WO2019042831A1 - Brittle acrylic films and forgery prevention labels comprising the same - Google Patents
Brittle acrylic films and forgery prevention labels comprising the same Download PDFInfo
- Publication number
- WO2019042831A1 WO2019042831A1 PCT/EP2018/072616 EP2018072616W WO2019042831A1 WO 2019042831 A1 WO2019042831 A1 WO 2019042831A1 EP 2018072616 W EP2018072616 W EP 2018072616W WO 2019042831 A1 WO2019042831 A1 WO 2019042831A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- meth
- polyalkyl
- acrylate
- forgery prevention
- film
- Prior art date
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- 230000002265 prevention Effects 0.000 title claims abstract description 82
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title abstract description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 169
- 239000010410 layer Substances 0.000 claims description 80
- 239000004609 Impact Modifier Substances 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- 239000011256 inorganic filler Substances 0.000 claims description 35
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 35
- 238000004519 manufacturing process Methods 0.000 claims description 33
- 239000011159 matrix material Substances 0.000 claims description 33
- -1 polyethylene Polymers 0.000 claims description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002699 waste material Substances 0.000 claims description 29
- 238000005520 cutting process Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 20
- 239000006096 absorbing agent Substances 0.000 claims description 18
- 239000000853 adhesive Substances 0.000 claims description 18
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 14
- 239000012963 UV stabilizer Substances 0.000 claims description 13
- 239000012790 adhesive layer Substances 0.000 claims description 13
- 239000011247 coating layer Substances 0.000 claims description 13
- 239000004408 titanium dioxide Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 230000001186 cumulative effect Effects 0.000 claims description 7
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 3
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 3
- 229920002799 BoPET Polymers 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 abstract description 19
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 22
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 19
- 239000002245 particle Substances 0.000 description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 239000000945 filler Substances 0.000 description 13
- 229920000193 polymethacrylate Polymers 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 239000012964 benzotriazole Substances 0.000 description 10
- 238000005498 polishing Methods 0.000 description 10
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 229920001169 thermoplastic Polymers 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004416 thermosoftening plastic Substances 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 230000004224 protection Effects 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 229940117958 vinyl acetate Drugs 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- PGMMQIGGQSIEGH-UHFFFAOYSA-N 2-ethenyl-1,3-oxazole Chemical class C=CC1=NC=CO1 PGMMQIGGQSIEGH-UHFFFAOYSA-N 0.000 description 2
- JDCUKFVNOWJNBU-UHFFFAOYSA-N 2-ethenyl-1,3-thiazole Chemical class C=CC1=NC=CS1 JDCUKFVNOWJNBU-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229940123457 Free radical scavenger Drugs 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920005377 Plexiglas® 7N Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 230000006378 damage Effects 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- JVPKLOPETWVKQD-UHFFFAOYSA-N 1,2,2-tribromoethenylbenzene Chemical class BrC(Br)=C(Br)C1=CC=CC=C1 JVPKLOPETWVKQD-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/58—Cuttability
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- B32B2307/00—Properties of the layers or laminate
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- B32B2307/582—Tearability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/582—Tearability
- B32B2307/5825—Tear resistant
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2519/00—Labels, badges
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/338—Applications of adhesives in processes or use of adhesives in the form of films or foils as tamper-evident tape or label
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
- C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
-
- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
- C09J2423/106—Presence of homo or copolymers of propene in the substrate
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/006—Presence of (meth)acrylic polymer in the substrate
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Definitions
- the present invention relates to brittle acrylic films made from impact-modified polyalkyl
- the films can be any suitable (meth)acrylate and forgery prevention labels comprising these films.
- the films can be any suitable (meth)acrylate and forgery prevention labels comprising these films.
- the films can be any suitable (meth)acrylate and forgery prevention labels comprising these films.
- the films can be any suitable (meth)acrylate and forgery prevention labels comprising these films.
- the films can be any suitable (meth)acrylate and forgery prevention labels comprising these films.
- the brittle acrylic films and the forgery prevention labels comprising these films have no intended break points such as slits, perforation etc.
- the forgery prevention labels of the present invention can therefore find use in documents, such as chip cards or passports, for example, in forgery prevention labels, road tax badges, for product theft prevention, or as price tags. Additionally, in contrast to other materials commonly employed for this purpose, the forgery prevention labels of the present invention have an excellent weathering stability and, in particular, an outstanding UV stability.
- Prior art Forgery prevention labels also known as security labels or anti-counterfeiting labels are known in the prior art.
- their bonding strength to a labelled substrate is high in comparison with the strength (flexural strength or tear strength) of the label itself. Therefore, ideally, such labels cannot be peeled off from the labelled article without destroying the label.
- Forgery prevention labels which cannot be removed without being destroyed are used in diverse areas of application such as securement of documents, such as of chip cards, passports, road tax badges, labels for securing products against theft, or price tags.
- a typical prior-art chip card consists of up to 12 individual parts, which are assembled and programmed in up to 30 separate process steps.
- the support layer, the layer having a magnetic strip, and separate laminate are applied for each function.
- one or more layers are needed to realize adequate protection from weathering, protection against scratching, and UV protection.
- a security layer which cannot be removed without being destroyed is applied to achieve anti- counterfeit security.
- the printing is often found on a separate outer layer, since the other above-mentioned layers are difficult to print.
- Labels of the prior art applied as road tax badges for adhesive bonding to glass screens generally comprise an optionally printable support layer made of PET, PVC, PE or BOPP.
- This second layer is generally composed of
- Forgery prevention labels made of pure PVC films are also known, especially in the form of white films. These films have a desirably low initial tear strength. Unfortunately, however, the PVC films have a relatively high resistance to tear propagation. This means that the PVC film may, under certain circumstances, be peeled off from the labelled substrate by a non-authorised person with only a minor, hardly noticeable tearing. Since forgery prevention labels are highly brittle, their manufacturing and handling on an industrial scale is significantly more difficult than manufacturing and handling of common self-adhesive labels. For instance, if a film, for instance a polyalkyl(meth)acrylate film for use in forgery prevention labels is manufactured by extrusion, handling and use of such film becomes problematic, since it can easily become broken or torn apart.
- US 6,280,835 suggests preparing brittle acrylic films by coating a polyethylene terephthalate foil used as a support with a liquid mixture which is obtained by dissolving a thermoplastic acrylic resin in a suitable solvent and mixing it with an inorganic filler.
- a liquid mixture which is obtained by dissolving a thermoplastic acrylic resin in a suitable solvent and mixing it with an inorganic filler.
- the extrusion step is avoided and the polyethylene terephthalate film provides the resulting multi-layer material with an adequate mechanical stability.
- the solvent residues in the resulting film act as plasticisers, thereby rendering the film more flexible.
- labels are typically manufactured from a label stock that comprises a face layer (facestock), an adhesive, e.g. a pressure-sensitive adhesive (PSA) layer adhered to the face layer, optionally, a release coating layer, and a support layer removably adhered to the adhesive layer or to the release coating layer.
