self-measured continuous process to form a multilayer film comprising at least two overlapping polym

专利摘要:
continuous self-measured process to form a multilayer film comprising at least two overlapping polymeric layers and multilayer film is presented a continuous and self-measured method for forming a multilayer film comprising at least two overlapping polymeric layers, and comprising the steps of : provide a substrate; providing two or more coating knives which are moved, independently of each other, from said substrate to form a normal gap on the substrate surface; move the substrate in relation to the coating knives in a downstream direction, supply liquid curable precursors of the polymers on the upstream side of the coating knives, thereby coating the two or more precursors through the respective spans as overlapping layers on the substrate ; optionally supplying one or more solid films and applying them essentially simultaneously to the formation of the adjacent lower polymeric layer and curing the precursor of the multilayer film that was obtained in this way; a lower layer of a curable liquid precursor being covered by an adjacent upper layer of a liquid precursor or a film, respectively, and essentially without exposing said lower layer of a curable liquid precursor.
公开号:BR112012018982B1
申请号:R112012018982
申请日:2011-01-27
公开日:2020-02-04
发明作者:Kuehneweg Bernd；Hitschamn Guido；D Forster Jan；Traser Steffen
申请人:3M Innovative Properties Co；
IPC主号:

专利说明:

“CONTINUOUS SELF-MEASURED PROCESS TO FORM A MULTILAYER FILM THAT UNDERSTANDS AT LEAST TWO OVERLAYED POLYMERIC LAYERS AND MULTILAYER FILM”
Description [001] The present description relates to a continuous process of forming a multilayer film that comprises at least two overlapping polymer layers. The present description also relates to a multilayer film which can be obtained by the process of the present description and which has advantageous optical properties and, in particular, a high transmission of visible light. The present description also relates to multilayer films in which the top layer comprises a polyurethane polymer and the bottom layer comprises a pressure sensitive adhesive based on (meth) acrylate.
Background [002] The properties of multilayer films can be altered widely by modifying, for example, the composition of layers, the sequence of layers in the multilayer film or the respective thickness of the layers. Multilayer films can therefore be customized for a wide variety of applications in different technical areas.
[003] Multilayer films can be obtained, for example, by laminating the corresponding single layer films using conventional lamination equipment. The resulting multilayer films tend to be separated into sheets, however, at the interfaces between the laminated layers when subjected to detachment and / or shear forces, specifically at elevated temperatures.
[004] US 4,818,610 (Zimmerman et al.) Features a pressure-sensitive adhesive tape comprising a plurality of overlapping layers in which at least one outer layer is a pressure-sensitive adhesive layer.
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2/100
US '610 adhesive tapes are prepared by sequentially applying liquid compositions, each comprising at least one photopolymerizable monomer, on a substrate. A lining can be attached to the top layer, and the plurality of overlapping layers is cured by subjecting them to irradiation in order to provide the adhesive tape. The method of making the adhesive tape is illustrated in the figures of US '610 which shows that the coating compositions form "rolling microspheres or banks" on the front of the coating knives or coating contact line formed by a pair of cylinders, respectively . The sequence of the overlapping layers obtained by the method according to US '610 can be distorted by the physical mixing that occurs between the layers.
[005] Sequential coating methods are also presented in JP 2001 / 187,362-A (Takashi et al.) And JP 2003 / 001,648-A (Takashi et al.).
[006] US 4,894,259 (Kuller) presents a process for the production of unified pressure-sensitive adhesive tape where a plurality of overlapping layers is simultaneously applied in a low-adhesion carrier by means of a coextrusion matrix with multiple pipes. The overlapping layers are subsequently subjected to irradiation in order to provide an adhesive tape. Figure 1 of US '259 illustrates the so-called “open face” light-curing process where the uppermost exposed layer is not covered with a removable UV-transparent strip during the irradiation step, so the irradiation step needs to be conducted in an inert atmosphere. It is also shown in US '259 that the light-curing coating is covered with a plastic film that is transparent to UV radiation so that overlapping layers can be irradiated through such a film in the air.
[007] The US '259 die coating method is more complicated and expensive compared to the US 4,818,610 knife coating method. At
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3/100 coating compositions need to be pumped through the matrix. According to SF Kistler and PM Schweizer [ed.], Liquid Film Coating, London 1997, Chapmann & Hall, p.9, matrix coating of the right column is called a pre-measured coating process “in which the amount of liquid applied to the mat per unit area is predetermined by an upstream fluid measuring device, such as the precision gear pump, and the remaining task of the coating device is to distribute that amount as evenly as possible in both directions, below and of the blanket ”. The pump provides an essentially constant volume flow that together with the velocity below the US ‘259 low adhesion support blanket mainly defines the thickness of the coating layer. The pre-measured matrix coating processes have several limitations. The pump introduces kinetic energy into the coating layers which should create a non-laminar flow pattern resulting in a high amplitude of physical mixing between variations in layer or thickness. Depending on the type of pump used, the volume flow may exhibit oscillations or other variations that translate, for example, in thickness variations or other lack of homogeneity of the coating layers. The geometry of the matrix piping needs to be adjusted to the flow behavior of the coating compositions so that a specific matrix may not be usable in a flexible manner for various coating processes. In US '259, the UV-transparent plastic film is attached to the top layer subsequent to the matrix coating step (ie, on the outside of the matrix) which results, for example, in the compacting of the multilayer film or the inclusion of bubbles of air between the plastic film or the top layer due to tolerances that are present in any technical process. It is not possible to place plastic film or any other film, such as a removable strip, in a non-intrusive way, in the multilayer stack of layers
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4/100 precursors so that a film fits tightly to the exposed surface of the top layer of the multilayer stack. Compression of the multilayer stack introduces, for example, variations in thickness or other lack of homogeneity in the multilayer stack. The liquid precursor can, for example, form a rolling microsphere in the longitudinal position in the downstream direction where the lining compresses the pile which can introduce turbulence in the multilayer pile which ultimately leads to the mixing of the layers. Leaving empty spaces between the film and the exposed top surface allows oxygen to access the top layer surface, which can inhibit precursor healing. It is also generally observed that in this case the surface of the top layer is less smooth, that is, it has a greater surface roughness Ra compared to a situation where the film is compressing the multilayer stack. Also, the formation of air bubbles is observed in the top layer.
[008] Pre-measured matrix coating processes for multilayer films are also presented, for example, in EP 0.808.220 (Leonard), US 5,962,075 (Sartor et al.), US 5,728,430 (Sartor et al. .), EP 1,538,262 (Morita et al.) And DE 101 30 680. US 2004 / 0.022.954 discloses a pre-measured coating process in which the coating layers are first superimposed before being transferred together to the substrate moving blanket. A coating process is disclosed in US 4,143,190.
[009] WO 01 / 89.673-A (Hools) presents a process of forming porous multilayer membranes in which two or more solutions of a polymer are formed on a support. The overlapping layers are then immersed in a coagulation solution to effect phase separation followed by drying to form a porous membrane. Coagulation occurs from the surface of a liquid film that first makes contact with the coagulation solution, with subsequent diffusion of the coagulant through the layers of
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5/100 multilayer liquid blade. The diffusion and coagulation process results in mixing at the interfaces between the overlapping layers.
Summary [0010] The present description provides a continuous, stable and low cost process for forming a multilayer film that comprises at least two overlapping polymer layers that do not have the limitations of state-of-the-art processes or only have them in mind. a lesser extent, respectively. The present description also provides a method of forming a multilayer film that is versatile and flexible and allows for easy fabrication of complex structures, comprising at least two layers of polymer. The present description also provides a multilayer film that optionally includes an additional layer that was initially included as a solid film in the curable precursor of the multilayer film. In addition, the present description presents multilayer films with advantageous optical properties as assessed, for example, by the extent of visible light transmission through the multilayer film.
[0011] Other objectives of the present description will be apparent to the person skilled in the art in the detailed description of the description provided below.
[0012] The present description refers to a continuous, self-measuring process of forming multilayer film that comprises at least two overlapping polymer layers, comprising the steps of:
(i) providing a substrate;
(ii) providing two or more coating knives that are moved, independently of each other, from said substrate to form a normal gap on the surface of the substrate;
(iii) moving the substrate in relation to the coating knives in a downstream direction, (iv) providing liquid polymer curable precursors to the surfaces to be
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6/100 upstream of the coating knives in this way by applying two or more precursors through the respective spans as overlapping layers on the substrate;
(v) optionally supplying one or more solid films and applying them essentially simultaneously to the formation of an adjacent lower polymer layer, and (vi) curing the precursor of the multilayer film that was obtained in this way;
a lower layer of a curable precursor liquid being covered by an adjacent upper layer of a curable precursor liquid or a solid film, respectively, and essentially without exposing said lower layer of a curable precursor liquid.
[0013] The present description also refers to a multilayer film that is obtained by the above method in which a removable strip that is fixed in step (v) of said method to the exposed surface of the top layer of the precursor of the multilayer film essentially simultaneously with the formation of such a top layer. These multilayer films are preferably light transmitters and comprise at least two overlapping polymer layers each having at least 80% transmission over the visible light through which the light transmission of such multilayer film is greater than transmitting a comparative multilayer film obtained by a method other than the above method in which the removable strip is attached to the exposed surface of the top layer surface in a position downstream of the formation of the top layer of the precursor of the multilayer film. The ratio between the transmission of the said multilayer film of the description and the transmission of the comparative multilayer film is preferably at least 1.002.
[0014] The present description also relates to a light-transmitting multilayer film comprising at least two layers of overlapping polymers, one of the outer layers comprising a polyurethane polymer obtained from the polymerization of a liquid precursor comprising fur
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7/100 minus an ethylenically unsaturated urethane compound and the other opposite outer layer comprises an adhesive, the multilayer film having a maximum wavefront aberration of a wavefront resulting from a flat wavefront of a length wave of λ = 635 nm that normally falls on the outer layer opposite the outer adhesive layer and transmitted through the multilayer film measured as the peak-to-valley value of the transmitted wavefront, less than 6 λ (= 3,810 nm). At least two layers of polymer superimposed, each preferably has a transmission of at least 80% in relation to visible light. The adhesive is preferably a pressure sensitive adhesive based on (meth) acrylate.
[0015] The present description preferably relates to an assembly comprising a light-transmitting multilayer film obtained by the above method and a glassy substrate, the multilayer film comprising at least two overlapping polymer layers, each having a transmission of at least 80% in relation to visible light, one of the outer layers of the multilayer film being an adhesive layer through which the multilayer is fixed to the vitreous substrate and the refractive index of the external adhesive layer is lower than refractive index of the opposite outer layer of the multilayer film. In a preferred embodiment, the difference between the refractive indices of the adhesive layer and the opposite outer layer is less than 0.030.
Description of the Figures [0016] Figure 1 is a schematic representation of a useful coating apparatus of the present description.
[0017] Figures 2a and 2b are schematic cross-sectional views of a coating knife that can be used in the present description.
[0018] Figure 3 is a schematic representation of the method of measuring the aberration of a wavefront resulting from a plane wavefront that
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8/100 is normally applied to the top surface of a multilayer film and transmitted through a multilayer film.
[0019] Figure 4 is a cross-sectional microphotography of a multilayer film prepared according to Example 2 below.
[0020] Figure 5 is a cross-sectional micrograph of the multilayer film prepared according to Example 5 below.
[0021] Figure 6 is a cross-sectional micrograph of the multilayer film prepared according to Example 11 below.
[0022] Figures 7a and 7b are microphotographs in cross section of the multilayer film prepared according to Example 12 below taken at different magnifications.
[0023] Figure 8 is a cross-sectional micrograph of the multilayer film prepared according to Example 13.
[0024] Figures 9a to 9i represent images from the Siemens Star test for a glass plate reference, the multilayer film from Example 22, the films from comparative examples 1a to 1c, the multilayer films from Examples 23 and 24, and the films comparative examples 2a and 2b.
[0025] Figure 10 is a schematic representation of a coating apparatus used in Example 24.
Detailed Description [0026] In the continuous and self-measured coating process of the present description, two or more liquid curable precursors of polymeric materials are applied as a coating on a substrate and cured to provide a multilayer film comprising at least two overlapping polymer layers .
[0027] The overlapping term as used above and below means that two or more of the layers of the liquid polymer precursors or the polymer layers of the multilayer film, respectively, are arranged on top of each
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9/100 one. The superimposed liquid precursor layers can be arranged directly next to each other so that the upper surface of the lower layer is in contiguity with the lower surface of the upper layer. In another arrangement, the overlapping liquid precursor layers are not in contiguity with each other but are separated from one another by one or more liquid precursor layers and / or one or more solid films or blankets.
[0028] The adjacent term as used above and below refers to two overlapping layers within the precursor multilayer film or cured multilayer film that are arranged directly next to each other, that is, which are in contiguity with each other.
[0029] The terms top and bottom layers, respectively, are used above and below to indicate the position of the liquid precursor layer in relation to the substrate surface that supports the precursor layer in the process of forming a multilayer film. The precursor layer disposed close to the substrate surface is called the bottom layer while the precursor layer disposed more distantly from the substrate surface in the normal direction to the substrate surface is called the top layer. It should be noted that the terms top and bottom layers used above and below in conjunction with the description of the method of making multilayer films do not have a clear meaning in relation to multilayer films as such. The term bottom layer is clearly defined in relation to the method of the present description as the layer adjacent to the substrate of the coating apparatus. Likewise, the outer layer of the multilayer film precursor which is opposite the bottom layer and which is applied last during the method, is clearly alluded to above and below as a top layer. Contrary to this, when reference to the cured multilayer film is made as such, its two opposite outermost layers are named above and below, for reasons of clarity, as outer layers.
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10/100 [0030] The overlapping and adjacent terms also apply to cured polymer layers and cured multilayer film, respectively.
[0031] The term precursor, as used above and below, indicates the material from which the polymers of the polymer layers corresponding to the multilayer film can be obtained by curing. The term precursor is also used to denote the stack of layers comprising at least two layers of liquid precursors from which the multilayer film of the present description can be obtained by curing. Curing can be carried out by curing with actinic radiation such as UV, γ (gamma) or with electronic beam radiation or thermal curing.
[0032] The process of the present description employs a substrate on which the two or more layers of the liquid precursors are coated, and two or more coating knives that are moved independently of each other from the surface of the substrate that receives the precursor from the multilayer film to form normal spans on the substrate surface.
[0033] The direction in which the substrate is moving is called up and down as the downstream direction. The upstream and downstream terms describe the longitudinal position to the extent of the substrate. A second coating knife that is disposed in a downstream position with respect to a first coating knife is also referred to above and below in an abbreviation manner as a downstream coating knife in relation to the first (upstream) coating knife.
[0034] The coating knives useful in the present description each have an upstream side (or surface), a downstream side (or surface) and a lower portion facing the substrate surface receiving the precursor of the multilayer film. The span is measured as the minimum distance between the bottom portion of the coating knives and the exposed surface of the substrate. The span can be essentially uniform in the transverse direction (that is, in the direction normal to the direction
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11/100 downstream) or can vary continuously or discontinuously in the transverse direction, respectively.
