EP3781633A1 - Décalcomanie sans film - Google Patents
Décalcomanie sans filmInfo
- Publication number
- EP3781633A1 EP3781633A1 EP19730919.8A EP19730919A EP3781633A1 EP 3781633 A1 EP3781633 A1 EP 3781633A1 EP 19730919 A EP19730919 A EP 19730919A EP 3781633 A1 EP3781633 A1 EP 3781633A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- decal
- filmless
- adhesive layer
- layer
- substrate
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000012790 adhesive layer Substances 0.000 claims description 77
- 239000010410 layer Substances 0.000 claims description 74
- 239000000463 material Substances 0.000 claims description 54
- 239000000758 substrate Substances 0.000 claims description 54
- 239000000853 adhesive Substances 0.000 claims description 45
- 230000001070 adhesive effect Effects 0.000 claims description 45
- 230000007704 transition Effects 0.000 claims description 21
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 14
- 229920001971 elastomer Polymers 0.000 claims description 14
- 239000005060 rubber Substances 0.000 claims description 13
- 229920001169 thermoplastic Polymers 0.000 claims description 12
- 239000004416 thermosoftening plastic Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000013536 elastomeric material Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920003051 synthetic elastomer Polymers 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 239000005061 synthetic rubber Substances 0.000 claims description 3
- 238000001723 curing Methods 0.000 description 14
- 239000000976 ink Substances 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- 238000007639 printing Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 206010043458 Thirst Diseases 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- -1 bromobutyl Chemical group 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920006132 styrene block copolymer Polymers 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 2
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000010943 off-gassing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000004033 plastic Chemical class 0.000 description 2
- 229920003023 plastic Chemical class 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- QQFBQBDINHJDMN-UHFFFAOYSA-N ethyl 2-trimethylsilylacetate Chemical compound CCOC(=O)C[Si](C)(C)C QQFBQBDINHJDMN-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
-
- 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
- C09J2407/00—Presence of natural rubber
-
- 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
- C09J2421/00—Presence of unspecified rubber
-
- 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
-
- 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
- C09J2463/00—Presence of epoxy resin
Definitions
- this application relates to a filmless decal, the filmless decal comprising an adhesive layer having a thickness of from 5 to 30 microns and a print layer on at least a portion of the adhesive layer.
- this application relates to an article comprising a substrate and the filmless decal.
- this application relates to a process for making a filmless decal.
- the process comprises providing an adhesive layer and applying a print layer on at least a portion of the adhesive layer to provide a filmless decal.
- the adhesive layer is a UV-cured adhesive layer
- the process may also include curing the adhesive layer using ultra-violet radiation to provide a UV-cured adhesive layer, and applying the print layer on at least a portion of the UV-cured adhesive layer to provide the filmless decal.
- Figure 1 provides a cross section of a film decal according to the state of the art.
- Figure la provides cross section of the transition area for a film decal.
- Figure 2 provides a cross section of a filmless decal on a substrate.
- Figure 2a provides a cross section of the transition area for a filmless decal on a substrate.
- Figure 3 provides a cross section of a stepped ridge filmless decal on a substrate.
- Figure 3a provides a cross section of the transition area for a stepped ridge filmless decal on a substrate.
- Figure 4 provides a flow chart for a process for making a filmless decal.
- Figures 5a-5g provide a cross section view of a manufacturing process for a filmless decal.
- Filmless decal 200 is shown in Figure 2 on substrate 220.
- Filmless decal 200 comprises adhesive layer 230 having a thickness of from 5 to 30 microns, or even from 5 to 20 microns, and print layer 250 on at least a portion of the adhesive layer.
- adhesive layer 230 having a thickness of from 5 to 30 microns, or even from 5 to 20 microns, and print layer 250 on at least a portion of the adhesive layer.
- substrate 220 is not itself part of filmless decal 200.
- the adhesives useful in adhesive layer 230 are not particularly limited and may include any of the well-known classes of UV-curable adhesive materials or any of the well- known pressure sensitive adhesive materials, particularly pressure sensitive adhesive materials that comprise a rubber-based elastomer material, as well as those that comprise acrylates.