- facestock face layer
- PSA pressure-sensitive adhesive
- the label stock is generally provided in form of a roll.
- Individual labels are usually produced by die cutting (kiss cutting) the face layer and the PSA layer, and then removing the surrounding waste matrix, leaving the individual labels adhered to the release liner. Since the material of the face layer is highly brittle, removal of the waste matrix becomes highly problematic since it can easily break or tear apart.
- Typical manufacturing processes for labels are run at speeds of at least 25 m/min or even higher. As the speed increases, the process becomes less stable and risk that the waste matrix breaks or tears apart upon removal increases. Slowing the process down or increasing the web width of the waste matrix to allow a better removal of the waste matrix, however, would result in a significant cost disadvantage, loss of efficiency, and may frequently be ineffective.
- WO 2016/156137 A1 describes forgery prevention labels having a high transparency and comprising poly(meth)acrylate films. These labels have a good weathering stability and are suitable for use in documents such as passports, forgery prevention labels, road tax badges, price tags etc.
- the inventors report that poly(meth)acrylate films perform best when they comprise not more than 10 wt.-% of an impact modifier.
- We subsequent studies showed that in some cases, in particular in the presence of considerable amount of inorganic fillers, such a low content of impact modifiers may become problematic during manufacturing of the labels, if the process for the manufacturing of such labels involves a kiss cutting (die cutting) step. Under these circumstances, the waste matrix can sometimes break or tear apart upon removal if the process is run at a high speed.
- the problem addressed by the present invention was to provide a brittle film which can be advantageously employed for the manufacturing of forgery prevention labels on an industrial scale.
- such film should be suitable for a cost effective process in which individual labels are produced by kiss cutting the face layer and the PSA layer and the surrounding waste matrix is subsequently removed, leaving the individual labels adhered to the support layer.
- the problem addressed by the present invention was provision of a brittle film for the manufacturing of forgery prevention labels which possess a low initial tear strength, a low tear propagation resistance and a short tear path to facilitate a complete rupture of the film during an attempt of its non-authorised removal but, nevertheless, can be produced and processed without tearing.
- the present invention addressed the problem of providing self-adhesive forgery prevention labels which can be manufactured in a highly efficient manner, are printable and suitable for a long-term outdoor use.
- the present invention addressed the problem of developing a safe and a cost-efficient process for the manufacturing the brittle film described above and the self-adhesive forgery prevention labels comprising the same.
- the present invention is based on a surprising finding that the behaviour of a brittle acrylic film during a die cutting (kiss cutting) process, followed by stripping of the waste matrix, strongly depends on the ratio between the impact modifier amount and the amount of the inorganic filler in the film.
- polyalkyl(meth)acrylate films in which the content of one or several impact modifiers n jm , expressed in wt.-% based on the total weight of the film, is described by the following relationship: .5*nf ⁇ n jm ⁇ nf rif being the content of one or several inorganic fillers, expressed in wt.-% based on the total weight of the film, is particularly suitable for processing by a kiss cut process. Therefore, forgery preventing labels comprising the film of the present invention can be advantageously manufactured upon employing a step in which individual labels are produced by kiss cutting, and the surrounding waste matrix is subsequently removed, leaving the individual labels adhered to the release liner. No undesired breaking of the waste matrix takes place, even at running speeds of at least 25 m/min or even higher.
- the content of one or several impact modifiers n jm is the content of neat impact modifiers.
- n jm is the content of neat impact modifier particles.
- the corresponding impact modifiers are rubbery particles
- n jm is the content of the rubbery particles in the polyalkyl(meth)acrylate film.
- the corresponding impact modifiers are core-shell or core-shell-shell particles
- n jm is the content of the entire particles in the polyalkyl(meth)acrylate film.
- one aspect of the present invention relates to a forgery prevention label comprising a polyalkyl(meth)acrylate film, wherein the polyalkyl(meth)acrylate film comprises: from 30.0 wt.-% to 92.5 wt.-% of a polyalkyl(meth)acrylate;
- UV-absorbers from 0.0 wt.-% to 5.0 wt.-% of one or several UV-absorbers
- the present invention relates to use of the polyalkyl(meth)acrylate film as specified above in a forgery prevention label.
- the present invention relates to a process for the manufacturing a forgery prevention label using the polyalkyl(meth)acrylate film as specified above.
- the present invention relates to a forgery prevention label comprising the polyalkyl(meth)acrylate film as specified above.
- the present invention relates to a laminate 4 for the manufacturing of a forgery prevention label, the laminate comprising at least the following layers:
- D1004-13 of from 50 N to 500 N.
- the present invention relates to use of the above laminate for the manufacturing of a forgery prevention label.
- the present invention relates to a forgery prevention label, characterized in that the forgery prevention label comprises at least the following layers in the order stated: a) a layer 6 consisting of extruded polyalkyl(meth)acrylate film;
- a support layer 9 wherein the forgery prevention label has a thickness of between 50 ⁇ and 300 ⁇ .
- the present invention relates to a process for the manufacturing of forgery prevention labels as specified above, the process comprising at least the following steps: extrusion of a polyalkyl(meth)acrylate film as defined above in an extruder, wherein the polyalkyl(meth)acrylate film is obtained; and
- the invention relates to use of the forgery prevention labels for the manufacturing of chip cards, documents, forgery prevention labels, other labels or price tags.
- FIG. 1 schematic representation of an endless label stock 1 after a kiss cutting process.
- the waste matrix 3 is removed from the support layer thereby leaving a plurality of individual forgery prevention labels 2 attached to the support layer.
- Fig. 2 side view of a laminate 4 for the manufacturing of forgery prevention labels comprising the liner layer 5 and the layer consisting of the polyalkyl(meth)acrylate film 6.
- Fig. 3 side view of a forgery prevention label 2 comprising at least the following layers: a) a layer consisting of the polyalkyl(meth)acrylate film 6;
- the polyalkyl(meth)acrylate film of the present invention has the following composition: from 30.0 wt.-% to 92.5 wt.-% of a polyalkyl(meth)acrylate;
- UV-absorbers from 0.0 wt.-% to 5.0 wt.-% of one or several UV-absorbers
- amou a polyalkyl(meth)acrylate
- UV-absorbers one or several UV-absorbers
- UV-stabilizers based on the weight of the polyalkyl(meth)acrylate film sum up to 100 wt.-% in total.
- UV-absorbers from 0.0 wt.-% to 5.0 wt.-% of one or several UV-absorbers
- n jm the content, in wt.-%, of one or several impact modifiers n jm in the polyalkyl(meth)acrylate film is described by the following relationship: 0.5*rif ⁇ rij m ⁇ nf
- the properties of the polyalkyl(meth)acrylate film of the present invention can be even further improved if the polyalkyl(meth)acrylate film comprises: from 30.0 wt.-% to 77.5 wt.-% of a polyalkyl(meth)acrylate;
- UV-absorbers from 0.0 wt.-% to 5.0 wt.-% of one or several UV-absorbers
- the polyalkyl(meth)acrylate film may comprise: from 30.0 wt.-% to 70.0 wt.-% of a polyalkyl(meth)acrylate;
- UV-absorbers from 0.0 wt.-% to 5.0 wt.-% of one or several UV-absorbers
- the polyalkyl(meth)acrylate film of the present invention consists of one single layer i.e. is a monolayer film.