[0035] The cross-sectional profile of the lower portion of the coating knife in the longitudinal direction is designed so that the precursor layer is formed and the excess precursor is eliminated. Such a cross-sectional profile can vary widely and can, for example, be essentially flat, curved, concave or convex. The profile can be sharp or square, or it can have a small radius of curvature providing a so-called toroidal profile. A hook type profile can be used to prevent suspension of the rear edge of the precursor layer at the edge of the knife. A coating knife that has a toroidal profile or a radius profile is shown, for example, in Figures 2a and 2b.
[0036] The coating knives can be arranged essentially in the normal position on the surface of the blanket, or they can be inclined so that the angle between the blanket and the surface downstream of the coating knife is preferably between 50 ° and 130 ° and more preferably between 80 ° and 100 °.
[0037] The bottom portion of the coating knife is preferably selected to extend at least transversely to the desired width of the coating in a direction essentially normal to the downstream direction. The coating knife is preferably arranged opposite a cylinder so that the substrate passes between the edge extending transversely of the coating knife and the cylinder. Therefore, the substrate is supported by the cylinder so that the substrate is not hanging in the normal position in the downstream direction. In this arrangement, the gap between the coating knife and the substrate surface can be precisely adjusted. If the coating knife is used in an unsupported arrangement, the substrate is held in place by its own tension but may be falling to a certain degree in the normal position in the downstream direction. The flaccidity of the substrate can be minimized by tidying the coating knife in relation to a range
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12/100 short of the substrate between adjacent cylinders. If a continuous substrate is used, sagging can be further minimized by guiding it in relation to an endless conveyor belt. Another option to avoid / minimize sagging is to guide the substrate in relation to the rigid surface.
[0038] The useful coating knives of the present description are solid, and they can be rigid or flexible. They are. preferably. produced from metals, polymeric materials, glass or similar. The flexible coating knives are relatively thin and preferably between 0.1 and 0.75 mm thick in the downstream direction and are preferably produced from flexible steel, such as stainless steel or nascent steel. Rigid coating knives can be made of polymeric or metallic materials, and are generally at least 1 millimeter, preferably at least 3 millimeters thick. A coating knife can also be provided by a continuously supplied polymer film that is tensioned and appropriately reflected by cylinders, bars, rods, beams, or the like to provide a coating edge that extends transversely towards the substrate. It is desired that the polymer film can be used simultaneously as a removable strip or as a solid film incorporated in the precursor of the multilayer film.
[0039] In the present description, the lower layer of a curable liquid precursor (i.e., any layer other than the top layer) is coated with an adjacent upper layer of a curable liquid precursor or a solid film, respectively, essentially from its beginning. . Therefore, the lower curable liquid precursor layer is directly covered by an adjacent upper layer of a curable liquid precursor layer or by the solid film, respectively, and essentially without exposing said lower liquid precursor layer. A solid film is preferably applied longitudinally to the upstream side of the coating knife which also provides the bottom layer of a
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13/100 curable liquid precursor. The film is therefore attached to the upper surface of the lower layer essentially during the formation of said layer and the lower layer is not exposed. The direct deposition of an upper layer of a curable liquid precursor on the upper surface of said lower layer without exposing such an upper surface of the lower layer, can be completed by properly arranging the two coating knives that form the two layers. In one embodiment, liquid precursors are applied using two coating stations that are in contiguity with each other in the downstream direction through which the walls at the rear of the coating chambers comprise or form, respectively, the knives. coating. The lower layer when formed by the corresponding coating knife is therefore directly covered with a curable liquid precursor to the upper layer contained in the corresponding coating chamber. In general, the coating knife forming an upper layer needs to be arranged so that the lower layer, after its formation on the corresponding coating knife, is essentially directly covered with the curable liquid precursor forming the top layer.
[0040] In another embodiment, a solid film, in particular a removable strip, is applied to the exposed surface of the top layer in an essentially simultaneous manner with the formation of such top layer. The solid film can be applied, for example, longitudinally to the surface upstream of the coating knife further downstream (i.e., the rear wall) of the coating apparatus. In this embodiment, the solid film is uniformly fixed to the exposed surface of the top layer in a tight fit, thereby avoiding compaction of the top layer or the multilayer stack, respectively, or the inclusion of air between the solid film and the exposed surface of the top layer.
[0041] Although the present inventors do not wish to be linked to such a theory, it is speculated that the deposition above a solid film or the precursor
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14/100 liquid forming the adjacent upper layer, respectively, in the lower liquid precursor layer, essentially simultaneous to the formation of the lower layer by means of coating knives, results in multilayer films characterized by superior properties. The multilayer films of the present description have, for example, both well-defined, relatively sharp interfaces between adjacent layers or films, respectively, and a strong anchoring of adjacent layers or films so that the films of the present description typically exhibit a resistance to peeling. T (T-peel strength) greater than the corresponding films obtained by laminating the corresponding layers. The multilayer films of the present description have, in addition, superior optical properties such as a high optical transmission, a low color change and a low maximum aberration of a wavefront resulting from a flat wavefront normally occurring after its transmission through a multilayer film.
[0042] In one embodiment, the present description, the precursor of the multilayer film is obtained with the use of a coating device comprising one or more coating stations. The coating stations may comprise one or more coating chambers and, if desired, a rolling microsphere upstream to a coating chamber further upstream. Each coating chamber has an opening system towards the moving substrate below the coating chambers so that liquid precursors are applied as layers superimposed on each other. The liquid precursor of the rolling microsphere is applied, for example, across the upstream surface of the upstream coating knife.
[0043] Each coating chamber has an upstream wall and a downstream wall preferably which extends essentially transversely with respect to the downstream direction. The wall further up the device
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15/100 cladding is also called the front wall, and the wall further downstream is the back wall of the cladding device, respectively. If two or more coating chambers are present, the downstream wall of an upstream coating chamber is preferably in an arrangement that is essentially contiguous with the wall upstream of the adjacent downstream coating chamber. This means that the distance between the upstream wall of an upstream coating chamber and the upstream wall of the adjacent coating chamber is preferably less than 2.5 millimeters, more preferably less than 1 millimeter and most preferably there is no distance between these walls. In a particular embodiment, the wall downstream of an upstream coating chamber and the wall upstream of the adjacent downstream coating chamber is integrated into a wall that is referred to above and below as an intermediate wall.
[0044] Each downstream wall comprises a coating knife facing the substrate. The coating knives are arranged above the exposed surface of the substrate to which the liquid precursors are attached thereby providing for clearance between the lower portion of the coating knife facing the substrate and the exposed surface of the substrate or the exposed layer of the liquid precursor or precursors fixed previously, respectively. The distance between the lower portion of the coating knife and the surface of the substrate as measured in a direction normal to the surface of the substrate is alluded to above and below as they go. The liquid precursors are supplied from the coating chamber to the upstream side of the respective coating knife. The gap between the coating knife and the substrate surface is adjusted to regulate the thickness of the respective coating in conjunction with other parameters including, for example, the speed of the substrate in the downstream direction, the thickness normal to the substrate of the liquid precursor layers or solid films, respectively, already applied, the viscosity of the liquid precursor to
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16/100 be applied through the respective span, the viscosity of the liquid precursor (s) already applied, the type, shape and profile of the coating knife, the angle with which the coating knife is oriented in relation to the normal of the substrate, the position of the knife longitudinally to the extension of the coating device in the downstream direction and the type of substrate.
[0045] The coating knife can be a separate element attached to the respective wall downstream or it can form the wall downstream, respectively. It is also possible for one or more downstream walls to be supplied as solid films, such as release films.
[0046] The knife profile can be optimized for a specific liquid precursor supplied through a coating chamber with the use of a rotary coating knife device equipped with several coating knives having a different knife profile. The person skilled in the art can therefore quickly change the cladding knives used as back wall, front wall or intermediate walls, respectively, in the different cladding chambers and evaluate the optimal sequence of cladding knife profiles in a cladding apparatus for production. of a specific multilayer film.
[0047] If the coating apparatus useful in the present description comprises only one coating chamber, both the upstream and downstream walls of the coating chambers comprise or form coating knives, respectively. The liquid precursor can be supplied to the edge upstream of the anterior wall, for example, by means of the so-called rolling microsphere, or it can be supplied by any type of feeder tank.
[0048] If the coating apparatus of the present description comprises two or more coating chambers, the front wall may or may not form a coating knife. If the front wall does not form a cladding knife, it can be arranged so that there is essentially no gap between the extension
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17/100 transverse from the lower portion of the anterior wall facing the substrate and the exposed surface of the substrate so that a leak upstream of the liquid precursor is reduced and / or minimized. If the front wall is a coating knife, the profile of its lower portion can be formed so that an upstream leak of the liquid precursor contained in the first upstream coating chamber is inhibited. This can be achieved, for example, with the use of a profile essentially of the radius type of the edge that extends transversely from the anterior wall facing the substrate.
[0049] Each coating chamber has a downstream wall, an upstream wall and two or more side walls that essentially extend in the downstream direction, through which the downstream wall of an upstream chamber and an upstream wall of an adjacent downstream chamber can be integrated into an intermediate wall. The cross section of the coating chambers in the downstream direction can vary widely and can be, for example, square, rectangular, polygonal or evenly or irregularly curved. The downstream wall, the upstream wall and / or the side walls may be present as separate elements, but it is also possible, for example, that a coating chamber is formed as a part or that the upstream walls and the side walls, for example, they are formed as a separate part of a wall downstream of a coating knife. In general it is preferred that the downstream wall is a separate element or part so that the cladding knives representing the downstream wall can be easily replaced, for example, by means of a rotary clad knife device. If the coating apparatus comprises two or more coating chambers, their respective cross sections are preferably selected so that the adjacent coating chambers can be arranged in a configuration that is essentially contiguous in the downstream direction. The upstream and downstream walls of the coating chambers are preferably essentially
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18/100 direct in the transverse direction to the downstream direction.
[0050] The extension of the coating chamber in the downstream direction, that is, the distance between the front wall and the rear wall of the coating chamber, is preferably between 2 mm and 500 mm and more preferably between 5 and 100 mm. Although the present inventors do not wish to be linked to such a theory, it is speculated that if the distance between the anterior wall and the posterior wall is very small, the flow of the liquid precursor towards the gap tends to become unstable which results in defects undesirable coatings such as streaks or brushmarks. If the distance between the front wall and the back wall of the coating chamber is too great, the continuous flow of the liquid precursor towards the gap can break so that the continuous coating of the moving substrate can end and / or mixing can occur . The flow pattern in the coating or recess chamber is discussed in more detail in US 5,612,092, column 4, line 51 to column 5, line 56. This passage is incorporated by reference in this specification.
[0051] The volume of the coating chambers is defined by their respective parallel cross-section to the substrate surface and their respective normal height to the substrate surface. The height of the coating chamber is preferably between 10 and 1,000 millimeters and more preferably between 25 and 250 millimeters. The volume of the coating chambers is preferably selected as a function of the coating width transverse to the downstream direction.
[0052] The coating chambers can be adjusted with heating or cooling means so that the viscosity of the liquid precursors can be controlled and adjusted if necessary.
[0053] Liquid precursors are preferably applied under ambient pressure so that the volume flow of the precursors results mainly from the
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19/100 shear forces acting on the precursors as a result of the movement of the substrates and, optionally, of the films or solid blankets introduced in the precursor of the multilayer film. The volume flow of the liquid precursors is aided by the hydrostatic pressure of the precursor comprised in the respective coating chamber. It is preferred, in the method of the present description, that the force resulting from the hydrostatic pressure is low in comparison to the drag force or forces exerted by the moving substrate and, optionally, moving solid films. The height of the liquid precursor in a coating chamber is preferably controlled so that that height corresponds to at least the width of the coating chamber in the downstream direction during the entire coating process. If the height of the liquid precursor in a coating chamber is less than the width of the coating chamber in the downstream direction, partial mixing of the precursor applied through such coating chamber with an adjacent lower precursor layer may occur. The height of the liquid precursor in the respective coating chamber is preferably kept essentially constant.
[0054] It is also possible that the coating chambers are pressurized with air or an inert gas such as nitrogen or argon. The coating apparatus can be equipped so that the coating chamber can be pressurized separately and individually, which may be desirable, for example, to counteract differences in viscosity between different liquid precursors or differences in height of the liquid precursor column in coating chambers. Preferably, the coating chambers are not completely filled with the respective liquid precursor so that the liquid precursor is pressurized via a gas atmosphere disposed on top of the liquid precursor. The total excess pressure exerted on the respective liquid precursor is selected so that the process continues to operate in an auto
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20/100 measured, that is, so that there is no inverse proportionality between the wet coating thickness of a precursor layer and the speed below the substrate mat. The total excess pressure exerted on the respective liquid precursor is preferably less than 50 kPa (0.5 bar) and more preferably not more than 25 kPa (0.25 bar). In an especially preferred embodiment, excess gas pressure is not applied, i.e. the process of the present description is preferably carried out under ambient conditions.
[0055] The substrate is moved relative to the coating knives in the downstream direction to receive a sequence of two or more layers of liquid precursors that are superimposed one on top of the other in the normal direction to the downstream direction.
[0056] The substrate can be a temporary support from which the multilayer film is separated and removed after curing. When used as a temporary support, the substrate preferably has a coating release surface adapted to allow clean removal of a cured multilayer film from the substrate. It may be desirable that the substrate, when providing temporary support, remains attached to the multilayer film when it is rolled up, for example, for storage. This is, for example, the case if the bottom layer of the multilayer film is an adhesive layer like a pressure sensitive adhesive layer. The coated release substrate protects the surface of the pressure-sensitive adhesive layer, for example, from contamination and allows the multilayer film to be rolled into a cylinder. The temporary substrate will then only be removed from the multilayer film by the end user when, for example, the multilayer film is attached to a surface. In other embodiments where the surface of the first layer of the multilayer film facing the substrate does not need to be protected, the substrate providing a temporary support can be removed and rolled up after curing the precursor layers and before the
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21/100 multilayer film storage. In another embodiment, the substrate providing a temporary support can be provided by an endless conveyor, preferably having an exposed release surface. The multilayer film obtained after curing the stack layers of liquid precursors separates from an endless belt and can be rolled up, for example.
[0057] Alternatively, the substrate can be integrated as a layer in the resulting multilayer film. In such a case, the substrate is continuously fed as a film or blanket and collected as a part of the multilayer film subsequent to the curing of the liquid precursor layer. The substrate surface can preferably be subjected, for example, to a corona treatment to improve or accentuate the anchoring of the cured lower polymer layer to the substrate. The anchoring of the polymeric layer below the substrate can also be improved by applying a so-called fixation layer to the substrate surface before coating the layer of the liquid precursor layer below the substrate. Fixing layers that are suitable in the present description include, for example, the 3M 4297 primer, a polyamide-based primer commercially available from 3M Co. or the 3M 4298 primer, a primer comprising an acrylic polymer and a chlorinated polyolefin. as active substances that are commercially available from 3M Co.