- Suitable UV-curable adhesives may be chosen, for instance, for their high
- UV-curable adhesive should also show good properties as a substrate for printing. For instance, the color- fastness, ability to add pigments to the adhesive (in order to enhance the colors of the printed layer) may be taken into consideration.
- UV-curable adhesives in adhesive layer 230 may be cured by processes known in the art. Generally, UV (or ultraviolet) light is emitted by a source and provides the energy to begin a reaction photoinitiator present in the UV-curable adhesive. Difference UV-curable adhesives use photoinitiators that are sensitive to different ranges of UV light. It is therefore important to match the material being cured with the light source being used.
- a UV-curable adhesive uses a broad spectrum of UV light with a concentration in the UVA range to achieve curing.
- Factors that influence the cure speed of UV-curable adhesive materials include light intensity provided on the UV-curable adhesive, the light wavelength being used, the
- UV-curable adhesive materials There are two basic types of UV-curable adhesive materials in widespread industrial use, acrylates and epoxies.
- acrylate refers to a broad range of materials including acrylates
- acrylates and similar functional groups.
- Acrylate systems react when exposed to UV-light (specifically UVA light) and in many cases also visible light. These materials exhibit a broad range of properties.
- adhesives may be colored (e.g., red, blue, black), opaque, fluorescing (which may be aesthetically desirable in the filmless decal application, or may provide a means for in-line process inspection), or thermally conductive.
- the physical properties of acrylate systems are generally easier to control than for epoxies and can include adhesion strength, viscosity, durometer, and appearance.
- Cure speeds for acrylate resins depend on formulation specifics, and of course, on the intensity and nature of the light used to cure them. Cure depth can also be varied with formulation and process specifics.
- surface tack can be controlled with acrylate containing UV-curable adhesive materials.
- Surface tack is generally caused by the interference of atmospheric oxygen with the free radical cure mechanism on the surface of the acrylate resins.
- This surface tack can be controlled by altering the curing process (e.g., light intensity, cure time, wavelength of light used) and can be adjusted as necessary to facilitate the application of print layer 250.
- Epoxy materials are the second main type of UV-curable adhesive materials.
- UV- curable adhesive materials containing epoxy resins may be formulated to exhibit some advantageous properties such as a tack free cure and superior adhesion to certain substrates.
- the development of the full properties of UV-curable adhesive materials containing epoxy resins may take longer than for acrylate materials. In such cases, heat is sometimes used to accelerate the curing. Further, curing of epoxy resins can be impeded by moisture and/or humidity.
- the adhesive layer may comprise a pressure sensitive adhesive, particularly a pressure sensitive adhesive comprising a rubber-based elastomeric material, or a pressure sensitive adhesive comprising an acrylate material.
- PSAs Pressure sensitive adhesives
- PSAs may possess one or more of the following properties: (1) aggressive and permanent tack, (2) adherence with no more than finger pressure, (3) sufficient ability to hold onto an adherend, and (4) sufficient cohesive strength.
- PSAs Materials that have been found to function well as PSAs include polymers designed and formulated to exhibit the requisite viscoelastic properties resulting in a desired balance of tack, peel adhesion, and shear holding power.
- PSAs are characterized by being normally tacky at room temperature (e.g., 20°C).
- Compositions are not necessarily considered to be PSAs merely because they are sticky or adhere to a surface.