- Such films can be manufactured by methods known to a skilled person such as solution coating, casting or extrusion, wherein the extrusion is particularly preferable in terms of high productivity and advantageous properties of the resulting film.
- the film can be conveniently manufactured by extrusion and e.g. subsequently stored for shipping to a customer or used immediately for the manufacturing of forgery prevention labels.
- the polyalkyl(meth)acrylate film of the present invention preferably has an initial tear resistance of from 0.1 N to 30.0 N, preferably from 1.0 N to 15.0 N.
- the film having an initial tear resistance lower than 0.1 N still would be suitable for use according to the present invention, a great attention would need to be taken during its manufacturing and handling, since the film can easily tear apart.
- the polyalkyl(meth)acrylate film of the present invention having an initial tear resistance of more than 30.0 N is highly suitable for the manufacturing process of forgery prevention labels
- use of forgery prevention labels with such a low brittleness could bear an increased risk that such label can be removed using a thin sharp blade (e.g. a razor blade) from the originally labelled substrate and subsequently re-attached onto a different substrate.
- the initial tear resistance is preferably in the range of from 1.0 N to 15.0 N.
- the initial tear resistance of the polyalkyl(meth)acrylate film can be measured by a common method known to a skilled person such as the method described in the norm ASTM D1004-13 and is typically measured in the direction of extrusion.
- the polyalkyl(meth)acrylate film has elongation at break ranging between 0.5% to 15%, whereby elongation at break ranging between 1.0% to 5.0% is particularly preferable. If the elongation at break is less than 0.5%, flexibility is excessively small, handling of the film becomes difficult and great care should be taken during manufacturing to avoid damaging the film. Under these circumstances, the manufacturing process may need to be run at a lower speed. On the other hand, when the elongation at break exceeds 15.0%, the brittleness of the film tends to be decreased.
- a minor mechanical deformation of the film i.e. less than 15%
- the elongation at break of the polyalkyl(meth)acrylate film can be measured by a common method known to a skilled person such as the one described in the norm ASTM D1004-13.
- the initial tear resistance of the polyalkyl(meth)acrylate film is at least 10 times as high, preferably at least 50 times as high, even more preferably at least 100 times as high as the resistance to tear propagation. This is particularly advantageous and ensures that even a minor film rupture occurring during an unauthorised attempt to remove the forgery prevention label from a substrate rapidly propagates through the entire label and results in a complete label destruction. This additionally reduces the risk of an unauthorised label removal.
- the polyalkyl(meth)acrylate film has resistance to tear propagation, of from 0.01 N to 1.0 N, more preferably of from 0.02 N to 0.2 N. The resistance to tear propagation can be measured according to the norm ASTM D1938-14 and is typically measured in the direction of extrusion.
- the major influencing factors are the amounts of impact modifiers and fillers. More particularly, an increase in concentration of the impact modifiers also increases the elongation at break, and so very small amounts or the complete absence of impact modifiers contribute to an elongation at break in accordance with the invention.
- the thickness of the polyalkyl(meth)acrylate film of the present invention is preferably in the range of 15 ⁇ to 120 ⁇ . When the thickness is less than 15 ⁇ , a great care should be taken during manufacturing and handling of the film to avoid its rupture. On the other hand, when the film thickness exceeds 120 ⁇ , its mechanical stability is rather high and this, again, increases the risk that the film does not break during an attempt of an unauthorised label removal. Additionally, a high film thickness will result in a high thickness of the forgery prevention label comprising the same, which may be disadvantageous for aesthetical or other reasons. From the standpoint of having a good balance between the handling and flatness, the thickness of the polyalkyl(meth)acrylate film is preferably in the range of 30 ⁇ to 90 ⁇ , a range of 40 ⁇ to 75 ⁇ being even more preferred.
- polyalkyl(meth)acrylate film of the present invention comprises from 30.0 wt.-% to 92.5 wt.-% of a polyalkyl(meth)acrylate, based on the weight of the
- Polyalkyl(meth)acrylates are usually obtained by free-radical polymerization of mixtures which typically comprise an alkyl(meth)acrylate, typically methyl methacrylate (a), and at least one further (meth)acrylate (b). These mixtures generally comprise at least 50 wt.-%, preferably at least 60 wt.- %, particularly preferably at least 80 wt.-%, and even more preferably at least 90 wt.-%, based on the weight of the monomers, of methyl methacrylate (a).
- the amount of methyl methacrylate (a) generally used is from 50.0 wt.-% to 99.9 wt.-%, preferably from 80.0 wt.-% to 99.0 wt.-% and particularly preferably from 90.0 wt.-% to 99.0 wt.-%, based on the weight of monomers.
- mixtures for production of polyalkyl(meth)acrylates can also comprise other (meth)acrylates (b) copolymerizable with methyl methacrylate (a).
- (meth)acrylate as used herein is meant to encompass methacrylates, acrylates and mixtures thereof.
- (Meth)acrylates may derive from saturated alcohols, e.g.
- oleyl (meth)acrylate 2-propynyl (meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate; and also aryl (meth)acrylates, such as benzyl (meth)acrylate or phenyl (meth)acrylate, cycloalkyl (meth)acrylates, such as 3- vinylcyclohexyl (meth)acrylate, bornyl (meth)acrylate; hydroxyalkyl (meth)acrylates, such as 3- hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- hydroxypropyl (meth)acrylate; glycol di(meth)acrylates, such as 1 ,4-butanediol (meth)acrylate, (meth)acrylates of ether alcohols, e.g.
- tetrahydrofurfuryl (meth)acrylate vinyloxyethoxyethyl (meth)acrylate
- amides and nitriles of (meth)acrylic acid e.g. N-(3- dimethylaminopropyl)(meth)acrylamide, A/-(diethylphosphono)-(meth)acrylamide, 1- methacryloylamido-2-methyl-2-propanol
- sulphur-containing methacrylates such as
- (meth)acrylate thiocyanatomethyl (meth)acrylate, methylsulphinylmethyl (meth)acrylate, bis((meth)acryloyloxyethyl) sulphide; polyfunctional (meth)acrylates, such as trimethyloylpropane tri(meth)acrylate.
- the amount of the (meth)acrylic comonomers (b) generally used is from 0.1 wt.-% to 50.0 wt.-%, preferably from 1.0 wt.-% to 20.0 wt.-% and particularly preferably from 1.0 wt.-% to 10.0 wt.-%, based on the weight of monomers, and the compounds here can be used individually or in the form of a mixture.
- the polymerization reaction is generally initiated by known free-radical initiators.