[0058] Substrates that are suitable both as temporary substrates or as substrates for incorporation into the multilayer film, respectively, can be selected from a group comprising polymeric films or webs, films or metal webs, woven or nonwoven webs, webs reinforced with glass fibers, carbon fiber blankets, polymer fiber blankets or blankets comprising endless glass filaments, polymer, metal, carbon fibers and / or natural fibers. Depending on the nature of the liquid precursor applied as a lower layer on the substrate and whether the substrate is used as a temporary support or as an integral layer of the film
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22/100 multilayer, the skilled person can decide without any contribution to the invention if the substrate surface treatment is necessary or desirable. It has been discovered by the present inventors that the method of the present description is relatively insensitive to the roughness of the exposed surface of the substrate. The surface roughness can be characterized by the arithmetic mean of the surface roughness Ra which can be measured, for example, by laser profilometry. Polymeric films suitable for use in the present description can have Ra values of, for example, 1 - 20 pm or, more preferably, 1 - 10 pm, while non-woven blankets can have Ra values between 10 and 150 pm and more preferably between 15 and 100 pm. The multilayer films obtained by the method of the present description have, essentially independent of the surface roughness Ra of the substrate, a layer of lower polymer with a homogeneous thickness longitudinally with the extension of the mat in the downstream direction. The average deviation of the thickness of the lower polymer layer in the normal direction to the downstream direction is preferably in relation to an arbitrarily selected distance of 10 millimeters less than 10%, with more preference less than 5% and with special preference less than 2.5%.
[0059] If the substrate is used as a temporary support, its optionally treated release surface, facing the coating knives, is preferably essentially impermeable with respect to the liquid precursor applied to the substrate.
[0060] If the substrate forms an integral part of the multilayer film subsequent to the curing of the precursor of the multilayer film, it is also desirable that the optionally treated surface of the substrate is essentially impermeable with respect to the lower precursor layer or that the lower liquid precursor by the least do not migrate to the opposite surface of the substrate before curing, respectively. If the substrates have a certain porosity, such as
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For example, non-woven substrates or paper, it may be desirable for the liquid precursor to penetrate the surface area in the main substrate area, respectively, so that the interfacial anchoring between the polymer layer and a substrate surface is improved. . The penetration or migration behavior of the liquid precursor in relation to a given substrate can be influenced, for example, by the viscosity of the liquid precursor and / or the porosity of the substrates.
[0061] The thicknesses of the liquid precursor layers normal to the substrate are mainly influenced by the gap between the lower portion of the coating knives and the substrate surface, the respective viscosities of the liquid precursors and the downstream speed of the substrate.
[0062] The thickness of the liquid precursor layers is preferably, independently of each, between 25 pm and 3,000 pm, more preferably between 75 pm and 2,000 pm and specifically preferably between 75 pm and 1,500 pm. The desirable thickness of the coating layer depends, for example, on the nature of the liquid precursor and the resulting layer of cured polymer.
[0063] The width of the gap necessary to provide a desired value for the thickness of the precursor layer depends on several factors such as the profile of the coating knife, the angle of the coating knife normal to the substrate, the speed downstream of the substrate, the number of layers of the liquid precursors to be coated, the absolute values of the viscosities of the liquid precursors and the ratio between the absolute values of the viscosity of the specific precursor and the absolute values of viscosity of the liquid precursor present in adjacent layers. In general, the span width needs to be greater than the desired thickness of the respective liquid precursor layer regulated by such span. It is presented, for example, in Kirk-Othmer, Encyclopedia of Chemical Technolog, 4 ^ta ed., Ed. by J. Kroschwitz et al., New York, USA, 1993, vol. 6, p. 610, as a general rule, that the
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24/100 thickness of the liquid precursor layer obtained by means of a coating knife disposed to the normal of the substrate and having a lower portion that extends transversely with a square profile disposed in parallel to the substrate, is about half the width of the span for a wide range of substrate speed.
[0064] The span width is measured in each case as the minimum distance between the bottom portion of the coating knife facing the substrate and the exposed surface of the substrate. The span is preferably adjusted to a value between 50 pm and 3,000 pm and more preferably between 100 pm and 2,500 pm.
[0065] The Brookfield viscosity of liquid precursors at 25 ° C is preferably between 100 and 50,000 mPa's, more preferably between 500 and 30,000 mPa's and particularly preferred between 500 and 25,000 mPa's. If the liquid precursor comprises solid particles such as pigments or electrically conductive and / or thermal particles, the viscosity of the liquid precursor is preferably between 1,000 and 30,000 mPa's and more preferably between 3,000 and 25,000 mPa's.
[0066] It has been discovered by the present inventors that liquid precursors that have a lower Brookfield viscosity can be coated faster and in a more slender way. If the thickness of the liquid precursor layer less than 500 pm is required, the Brookfield viscosity of the liquid precursor is preferably less than 15,000 mPa's and more preferably between 500 mPa's and 12,500 mPa's.
[0067] If the viscosity of the liquid precursor is less than about 100 mPa's, the coated layer tends to become unstable and the thickness of the precursor layer can be difficult to control. If the viscosity of the liquid precursor is greater than about 50,000 mPa's, the coating of homogeneous films tends to become difficult due to high shear forces induced by high viscosity. If the
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25/100 liquid precursor comprises curable monomers and / or oligomers, the viscosity of the precursor can be increased, within the above value ranges, in a controlled manner through partial polymerization of the precursor to provide a desirable coating. Alternatively, the viscosity of the liquid precursor can be increased and adjusted by adding thixotropic agents such as pyrolyzed silica and / or polymer additions such as block copolymers (Butadiene Styrene Rubber or SBRs, Satin Vinyl Foam or EVAs, Polyvinyl Ether, Polyalphaolefins ), silicones or acrylics. The viscosity of the liquid precursor can also be reduced, for example, by increasing the amount of curable monomers and / or oligomers.
[0068] It has been found that in a stack of liquid precursor layers, the relative and / or absolute thickness of a first upper layer of a liquid precursor having a first Brookfield viscosity at 25 ° C is typically increased with increasing speed at downstream of the substrate compared to the relative and / or absolute thickness of the second layer of the liquid precursor which is adjacent to the first layer, and the precursor of which has a second Brookfield viscosity at 25 ° C which is less than that of said first precursor . The term relative thickness of a specific liquid precursor layer is defined as the ratio of the thickness of that precursor layer to the thickness of the complete stack of liquid precursor layers before curing, that is, the thickness of the precursor multilayer film.
[0069] It has also been found that the ratio between the Brookfield viscosities of the liquid precursors of an upper liquid precursor layer and an adjacent lower liquid precursor layer within a stack of precursor layers is preferably between 0.1 and 10 and more preferably between 0.2 and 7.5. It has been found that if such a ratio is outside these preferential ranges, the thickness of such liquid precursor layers may become inhomogeneous in the downstream direction.
[0070] The speed downstream of the substrate is preferably between 0.05 and
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26/100
100 m / min, more preferably between 0.5 and 50 m / min and especially preferably between 1.5 and 50 m / min. If the speed downstream of the substrate is less than 0.05 m / min, the flow of liquid precursors towards the gap becomes slow and unstable, resulting in coating defects. If the speed downstream of the substrate is greater than 100 m / min, turbulence can occur at the interfaces between precursor layers which can, depending on the viscosity and rheology of the precursors, result in uncontrolled mixing and / or coating defects.
[0071] It has been discovered by the present inventors that for the specific viscosity of the liquid precursor, the quality of the coating can deteriorate in an unacceptable manner if the speed downstream of the substrate is selected too high. The deterioration in quality can be reflected in the carrying of the air bubbles or in the occurrence of a non-uniform and irregular coating. The coating speed is preferably adapted so that all the liquid precursor layers in a pile of such layers are coated uniformly and with a high quality, that is, the layer most sensitive to speed determines the downstream speed as a whole. . If the substrate downstream speed is selected too low, a reduction in the thickness of the layer may not be attainable by reducing the corresponding span width only, but an increase in the downstream speed may also be necessary. It has also been discovered by the present inventors that the speed downstream of the substrate is preferably selected from the maximum and minimum values specified above. In such a downstream speed range, the thickness of the liquid precursor layers is relatively insensitive to variations in the downstream speed so that a thickness of the liquid precursor layer can be largely regulated by the width of the span.
[0072] The liquid precursors suitable in the present description comprise a wide range of precursors that can be cured by
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27/100 exposure to actinic radiation and, in particular, UV-radiation, gamma-radiation and electronic beam or by exposure to heat. Liquid precursors are preferably transmitters of visible light. In a preferred embodiment, the precursors used in the multilayer film of the present description are selected so that a single cured film of the precursor with a thickness of 300 pm has a transmission of at least 80% in relation to visible light (D65) as measured from according to the test method specified in the test section below. The precursor used in the multilayer films of the present description has, more preferably, when present as a single cured film with a thickness of 300 pm, a transmission of at least 90% and with special preference of at least 95%.
[0073] The light transmission of the multilayer film in relation to visible light resulting from the light transmission of the overlapping polymer layers is preferably at least 80%, more preferably at least 85% and most preferably at least 90%.
[0074] Precursors of cure, which do not include the release of condensed molecules of low molecular weight such as water or alcohol molecules or include such release only in a low amount, are usually preferred because the condensed molecules of precursor layers of non-liquid exposed may not typically be fully discharged from the multilayer film.
• the multilayer film forming method of the present description is highly versatile and allows to produce a wide range of multilayer films with customized properties.
[0075] While the present inventors do not wish to be bound by such considerations, it is speculated that the method of the present description establishes a high quality laminar flow regime that is not accessible by prior art methods.
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28/100 [0076] In contrast to the pre-measured matrix coating methods of making multilayer films that are presented in the prior art, the process of the present description is a self-measured process in which the flow of curable liquid precursors mainly results from shear forces. These are supplied by the substrate or the layers already attached to it in movement in the downstream direction thereby exercising a drag flow in the respective liquid precursors. Shear forces are also provided by the solid film or films, respectively, if present, moving initially longitudinally on the upstream side of the coating knife towards the substrate and then, after being reflected on the edge extending from the coating knife, parallel to the substrate in the downstream direction. It is believed that the volume flow resulting from these shear forces is essentially laminar and stable and that any turbulence that may occur, for example, when the formation of liquid precursor layers in the respective spans, is effectively attenuated by the essentially simultaneous application of the precursor layers. liquid and optionally solid film or films on top of each other. The essentially simultaneous application of an adjacent upper liquid precursor to a lower liquid precursor layer is preferably provided through the proper arrangement of the coating knives. The essentially simultaneous application of an adjacent upper solid film, if present, is preferably provided by guiding such film along the surface upstream of the coating knife forming the lower precursor layer.
[0077] In pre-measured matrix coating processes for the manufacture of multilayer films, the volume flow that is provided by the metering pump is equal to the flow that leaves the matrix. Therefore, such a flow is essentially constant regardless of the speed below the substrate mat so that the thickness of the precursor layer coated on the substrate or a layer
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Preceding precursor 29/100, respectively, is essentially inversely proportional to the speed below the substrate blanket. Contrary to this, in the self-measured coating process of the present description the volume flow applied through the respective coating knife to the mat is not constant but varies with the mat speed and the wet thickness of a coated precursor layer is mainly influenced by the interactions of the flow of the liquid precursor with the coating apparatus of the present description (cf. SF Kistler et al., Liquid Film Coating, loc cit., p.10, bottom left column and chapters 12 and 13). In the present description, the volume flow tends to increase with increasing speed of the mat so that there is no inverse proportional relationship between the thickness of the wet film and the speed below the substrate mat. The self-measured process of the present description is further characterized by the presence of an excess of liquid precursors in the respective coating chamber which is measured by the coating knife of the moving mat. In contrast, the pre-measured matrix coating processes are characterized by a constant volume flow so that what is transmitted by the pump is also applied to the moving mat. Therefore, the self-measured process of the present description is fundamentally different from the pre-measured matrix coating process used in the prior art.
[0078] The multilayer films obtained by the method of the present description preferably have essentially homogeneous properties such as, for example, an essentially homogeneous thickness of the polymer layers cured in the transverse direction. It is speculated by the present inventors that the stable flow pattern established by the shear force regime of the present description results in a flow history of liquid precursors that are essentially constant in relation to the coating width of all precursors. The average deviation in the thickness of the cured layers of the multilayer film in one direction
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30/100 normal to the downstream direction is preferably in relation to an arbitrarily selected distance of 10 mm less than 5%, with more preference less than 2.5% and with special preference less than 2%. The excellent uniformity of the cured multilayer films can be taken, for example, from microphotographs in cross section in Figures 4 to 8 below.
[0079] In the method of the present description, the volume flow mainly results from a shear force regime that is mainly controlled by the spans between the respective coating knives and the substrate, the arrangement of the coating knives in relation to each other, the geometry of the lower portion of the coating knives, the speed of the substrate and the viscosity of the curable liquid precursors. These parameters are easy to control and can vary widely without adversely affecting the stable flow pattern, which is essentially laminar and essentially homogeneous in the transverse direction. In the process of the present description, the gaps between the respective coating knives and the substrate can be modified and adjusted over a wide range while the coating process is taking place. The process of the present description is therefore more versatile and easier to handle compared to the pre-measured matrix coating processes for multilayer piles of the latest generation wet precursor layers.
[0080] The method of the present description presents innovative multilayer films with exclusive properties and, in particular, with preferred optical properties such as, in particular, a high optical transmission for visible light. While the present inventors do not wish to be bound by such a theory, it is speculated that this is the result of micro-diffusion that occurs at the interface between adjacent layers.
[0081] It is believed that the extent of such microdiffusion is on the one hand small enough so that it does not affect the integrity of the adjacent layers. That
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31/100 can be removed, for example, from the microphotographs of Figures 4 to 8 that clearly show interfaces with sharp edges and recognizable between adjacent layers. This can be demonstrated, for example, by adding a dye to one of the pairs of adjacent cured layers while not adding a dye to another cured layer. Cross-sectional microphotographs of such multilayer films preferably show an abrupt transition from the dyed layer to the non-dyed layer, and the interface is preferably not blurred.
[0082] It is believed that the extent of such micro-diffusion is, on the other hand, large enough to provide a micro-gradient at the interface that results, for example, in a gradual transition between the refractive indices of the adjacent layers and consequently in a larger transmission. The appearance of the interface between two adjacent liquid precursor layers and consequently the extent of microdiffusion can be influenced mainly by the viscosity of the liquid precursors of two adjacent precursor layers. Typically, the sharper the edge of the interfacial area between two adjacent precursor layers, the higher the viscosity of the two liquid precursors. It is believed that interfacial micro-diffusion or micro-mixing can be increased by decreasing the Brookfield viscosity of at least one of the precursors of the adjacent layers to less than 5,000 mPa's, more preferably less than 2,500 mPa's and especially preferably 500 at 1,500 mPa's. It is believed that the interfacial microdiffusion is further increased when the liquid precursor of both adjacent layers shows, independently of each other, a Brookfield viscosity less than 5,000 mPa's, more preferably less than 2,500 mPa's and specifically preferably between 500 - 1,500 mPa's.
[0083] Micro-diffusion is also believed to increase the bond strength between adjacent layers of the multilayer film after curing, which is reflected, for example, in improved mechanical properties such as resistance to
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32/100 greater detachment T (peel strength).
