesion-regulating material (2), is present between the damagable layer (3) and said first adhesive layer (5), said further pattern behaving like material (2) with respect to its adhesion to layers (3) and (5).
8. Multilayer film according to claim 6 or 7, characterized in that the damagable layer (3) comprises a non-oriented polypropylene, a linear low density polyethylene (LLDPE) or a hot-melt adhesive as characterized in claim 3 or 4.
9. Multilayer film according to claim 6 or 7, characterized in that the damagable layer (3) comprises a brittle, frangible material.
10. Multilayer film according to claim 9, characterized in that the damagable layer (3) contains a filler which increases the brittleness of the layer.
11. Multilayer film according to any of the claims 1 to 10, characterized in that the cover layer (1) comprises an abrasion-resistant polymeric film.
12. Multilayer film according to claim 11, characterized in that the cover-layer (1) comprises a corona-treated or primed polyethylene terephthalate (PET) film.
13. Multilayer film according to any of the claims 1 to 12, characterized in that the adhesion-regulating material (2) or (2'), respectively, is an adhesion-reducing or adhesive repellent material.
14. Multilayer film according to any of the claims 1 to 13, characterized in that the first or second adhesive layer (5) or (5'), respectively, comprises a layer of pressure-sensitive adhesive (PSA) or a hot-melt adhesive.
15. Multilayer film according to claim 4, characterized in that the damagable layer (3) is corona-treated on the side facing the cover layer (1).
16. Multilayer film according to claim 8, characterized in that the damagable layer (3) is treated on both sides to improve adhesion to adjacent layers.
17. Multilayer film according to any of the claims 1 to 16, characterized in that a verification marking (4) is provided within the film or between the film and the substrate (6).
18. Multilayer film according to claim 17 characterized in that said verification marking (4) is associated with said damagable layer (5) so that damage to the damagable layer (5) results in irreversible damage to said verification marking (4).
19. Multilayer flm according to any of the claims 1 to 18, characterized in that the cohesive strength c of the damagable layer (3) is lower than the cohesive strength of the cover layer (1).
20. The use of the transparent multilayer film according to any of the claims 1 through 19 for protection of data on documents.
21. The use of the transparent multilayer film according to any of the claims 1 to 19 as a tamper-proof label.
22. Tamperproof document or label, comprising a multilayer film according to any of the claims 1 to 19, bonded by means of an adhesive layer (5) to a datacarrier (6), whereby the adhesive strength f between the adhesive layer (5) and the data carrier (6) is about the same as or greater than the cohesive strength c of the layer (3) and/or the cohesive strength e of the adhesive layer (5).
CA002194454A 1994-07-08 1995-06-28 Transparent multilayer film and its use for protection of data on documents as well as a tamper-proof label Abandoned CA2194454A1 (en)

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DEP4424148.8 1994-07-08
DE4424148 1994-07-08
PCT/US1995/008191 WO1996002048A1 (en) 1994-07-08 1995-06-28 Transparent multilayer film and its use for protection of data on documents as well as a tamper-proof label

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US5060981A (en) * 1989-09-19 1991-10-29 Minnesota Mining And Manufacturing Company Transparent overlay for protecting a document from tampering
DE3941257C2 (en) * 1989-12-14 1998-09-03 Unipress Olaf Kierchner Multi-layer film composite with adhesive labels that can be removed from a carrier web
DE4018737A1 (en) * 1990-06-12 1991-12-19 Schreiner Etiketten SELF-ADHESIVE LABEL FOR ATTACHING AND SEALING A PASSAGE
US5042842A (en) * 1990-06-26 1991-08-27 Avery International Corporation High security label
US5061535A (en) * 1990-06-28 1991-10-29 Minnesota Mining And Manufacturing Company Patterned silicone release coated article
US5082702A (en) * 1990-08-20 1992-01-21 Minnesota Mining And Manufacturing Company Tamper-indicating tape
US5169707A (en) * 1991-05-08 1992-12-08 Minnesota Mining And Manufacturing Company Retroreflective security laminates with dual level verification
WO1993005124A1 (en) * 1991-09-06 1993-03-18 Bank Of Canada Adhesive for thin film security device

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US5629093A (en) 1997-05-13
KR970705113A (en) 1997-09-06
HK1013877A1 (en) 1999-09-10
DE69504082T2 (en) 1999-04-22
EP0770251A1 (en) 1997-05-02
EP0770251B1 (en) 1998-08-12
AU2952595A (en) 1996-02-09
DE69504082D1 (en) 1998-09-17
WO1996002048A1 (en) 1996-01-25
BR9508256A (en) 1997-11-18
JPH10502745A (en) 1998-03-10

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