- the preferred initiators are inter alia the azo initiators well known to persons skilled in the art, e.g. AIBN and 1 , 1-azobiscyclohexanecarbonitrile, and peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, ieri-butyl 2-ethylperhexanoate, ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, ieri-butyl peroxybenzoate, ieri-butylperoxy isopropyl carbonate, 2,5-bis(2-ethylhexanoylperoxy)-2,5- dimethylhexane, ieri-butyl 2-ethylperoxyhexanoate, ieri-butyl 3,5,5-trimethylper
- 1-alkenes such as 1-hexene, 1-heptene
- branched alkenes such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methyl-1-pentene
- acrylonitrile vinyl esters, such as vinyl acetate; styrene, substituted styrenes having an alkyl substituent in the side chain, e.g. a-methylstyrene and a-ethylstyrene, substituted styrenes having an alkyl substituent on the ring, e.g.
- vinyltoluene and p-methylstyrene halogenated styrenes, such as monochlorostyrenes, dichlorostyrenes, tribromostyrenes and tetrabromostyrenes; heterocyclic vinyl compounds, such as 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl-4- vinylpyridine, 2,3-dimethyl-5-vinylpyridine, vinylpyrimidine, vinylpiperidine, 9-vinylcarbazole, 3- vinylcarbazole, 4-vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, A/-vinylpyrrolidone, 2- vinylpyrrolidone, A/-vinylpyrrolidine, 3-vinylpyrrolidine, /V-vinylcaprolactam, /V-vinylbutyrolactam, vinyloxolane, vinylfuran, vinylthiophene,
- the amount of these comonomers (c) generally used is from 0.0 wt.-% to 10.0 wt.-%, preferably from 0.0 wt.-% to 5.0 wt.-% and particularly preferably from 0.0 wt.-% to 2.0 wt.-%, based on the weight of monomers, and the compounds here can be used individually or in the form of a mixture. Further preference is given to polyalkyl(meth)acrylates which are obtainable by polymerization of a composition having, as polymerizable constituents: (a) from 50.0 wt.-% to 99.9 wt.-% of methyl methacrylate,
- polyalkyl(meth)acrylates composed of from 85.0 wt.-% to 99.5 wt.% of methyl methacrylate and from 0.5 wt.-% to 15.0 wt.-% of methyl acrylate, the amounts here being based on 100 wt.-% of the polymerizable constituents.
- Particularly advantageous copolymers are those obtainable by copolymerization of from 90.0 wt.-% to 99.5 wt.-% of methyl methacrylate and from 0.5 wt.-% to 10.0 wt.-% of methyl acrylate, where the amounts are based on 100 wt.-% of the polymerizable constituents.
- the polyalkyl(meth)acrylates may comprise 91.0 wt.-% of methyl methacrylate and 9.0 wt.-% of methyl acrylate, 96.0 wt.-% of methyl methacrylate and 4.0 wt.-% of methyl acrylate or 99.0 wt.-% of methyl methacrylate and 1.0 wt.-% of methyl acrylate.
- the weight-average molar mass Mw of the employed polyalkyl(meth)acrylates is usually above 80 000 g/mol, determined by means of gel permeation chromatography (GPC with reference to PMMA as a calibration standard, as for all of the Mw determinations on the matrix PMMA and THF as an eluent), more preferably > 120 000 g/mol.
- GPC gel permeation chromatography
- the weight-average molar mass Mw of the polyalkyl(meth)acrylates is generally in the range from 80 000 g/mol to 300 000 g/mol. Particularly advantageous mechanical properties are obtained from foils with polyalkyl(meth)acrylates having an average molar mass Mw in the range from
- the polyalkyl(meth)acrylate has an average molar weight Mw of from 80 000 g/mol to 200 000 g/mol and is obtainable by polymerization of a composition whose polymerizable constituents comprise, based on the weight of the polymerisable composition: (a) from 80.0 wt.-% to 99.0 wt.-% of methyl methacrylate, and
- Impact modifiers for use in the present invention per se are well known and may have different chemical compositions and different polymer architectures.
- the impact modifiers may be crosslinked or thermoplastic.
- the impact modifiers may be in particulate form, as core- shell or as core-shell-shell particles.
- particulate impact modifiers have an average particle diameter between 20 nm and 500 nm, preferably between 50 nm and 450 nm, more preferably between 100 nm and 400 nm and most preferably between 150 nm and 350 nm.
- Porate in this context means crosslinked impact modifiers which generally have a core-shell or core-shell-shell structure.
- Average particle diameter can be determined by a method known to a skilled person, e.g. by photon correlation spectroscopy according to the norm DIN ISO 13321 :1996.
- the particulate impact modifiers are crosslinked particles obtained by means of emulsion polymerization whose average particle diameter is in the range from 10 nm to 150 nm, preferably from 20 nm to 100 nm, in particular from 30 nm to 90 nm.
- These are generally composed of at least 20.0 wt.-%, preferably from 20.0 wt.-% to 99.0 wt.-%, particularly preferably in the range from 30.0 wt.-% to 98.0 wt.-%of butyl acrylate, and from 0.1 wt.-% to 2.0 wt.-%, preferably from 0.5 wt.-% to 1.0 wt.-% of a crosslinking monomer, e.g. a polyfunctional
- (meth)acrylate e.g. allyl methacrylate and, if appropriate, other monomers, e.g. from 0.0 wt.-% to 10.0 wt.-%, preferably from 0.5 wt.-% to 5.0 % wt.-%, of C ⁇
- -C4-alkyl methacrylates such as ethyl acrylate or butyl methacrylate, preferably methyl acrylate, or other vinylically polymerizable monomers, e.g. styrene.
- Preferred impact modifiers are polymer particles which can have a two- or three-layer core-shell structure and are obtained by emulsion polymerization (see, for example, EP-A 0 1 13 924, EP-A 0 522 351 , EP-A 0 465 049 and EP-A 0 683 028).
- the present invention typically requires suitable average particle diameter of these emulsion polymers in the range from 20 nm and 500 nm, preferably between 50 nm and 450 nm, more preferably between 150 nm and 400 nm and most preferably between 200 nm and 350 nm.
- a three-layer or three-phase structure with a core and two shells can prepared as follows.
- the innermost (hard) shell can, for example, be composed in essence of methyl methacrylate, of small proportions of comonomers, e.g. ethyl acrylate, and of a proportion of crosslinking agent, e.g. allyl methacrylate.
- the middle (soft) shell can, for example, be composed of a copolymer comprising butyl acrylate and, if appropriate, styrene, while the outermost (hard) shell is in essence the same as the matrix polymer, thus bringing about compatibility and good linkage to the matrix.
- the proportion of polybutyl acrylate in the core or in the shell of the impact modifier of a two- or three-layer core-shell structure is decisive for the impact-modifying action and is preferably in the range from 20.0 wt.-% to 99.0 wt.-%, particularly preferably in the range from 30.0 wt.-% to 98.0 wt.-%, even more preferably in the range from 40.0 wt.-% to 97.0 wt.-%, based on the total weight of the impact modifier.