[0084] The cured polymer top layer of the multilayer film preferably has an excellent finish of its exposed surface, that is, low surface roughness as assessed, for example, in terms of the surface roughness Rz.
[0085] The exclusive properties of the method of the present description are reflected in the properties of the multilayer films obtained by such method and of the sets comprising such multilayer films, respectively. A preferred set of the present description comprises a light transmitting multilayer film obtainable by the method of the present description and a glassy substrate. The multilayer film used in such a set is fixed through an external adhesive layer of the vitreous substrate, with the overlapping polymer layers of the multilayer film each having a transmission of at least 80% in relation to visible light and the index of refraction of the adhesive layer is lower than the refractive index of the opposite outer layer. The transmission of the polymer layers in relation to visible light is measured according to the test method specified in the test section below for cured single precursor layers having a thickness of 300 pm each. The precursor layers used in multilayer films of the present description more preferably have a transmission of at least 90% and, in particular, at least 95% as a single cured film of 300 µm thickness. The light transmission of the multilayer film in relation to the visible light that results from a light transmission of the overlapping polymer layers is preferably at least 80%, more preferably at least 85% and most preferably at least 90%. If desired, the multilayer film may comprise solid light-transmitting films such as, for example, light-transmitting polymeric films or mats. It was found that sets with an advantageous transmission in relation to visible light
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33/100 are obtained if the refractive index of the external adhesive layer fixed to the glassy substrate is lower than the refractive index of the opposite external layer. This requirement is counterintuitive and is believed to be based on the interfacial microdiffusion described above. The glassy substrate can be selected from conventional silica-based glasses such as float glass, but also from polymer glasses such as acrylic glass, polycarbonate glass or polyethylene terephthalate glass. The glass refractive index suitable in the present description n589 nm, 23 ° c is preferably between 1.48 and 1.52.
[0086] When the multilayer film useful in the above set is manufactured, the adhesive layer may preferably be coated as the top layer (which is attached to the glass substrate surface in the set and thus forms an unexposed outer layer of the multilayer film) and covered, for example, with a removable strip while the opposite outer layer is preferably coated as the bottom layer (which forms the outer layer of the opposite set of the adhesive layer). It is, however, also possible that the adhesive layer of the multilayer film used in the set is coated as a lower layer during the method; in such a case the substrate is preferably integrated into the multilayer film and forms a removable strip attached to the adhesive layer. In the above set, the difference between refractive indices of the two outer layers (= outer layer opposite the adhesive layer and adhesive layer, respectively) is preferably less than 0.030. More preferably, the outer adhesive layer of the multilayer film has a refractive index n589n, 23 ° c which is not more than 0.0025, more preferably not more than 0.0020, with special preference not more than 0.0015, highly preferably not more than 0.0010 and most preferably not more than 0.0008 less than the refractive index n589n, 23 ° C of the opposite outer layer. In such films, transmission is measured according to the test method specified in the test section below for single precursor layers that have a thickness of
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34/100
300 pm each. The transmission is at least 80%, more preferably at least 90% and with special preference at least 95% for each cured layer. In a more preferred embodiment, the refractive indices of the precursor layers disposed between two outer layers, if present, are greater than the refractive index of the external adhesive layer and less than the refractive index of the opposite external layer. Refractive indices are measured at a wavelength of 589 nm and a temperature of 23 ° C as described in the test section below.
[0087] The method of the present description also allows the incorporation of solid films such as polymeric films or blankets, films or metal blankets, woven or non-woven blankets, reinforced fiberglass blankets, carbon fiber blankets, polymer fiber blankets or blankets comprising endless filaments of glass, polymer, metal, carbon fibers and / or natural fibers. In a coating apparatus containing one or more coating chambers as solid films, any intermediate wall and the rear wall, respectively, can be introduced longitudinally to the surface upstream of the front wall. In the schematic illustration of Figure 1 showing an arrangement of 3 coating chambers and a rolling microsphere arranged upstream to the upstream coating chamber, a solid film is guided through the upstream surface of the intermediate wall further upstream thereby positioning the solid film in a tight fit on the second liquid precursor layer provided by the first upstream coating chamber. Figure 1 also shows the insertion of a removable strip longitudinally to the surface upstream of the rear wall. This arrangement provides a precursor comprising a multi - layer precursor layer 4, a solid film inserted between ^the 2 and 3 ^the bottom precursor layer and a removable strip attached to the exposed surface of the top layer. This is just an example, and the person skilled in the art will select the
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35/100 suitable solid film or films by providing a specific multilayer film with a desired profile of properties and the arrangement and number of such films within a multilayer film will vary. If less than four liquid layers are required, the corresponding number of downstream coating knives and / or the rolling microsphere are omitted. The removable top strip if desired is attached to the exposed surface of the top layer in a tight fit, i.e., for example through the surface upstream of the coating knife further downstream of the modified assembly.
[0088] If the solid film is a removable strip, it can be disposed under the precursor bottom layer or on top of the multilayer film bottom layer to protect exposed bottom surfaces and top precursor layers, respectively. A release film when included in a multilayer film as an intermediate layer between the bottom and the top polymer layer, respectively, introduces a predetermined breaking surface in a multilayer film. This can be used, for example, to prepare a stack of multilayer films in a single production process from which individual multilayer films can be easily obtained by longitudinal detachment from the release surface.
[0089] Solid films, in addition to removable strips, form an integral part of a cured multilayer film. Solid films are also called support in a multilayer film.
[0090] In one embodiment, the multilayer films of the present description comprise at least two layers of polymer superimposed on the polymer layers that can be obtained by the method of the present description with a removable strip being applied to the exposed surface of the top layer of the precursor essentially simultaneous to the formation of such a layer. This is preferably done by guiding and applying a removable strip across the surface upstream of the
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36/100 downstream coating, that is, the surface upstream of the rear wall of the coating apparatus. This is schematically illustrated in Figure 1. In an alternative embodiment, the rear wall can be provided by the removable strip which is properly tensioned and reflected by cylinders, bars, rods, beams or the like to provide an edge extending transversely towards the substrate. In that case, the additional back wall can be omitted.
[0091] Since the removable strip is applied to the exposed surface of the liquid precursor top layer essentially simultaneous to the formation of such a layer, it is uniformly attached to the top layer in a tight fit without exerting too much pressure or insufficient pressure, respectively , during the application of the ceiling. Since the liner is arranged in a tight fit, the formation of voids between the liner and the surface of the liquid layer is essentially avoided. Likewise, since the removable strip is applied longitudinally to the surface upstream of the coating knife forming the liquid layer, the lining is uniformly attached to the surface of the liquid layer essentially without creating turbulence in the liquid layer and the like. Therefore, the problems discovered when the lining is fixed to the exposed surface of a liquid layer subsequent to the formation of said liquid layer in a prior art matrix coating process can be largely avoided or at least lessened in the process according to the present description. This is the exclusive advantage of the process of the present description, which translates into multilayer films with superior properties that can be obtained using the method of the present description in which a removable strip is attached to the surface exposed to the top layer of the precursor of essentially simultaneous to the formation of said layer and subsequent curing. If desired, the removable strip can be removed.
[0092] In prior art methods of making multilayer films, a removable strip, if present, was typically applied to the
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37/100 surface exposed to the precursor top layer subsequent to the formation of such a layer. In such methods, the removable strip was placed over the exposed top layer using, for example, a guide cylinder, bar, rod or beam. Such a method requires an exact positioning of the distance between the substrate surface and the guide cylinder, which can be difficult under practical conditions. If the distance is too small, too much pressure is exerted on the top precursor liquid layer which results in a distortion of the uppermost layer and the formation of a fluid microsphere. The fluid microsphere induces a turbulent flow in the stack of a liquid precursor layer so that mixing can take place. If the distance between the guide cylinder and the substrate is too great, air entrapment can occur between the removable strip and the exposed surface of the liquid precursor top layer. This results in a poor surface finish of the topmost cured layer of the multilayer film characterized by high Rz values. Also, the healing of the uppermost surface may be sensitive to oxygen. If the liquid precursor top layer comprises, for example, the precursor to an acrylate-based pressure sensitive adhesive, UV curing of such precursor may be prevented by the presence of oxygen so that insufficient curing can occur and, consequently, insufficient curing , distinctly decreased properties of the pressure sensitive adhesive layer.
[0093] When a removable strip is applied to the exposed surface of the precursor top layer through a suitable cylinder, bar, rod, microsphere or the like arranged downstream to the surface downstream of the rear wall, the exposed surface of the top layer is exposed to the ambient atmosphere in the distance between the rear wall and such a downstream coating knife that can result in a degradation of the top layer. The distance that is schematically illustrated in Figure 10 is also referred to above and below as the “open face” distance.
[0094] It was surprisingly found that the multilayer film
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38/100 cured light transmitter of the present description which is obtained by fixing a removable strip to the exposed surface of the top layer of the precursor essentially simultaneously with the formation of such a layer with subsequent curing, has improved optical properties such as, in particular, a higher transmission compared to a corresponding multilayer film obtained by attaching a removable strip to the stack of liquid precursor layers subsequent to the formation of the precursor top layer, for example, through a suitable cylinder or bar knife at a distance " open face ”in a direction downstream of the surface downstream of the rear wall of the coating device. Consequently, the multilayer films of the present description which are obtained by attaching a removable strip to the exposed surface of the top layer of the precursor essentially simultaneously with the formation of such layer with subsequent curing, are preferred.
[0095] The ratio between the transmission of the multilayer film obtained by fixing a removable strip to the exposed surface of the top layer of the precursor essentially simultaneously with the formation of such a layer, that is, for example, longitudinally to the inner surface of the coating knife further downstream, and the transmission of the corresponding multilayer film obtained by the subsequent application of a release layer at an “open face” distance in a downstream direction to which the top layer is formed is at least 1.002, with more preference for at least at least 1.003 and with a special preference of at least 1.005.
[0096] In such multilayer films, the precursor materials are preferably selected so that the corresponding single cured layers, when measured at a thickness of 300 pm, each have a transmission of at least 80% in relation to visible light as measured according to the test method specified in the test section below. The precursor layers used in the multilayer films of the present description have, more preferably, when present as a single cured film of 300 pm thickness, a transmission of
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39/100 at least 90% and with a special preference of at least 95%. The light transmission of the multilayer film in relation to visible light that results from light transmission of the overlapping polymer layers is preferably at least 80%, more preferably at least 85% and most preferably at least 90% . If desired, the multilayer film may comprise solid light-transmitting films such as, for example, light-transmitting polymeric films or blankets.
[0097] It was more specifically discovered by the present inventors that the multilayer films of the present description obtained by curing a precursor in which a removable strip is applied to a surface exposed to the top layer of the precursor in an essentially simultaneous manner to the formation of such a layer of top with subsequent curing, have advantageous properties compared to (i) laminated multilayer films obtained by laminating the corresponding precursor layer cured on top of each other;
(ii) multilayer films obtained by the prior art matrix coating method (presented, for example, in US 4,894,259 / Kuller) where the removable strip is attached to the exposed surface of the top layer surface in a position downstream of coating knife further downstream, that is, at an “open face” distance;
(iii) multilayer films obtained where the removable strip is attached to the exposed surface of the top layer surface in a position downstream of the coating knife further downstream, that is, at an “open face” distance; and (iv) multilayer films obtained by applying one or more liquid precursor layers to one or more cured precursor films or one or more laminates of which precursor films with subsequent curing, without restriction if the removable strip (if applied) was fixed through the surface upstream of the rear wall or an additional coating knife downstream.
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40/100 [0098] It has been discovered, for example, that the transmission of light to the visible light of the multilayer of the present description with a removable release strip applied to the precursor top layer essentially simultaneous to its formation is greater than the transmission of light to the visible of the corresponding multilayer film as defined in (i) to (iv). It has also been found that, for example, the multilayer film of the present description with a removable strip applied across a surface upstream of the back wall has greater mechanical stability and, in particular, greater resistance to T-peel strength than corresponding multilayer films as defined in (i) and (iv) above.
[0099] Suitable liquid precursors in the present description preferably comprise at least one compound that has a radiation-curable ethylene group. In a preferred embodiment, the radiation-curable ethylene group is a (meth) acrylate group. In another preferred embodiment, the radiation curable ethylene group is a functional mono and / or poly (meth) acrylate oligomer compound comprising at least one urethane bond. The term "oligomer" as used above and below refers to polymeric compounds of relatively low molecular weight. Functional poly (meth) acrylate oligomer compounds comprising at least one urethane bond preferably have a weight average molecular weight Mw between 500 and 35,000 and more preferably between 1,000 and 30,000. Such oligomeric compounds are typically liquid at room temperature and ambient pressure whereby the Brookfield viscosity is preferably less than 500 Pa's and more preferably less than 200 Pa's at 25 ° C.
[00100] The liquid precursor of the present description is preferably essentially solvent-free, i.e., it does not essentially comprise any non-reactive solvent such as, for example, methanol, acetone, dimethyl sulfoxide, or toluene. It is, however, possible, but not preferential, that the precursor understands
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41/100 small amounts of one or more of such non-reactive solvents, preferably less than 2 ppc and more preferably less than 1 ppc with respect to the mass of the precursor in order to decrease the viscosity of the liquid precursor.
[00101] A preferred liquid precursor suitable in the present description is curable to a pressure sensitive adhesive. Specifically, a pressure sensitive adhesive based on (meth) acrylate is preferred.
[00102] The liquid precursor of the pressure sensitive adhesive based on (meth) acrylate comprises one or more (meth) alkyl acrylates, that is, one or more alkyl ester monomers of (meth) acrylic acid. Useful (meth) alkyl acrylates include linear or branched unsaturated monofunctional (meth) acrylates of non-tertiary alkyl alcohols, alkyl groups having 4 to 14 and, in particular, 4 to 12 carbon atoms. Examples of such lower alkyl acrylates that are useful in liquid precursors of (meth) acrylate based adhesives include n-butyl, n-pentyl, n-hexyl, cyclohexyl, isoheptyl, n-butyl acrylates and (meth) acrylates. -nonyl, n-decyl, isohexyl, isobornyl, 2-ethyl octyl, iso-octyl, 2-ethyl hexyl, tetrahydrofurfuryl, ethyl ethoxy ethyl, phenoxy ethyl, cyclic formal trimethylpropane, 3,3,5-trimethyl cycle -hexyl, t-butylcyclohexyl, t-butyl. Preferred alkyl acrylates include isooctyl acrylate, 2-ethyl hexyl acrylate, n-butyl acrylate, hydrofurfuryl tetra acrylate, isobornyl acrylate, ethyl ethoxy ethyl acrylate, ethyl phenoxy acrylate, 3.3 acrylate, 5- trimethylcyclohexyl, and cyclohexyl acrylate. Particularly preferred alkyl acrylates include isooctyl acrylate and tetrahydrofurfuryl acrylate. Particularly preferred (meth) alkyl acrylates include butyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
[00103] The liquid precursor of the pressure sensitive adhesive based on (meth) acrylate preferably comprises up to 5 (meth) alkyl acrylates and, in particular, 1 - 4 (meth) alkyl acrylates. The amount of alkyl acrylate compounds in relation to the total mass of monomers, oligomers and / or polymers
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42/100 functionalized (meth) acrylate, with the exception of crosslinkers, is preferably at least 75% by weight, more preferably at least 85% by weight and most preferably between 85 and 99% by weight.