- the rubber-based elastomeric material for use herein is selected from the group consisting of natural rubbers, synthetic rubbers, thermoplastic elastomeric materials, non-thermoplastic elastomeric materials, thermoplastic hydrocarbon elastomeric materials, non-thermoplastic hydrocarbon elastomeric materials, and any
- the rubber-based elastomeric material for use herein is selected from the group consisting of halogenated butyl rubbers, in particular bromobutyl rubbers and chlorobutyl rubbers; halogenated isobutylene-isoprene copolymers; bromo- isobutylene-isoprene copolymers; chloro-isobutylene-isoprene copolymers; block copolymers; olefmic block copolymers; butyl rubbers; synthetic polyisoprene; ethylene-octylene rubbers; ethylene-propylene rubbers; ethylene-propylene random copolymers; ethylene-propylene-diene monomer rubbers; polyisobutylenes; poly(alpha-olefm); ethylene-alpha-olefm copolymers; ethylene-alpha-olefm block copolymers; styrenic block cop
- a UV-curable adhesive when used, they may be chosen for their high transparency. In situations where vibrant colors are provided on a filmless decal to be applied onto a colored substrate, however, such transparency can result in filmless decals that do not give sufficient contrast (e.g., the color of the substrate can be seen through the decal).
- inorganic pigments or pastes into the uncured UV-curable adhesives.
- Suitable materials include titanium dioxide, zinc oxide, calcium carbonate, and mixtures thereof.
- all of these materials have relatively high material density. Incorporation of such pigments into a UV- curable adhesive may not be stable and, even when they are, they may interfere with the curing process and thus negatively affect the adhesion of the filmless decal to the substrate.
- a pressure sensitive adhesive comprising a rubber-based elastomeric material.
- inorganic pigments or pastes such as titanium dioxide, zinc oxide, calcium carbonate, and mixtures thereof may be added.
- the level of the pigment can be adjusted based upon color performance, material handling factors, formulation stability, and the like. Typical loadings may range from 5 to 150 parts per hundred rubber (by weight as measured against the weight rubber-based elastomeric material). In particular, from 20 to 100 phr, from 10 to 80 phr, or even from 10 to 50 phr.
- Print layer 250 may be provided by any printer capable of printing onto the adhesive layer 230.
- the UV-curable resin may be pre-cured before printing or may be cured simultaneous to the laying of print layer 250.
- Rho 162 TS roll-to-toll flatbed UV inkjet printer (available from Durst Phototechnik Digital Technology GmbH, Lienz, Austria).
- the Rho 162 is available as a roll-to-roll or flatbed inkjet printer designed specifically to apply UV-curable inks available from 3M Company ( Saint Paul, Minnesota, USA).
- Useful materials for preparing print layer 250 include any print materials (e.g., inks) that are suitable to the technical and aesthetic effects of the desired end use of the filmless decal.
- 3M 8800 series UV curable inks may be especially useful.
- Such inks which may dual cure in the Rho 162 in one single step with the UV-curable adhesive layer.
- This ink was specifically designed as part of the 3MTMMCS (Matched Component System) for application using the Rho 161 or Rho 162 printer.
- print layer 250 is on at least a portion of adhesive layer 230
- the print layer may completely cover adhesive layer 230 or may cover only a portion of adhesive layer 230.
- the choice here will generally depend on considerations such as the weight of the filmless decal, the thickness of the filmless decal, the aesthetic design to be imparted by the filmless decal, or any combination of these factors.
- print layer 250 does not completely cover adhesive layer 230
- adhesive layer 230 is optically clear.
- adhesive layer 230 may be chosen (or, e.g., pigments or other additives may be provided) such that the adhesive that is not covered by print layer 250 demonstrates a desired optical characteristic (e.g., a desired color, finish, or the like).
- print layer 250 may stop before the edge of adhesive layer 230, in order to provide a stepped changed in height of the filmless decal, where transition area 2a shows a more gradual ridge profile, thus minimizing the aerodynamic and aesthetic effects of the ridge itself.
- transition area 2a shows a more gradual ridge profile, thus minimizing the aerodynamic and aesthetic effects of the ridge itself.
- print layer 250 extends all the way to the edge of adhesive layer 230, as shown in Figure 2.
- ridge height h2 is generally smaller than ridge height hi, providing for a smoother transition provided by the filmless decal, better aesthetics, and potentially better aerodynamics.