- Thermoplastic impact modifiers have a different mechanism of action than particulate impact modifiers. They are generally mixed with the matrix material.
- preferred sizes for these domains the size of which can be determined, for example, by electron microscopy, correspond to preferred sizes for the core-shell particles.
- thermoplastic impact modifiers There are various classes of thermoplastic impact modifiers.
- One example thereof are aliphatic TPUs (thermoplastic polyurethanes) e.g. Desmopan® products commercially available from Covestro AG.
- TPUs Desmopan® WDP 85784A, WDP 85092A, WDP 89085A and WDP 89051 D are particularly suitable as impact modifiers.
- thermoplastic polymers for use according in the foil of the present invention as impact modifiers are methacrylate-acrylate block copolymers, especially acrylic TPE, which comprises PMMA-poly-n-butyl acrylate-PMMA triblock copolymers, and which are commercially available under the Kurarity® product name by Kuraray.
- the poly-n-butyl acrylate blocks form nanodomains in the polymer matrix having a size between 10 nm and 20 nm.
- thermoplastic impact modifiers comprising PVDF is also possible. However, use of such modifiers is less advantageous, because their presence in the polyalkyl(meth)acrylate film tends to worsen the printability of the film.
- the cumulative content of the polyalkyl(meth)acrylate and the impact modifier (hereinafter referred to as "impact-modified polyalkyl(meth)acrylate”) in the polyalkyl(meth)acrylate film is from 60 wt.-% to 95 wt.-%, more preferably from 65.0 wt.-% to 90.0 wt.-%, even more preferably from 70.0 wt.-% to 85.0 wt.-%, yet even more preferably from 75.0 wt.-% to 80.0 wt.-%, based on the weight of the polyalkyl(meth)acrylate film.
- the presence of the inorganic filler in the polyalkyl(meth)acrylate film of the present invention serves several purposes. It is due to the presence of inorganic fillers in the specified amounts that polyalkyl(meth)acrylate film has a rough surface with a non-glossy appearance and can be printed easily.
- the printing may be accomplished substantially by any method known in the prior art such as laser printing, inkjet printing, flexographic printing, digital printing or screen printing.
- the presence of the inorganic fillers allows rendering the polyalkyl(meth)acrylate film to have a desired colour and degree of transparency.
- the presence of titanium dioxide in the polyalkyl(meth)acrylate film will render the film white and substantially non-transparent.
- the amount of the inorganic filler was surprisingly found to have a strong effect on the film behaviour during its handling, in particular, the behaviour of the waste matrix after the kiss cutting step during manufacturing of forgery prevention labels.
- polyalkyl(meth)acrylate film is higher than the content of one or several inorganic fillers in the polyalkyl(meth)acrylate film rif the brittleness of the film will be rather low.
- the risk of an unauthorised removal of the forgery prevention label from the original substrate will significantly increase.
- polyalkyl(meth)acrylate film obeys the following relationship:
- polyalkyl(meth)acrylate film obeys the following relationship: 0.6*nf ⁇ n im ⁇ 0.8*n f nf being the content, in wt.-%, of one or several inorganic fillers in the polyalkyl(meth)acrylate film.
- Inorganic fillers for use in the present invention are not particularly limited and can, for instance, be selected from titanium dioxide, zinc sulphide, silica, barium sulphate, aluminium trihydroxide or calcium carbonate or mixtures thereof.
- the inorganic fillers show a 45 ⁇ screen residue of not more than 0.1 wt.-%, i.e.
- substantially no agglomerates with a particle size larger than 45 ⁇ are present, which is highly advantageous for use according to the present invention.
- This allows the inorganic filler to be distributed in the matrix of poly(meth)acrylate film in a particularly homogeneous manner without large filler agglomerates being present so that the resulting film shows a substantially uniform visual appearance and has appropriate mechanical properties.
- the presence of substantial amounts of larger filler agglomerates in the film is disadvantageous, since such agglomerates tend to initiate film cracks thereby reducing the initial tear strength at a random position of the film.
- the inorganic fillers have a weight-average particle diameter d5Q ranging between 0.05 ⁇ and 10.0 ⁇ , more preferably between 0.1 ⁇ and 5.0 ⁇ , particularly preferably between 0.1 ⁇ and 1.0 ⁇ , even more preferably between 0.1 ⁇ and 0.5 ⁇ .
- the weight-average particle diameter d5Q can be determined by a method known to a skilled person, e.g. by photon correlation spectroscopy according to the norm DIN ISO 13321 :1996 upon using a commercially available instrument such as N5 Submicron Particle Size Analyzer from Beckman Coulter Inc or SZ-10 Nanoparticle Analyzer from Horiba Scientific Ltd.
- the oil absorption of the inorganic filler is not less than 5 g/100 g filler, preferably not less than 10 g/100 g filler and particularly preferably not less than 15 g/100 g filler. It is further advantageous that the oil absorption of the inorganic filler is not more than 100 g/100 g filler, preferably not more than 70 g/100 g filler and particularly preferably not more than 50 g/100 g filler.
- the oil absorption can be determined according to the norm DIN EN ISO 787-5:1980.
- titanium dioxide can be advantageously employed as a filler.
- Titanium dioxide in form of rutile or anatase may be used, whereby titanium dioxide in form of rutile is particularly preferred due to its low photocatalytic activity.
- Such material can be manufactured by chloride process and is commercially available from various suppliers such as e.g. KRONOS TITAN GmbH (Leverkusen, Germany).
- Suitable titanium dioxide fillers may be with or without modifications with water-insoluble oxides of aluminium, silicon, zinc, or other agents; these reagent materials are introduced specifically to improve those properties for which the pigment is used.
- the titanium dioxide fillers should ideally be free of extenders such as barium sulphate, clay, magnesium silicate, whiting, etc. Particularly preferred are titanium dioxide fillers of types II, III and IV according to the classification ASTM D476-15.
- UV absorbers and UV stabilizers are well known and are described in detail by way of example in Hans Zweifel, Plastics Additives Handbook, Hanser Verlag, 5th Edition , 2001 , p. 141 ff.
- Light stabilizers are understood to include UV absorbers, UV stabilizers and free-radical scavengers.
- UV absorbers can by way of example derive from the group of the substituted benzophenones, salicylic esters, cinnamic esters, oxanilides, benzoxazinones, hydroxyphenylbenzotriazoles, triazines or benzylidenemalonate.
- the best-known representatives of the UV stabilizers/free-radical scavengers are provided by the group of the sterically hindered amines (hindered amine light stabilizer, HALS).
- polyalkyl(meth)acrylate film is composed of the following components:
- component A a UV absorber of benzotriazole type
- component B a UV absorber of triazine type
- component C a UV stabilizer (HALS compound).