[00104] The liquid precursor to pressure sensitive adhesive based on (meth) acrylate can further comprise one or more moderately polar and / or strongly polar monomers. Polarity (ie, the hydrogen bonding ability) is often described using terms such as 'strongly', 'moderately' and 'weakly'. References that describe these and other solubility terms include 'Solvents', Paint Testing Manual, 3rd ed., G.G. Seward, Ed., (American Society for Testing and Materials), Philadelphia, Pennsylvania, and ‘A ThreeDimensional Approach to Solubility’, Journal of Paint Technology, Vol. 38, No. 496, pp. 269 - 280. Examples of strongly polar monomers include acrylic acid, methacrylic acid, itaconic acid, alkyl hydroxy acrylates, acrylamides and substituted acrylamides while, for example N-vinyl pyrrolidone, N-vinyl caprolactam, acrylonitrile, vinyl chloride, diallyl phthalate N, N-dialkyl amino (meth) acrylates are typical examples of moderately polar monomers. In addition examples of polar monomers include cyano acrylate, fumaric acid, crotonic acid, citronic acid, maleic acid, β-carboxy ethyl acrylate or sulfoethyl (meth) acrylate. The alkyl (meth) acrylate monomers listed above are typical examples of relatively weakly polar monomers. The amount of strongly polar and / or more moderately polar monomers is not so high and, in particular, does not exceed 25% by weight with respect to the total mass of functionalized (meth) acrylate monomers, oligomers and / or polymers with the exception of crosslinkers.
[00105] The liquid precursor to pressure-sensitive adhesive based on (meth) acrylate may further comprise one or more monomers of mono or multifunctional silicone (meth) acrylate. Exemplary silicone acrylates are the Tego Rad products from Evonik, Germany,
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43/100 methacryloxyurea siloxanes or acrylamido starch siloxanes.
[00106] Ethylenically and partially unsaturated or mono-perfluorinated oligomers can also be part of the liquid precursor formulation. Examples are Sartomer CN 4001 perfluoropolyether acrylate, available from Sartomer Inc, or F-II oligomer, synthesized as detailed in the “List of used materials” below.
[00107] The liquid precursor of the pressure sensitive adhesive based on (meth) acrylate preferably comprises one or more crosslinkers in an amount effective to optimize the cohesive or internal resistance of the cured pressure sensitive adhesive. Crosslinkers useful for use in the liquid precursor of the pressure sensitive adhesive based on (meth) acrylate include, for example, benzaldehyde, acetaldehyde, anthraquinone, various compounds of the benzophenone type and of the vinyl-methyl-s-triazine type, such as 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -striazine. Functional polyacrylic monomers such as, for example, trimethylol propane triacrylate, pentaerythritol tetraacrylate, ethylene glycol 1,2-diacrylate, tripropylene glycol diacrylate, 1,6-hexane diol diacrylate or 1,12dodecanediol diacrylate are preferred. The compounds mentioned above, which can be substituted or unsubstituted, are intentionally illustrative and in no way limiting. Other useful crosslinkers that could be used are thermal crosslinkers. Exemplary thermal crosslinkers include: melamine, multifunctional aziridines, multifunctional isocyanates, di-carbonic acids / carbonic acid anhydride, oxazoles, metal chelates, amines, carbodiimides, oxazolidones, and epoxy compounds. Hydroxy-functional acrylates such as 4-hydroxybutyl (meth) acrylate or hydroxyethyl (meth) acrylate can be cross-linked, for example, with isocyanate compounds or amine compounds.
[00108] Copolymerizable crosslinkers, free of radicals and hydrolyzables, such as monoethylenically mono, di and trialoxy unsaturated silane compounds including,
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44/100 but not limited to, methacryloxypropyltrimethoxysilane, vinildimethylethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriphenoxysilane, and the like are also useful crosslinking agents.
[00109] Apart from the photosensitive, moist, thermal crosslinking agents, the crosslinking can be carried out using high energy electromagnetic radiation such as gamma radiation or electronic beam.
[00110] The cross-linking compounds are preferably present in an amount of 0.01 to 10 ppc, in particular between 0.01 and 5 ppc and very specifically between 0.01 and 3 ppc.
[00111] The liquid precursor to the pressure sensitive adhesive based on (meth) acrylate preferably comprises one or more photoactivable polymerization initiators such as, for example, benzoin ethers (for example, benzoyl methyl ether, isopropyl ether of benzoyl, benzoyl ethers substituted as anisoin methyl ether), acetophenones (eg 2,2-diethoxyacetophenone), acetophenones substituted as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-phenyl-2 -hydroxy-2-methyl-1-propanone, substituted alpha-ketol (for example, 2-methyl-2-hydroxy-propiophenone), aromatic sulfonyl chloride, and photoactive oximes such as 1-phenyl-1,1-propanedione-2 - (O-ethoxy carbonyl) oxime and / or thermally activable initiators such as, for example, organic peroxides (for example, benzoyl peroxide and lauryl peroxide) and 2,2'-azobis (isobutyronitrile). The liquid precursor preferably comprises between 1 and 3 and, in particular, between 1 and 2 photoinitiating compounds; liquid precursors comprising only a photoinitiating compound are especially preferred. The photoinitiating compounds are preferably present in an amount of 0.01 to 2.00 ppc, in particular, between 0.05 to 1.00 ppc and very specifically between 0.1 to 0.5 ppc.
[00112] The liquid precursor to the pressure sensitive adhesive based on (meth) acrylate can comprise other components and adjuvants such as
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45/100 taquifiers, plasticizers, reinforcing agents, dyes, pigments, light stabilizing additives, antioxidants, fibers, electrically and / or thermally conductive particles, flame retardants, surface additives (flow additives), rheology additives, nanoparticles , gasification additives, glass bubbles, polymeric bubbles, microspheres, hydrophobic or hydrophilic silica, calcium carbonate, blowing agents, reinforcing and hardening agents.
[00113] The liquid precursor to the pressure sensitive adhesive based on (meth) acrylate is preferably prepared by adding part of the photoinitiating compounds to a monomer mixture comprising the alkyl (meth) acrylate monomers and the monomers strongly polar and / or moderately polar, and partial polymerization of such a mixture to a syrup of a coatable viscosity of, for example, 300 to 35,000 mPa's (Brookfield, 25 ° C). The viscosity of the resulting precursor is further adjusted by adding other compounds such as crosslinking compounds, the rest of the photoinitiating compounds, silicone (meth) acrylates and any additives and adjuvants as they may be used. The viscosity of the resulting precursor can also be adjusted by adding a small amount of typically less than 5 ppc of a polymeric additive such as, for example, photopolymerizable reactive polyacrylates. The partial polymerization of the monomer mixture is preferably carried out with suitable UV lamps that have a wavelength between 300 to 400 nm with a maximum of 351 nm at an intensity preferably between about 0.1 to about 25 mW / cm ² . The exposure is preferably between 900 to 1,500 mJ / cm ² . Polymerization can be stopped by removing UV and / or introducing, for example, oxygen scavengers. An example of a suitable UV curing station is described in conjunction with the coating apparatus described in the examples below.
[00114] Another preferred liquid precursor suitable in the present description is UV curable and comprises at least one ethylenically compound
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46/100 unsaturated which comprises at least one urethane bond. Such compounds are preferably monomers or oligomers, and / or at least one of the ethylenically unsaturated groups is preferably a (meth) acrylate group. Such a precursor can be polymerized to a polyurethane acrylate polymer, i.e., to a polymer comprising urethane bonds. Specifically preferred is a liquid precursor that comprises one or more monomer and / or multi (meth) acrylate functional monomer or oligomers comprising at least one urethane bond, one or more monomer compounds comprising one or more ethylenically unsaturated groups, but no urethane binding, and one or more photoinitiators.
[00115] Functional mono and multi (meth) acrylate oligomers comprising at least one urethane bond are available for sale, for example, from Rahn AG, Zurich, Switzerland under the trade name GENOMER. GENOMER 4188 is a mixture consisting of 80% by weight of a functional polyester monoacrylate based oligomer comprising at least one urethane bond, and 20% by weight of 2-ethyl hexyl acrylate; the oligomer comprised by GENOMER 4188 has an average molecular weight Mw of about 8,000 and the average functionality of the acrylate is 1 ± 0.1. GENOMER 4316 is a trifunctional aliphatic polyurethane acrylate characterized by a viscosity of 58,000 mPas at 25 ° C and a glass transition temperature Tg 4 ° C. GENOMER 4312 is an aliphatic trifunctional polyester urethane acrylate characterized by a viscosity of 50,000 to 70,000 mPas at 25 ° C.
[00116] Functional oligomer compounds of mono or multi (meth) acrylate each have at least one urethane bond, preferably at least 2 and more preferably at least 4 urethane bonds.
[00117] Functional mono and multi- (meth) acrylate oligomers and their preparation are presented on p. 4, line 24 - p. 12, line 15 of WO2004 / 000.961 whose
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47/100 passage is incorporated by reference.
[00118] The amount of the one or more functional mono or multi (multi) acrylate oligomers comprising at least one urethane bond with respect to the total mass of monomers, oligomers and / or functionalized (meth) acrylate polymers with the exception of crosslinkers it is preferably from 30 to 97.5% by weight and more preferably from 45 to 95% by weight.
[00119] The suitable liquid precursor of the polyurethane polymer in the present description preferably further comprises one or more monomer compounds which comprise one or more ethylenically unsaturated groups but without urethane bonding. Examples of suitable ethylenically unsaturated groups include vinyl, vinylene, allyl and, in particular, (meth) acrylic groups. The amount of such compounds with one or more ethylenically unsaturated groups with respect to the total mass of functionalized (meth) acrylate monomers, oligomers and / or polymers, with the exception of crosslinkers, is preferably 2.5 to 70% in weight and more preferably 5 to 55% by weight.
[00120] Compounds with one or more (meth) acrylic groups can preferably be selected from weakly polar (meth) acrylate monomers, moderately polar and / or strongly polar monomers and the two or more crosslinkers functionalities of an acrylic group presented above together with the liquid precursor of the pressure sensitive adhesive based on acrylate.
[00121] The liquid precursor of the polyurethane polymer preferably comprises one or more monofunctional (meth) acrylate compounds that have a glass transition temperature of the corresponding homopolymer less than 10 ° C. Preferred examples of such monomers include n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethyl hexyl acrylate, isooctyl acrylate, caprolactone acrylate, isodecyl acrylate, tridecyl acrylate, (la) methyl acrylate,
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48/100 methoxy-polyethylene glycol mono (meth) acrylate, lauryl acrylate, tetrahydrofurfuryl acrylate, ethoxy-ethoxyethyl acrylate and ethoxylated nonyl acrylate. Especially preferred are 2-ethyl hexyl acrylate, isooctyl acrylate and tetrahydrofurfuryl acrylate.
[00122] The liquid precursor of the polyurethane polymer preferably comprises one or more monofunctional (meth) acrylate compounds that have a glass transition temperature of homopolymers corresponding to 50 ° C or more. Preferred examples of such monomers include acrylic acid, N-vinyl pyrrolidone, N-vinyl caprolactam, isobornyl acrylate, acryloyl morpholine, isobornyl (meth) acrylate, ethyl phenoxy acrylate, (meth) phenoxy ethyl acrylate, (met) methyl acrylate and acrylamide. Specifically preferred are area acrylic acid, isobornyl acrylate and N-vinyl caprolactam.
[00123] Examples of compounds with two or more ethylenically unsaturated groups which are suitable in the liquid curable polymer precursor comprised in the layer or layers of the multilayer film of the present description include C2 - C12 diol hydrocarbon diacrylates such as 1,6-hexane diol diacrylate , C4 - C14 hydrocarbon divinyl ethers as hexane diol divinyl ether and C3 - C12 hydrocarbon triol acrylates as trimethylolpropane acrylate. Two or more functional acrylate monomers and, in particular, two or three functional acrylate monomers are preferred.
[00124] The liquid precursors described above are to exemplify the present description without limiting it.
[00125] In another preferred embodiment, the light-transmitting multilayer films according to the present description comprise at least two overlapping polymer layers, one of the outer layers of the multilayer comprising a polyurethane polymer and the opposite outer layer of the multilayer film comprises an adhesive and more preferably an adhesive
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49/100 pressure sensitive based on (meth) acrylate. Such a multilayer film has a maximum wavefront aberration of a wavefront resulting from a plane wavefront of a wavelength of λ = 635 nm, normally affecting the top layer and transmitted through a multilayer film, measured as the peak-valley value of the transmitted wavefront, less than 6 λ (= 3,810 nm).
[00126] The value of the maximum aberration of a measured flat wavefront subsequent to its transmission through a multilayer film of the present description characterizes the distortion of wavefront experiences as a result of its interaction with the multilayer film. The lower the aberration value of the maximum wavefront, the higher the optical quality of the film (for example, the less distortion of an image projected through the film).
[00127] Each layer of overlapping polymer preferably has a transmission of at least 80% in relation to visible light. The transmission of the polymer layers is measured according to the test method specified in the test section below for single cured precursor layers that have a thickness of 300 pm each. The precursor layers used in multilayer films of the present description have, more preferably, when present as a single cured film of 300 pm thick, a transmission of at least 90% and with a special preference of at least 95%. The light transmission of the multilayer film in relation to visible light that results from light transmission of the overlapping polymer layers is preferably at least 80%, more preferably at least 85% and most preferably at least 90% . If desired, the multilayer film may comprise solid light-transmitting films such as, for example, light-transmitting polymeric films or mats.
[00128] The precursor liquid top layer is provided by a polyurethane polymer. The term polyurethane polymer as used above and below refers to cured polymers that comprise at least one urethane bond that is
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50/100 typically formed by the reaction of functional isocyanate monomers and hydroxy-functional monomers. In the present description, the term polyurethane polymer, preferably, refers to a polymer obtained by the polymerization of a liquid precursor that comprises at least one ethylenically unsaturated compound that comprises at least one urethane bond.
[00129] In the present description, the polyurethane polymer is preferably obtained by curing a liquid precursor that comprises one or more compounds of functional mono and / or poly (meth) acrylate oligomers that comprise at least one bond of urethane, one or more monomer compounds that comprise one or more ethylenically unsaturated groups but without urethane bonding and one or more phototoinitiators. Such a preferred liquid precursor of a polyurethane polymer is described in detail above.
[00130] The outer layer of these preferred multilayer films opposite the outer polyurethane layer preferably comprises a pressure sensitive adhesive based on cured (meth) acrylate which is preferably obtained by curing the preferred liquid precursor of an adhesive corresponding pressure sensitive shown above.