- the smoothness of the transition is a property determined by both ridge height h2 and the distance over which the ridge height is achieved, indicated by ridge depth 12
- filmless decal 200 may be applied to substrate 220. Again, for the sake of simplicity in visualizing filmless decal 200 in use, it is shown in Figure 2 on substrate 220, but to be clear, substrate 220 is not itself part of filmless decal 200. Suitable materials for substrate 220 include, but are not limited to filled polymer composites (e.g., carbon fiber composites, glass fiber filled composites), metals (e.g., aluminum and aluminum alloys, steel, and titanium).
- filled polymer composites e.g., carbon fiber composites, glass fiber filled composites
- metals e.g., aluminum and aluminum alloys, steel, and titanium.
- substrates for filmless decal 200 may be chosen according to the desired end use application. For instance, while it is discussed herein to use such filmless decals for bicycle frame customization, they may also be used for the customization of car or bike tire rims, to apply to the outside of metal or sheet molded composite industrial equipment such as air compressors or other metal powder coated materials.
- sheet molded compounds and other plastic compounds e.g., ABS, especially as used in industrial and/farm equipment
- sheet molded compounds and other plastic compounds tends to outgas. This can result, when a calendared film or laminate film is applied, to forming bubbles which can affect the aesthetics of the films and/or cause adhesive failure.
- filmless decals described herein may allow outgassing.
- articles of the present invention may further include topcoat layer 260 covering at least a portion of filmless decal 200, at least a portion of substrate 220, and at least a portion of transition area 2a.
- Suitable materials for topcoat layer 260 include, but are not limited to polyurethane materials, powder coating materials, and epoxy enamels.
- decals When decals generally are applied used outside (e.g., in industrial and/or agricultural applications) weathering can occur, especially when there is not a topcoat on a decal (which topcoats are often avoided if the decal is too thick, such as with a film containing decal). Further, because vibration and/or shear forces, prior art decals can be sheared off or damaged. In contrast, the combination of a smooth profile and the use of a topcoat, as described in some embodiments of this application, can provide for a more robust decal solution that does not suffer the same weathering and/or damage in use as film containing decals.
- Stepped ridge filmless decal 300 comprises adhesive layer 330 having a thickness of from 5 to 30 microns, and print layer 350 on at least a portion of adhesive layer 330.
- adhesives useful in adhesive layer 330 are the same as those described above with regard to adhesive layer 230.
- Print layer 350 may be provided by any printer capable of printing onto the adhesive layer 330.
- a UV-curable resin may be pre-cured before printing, or may be cured simultaneous to the laying of print layer 350.
- Rho 162 TS roll-to-toll flatbed UV inkjet printer (available from Durst Phototechnik Digital Technology GmbH, Lienz, Austria).
- the Rho 162 is available as a roll-to-roll or flatbed inkjet printer designed specifically to apply UV-curable inks available from 3M Company ( Saint Paul, Minnesota, USA).
- Useful materials for preparing print layer 350 include any print materials (e.g., inks) that are suitable to the technical and aesthetic effects of the desired end use of the filmless decal.
- 3M 8800 series UV curable inks may be especially useful.
- Such inks which may dual cure in the Rho 162 in one single step with the UV-curable adhesive layer.
- This ink was specifically designed as part of the 3MTMMCS (Matched Component System) for application using the Rho 161 or Rho 162 printer.
- print layer 350 when it is explained that print layer 350 is on at least a portion of adhesive layer 330, it may be that the print layer covers only a portion of adhesive layer 330.
- print layer 350 may stop, as shown, other than at the edge of adhesive layer 330, to provide a stepped changed in height of the filmless decal. This effect is shown in more detail in transition area 3a (indicating a more gradual ridge profile, thus minimizing the aerodynamic and aesthetic effects of the ridge itself).
- ridge height h3 may be substantially the same as ridge height h2, there is provided yet an even smoother transition by the filmless decal on substrate 320, because substantially the same height is covered over a larger ridge depth 13.
- This smoother transition effect may lead, for instance, to better aesthetics, and potentially better aerodynamics. Furthermore, it may make such filmless decals more robust and less prone to accidental damage when the surface of substrate 320 is washed (e.g., power washed), scraped, abraded, impacted, sand blasted, or otherwise disturbed.