- HALS compound a UV stabilizer
- UV absorbers of benzotriazole type (Component A) that can be used are 2-(2- hydroxy-5-methylphenyl)benzotriazole, 2-[2-hydroxy-3,5-di(a,a-dimethylbenzyl)phenyl]- benzotriazole, 2-(2-hydroxy-3,5-di-ieri-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-butyl-5-methyl- phenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-ieri-butylphenyl)-5-chlorobenzotriazole, 2-(2- hydroxy-3,5-di-ieri-amylphenyl)benzotriazole, 2-(2-hydroxy-5-ieri-butylphenyl)benzotriazole, 2-(2- hydroxy-3-sec-butyl-5-ieri-butylphenyl)benzotriazole and 2-(2-hydroxy-5-ieri-octylphenyl)
- the amounts used of the UV absorbers of benzotriazole type are from 0.1 wt.-% to 5.0 wt.-%, preferably from 0.2 wt.-% to 3.0 wt.-% and very particularly preferably from 0.5 wt.-% to 2.0 wt.-%, based on the weight of the polyalkyl(meth)acrylate film. It is also possible to use mixtures of different UV absorbers of benzotriazole type.
- Triazine type UV absorbers such as 2-(4,6-diphenyl-1 ,3,5-triazin-2-yl)-5- hexyloxyphenol, are preferably used in combination with the Component A.
- the poly(meth)acrylate film used in accordance with the invention is preferably produced by means of an extrusion process.
- an extruded poly(meth)acrylate film is substantially free of volatile organic compounds such as solvents, which is highly advantageous for toxicological and environmental reasons.
- the above-described components of the polyalkyl(meth)acrylate film can be blended before or even during the extrusion step.
- a line having at least the following components can be used: an extruder,
- a hot melt is extruded from the die of the extruder onto a nip between two polishing rolls or onto a chill roll.
- the optimum melt temperature is dependent, for example, on the composition of the mixture and may therefore vary within wide ranges.
- Preferred temperatures of the PMMA moulding composition up to the point of die entry are in the range from 150 to 300°C, more preferably in the range from 180°C to 270°C and very preferably in the range from 200°C to 260°C.
- the temperature of the polishing rolls is preferably less than or equal to 150°C, more preferably between 60°C and 140°C.
- the temperature of the die is higher than the temperature of the mixture prior to die entry.
- the die temperature is preferably set 10°C, more preferably 20°C and very preferably 30°C higher than the temperature of the mixture prior to die entry. Accordingly, preferred temperatures of the die are in the range from 160°C to 330°C, more preferably 190°C to 300°C.
- the polishing stack may consist of two or three polishing rolls. Polishing rolls are widely known in the art and are used to obtain a high gloss. Nevertheless, rolls other than polishing rolls e.g. matt rolls can also be used in the method of the invention. The nip between the first two polishing rolls forms a sheet which becomes a film by virtue of the simultaneous cooling.
- the sheet of melt may be deposited onto a single cooled roll, which transports it further. Chill rolls are preferably located over the polishing stacks.
- a filter may be optionally located before the entry of the melt into the die.
- the mesh size of the filter is guided generally by the starting materials used, and may therefore vary within wide ranges. Mesh sizes generally are in the range from 300 ⁇ to 20 ⁇ . Filters having two or more screens of different mesh size may also be located before the point of die entry. These filters are available
- a static mixing element may be installed upstream of the flat film die.
- This mixing element can be used to mix components such as pigments, stabilizers or additives into the polymer melt, or up to 5 wt% of a second polymer, for example in the form of a melt, may be mixed from a second extruder into the poly(meth)acrylate.
- the pressure with which the melted mixture is pressed into the die may be controlled, for example, via the speed of the screw.
- the pressure is typically within a range of from 40 bar to 150 bar, without this limiting the method of the invention. Accordingly, the speed with which the films can be obtained in accordance with the invention is generally greater than 5 m/min, more particularly greater than 10 m/min.
- a melt pump may additionally be installed upstream of the flat film die.
- a liner layer 5 is bound to the polyalkyl(meth)acrylate film 6 from the step i) downstream of the extruder at a temperature below the glass transition temperature of the polyalkyl(meth)acrylate, whereby a laminate 4 is obtained.
- the resulting laminate 4 will typically consist of the following two layers (cf. Fig. 2): ⁇ layer formed by the polyalkyl(meth)acrylate film 6; and
- the liner layer is self-adhesive.
- Such self-adhesive liner typically has an adhesive layer which can be advantageously used for binding the liner to polyalkyl(meth)acrylate films 6 having a matt surface.
- the liner layer has a layer of a polyethylene-copolymer instead of an adhesive layer.
- Such liners are advantageously employed for for polyalkyl(meth)acrylate films 6 having a glossy surface.
- the liner layer preferably has an initial tear resistance, measured according to ASTM D1004-13, of from 50 N to 500 N.
- the material of the liner layer is not particularly limited, as long as the liner layer has a sufficient tear resistance and can be selected from one of the following: polyethylene, polypropylene, polyethylene terephthalate or mixtures thereof, whereby a biaxially oriented polypropylene or a biaxially oriented polyethylene terephthalate are particularly preferred.
- the laminate will undergo a step of binding an adhesive layer, optionally, a release coating layer and a support layer to deliver a label stock.
- the adhesive layer substantially consists of a pressure sensitive adhesive (PSA).
- PSA pressure sensitive adhesive
- the support layer typically comprises a paper or plastic film material and may be coated by release coating layer.
- release coating layer Various release coating compositions are known such as those described
- Non-PSA adhesive compositions may also be used particularly for embodiments wherein the form support layer is porous (e.g. paper), the form substrate being exposed on the non-viewing surface of the label.
- PSAs suitable in the present invention are preferably selected from the group consisting of alkylacrylate polymers and copolymers; copolymers of alkylacrylates with acrylic acid; terpolymers of alkylacrylates, acrylic acid, and vinyl-lactates; alkyl vinyl ether polymers and copolymers;
- polyisoalkylenes polyalkyldienes; alkyldiene-styrene copolymers; styrene-isoprene-styrene block copolymers; polydialkylsiloxanes; polyalkylphenylsiloxanes; natural rubbers; synthetic rubbers; chlorinated rubbers; latex crepe; rosin; cumarone resins; alkyd polymers; and polyacrylate esters and mixtures thereof.
- examples include polyisobutylenes, polybutadienes, or butadiene-styrene copolymers, and mixtures thereof (such polymers and copolymers preferably have no reactive moieties, i.e. are not oxidized in the presence of air); silicone-based compounds such as polydimethylsiloxane, and polymethylphenylsiloxane combined with other resins and/or oils.
- PSAs also include tackified thermoplastic resins and tackified thermoplastic elastomers, wherein the tackifier comprises one or more compounds which increases the tack of the composition.