[00131] It has been discovered by the present inventors that the multilayer film of the present description comprising an outer layer comprising a polyurethane polymer and an opposite outer layer comprising an adhesive and, in particular, a pressure-sensitive adhesive layer based on (met) acrylate which has favorable optical properties such as, in particular, a maximum low aberration of a flat wave front subsequent to its transmission through the cured multilayer film, a high transmission, a low opacity and / or a low color change such as can be evaluated by the methods of the present invention described in the test section below.
[00132] The outer layer of the multilayer film comprising a polymer
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51/100 polyurethane also provides advantageous mechanical properties such as a high scratch resistance to the multilayer film as can be assessed by the methods in the test section below.
Detailed Description of the Figures [00133] Figure 1 represents a coating apparatus 1 useful in the present description. The coating apparatus 1 comprises an anterior wall 11, two intermediate walls 13 and a posterior wall 12 forming three coating chambers 16 (referenced by Figures II to IV). A rolling microsphere 17 (also referenced by Figure I) is arranged upstream to the front wall 11. The walls 11, 12, 13 are formed by cladding knives that are normally arranged on a substrate 2 in the downstream direction 3 so that gaps 100 are formed between the bottom portion of the coating knives 11, 12, 13 and the substrate. Each of the coating chambers is 101 in width and all are filled with liquid precursors. A solid film 14 is applied across the upstream surface of the upstream intermediate wall 13 and introduced between a second and third liquid precursor layers. A release film or liner 15 is applied across the surface upstream of the rear wall 12 and attached to the top of the precursor top layer. The coating stations formed by the rolling microsphere and the three coating chambers downstream are identified in the reference by the Roman numerals I, II, III and IV.
[00134] Figure 2a is an enlarged representation of the coating knife that is used as an anterior wall 11, intermediate wall 13 and posterior wall 12 in the coating apparatus of Figure 1. The coating knife has a toroidal or profile profile. radius providing a transversely extending coating edge 18. Figure 2b is an enlarged cross-sectional view of the lower portion of the coating knife of Figure 2a showing the toroidal profile in more detail. The toroidal profile is represented by the circumference of
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52/100 a quadrant circle that has a radius R.
[00135] Figure 3 is a schematic representation of a measurement arrangement suitable for measuring the maximum wavefront aberration of a flat 204 wavefront transmitted through a cured multilayer film 20 mounted on a 205 glass plate. The light it is provided by a laser diode coupled to fiber 201 enlarged in a spherical wavefront 202 and collimated by an aspherical collimation lens 203. The plane wavefront 204 of collimated light passes through sample 20 and glass plate 205 and is depicted on a Shack-Hartmann 210 sensor by a Kepler 207 telescope. The Shack-Hartmann sensor determines the local slope of an optical wavefront using a micro-lens assembly and a CCD integrated circuit camera. The deformed wavefront is then reconstructed by Shack-Hartmann's measuring device software by numerical integration. The maximum wavefront aberration of a flat wavefront resulting from a multilayer film alone is obtained by subtracting the value of a maximum wavefront aberration from a measured flat wavefront for the glass plate alone.
[00136] Figures 4 to 8 are cross-sectional microphotographs of cured multilayer films prepared in examples 2, 5, 11, 12 and 13, respectively. The figures are described in detail in the corresponding example sections.
[00137] Figures 9a to 9i are images from the Siemens Star test for multilayer films of Examples 22 (Figure 9b), 23 (Figure 9f) and 24 (Figure 9g), for conformable, flexible and comparative 2-layer films, which comprise a top layer of polyurethane or polyethylene and a bottom layer of the pressure sensitive adhesive commercially available from 3M (Figures 9c - 9e) and for Comparative Examples 2a and 2b (Figures 9h and 9i). Figure 9a is an image of the Siemens Star test for a glass plate used as a reference. The figures are
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53/100 explained in more detail in the example section below.
[00138] Figure 10 is a schematic representation of a coating apparatus used in Comparative Example 2a.
Examples [00139] The present description will be illustrated by the examples described below. Before that, the coating apparatus used in the Examples and test methods that are used to characterize cured liquid precursors and / or multilayer films are described. The concentrations above and below are given as% by weight or as ppc (parts per hundred resin). The term% by weight provides the mass of the polymers, oligomers or functionalized (meth) acrylate monomers, respectively, with the exception of crosslinking compounds with respect to the total mass of such polymer, oligomer, and functionalized (meth) acrylates monomer with the exception of crosslinkers through which such mass is established as 100% by weight. The amount of other compounds such as crosslinkers, initiators or additives such as fillers, polymeric additives, tachifiers or plasticizers is given in parts by weight, designated as ppc (parts per hundred resin) in relation to such a total mass of 100% by weight.
Coating apparatus [00140] Coating apparatus used in the Examples is schematically shown in Figure 1. The coating apparatus used in the Examples comprised up to four coating knives normally disposed with respect to the substrate in motion under the coating apparatus in the downstream direction. so that a rolling microsphere and up to 3 coating chambers, that is, up to 4 coating stations including the rolling microsphere upstream until a first coating knife could be used, which are also indicated in Figure 1 by consecutive Roman numerals I, II , III and IV starting with the said upstream rolling microsphere identified by reference number I. If less
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54/100 that 4 coating chambers or coating stations were used, the corresponding number of unused downstream coating knives was removed. For example, in the case of a two-layer film, the two coating knives further downstream were removed so that the single rolling microsphere I and the first coating chamber II were present; if a removable strip 15 was attached to the exposed surface of the top layer it was fed in such a fit through the surface upstream of the coating knife further downstream, i.e., the coating knife downstream of chamber II. The cladding knives were held by transverse support elements rigidly mounted to two longitudinal support elements that extend in the downstream direction. The transversal support elements were extended in the normal downstream direction.
[00141] The width of the three coating chambers II to IV in the direction of the user can be modified as follows:
Coating station Width range in the downstream direction [mm] Volume range [ml] of the coating chambers II 4-157 26-1005 III 4-157 26-1005 IV 4-157 26-1005
[00142] The cladding chambers were limited in the normal direction to the downstream direction by the anterior wall and the first intermediate wall (cladding station II), by the 1 ^st and 2 ^to intermediate walls (cladding station III) and by the 2 ^nd wall intermediate and the back wall (coating station IV). The coating chambers were limited in the downstream direction by two scraper sides produced from polytetrafluoroethylene (PTFE) bars that were arranged normal to the coating knives. The height of the coating chambers as measured from the surface of the substrate to the upper exposed surface of
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55/100 cross-support elements were about 40 millimeters for each of the three coating chambers providing the volumes of the coating chambers as mentioned in the table above.
[00143] The coating knives were each produced from 8 millimeters of thick rigid aluminum plate having a toroidal profile which is shown in Figures 2a and 2b. The profiles of all four coating knives were identical. The rounded edge was represented by the circumference of a quadrant circle that has a radius of 5 millimeters. The width of the span of the respective coating knife in relation to the surface of the substrate could be adjusted free of play by preloaded screws that were supported by the transverse support elements.
[00144] The width of the gap between the edge extending transversely of the respective coating knife and the surface substrate can be modified as follows: _______________________________________________________________
Coating knives Span range with [m] Previous wall 0 - 5,000 1 ^the middle wall 0 - 5,000 2 ^the middle wall 0 - 5,000 Back wall 0 - 5,000
[00145] The substrate was unwound from a crank and transferred under the coating apparatus with a downstream speed that can be changed between 0.01 m / min and 6 m / min. The substrate was tensioned by tension-controlled unwinding cylinders, and two cylinders arranged after the curing station transported the cured film.
[00146] The coating apparatus was furthermore equipped so that a removable strip, after unwinding from a crank, could be guided by the surface upstream of the coating knife from the rear wall and fixed through
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56/100 of the coating knife toroidal profile directly on the exposed surface of the uppermost liquid precursor layer of the layer stack. This is shown schematically in Figure 1.
[00147] The cladding apparatus was, moreover, equipped so that a support, after unwinding from a crank, could be guided by the surface upstream of the anterior wall or 1 ^to 2 ^the intermediate wall, respectively, and fixed through the corresponding toroidal profile edge of the coating knife directly on the respective precursor liquid layer applied through such a coating knife intermediate wall. The substrate formed an integral part of a multilayer film after curing.
[00148] The stack of liquid precursor layers thus prepared was subsequently passed through a UV curing station with a length of 3 m. The curing was carried out both from the top, that is, in one direction, towards the exposed liquid precursor layer optionally covered with a removable strip, and from the bottom, that is, in one direction, towards the substrate, from so that the intensities provided in both directions were maintained at equal levels. The radiation was provided by fluorescent lamps at a wavelength between 300 - 400 nm with a maximum at 351 nm. The total radiation intensity radiated cumulatively from the top and bottom and the respective length of the two coating zones was as follows:
Zone 1(length 200 cm) Zone 2(length 100 cm) Total intensity [molecular weight / cm ² ] 2.07 4.27
Test methods used
Brookfield viscosity [00149] The viscosity of liquid precursors was measured at 25 ° C according to
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57/100 with DIN EN ISO 2555: 1999 using a Brookfield DV-II Digital Viscometer commercially available from Brookfield Engineering Laboratories, Inc.
Adhesion at 90 ° [00150] A sample of cured multilayer film comprising two layers and having dimensions of 12.7 mm wide by 200 mm long was provided. One layer was a pressure sensitive adhesive layer covered with a removable strip, and the other layer was a non-stick polyurethane polymer layer. Both, the multilayer films prepared according to the method of the present description and the comparative multilayer films obtained by laminating the individual layer were tested.
[00151] The removable strip was removed from the pressure sensitive adhesive layer and the multilayer film was fixed through its adhesive surface exposed to a clean glass plate with the use of light finger pressure. Before applying the multilayer film, the glass plate was rubbed with a cloth three times with methyl ethyl ketone and once with heptane. The multilayer film was rolled twice in each direction with a FINAT standard test cylinder (6.8 kg) at a speed of approximately 10 mm / s. After applying the multilayer to the glass surface, the resulting set was kept for a period of 24 hours in ambient conditions before the test. The adhesiveness was then measured using a tensile tester (Model Z020 from Zwick GmbH, Ulm, Germany) at a detachment speed of 300 mm / min. The test plate was kept in a mobile jar for 90 ° detachment tests from the tensile tester. The multilayer film sample was folded back at an angle of 90 ° and its free ends attached to the upper jaw of the tensile tester in a configuration commonly used for 90 ° measurements. Three samples were measured and the results averaged. The results were reported at N / 12.7 mm.
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58/100
Detachment resistance T (T-Peel Strength) [00152] A sample of a multilayer film was provided which comprises two layers and has dimensions of 12.7 mm wide 200 mm long. One layer was a pressure sensitive adhesive layer covered with a removable strip, and the other layer was a non-stick polyurethane polymer layer. Both, the multilayer films prepared according to the method of the present description and the comparative multilayer films obtained by laminating the individual layers were tested.
[00153] A 3M 444 pressure sensitive double-sided adhesive tape was attached to the non-stick surface of the polyurethane-based polymer layer of the multilayer film. The removable strip was removed from the pressure-sensitive adhesive layer of the multilayer film and the resulting assembled laminated film was placed between two strips of anodized aluminum using light finger pressure and leaving two 25 mm long aluminum flaps at the end of each aluminum strip. The resulting assembled laminated film was rolled twice in each direction with a FINAT standard test cylinder (6.8 kg) at a speed of approximately 300 mm / min. The samples were kept for 24 hours in ambient conditions before the tests. The free aluminum flaps were folded back to 90 ° in opposite directions and respectively tightened on the upper and lower jaws of a tensile tester (Model Z020 from Zwick GmbH, Ulm, Germany) and separated at a detachment speed of 300 mm / min. Three samples were measured and the results averaged. The results were reported at N / 12.7 mm.
Optical properties of multilayer films
Sample preparation:
[00154] A sample of multilayer film was provided that comprises two layers and has dimensions of 6 cm wide by 6 cm long.
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59/100 provided. One layer was a pressure sensitive adhesive layer covered with a removable strip, and the other layer was a non-stick polyurethane polymer layer. Both, the multilayer films prepared according to the method of the present description and the comparatives are commercially available from 3M as indicated below have been tested.
[00155] The removable strip has been removed from the pressure sensitive adhesive layer of the multilayer films. The exposed surface of the pressure sensitive adhesive of the multilayer film was rinsed with water to reduce initial adhesion and to ensure defect-free lamination of the film through its adhesive surface to a clear, 2 mm thick float glass plate available next to the surface. Saint-Gobain Glass Deutschland GmbH, Germany. After wet lamination, the remaining water was carefully removed with a lint-free cloth and the samples were stored for at least 16 hours at room temperature to dry completely.
a) Transmission, loss of transmission, absorption, opacity, clarity, lightness and color change of multilayer films and reflection from the surface of the exposed uppermost cured layer of the multilayer film.
[00156] Samples of a multilayer film laminated to a glass were placed in the sample holder of the HunterLab UltraScan XE measurement system, available commercially from Hunter Associates Laboratory, Inc., Reston, VA, USA. The samples were evaluated with an integrating sphere (“Ulbricht-Kugel”) using a D65 light source and an observation angle of 2 °. The 2 mm thick glass plate specified above was used without the multilayer film as a reference.
[00157] The color coordinates of the multilayer film were measured according to the CIE 1931 test method and reported in terms of Y, x, y values. The Y value correlates with the lightness of the film. The color change in relation to the
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60/100 reference glass was evaluated in terms of dx and dy values, respectively, representing the difference in x and y values of the multilayer film with respect to x and y values of the flat glass plate.
[00158] Transmission is defined as the ratio between the light intensity from the multilayer film and the intensity of the incident light. The transmission was measured as the total transmission which is a combination of regular and diffuse transmission. The measurement was conducted according to ASTM E 1438. The loss of transmission is defined as the difference between the intensity of the incident light and the intensity of the light coming from the multilayer film. Transmission and transmission loss were reported in%.
[00159] Absorption is the ratio between the difference between the incident intensity and the transmitted intensity, and the incident intensity. Absorption and transmission add up to 1. Absorption is recorded in%.
[00160] Reflection was measured as total reflection, which is a combination of specular and diffuse reflection. The measurement was carried out as described in DIN 5036, part 3.
[00161] Opacity was measured in transmissive mode according to ASTM D-1003-95. Opacity is defined as the ratio between the diffuse transmission and the total transmission.
[00162] The clarity was measured in the transmission mode according to ASTM D-1003 and D-1044.
b) Refractive index of the cured multilayer film and cured single precursor layers.
[00163] Refractive index of the cured single precursor layers was measured according to ISO 489 using an Abbé refractometer at a wavelength of 589 nm and a temperature of 23 ° C.
c) Optical quality of the multilayer film
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61/100 (i) Siemens star test [00164] A Siemens Star printed with 36 black sectors and 36 white sectors and a diameter of 144 mm was fixed to a vertical wall. A digital photography camera, Canon EOS 450 D, obtained from Canon Deutschland GmbH, Krefeld, Germany, was placed at the front of the Siemens Star with a distance of 1000 mm between lens and Siemens Star. A sample of multilayer glass laminated film was then placed between the camera and Siemens Star, with a distance of 750 mm from the Siemens Star and 250 mm from the camera lens, respectively. Siemens Star and the sample were oriented perpendicular to and centered around the optical axis of the camera.