- adhesive layer 330 may be visible (especially where a clear topcoat layer is used).
- adhesive layer 330 is optically clear.
- adhesive layer 330 may be chosen (or, e.g., pigments or other additives may be provided) such that the adhesive that is not covered by print layer 350 demonstrates a desired optical characteristic (e.g., a desired color, finish, or the like). More specifically, such a stepped profile design may take advantage of adhesive layer 330 to provide an outline of the decal, accentuating print layer 350, and possibly providing aesthetically pleasing contrast to the design (in addition to the more gradual ridge profile).
- stepped ridge filmless decal 300 may be applied to substrate 320.
- suitable materials for substrate 320 include, but are not limited to filled polymer composites (e.g., carbon fiber composites, glass fiber filled composites), metals (e.g., aluminum and aluminum alloys, steel, and titanium).
- substrates for filmless decal 300 may be chosen according to the desired end use application. For instance, while it is discussed herein to use such filmless decals for bicycle frame customization, they may also be used for the customization of car or bike tire rims, to apply to the outside of metal or sheet molded composite industrial equipment such as air compressors or other metal powder coated materials.
- sheet molded compounds and other plastic compounds e.g., ABS, especially as used in industrial and/farm equipment
- sheet molded compounds and other plastic compounds tends to outgas. This can result, when a calendared film or laminate film is applied, to forming bubbles which can affect the aesthetics of the films and/or cause adhesive failure.
- filmless decals described herein may allow outgassing.
- articles of the present invention may further include topcoat layer 360 covering at least a portion of stepped ridge filmless decal 300, at least a portion of substrate 320, and at least a portion of transition area 3a.
- Suitable materials for topcoat layer 360 include, but are not limited to polyurethane materials, powder coating materials, and epoxy enamels.
- topcoat layer When decals generally are applied with a topcoat layer and used outside (e.g., in industrial and/or agricultural applications) weathering can occur, especially when there is not a topcoat on a decal (which topcoats are often avoided if the decal is too thick, such as with a film containing decal). Further, because vibration and/or shear forces, prior art decals can be sheared off or damaged. In contrast, the combination of a smooth profile and the use of a topcoat, as described in some embodiments of this application, can provide for a more robust decal solution that does not suffer the same weathering and/or damage in use as film containing decals.
- step 405 to apply an adhesive layer to a carrier layer.
- step 410 indicates an optional step of curing of a UV-curable adhesive layer to give a UV-cured adhesive layer (when such adhesives are used).
- a print layer may be applied to at least a portion of the adhesive layer per step 420.
- one may optionally apply a transfer tape to the resulting filmless decal in step 425 and remove carrier layer 430.
- the resulting filmless decal with a transfer tape instead of the initial carrier layer may then optionally be applied to a substrate surface per step 435, and the optional transfer layer removed, if present, in step 437.
- the process may include optionally applying a topcoat layer per step 440.
- UV-curable adhesive layer when it is discussed to cure a UV-curable adhesive layer or a UV-cured adhesive layer is discussed, it is understood that at least the surface upon which the print layer is applied is cured. Curing may extend more or less into the adhesive layer, but complete curing does not extent all the way to the surface opposite the print layer, as such curing (or at least complete curing) would reduce the adhesive capacity of the adhesive layer when applied, for instance, to a substrate. Such UV curing may take place well before the print layer is applied to the UV-cured adhesive layer, or may take place essentially simultaneous to applying the print layer to the newly UV-cured adhesive layer.
- FIG. 5a A more specific example of manufacturing of a filmless decal is shown in Figures 5a to 5g.
- optional carrier layer 510 with adhesive layer 530 disposed thereon.
- step 5b to at least a portion of adhesive layer 530 is applied print layer 550.
- step 5c transfer layer 570 is added to the face of print layer 550 that is opposite adhesive layer 530.
- optional carrier layer 510 is then removed to expose the surface of adhesive layer 530 opposite print layer 550.
- step 5e the entire assembly may be applied to substrate 520 by making contact between the exposed surface of adhesive layer 530 and substrate 520.