- tackified thermoplastic resin useful as an aggressively PSA is the combination of a vinyl acetate/ethylene copolymer known under the trade designation
- VYNATHENE EY 902-30 available from Quantum Chemicals, Cincinnati, Ohio
- tackifiers known under the trade designations PICCOTEX LC (a water-white thermoplastic resin produced by copolymerization of vinyltoluene and alpha-methylstyrene monomers having a ring and ball softening point of about 87°C to 95°C, available from Hercules Incorporated, Wilmington, Del.) and WINGTACK 10 (a liquid aliphatic C-5 petroleum hydrocarbon resin available from Goodyear Chemical) and an organic solvent such as toluene.
- PICCOTEX LC a water-white thermoplastic resin produced by copolymerization of vinyltoluene and alpha-methylstyrene monomers having a ring and ball softening point of about 87°C to 95°C, available from Hercules Incorporated, Wilmington, Del.
- WINGTACK 10 a liquid aliphatic C-5 petroleum hydrocarbon resin available from Goodyear Chemical
- thermoplastic elastomer useful as an aggressively PSA is the combination of the styrene- poly(ethylene-butylene)-styrene block copolymer known under the trade designation KRATON G1657 (available from of Shell Chemicals) with one or more of the low molecular weight hydrocarbon resins known under the trade designation REGALREZ (from Hercules) and an organic solvent such as toluene. Both of these formulations may be coated using a knife coater and air- dried, or air-dried followed by oven drying. Of course, the invention is not limited to use of these specific combinations of thermoplastic resins, thermoplastic elastomers, and tackifiers.
- Some presently preferred PSAs exhibit extended shelf life and resistance to detackifying under atmospheric conditions, and include acrylic-based copolymer adhesives as disclosed in U.S. Pat. No. Re 24,906.
- acrylic-based copolymer adhesives as disclosed in U.S. Pat. No. Re 24,906.
- One example of such an acrylic-based copolymer is a 95.5 : 4.5 (measured in parts by weight of each) isooctylacrylate/acrylic acid copolymer.
- Another preferred adhesive is the copolymer of a 90 : 10 weight ratio combination of these two monomers.
- Acrylic-based PSAs can be coated out of a coatable composition comprising an organic solvent, such as a heptane: isopropanol solvent mixture, and the solvent subsequently evaporated, leaving a pressure-sensitive adhesive coating.
- This layer is preferably from about 0.038 centimeters (cm) to about 0.1 1 cm (5 to 15 mils) thick when the substrate is a retroreflective sheeting material.
- PSAs useful in the invention also may be characterized by having "180°C peel adhesion" ranging from about 10 to about 1000 g/cm, more preferably at least about 50 g/cm.
- 180 °C peel adhesion typically ranges from about 200 g/cm to about 600 g/cm, measured using a standard test procedure. In this procedure, the force necessary to remove (i.e. peel) a PSA- coated substrate from a test substrate when the PSA-coated substrate is peeled from the test substrate is termed the "peel adhesion" value.
- a standard glass plate is cleaned using a solvent (such as one wash of diacetone alcohol followed by three washes of n-heptane).
- a sample having a PSA-backsize coating is then applied along the center of the standard glass plate, PSA side down.
- the sample is then rolled once with a 2.04 kg hand roller.
- the standard glass plate is then secured to a horizontal platen in a standard peel adhesion tester such as that known under the trade name "IMASS.”
- One end of the sample is then attached to a hook which is a part of the peel adhesion tester.
- the sample is peeled from the standard glass plate at a 180 °C angle (i.e., one end of the sample is pulled toward the other end) by moving the platen horizontally at a speed of 228.6 cm/min, and the force required recorded, in g/cm of sample width, for various dwell times.
- the release coating layer 8 which is typically a siloxane coating, serves the purpose of reducing the adhesion between the adhesive layer 7 and the support layer 9.
- the release coating layer 8 allows to achieve a kinetic coefficient of friction below 0.35, preferably below 0.25, determined according to the norm ASTM D1894-14.
- the label stock will undergo a kiss cutting to form a plurality of individual self-adhesive forgery prevention labels bound to a support layer 9.
- the kiss cutting may be performed by means of a mechanical die cutting as described in US 201 1/0132522 A1 or by using a laser.
- the waste matrix surrounding the individual self-adhesive forgery prevention labels will be peeled off from the support layer without any risk of rupture.
- the distance between individual labels i.e. the width of the stripes in the waste matrix
- the release force during this operation is below 30 g/inch, preferably below 20 g/inch, even more preferably from 1 g/inch to 10 g/inch, measured using T- peel test with a 7475 tape from TESA.
- Forgery prevention label 2 of the present invention comprise at least the following layers in the order stated (cf. Fig. 3): a layer 6 consisting of extruded polyalkyl(meth)acrylate film as described above; an adhesive layer 7;
- the forgery prevention label the present invention has a thickness of between 50 ⁇ and 300 ⁇ , more preferably between 100 ⁇ and 200 ⁇ .
- the PMMA layer 6 may have a thickness of from 20 ⁇ to 100 ⁇ , more preferably of from 30 ⁇ to 75 ⁇ , even more preferably of from 40 ⁇ to 60 ⁇ ;
- the adhesive layer 7 may have a thickness of from 10 ⁇ to 40 ⁇ , more preferably of from 20 ⁇ to 30 ⁇ ;
- the release coating layer 8 may have a thickness of from 0.01 ⁇ to 1.5 ⁇ , preferably of from 0.5 ⁇ to 1.2 ⁇ , more preferably of 0.6 ⁇ to 0.8 ⁇ ;
- the support layer 9 may have a thickness of from 20 ⁇ to 70 ⁇ , preferably of from 30 ⁇ to 50 ⁇ ;
- the size of the forgery prevention labels can in principle be freely selected and is only limited in by the dimension extrusion die and/or the polishing stack used for their production. This means that the formats are substantially freely selectable.
- the trimming and kiss cutting of the poly(meth)acrylate film is preferably accomplished by means of die cutting, cutting, laser cutting or laser die cutting. Particular preference is given to laser cutting or laser die cutting.
- the poly(meth)acrylate films produced in accordance with the invention may be provided additionally with ridges, cuts, slits or perforation or notches in order to additionally facilitate destruction of the labels during an attempt of their non-authorised removal.
- additional means are not essential.
- the forgery prevention labels are highly suitable for producing chip cards, documents, forgery prevention labels, other labels or price tags.
- One illustrative example of the use is that, for example, of toll stickers which are mounted on the inside of the vehicle screen.
- the forgery prevention label of the present invention bearing a photograph of an individual can be used in documents such as identity cards or passports. The label bearing the photograph will become destroyed upon an unauthorised attempt to peel it off from the passport in order to transfer it to a different passport.
- Example 1 (comparative) A polyalkyl(meth)acrylate film having a total thickness of 50 ⁇ was prepared using a compounded mixture of the following composition: a) 20.0 wt.-% of a material comprising 47 wt.-% of a butylacrylat-based acrylic core-shell-shell impact modifier,
- the extrusion was carried out at the extrusion speed of 7.3 m/min using a 35 mm-diameter single screw extruder and a 25 mm-diameter single screw co-extruder MX 10 from Dr. Collin GmbH (Ebersberg, Germany) under the following conditions:
- Screw temperature in the extruder 240°C to 270°C
- the extruded polyalkyl(meth)acrylate film had elongation at break below 5%.