[00165] The focal length of the camera was set at 55 mm with an aperture of 5.6. The camera has been set to the highest resolution mode, sensitivity to ISO 100. The lighting conditions have been adjusted accordingly to allow a well-exposed digital image.
[00166] The imaging device cannot perfectly reflect the pattern with alternating white and black sectors from Siemens Star. Starting in the middle of the pattern, there is an indistinct zone, the so-called gray ring, where the black and white sectors cannot be distinguished. The size of the gray ring was used to determine the optical quality of the films.
[00167] Digital photography has been modified with a photo editing program or presentation program such as Microsoft PowerPoint. Here, the contrast of the photograph was set at 100% resulting in a black-and-white photograph. In the center there is a uniform black or white circular area. A qualitative assessment of digital photographs is based on the fact that the larger the diameter of this circle, the worse the resolution.
[00168] For a quantitative assessment, a thin line-circle has to be positioned inside the photograph to measure the resulting black or white circle
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62/100 (gray ring). Then, the light level is adjusted so that the diameter of the white circle or the black circle (which does not solve the lines) is minimal. If the area is not exactly a circle, the line must be positioned so that it represents the average of most Siemens Star sectors. The circle line represents the gray ring (Siemens Stars inner circle). The diameter of the small circle was searched for in the software and was recorded as “d”. A second circle line was positioned longitudinally from the outer perimeter of Siemens Star. The diameter of this circle was measured and recorded as "D". The Siemens Star printed diameter of 144 mm was used as a “D_real” reference value.
[00169] The resolving power of a given optical system could be characterized by the spatial frequency of an object detail that could still be resolved. Spatial frequency is commonly described as the number of black and white line pairs per mm (lp / mm) that could be distinguished by the optical system. The spatial frequency of Siemens Star used with n = 36 pairs of black and white sectors is 0.08 lp / mm on the outer perimeter and increasing to infinity lp / mm in the center.
[00170] The resolution power r in lp / mm for sample measurements could be calculated as follows:
r = (n * D) / (d * D_real * π) [00171] The higher the spatial frequency evaluated for the resolution power r, the better the details of an object that could be resolved and the better the performance of the tested sample.
(ii) Measurement of the wavefront deformation [00172] The optical wavefront deformation caused by a multilayer film obtained by the method of the present description or by comparative multilayer films, respectively, was measured with an optical analysis system that comprises a Shack-Hartmann (SSH) sensor. Multilayer film samples
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63/100 laminated to a glass were prepared as described in the Sample Preparation section above and placed in the sample holder of the SSHInspect-TL-SHR-2 “optical test system commercially available from Optocraft GmbH, Erlangen, Germany. The sample is illuminated with 635 nm wavelength light provided by a laser diode coupled to the fiber and collimated by a highly accurate aspherical collimation lens. A flat wavefront of collimated light passes through a sample and is portrayed on the Shack-Hartmann sensor by a Kepler telescope. The sample is located in the focal plane of the Kepler telescope so that deformations of the optical wavefront induced by the sample are shown in the Shack-Hartmann sensor. The Shack-Hartmann sensor determines the local slope of the optical wavefront using a micro-lens assembly and a CCD integrated circuit camera. The measurement system software then reconstructed the integration-deformed wavefront. The optical quality of the samples was characterized by the maximum deformation of the wavefront, recorded as the “peak-to-valley value” of the deformed wavefront to an estimated diameter of 30 mm and measured in multiples of the wavelengths used. The lower the aberration value of the maximum wavefront, the better the optical quality of the film (for example, less distortion of an image projected through the film).
[00173] The wavefront sensor system was activated under the following conditions:
Maximum diameter of a surface area as assessed: up to 53 mm Surface diameterevaluated 30 mm Light source: λ = 635 nm, coupled to fiber in a simple way
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SSHCAM: SHR-150,side resolution: 78x59 micro-lenses Lighting: Flat wave lighting with auxiliary collimation lens
d) Mechanical quality of the exposed surface of the cured layer more superior to the multilayer film
Sample preparation [00174] A sample of the multilayer film was provided which comprises two layers and which is 4 cm wide by 15 cm long. One layer was a pressure sensitive adhesive layer covered with a removable strip, and the other layer was a non-stick polyurethane polymer layer. The removable strip applied to the surface of the adhesive layer was removed and the sample was attached to a 3 mm thick glassy substrate.
(i) Measurement of abrasion resistance [00175] A large block of steel wool 2.54 cm x 2.54 cm grade # 0000 available from hutproducts.com under the designation “113-Magic Sand” was laminated on a steel block of 300 g that has a square cross section of 2.54 cm x 2.54 cm wide and a height of 6 cm. The block was laterally moved over the test sample without exerting any additional normal manual force. A back-and-forth movement was counted as a cycle. The measurement was made after several cycles, the first slightly irreversible scratches that appeared on the exposed surface of the test samples.
(ii) Hardness content of the pencil (Ericson Test) [00176] Several pencils of different hardness levels are sharpened and used to write, with normal manual pressure, on the exposed surface of the test sample. Pencils were used with hardness levels from 6B (the softest) to 9H (the hardest) starting with the softest.
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65/100 [00177] The test consists of defining the hardest pencil that does not leave irreversible traces on the exposed surface of the uppermost cured layer.
List of materials used [00178] GENOMER 4316, aliphatic trifunctional polyurethane acrylate, viscosity (mPas) 58,000 at 25 ° C, Tg 4 ° C, commercially available from Rahn AG, Zurich, Switzerland.
[00179] GENOMER 4312, aliphatic trifunctional aliphatic polyester, urethane acrylate, viscosity (mPas) 50,000 - 70,000 at 25 ° C, commercially available from Rahn AG, Zurich, Switzerland.
[00180] MAUS oligomer, alpha, omega-dimethacryloxyurea-polydimethyl siloxane, Mw ~ 14,000, prepared as described in WO 92 / 16.593, p.26 (where it is called 35K MAUS).
[00181] RE 285, tetrahydrofurfuryl acrylate (THF acrylate), commercially available from Cray Valley, Paris, France.
[00182] Isooctyl acrylate (AIO), isooctyl alcohol and acrylic acid ester, commercially available from the Sartomer Company (CRAY VALLEY), France.
[00183] Acrylic acid (AA), commercially available from BASF AG, Germany.
[00184] 2-Ethyl hexyl acrylate (2-EHA), commercially available from BASF AG, Germany.
[00185] SR506D, isobornyl acrylate (AIB), monofunctional acrylic monomer with a high Tg of 66 ° C, commercially available from the Sartomer Company (CRAY VALLEY), France.
[00186] 1,6-hexane diol diacrylate (DAHD), a fast-curing diacrylate monomer, available for sale from the Sartomer Company (CRAY VALLEY), France.
[00187] Sartomer SR399LV, low viscosity penta acrylate
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66/100 dipentaerythritol, commercially available from Sartomer (CRAY VALLEY), France.
[00188] SR306, tripropylene glycol diacrylate (DATPG), commercially available from Empresa Sartomer (CRAY VALLEY), France.
[00189] F-oligomer is an oligomer containing heptafluoropropylene oxide (HFPO). For the preparation 0.075 eq of (HFPO) -alc, [(F (CF (CFs) CF2O) 6.85CF (CFs) CF2 (O) NH CH2CH2OH, synthesized according to the procedure WO 2007 / 124.263, pages 19 - 21 , “2. Synthesis of intermediates”], 0.5 eq of Tolonate HDB, HMDI biuret available from Rhodia, and 0.425 eq of Sartomer SR 344, pentaerythritol triacrylate available from Sartomer, are reacted according to the procedure as described in WO 2007 / 124.263, p.23, Example 19.
[00190] DAROCUR 1173, 2,2-dimethyl-2-hydroxy acetophenone, commercially available from Ciba Specialty Chemicals, Basel, Switzerland.
[00191] Omnirad BDK, phenyl 2,2-dimethoxy-2-acetophenone (UV initiator), commercially available from iGm resins, Waalwijk, Netherlands.
[00192] Tego Rad 2100, silicon acrylate, commercially available from Evonik Tego Chemie GmbH, Germany.
[00193] Irgacure 500, 1: 1 mixture, by weight, 50% 1-hydroxy-cyclohexylphenyl ketone and 50% benzophenone, liquid photoinitiator, commercially available from Ciba Specialty Chemicals, Basel, Switzerland.
[00194] VAZPIA, acetyl acrylamide photoinitiator, prepared as described in US 5,506,279, col. 14, Example 1.
[00195] ORASOL RED 2B in red color, commercially available from Ciba Specialty Chemicals, Basel, Switzerland.
[00196] EPODYE IN YELLOW COLOR, powdered fluorochrome, commercially available from Struers, Germany.
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List of used curable liquid precursors
Precursor liquid I [00197] 94.95% by weight of GENOMER 4316 and 5.05% by weight of THF acrylate were combined in a glass vessel and mixed for 30 minutes. Then 1 ppc of DAROCUR 1173 and 0.05 ppc of Orasol Red B2 in red was added and the resulting mixture was stirred for 1 hour to provide liquid precursor I.
[00198] The composition of liquid precursor I and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Liquid precursor II [00199] 94.95% by weight of GENOMER 4312 and 5.05% by weight of THF acrylate were combined in a glass vessel and mixed for 30 minutes. Then 1 ppc of DAROCUR 1173 was added and the resulting mixture was stirred for 1 hour to provide liquid precursor II.
[00200] The composition of liquid precursor II and its Brookfield viscosity as determined by the test method described above and summarized in Table 1.
Liquid precursor III [00201] 69.7% by weight of GENOMER 4316 and 30.3% by weight of THF acrylate were combined in a glass vessel and mixed for 30 minutes. Then 1 ppc of DAROCUR 1173 and 0.05 ppc of Epodye in yellow color were added and the resulting mixture was stirred for 1 hour to provide liquid precursor III.
[00202] The composition of liquid precursor III and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Liquid precursor IV [00203] 90% by weight of isooctyl acrylate and 10% by weight of acid
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68/100 acrylic were combined with 0.04 ppc of Omnirad BDK as a photoinitiator in a glass vessel and the mixture stirred for 30 minutes. The mixture was partially polymerized under a nitrogen-rich atmosphere by UV radiation at a degree of polymerization of approximately 8% and a Brookfield viscosity of 3,200 mPa's at 25 ° C. After curing 0.12 ppc of 1,6-hexane diol diacrylate as a crosslinker and 0.16 ppc of Omnirad BDK as a photoinitiator were added and the resulting mixture was thoroughly stirred for 30 minutes to provide liquid precursor IV.
[00204] The composition of the liquid precursor IV and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Precursor liquid V [00205] 84 wt% isooctyl acrylate, 15 wt% isobornyl acrylate, isooctyl and 1 wt% acrylic acid were combined with 0.02 ppc of VAZPIA as a photoinitiator in a glass vessel and the mixture stirred for 30 minutes. The mixture was partially polymerized under a nitrogen-rich atmosphere by UV radiation at a degree of polymerization of approximately 8% and a Brookfield viscosity of 4,720 mPa's at 25 ° C. Subsequent to curing, 0.05 ppc of 1,6-hexane diol diacrylate as a 0.1 ppc crosslinker of Omnirad BDK as a photoinitiator was added and the resulting mixture was thoroughly stirred for 30 minutes to provide liquid precursor V.
[00206] The composition of liquid precursor V and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Precursor liquid VI [00207] 89.3% by weight of liquid precursor V was combined with 10.7% by weight of the MAUS oligomer and 0.25 ppc of HDDA as a crosslinker in a
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69/100 glass and the mixture stirred for 30 minutes to provide liquid precursor VI.
[00208] The composition of liquid precursor VI and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Liquid precursor VII [00209] 76.1% by weight of SR 399LV, 19.1% by weight of TPGDA, 1.9% by weight of the F II oligomer and 2.9% by weight of Irgacure 500 were combined in one glass vessel and shaken for 30 minutes to provide liquid precursor VII.
[00210] The composition of liquid precursor VII and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Precursor liquid VIII [00211] 84 wt% AIO, 15 wt% AIB and 1 wt% AA were combined with 0.2 ppc VAZPIA as a photoinitiator in a glass vessel and stirred for 30 minutes. The mixture was polymerized by UV radiation at a degree of polymerization of approximately 8% and Brookfield viscosity of 12,020 mPa ^ s at 25 ° C. Subsequent to curing, 0.05 ppc of 1,6-hexane diol diiacrylate as a crosslinker and 0.1 ppc of Omnirad BDK as a photoinitiator were added and the resulting mixture was thoroughly stirred for 30 minutes to provide liquid precursor VIII.
[00212] The composition of liquid precursor VIII and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Liquid precursor IX [00213] 89.3% by weight of liquid precursor VII was combined with 10.7% by weight of the MAUS oligomer and 0.25 ppc of HDDA as a crosslinker in a glass vessel and the mixture stirred for 30 minutes to provide liquid precursor IX.
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70/100 [00214] The composition of liquid precursor IX and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Liquid precursor X [00215] 94.24% by weight of GENOMER 4316 and 5.76% by weight of THF acrylate were combined in a glass vessel and mixed for 30 min. Then 0.25 ppc of DAROCUR 1173 was added and the resulting mixture was stirred for 1 hour to provide liquid precursor X.
[00216] The composition of the liquid precursor X and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Liquid precursor XI [00217] 94.57% by weight of GENOMER 4316 and 5.43% by weight of THF acrylate were combined in a glass vessel and mixed for 30 min. Then 0.6 ppc of DAROCUR 1173 was added and the resulting mixture was stirred for 1 hour to provide liquid precursor XI.
[00218] The composition of liquid precursor XI and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Precursor liquid XII [00219] 87.5% by weight of AIOA and 12.5% by weight of AA were combined with 0.04 ppc of Omnirad BDK as a photoinitiator in a glass vessel and stirred for 30 minutes. The mixture was partially polymerized under a nitrogen-rich atmosphere by UV radiation at a degree of polymerization of approximately 8% and a Brookfield viscosity of 4,120 mPa's at 25 ° C. Subsequent to curing, 0.12 ppc of HDDA as a crosslinker, 0.16 ppc of Omnirad BDK as a photoinitiator and 5 ppc of Tego Rad 2100 were added and the resulting mixture was thoroughly stirred by
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71/100 minutes to provide liquid precursor XII.
[00220] The composition of liquid precursor XII and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Precursor liquid XIII [00221] 87.5 wt% isooctyl acrylate and 12.5 wt% acrylic acid were combined with 0.04 ppc of Omnirad BDK as a photoinitiator in a glass vessel and stirred for 30 minutes. The mixture was partially polymerized under a nitrogen-rich atmosphere by UV radiation at a degree of polymerization of approximately 8% and Brookfield viscosity of 4,100 mPa's at 25 ° C. Subsequent to curing, 0.1 ppc of 1,6-hexane diol diacrylate as a crosslinker and 0.16 ppc of Omnirad BDK as a photoinitiator were added and the resulting mixture was thoroughly stirred for 30 minutes to provide liquid precursor XIII.