- transfer layer 570 can be removed, and in step 5g, topcoat layer 560 may be applied.
- Embodiment 1 A filmless decal comprising an adhesive layer having a thickness of from 5 to 30 microns and a print layer on at least a portion of the adhesive layer.
- Embodiment 2 The filmless decal of embodiment 1, wherein the adhesive layer comprises a UV-cured adhesive layer.
- Embodiment 3 The filmless decal of embodiment 2, wherein the UV-cured adhesive layer has a thickness of from 5 to 20 microns.
- Embodiment 4 The filmless decal of any of embodiments 2 to 3, wherein the UV-cured adhesive layer comprises an adhesive selected from the group consisting of an acrylate and an epoxy.
- Embodiment 5 The filmless decal of any of the embodiments 2 to 4, wherein the adhesive is an acrylate.
- Embodiment 6 The filmless decal of any of embodiments 2 to 5, wherein the UV-cured adhesive layer and the print layer define a first height, and the first height is less than 50 microns.
- Embodiment 7 The filmless decal of any of embodiments 2 to 6, wherein the first height is less than 30 microns.
- Embodiment 8 The filmless decal of embodiment 1, wherein the adhesive layer comprises a pressure sensitive adhesive.
- Embodiment 9 The filmless decal of embodiment 8, wherein the pressure sensitive adhesive is selected from the group consisting of a rubber-based elastomeric material, and an acrylate material.
- Embodiment 10 The filmless decal of embodiment 9, wherein the rubber-based elastomeric material is selected from the group consisting of natural rubbers, synthetic rubbers, thermoplastic elastomeric materials, non-thermoplastic elastomeric materials, thermoplastic hydrocarbon elastomeric materials, non-thermoplastic hydrocarbon elastomeric materials, and any combinations or mixtures thereof.
- Embodiment 11 An article comprising a substrate and the filmless decal of any of the preceding embodiments.
- Embodiment 12 The article according to embodiment 11, wherein the filmless decal has an edge, and the edge of the filmless decal and the substrate define a transition area.
- Embodiment 13 The article according to embodiment 12, further comprising a topcoat layer covering at least a portion of the filmless decal, at least a portion of the substrate, and at least a portion of the transition area.
- Embodiment 14 The article according to any of embodiments 11 to 13, wherein the substrate is selected from a metal and a polymer composite.
- Embodiment 15 A process for making a filmless decal, the process comprising:
- Embodiment 16 The process according to embodiment 15, further comprising applying the adhesive layer onto a carrier layer.
- Embodiment 17 The process according to any one of embodiments 15 to 16, further comprising applying the filmless decal onto a substrate surface.
- Embodiment 18 The process according to embodiment 17, wherein the substrate surface is curved.
- Embodiment 19 The process according to any one of embodiments 17 to 18, wherein the filmless decal has an edge, and the edge of the filmless decal and the substrate surface define a transition area.
- Embodiment 20 The process according to embodiment 19, further comprising applying a topcoat layer covering at least a portion of the filmless decal, at least a portion of the substrate surface, and at least a portion of the transition area.
- Transfer tape 467MP on a release liner was printed with various colors using a DEIRST Rho 162 ETV-printer (Durst) (using 3M ETV 8800 series inks).
- Application tape was printed with various colors using a DEIRST Rho 162 ETV-printer (Durst) (using 3M ETV 8800 series inks).
- SCPS100 was then applied to the printed transfer tape 467MP and adhered to an ALET36 Q Panel.
- the printed layer was measured as 50 pm.
- ETV-curable pressure sensitive adhesive 7555T PCA (3M Company) was applied to a liner material using a K-bar.
- the adhesive had a thickness of 6 pm.
- the adhesive was then cured using a UV-lamp of 400 W having an energy dose of 0.8 mJ/cm 2 .
- the adhesive was laminated with a release liner (silicone coated release liner available under the tradename Akrosil from Mondi Akrosil, Pleasant Prarie, Wisconsin, ETSA) for further handling.