- the extruded polyalkyl(meth)acrylate film was used for the preparation of self- adhesive forgery prevention labels upon using a label manufacturing machine MPS EF Flexo from MPS Systems B.V. (Arnhem, The Netherlands).
- the amount of impact modifier in the polyalkyl(meth)acrylate film was about 9.4 wt.-% i.e. less than 1/2 of the amount of titanium dioxide.
- the example shows that such a low amount of impact modifier has a negative effect on the properties of the waste matrix during the waste matrix stripping step.
- a polyalkyl(meth)acrylate film having a total thickness of 50 ⁇ was prepared using a compounded mixture of the following composition: a) 30.0 wt.-% of a material comprising 47 wt.-% of a butylacrylat-based acrylic core-shell-shell impact modifier,
- the extruded polyalkyl(meth)acrylate film had elongation at break of 4 to 6%. Subsequently, the extruded polyalkyl(meth)acrylate film was used for the preparation of self- adhesive forgery prevention labels upon using a label manufacturing machine MPS EF Flexo from MPS Systems B.V. (Arnhem, The Netherlands).
- polyalkyl(meth)acrylate film of Example 2 could be successfully used for the manufacturing of self- adhesive forgery prevention labels. No undesired rupture of the waste matrix took place.
- the tear resistance tests were carried out using a testing system Zwick Roell Z005, available from Zwick GmbH & Co. KG (Ulm, Germany) with 4 identical samples, wherein 5 tests were carried out for each sample.
- the initial tear resistance measured using samples having a width of from 10 mm to 20 mm according to the norm ASTM D1004-13 in the direction of extrusion of the films was 5.8 N to 7.0 N.
- the resistance to tear propagation measured using 25 mm wide samples according to the norm ASTM D1938-14 in the direction of extrusion of the films, was 0.03 N.
- the amount of the impact modifier in the polyalkyl(meth)acrylate film was about 14.1 wt.-% i.e. in accordance with the present invention.
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
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KR1020207009035A KR102230839B1 (en) | 2017-08-30 | 2018-08-22 | Brittle acrylic film and anti-counterfeiting label containing the same |
RU2020109400A RU2734223C1 (en) | 2017-08-30 | 2018-08-22 | Fragile acrylic films and labels to prevent tampering containing thereof |
BR112020003553-0A BR112020003553B1 (en) | 2017-08-30 | 2018-08-22 | FALSIFICATION PREVENTION LABEL THAT UNDERSTANDS A POLYALKYL (MET) ACRYLATE FILM, PROCESS FOR THE MANUFACTURE OF THE SAME AND ITS USE, LAMINATED FOR THE MANUFACTURE OF THE SAME, PROCESS FOR THE MANUFACTURE OF A LAMINATE |
CA3073783A CA3073783C (en) | 2017-08-30 | 2018-08-22 | Brittle acrylic films and forgery prevention labels comprising the same |
US16/636,765 US20210032502A1 (en) | 2017-08-30 | 2018-08-22 | Brittle acrylic films and forgery prevention labels comprising the same |
JP2020512517A JP6756945B1 (en) | 2017-08-30 | 2018-08-22 | Brittle acrylic film and tamper-proof labels containing them |
SG11202001646YA SG11202001646YA (en) | 2017-08-30 | 2018-08-22 | Brittle acrylic films and forgery prevention labels comprising the same |
IL272816A IL272816B1 (en) | 2017-08-30 | 2018-08-22 | Brittle acrylic films and forgery prevention labels comprising the same |
MX2020001992A MX2020001992A (en) | 2017-08-30 | 2018-08-22 | Brittle acrylic films and forgery prevention labels comprising the same. |
CN201880056122.9A CN111032349B (en) | 2017-08-30 | 2018-08-22 | Brittle acrylic film and security label comprising said film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP17188466.1A EP3450163B1 (en) | 2017-08-30 | 2017-08-30 | Brittle acrylic films and forgery prevention labels comprising the same |
EP17188466.1 | 2017-08-30 |
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WO2019042831A1 true WO2019042831A1 (en) | 2019-03-07 |
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PCT/EP2018/072616 WO2019042831A1 (en) | 2017-08-30 | 2018-08-22 | Brittle acrylic films and forgery prevention labels comprising the same |
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US (1) | US20210032502A1 (en) |
EP (1) | EP3450163B1 (en) |
JP (1) | JP6756945B1 (en) |
KR (1) | KR102230839B1 (en) |
CN (1) | CN111032349B (en) |
BR (1) | BR112020003553B1 (en) |
CA (1) | CA3073783C (en) |
ES (1) | ES2750874T3 (en) |
IL (1) | IL272816B1 (en) |
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PL (1) | PL3450163T3 (en) |
RU (1) | RU2734223C1 (en) |
SG (1) | SG11202001646YA (en) |
TW (1) | TWI714879B (en) |
WO (1) | WO2019042831A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2020173686A1 (en) | 2019-02-27 | 2020-09-03 | Röhm Gmbh | Forgery prevention labels for high-temperature applications |
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EP3988294A1 (en) * | 2020-10-26 | 2022-04-27 | Röhm GmbH | Laser engravable labels |
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- 2018-08-22 KR KR1020207009035A patent/KR102230839B1/en active IP Right Grant
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WO2020173686A1 (en) | 2019-02-27 | 2020-09-03 | Röhm Gmbh | Forgery prevention labels for high-temperature applications |
US11285708B2 (en) | 2019-02-27 | 2022-03-29 | Röhm Gmbh | Forgery prevention labels for high-temperature applications |
Also Published As
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BR112020003553A2 (en) | 2020-09-01 |
CA3073783A1 (en) | 2019-03-07 |
KR20200047630A (en) | 2020-05-07 |
EP3450163B1 (en) | 2019-07-17 |
PL3450163T3 (en) | 2020-03-31 |
TW201912704A (en) | 2019-04-01 |
SG11202001646YA (en) | 2020-03-30 |
BR112020003553B1 (en) | 2021-03-16 |
JP6756945B1 (en) | 2020-09-16 |
US20210032502A1 (en) | 2021-02-04 |
CN111032349A (en) | 2020-04-17 |
KR102230839B1 (en) | 2021-03-23 |
IL272816B1 (en) | 2024-04-01 |
JP2020531922A (en) | 2020-11-05 |
MX2020001992A (en) | 2021-02-04 |
TWI714879B (en) | 2021-01-01 |
RU2734223C1 (en) | 2020-10-13 |
ES2750874T3 (en) | 2020-03-27 |
CA3073783C (en) | 2021-12-07 |
CN111032349B (en) | 2022-04-15 |
IL272816A (en) | 2020-04-30 |
EP3450163A1 (en) | 2019-03-06 |
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