- a release liner silicone coated release liner available under the tradename Akrosil from Mondi Akrosil, Pleasant Prarie, Wisconsin, ETSA
- a print layer was applied using a DURST Rho 162 UV-printer. This printed adhesive was then transferred with the aid of application tape SCPS100 onto an ALU36 Q panel. The resulting panel had a print layer of 16pm and an adhesive of 6pm for a total layer thickness of 22 pm.
- a filmless decal was prepared as described in Example 2. Instead of transferring the filmless decal to an ALU36 Q panel, the filmless decal of Example 3 was transferred onto a carbon treated bike frame substrate. Application tape SCPS100 was also used for this transfer. The filmless decal demonstrated good adhesion to the substrate.
- PSA 1 was prepared by adding, to a 1 liter jar and dissolving overnight until a clear amber and uniform solution was obtained, the materials of Table 2.
- Example 5 In a next step, a filmless decal prepared as described in Example 4, having a titanium dioxide loading of 120 phr and coated onto a siliconized liner, was printed with a Roland Versa ETV Print & Cut LEC-330 using a master profile with 250% ink CMYK. The film adhesion properties to an aluminum substrate were tested before and after printing. The results of 180° peel strength testing on an aluminum substrate with and without primer, and with all samples reinforced with IJ180LE print film, are shown in Table 4. Times given are the waiting time, in hours, between the time of adhesion to the substrate and the time of testing. The temperatures are the temperatures (in C) at which the samples were held during the times given. Peel strengths are given in Newtons per inch.
- Example 6 In a next step, a filmless decal prepared as described in Example 4, having a titanium dioxide loading of 120 phr and coated onto a siliconized liner was printed with a Roland Versa ETV Print & Cut LEC-330 using a master profile with 250% ink CMYK was analyzed against an identical unprinted film. Film shrinkage in cross-web and down-web (CW and DW, respectively) direction under printed and unprinted conditions was tested as summarized in Table 5. Times given are the waiting time, in hours, between the time of adhesion to the substrate and the time of testing. The samples were held at 70 °C during the times given. Shrinkage is given in millimeters. The shrinkage reported is the average of CW and DW measurements.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US201862659920P | 2018-04-19 | 2018-04-19 | |
US201962823485P | 2019-03-25 | 2019-03-25 | |
PCT/IB2019/053277 WO2019202570A1 (fr) | 2018-04-19 | 2019-04-19 | Décalcomanie sans film |
Publications (1)
Publication Number | Publication Date |
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EP3781633A1 true EP3781633A1 (fr) | 2021-02-24 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP19730919.8A Withdrawn EP3781633A1 (fr) | 2018-04-19 | 2019-04-19 | Décalcomanie sans film |
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EP (1) | EP3781633A1 (fr) |
CN (1) | CN112004897A (fr) |
WO (1) | WO2019202570A1 (fr) |
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WO2022259852A1 (fr) * | 2021-06-08 | 2022-12-15 | 日東電工株式会社 | Feuille adhésive pour jantes de bicyclette |
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JP2006299019A (ja) * | 2005-04-18 | 2006-11-02 | Three M Innovative Properties Co | 支持基材を有しない紫外線硬化型粘着テープまたはフィルム |
JP5305595B2 (ja) * | 2007-01-10 | 2013-10-02 | 日東電工株式会社 | 熱接着シート |
CN103740298A (zh) * | 2012-04-06 | 2014-04-23 | 上海加富橡胶制品有限公司 | 在橡胶制品中附加标识的方法及不干胶在轮胎制造中的用途 |
EP2746043A1 (fr) * | 2012-12-20 | 2014-06-25 | 3M Innovative Properties Company | Matériau stratifié à double fonctionnalité |
-
2019
- 2019-04-19 WO PCT/IB2019/053277 patent/WO2019202570A1/fr active Application Filing
- 2019-04-19 CN CN201980026562.4A patent/CN112004897A/zh active Pending
- 2019-04-19 EP EP19730919.8A patent/EP3781633A1/fr not_active Withdrawn
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CN112004897A (zh) | 2020-11-27 |
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