[00222] The composition of the liquid precursor XIII and its Brookfield viscosity as determined by the test method described above are summarized in Table 1.
Table 1
Precursor Composition Brookfield Viscosity I 94.05% by weight of the GENOMER 43165.05% by weight of THF acrylate1 ppc of Darocur 11730.05 ppc of Orasol Red B2 (colorred) 24,900 mPas II 94.05% by weight of the GENOMER 43125.05% by weight of THF acrylate1 ppc of Darocur 1173 19,900 mPas
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Precursor Composition Brookfield Viscosity III 69.7% by weight of the GENOMER 431630.3% by weight of THF acrylate1 ppc of Darocur 11730.05 ppc of Epodye Yellow in colorYellow 1,650 mPas IV 90% by weight of AIO10% by weight of acrylic acid0.12 ppc of HDDA0.2 ppc of Omnirad BDK 3,200 mPas V 84% by weight of AIO15% by weight of IBOA1.0% by weight of acrylic acid0.05 ppc of HDDA0.1 ppc of Omnirad BDK0.2 ppc of VAZPIA 4,720 mPas SAW 89.3% by weight of liquid precursor liquid V10.7% by weight of BAD oligomer0.25 ppc of HDDA 3,380 mPas VII 76.1% by weight of SR399LV19.1% by weight of TPGDA1.9% by weight of F-oligomer II2.9% by weight of Irgacure 500 480 mPas VIII 84% by weight of AIO15% by weight of IBA1.0% by weight of acrylic acid 12,020 mPas
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Precursor Composition Brookfield Viscosity0.05 ppc of HDDA0.1 ppc of Omnirad BDK0.2 ppc of VAZPIAIX 89.3% by weight of liquid precursor liquid V10.7% by weight of BAD oligomer0.15 ppc of HDDA 3,350 mPas X 94.24% by weight of the GENOMER 43165.76% by weight of THF- acrylate0.25 ppc of Darocur 1173 24,800 mPas XI 94.38% by weight of GENOMER 43165.42% by weight of THF- acrylate0.60 ppc of Darocur 1173 25,000 mPas XII 87.5% by weight of AIO12.5% by weight of acrylic acid0.12 ppc of HDDA0.2 ppc of the Omnirad BDK5 ppc of Tego Rad 2100 4, 120 mPas XIII 87.5% by weight of AIO12.5% by weight of acrylic acid0.1 ppc of HDDA0.2 ppc of the Omnirad BDK 4,100 mPas
Examples 1 to 4 [00223] A coating apparatus was used which comprises two coating stations I and II as described above and schematically shown in Figure 1. A removable strip Hostaphan 2SLK, 75 qm, Mitsubishi was
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74/100 used as a substrate and the downstream speed was modified as indicated in Table 2 below. The anterior and posterior walls were each formed by cladding knives each having a lower portion of toroidal profile and dimensions as described above. The width of the coating chamber (coating station II) in a downstream direction and the gaps between the edge extending transversely from the coating knives and the surface of the substrate are shown in Table 2 below.
[00224] The liquid precursor I was measured at the front of the upstream side of the anterior wall as a rolling microsphere I and the liquid precursor III was filled in the coating chamber. Subsequent to the stacking of the two liquid precursor layers, a removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was applied to an exposed surface of the liquid precursor layer III through the surface upstream of the back wall of the coating knife. The removable strip used as a substrate remained attached to the bottom layer.
[00225] The stack of the two liquid precursor layers between two removable strips was cured by passing it through the UV curing station described in the coating apparatus above to provide the multilayer film comprising two layers of polyurethane.
[00226] Subsequent to curing, the two removable strips attached to the exposed surfaces of the multilayer film were removed and the thicknesses of the cured polyurethane layers were evaluated by taking microphotographs of the cross sections of the multilayer films. The cross sections were obtained by freezing the samples in liquid nitrogen and breaking the samples (cryo fracture) and the microphotographs were taken using a light microscope (ML), Reichert Jung, Polyvar MET. Equipment configurations:
Polyvar MET: incident light / transmitted light / dark field
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Magnification: 100x [00227] The microphotograph of a cross section of the multilayer film from Example 2 is shown in Figure 4. The microphotograph shows a multilayer film comprising 2 layers that are fixed on a sample holder. The bottom layer attached to the sample holder is a red polyurethane layer obtained from liquid precursor I, and the top layer is cured liquid precursor
III. The dark area below the multilayer film is caused by the sample holder. It can be concluded from Figure 2 that the two layers are clearly and precisely separated from each other indicating that essentially no mixing occurs at the interface between the two layers of polyurethane. The thickness value of the cured polyurethane layers is recorded in Table 2 below. The clear layer at the top of the photograph appears slightly red in some areas due to reflections of the light that pass through the red light. Changing the lighting direction moves this effect to different locations in the photograph.
Table 2
Exemplo Downstream speedSpeed of [m / min] Coating station I Coating station II Multilayer film Net price Downstream width of coating chamber [mm] Span [μ m] Net price Downstream width of coating chamber [mm] Span [μ m] Thickness of the bottom layer [im] Top layer thickness [im] 1 0.75 I microsphere 20 III 10 30 152 88
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rolling 0 0 2 1.5 I microsphere 20 III 10 30 102 163 rolling 0 0 3 3 I microsphere 20 III 10 30 102 182 rolling 0 0 4 6 I microsphere 20 III 10 30 110 197 rolling 0 0
Examples 5 to 11 [00228] A coating apparatus comprising two coating stations I and II as described above and schematically shown in Figure 1 was used. A removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was used as a substrate, and the Downstream speed has been modified as shown in Table 3 below. The anterior and posterior walls were each formed by cladding knives, each having a lower portion with a toroidal profile and dimensions as described above. The width of the coating chamber (coating station II) in the downstream direction and the gaps between the lower portion of the coating knives and the surface of the substrate are shown in Table 3 below.
[00229] The liquid precursor I or III, respectively, was measured at the front of the upstream side of the anterior wall as a rolling microsphere (coating station I) and the liquid precursor IV was filled in the coating station II. Subsequent to the formation of the stack of two liquid precursor layers, a removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was applied to the exposed surface of the liquid precursor layer IV through the wall upstream of the back wall coating knife. The removable strip used as a substrate remained attached to the bottom layer.
[00230] The stack of two liquid precursor layers between two removable strips was cured by passing it through the UV curing station described
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77/100 in the above coating apparatus to provide the multilayer film comprising a polyurethane backing layer and a pressure sensitive adhesive top layer.
[00231] After curing, the two removable strips applied to the exposed urethane top layer and the pressure sensitive adhesive bottom layer were removed and the thicknesses of the cured layers of polyurethane and pressure sensitive adhesives, respectively, were evaluated using microphotographs of cross-sections of multilayer films. The cross sections were obtained by freezing the samples in liquid nitrogen and breaking them (cryo fracture) and the microphotographs were taken using a light microscope (ML), Reichert Jung, Polyvar MET. Equipment configurations:
Polyvar MET: incident light / transmitted light / dark field
Magnification: 100x [00232] Microphotographs in cross section of the multilayer films of Examples 5 and 11 are shown in Figures 5 and 6. The multilayer films of Example 5 and 11 each comprise 2 layers through which the lower layer is fixed in each case to a sample holder.
[00233] In the microphotography of Figure 5 (Example 5), the bottom layer of the multilayer film is the cured pressure sensitive adhesive layer while the exposed top layer is the cured polyurethane layer. The clear layer of the pressure sensitive adhesive appears slightly red or yellow in some areas according to the reflections of light that pass through the colored polyurethane layer. Changing the lighting direction moves this effect to different locations in the photograph. It can be concluded from Figure 5 that two layers of the multilayer film are clearly and precisely separated from each other indicating that essentially no mixing took place in the
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78/100 precursor of the multilayer film at the interface between the polyurethane layer and the pressure sensitive adhesive layer.
[00234] In the microphotography of Figure 6 (Example 11), the bottom layer of the multilayer film is the cured pressure sensitive adhesive layer while the top layer is the cured polyurethane layer. The clear layer of pressure-sensitive adhesive appears slightly cloudy because the brittle behavior of the polymer during cryo fracture results in a glassy fracture pattern on the surface of the cross section. The top layer of polyurethane appears slightly yellow due to the yellow dye added with a small dark band on the top of the layer. Such a result of the strip of the portion of the multilayer sample extending behind the plane of the cross section; such a portion can be seen because the multilayer film is slightly folded into DT.
[00235] It can be concluded from Figure 6 that two layers of the multilayer film are clearly and precisely separated from each other indicating that essentially no mixing occurred in the precursor of the multilayer film at the interface between the polyurethane layer and the pressure sensitive adhesive layer .
[00236] The values of the cured polymer layer thickness of the multilayer film are recorded in Table 3 below.
Table 3
Example Downstream speed [m / min] Coating station I Coating station II Multilayer film Precursor Width a Go Precursor Width a Go Thickness Thickness liquid downstream of [m] liquid downstream of [m] gives gives camera of camera oflayer layer coating coatingbackground top
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[mm] [mm][m] [m] 5 0.75 I microsphererolling 200 IV 10 300 130 53 6 1.5 I rolling microsphere 200 IV 10 300 129 71 7 3 I rolling microsphere 200 IV 10 300 121 92.5 8 6 I rolling microsphere 200 IV 10 300 134 80 9 1.5 III rolling microsphere 200 IV 10 300 122 71 10 3 III rolling microsphere 200 IV 10 300 120 70 11 6 III rolling microsphere 200 IV 10 300 122 90
Examples 12 and 13 [00237] A coating apparatus was used which comprises three coating stations I, II and III, respectively, as described above and schematically shown in Figure 1. A removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was used as a substrate, and the downstream speed has been modified as indicated in Table 4 below. The anterior wall, the intermediate wall and the posterior wall were each formed by cladding knives each having a lower portion of toroidal profile as described above. The width of the coating chambers in a downstream direction and the gaps between the edge extending across the coating knife and the surface of the substrate are shown in Table 4 below.
[00238] The liquid precursor II or VII, respectively, was measured in the
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80/100 front of the upstream side of the anterior wall as a rolling microsphere (coating station I) and liquid precursor I or III, respectively, was filled into a coating station II (the first coating chamber in a downstream direction). The liquid precursor IV was filled in a coating station III (a second coating chamber in a downstream direction). Subsequent to the formation of the pile of three liquid precursor layers, a removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was applied to the exposed surface of the liquid precursor layer IV through the wall upstream of the back wall coating knife. The removable strip used as a substrate remained attached to the bottom layer.
[00239] The stack of the three liquid precursor layers between the two removable strips was cured by passing it through the UV curing station described in the above coating apparatus to provide a 3-layer multilayer film comprising a non-polyurethane backing layer. - sticky, a layer in the middle of non-sticky polyurethane and a top layer of pressure sensitive adhesive.
[00240] Subsequent to curing, the removable strips applied to the outer layers of the multilayer film were removed and the thicknesses of the individual cured layers were assessed by taking microphotographs of cross sections of multilayer films. The cross sections were obtained by freezing the samples in liquid nitrogen and breaking them (cryo fracture) and the microphotographs were taken using a light microscope (ML), Reichert Jung, Polyvar MET. Equipment configurations:
Polyvar MET: incident light / transmitted light / dark field
Magnification: 100x [00241] A cross section of a multilayer film from Example 12 is
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81/100 shown in Figure 7a. The microphotography shows 3 layers of the cured multilayer film and a dark area below the film that is caused by the sample holder. The bottom layer of the multilayer film attached to the sample holder is the cured pressure sensitive adhesive layer while the middle layer and the exposed top layer are cured polyurethane layers. The clear bottom layer of pressure-sensitive adhesive appears streaked and slightly red in some areas due to reflections of light passing through the red layer in the middle. The top layer of clear polyurethane appears slightly green / yellow with a dark band on the top of the layer. Such a result of the strip of the portion of the multilayer sample extending behind the plane of the cross section; such a portion can be seen because the multilayer film is slightly folded into DT.
[00242] A macrophotography of a cross-section of the multilayer film of Example 12 taken at a magnification of about 30x is shown in Figure 7b under ambient light in relation to the black glossy curved surface. Under these conditions, the top and bottom layers of the multilayer film appear clear, as previously stated above, and distinctly separate from the red colored middle layer. The slightly blurred appearance of macrophotography is due to a limited number of pixels in a photograph taken with a Canon Poweshot SX 100 IS, obtained from Canon Deutschland GmbH, Krefeld, Germany, using a focal length of 6 mm and the distance between lens and object about 5 mm.
[00243] It can be concluded from Figure 7a that the three layers are clearly and precisely separated from each other indicating that there is essentially no mixing at the interface between the two polyurethane layers as well as at the interface of the polyurethane layer and the adhesive-sensitive layer. pressure. The thickness value of the cured layers is recorded in Table 4 below.
[00244] A photomicrograph of a cross section of a film
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82/100 multilayer from Example 13 is shown in Figure 8. The microphotograph shows 3 layers of cured multilayer film and a dark area below the film that is caused by the sample holder. The bottom and middle layers of the multilayer film are cured, non-sticky polyurethane layers while the top layer is a pressure sensitive adhesive layer. The pressure sensitive adhesive top layer and the polyurethane bottom layer of the multilayer film are clear but appear slightly yellow due to reflections of light passing through the yellow colored middle layer. Changing the lighting direction moves this effect to different locations in the photograph. It can be concluded from Figure 8 that the three layers are clearly and precisely separated from each other indicating that essentially no mixing occurs at the interface between the layers. The thickness value of the cured layers is recorded in Table 4 below.
Examples 14 to 18 [00245] Hostaphan 2SLK, 75 pm, Mitsubishi was used as a substrate, and the downstream speed was modified as indicated in Table 4 below. The anterior wall, the intermediate wall or walls, respectively, and the rear wall were each formed by cladding knives each having a lower portion with toroidal profile and dimensions as described above. The width of the coating chambers in a downstream direction and the gaps between the edge extending across the coating knife and the surface of the substrate are shown in Table 4 below. A two-layer multilayer film was obtained in Examples 14 to 17 while the example 18 multilayer film had 3 layers.
[00246] The liquid precursor I was applied to an upstream coating station I (rolling microsphere) and the liquid precursor V, VI or VIII, respectively, was filled into a coating station II or III, respectively (coating chambers) . Subsequent to the formation of the stack of the two precursor layers
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83/100 liquid, a removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was applied to an exposed surface of the liquid precursor layer III through the wall upstream of the back wall of the coating knife. The removable strip used as a substrate remained attached to the bottom layer.
[00247] The stack of two or three liquid precursor layers, respectively, between the two removable strips was cured by passing it through the UV curing station described in the coating apparatus above to provide the corresponding 2 or 3 layer multilayer films, respectively .
[00248] The composition of the precursor multilayer film and the total polymer layer thickness of the cured multilayer film are summarized in Table 4 below.
[00249] The optical properties of multilayer films measured according to the test method specified above are summarized in Tables 5 and 6 below.
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Table 4
Ex. Downstream speed [m / min] Coating station I Coating station II Coating station III Multilayer film Liquid precursor Downstream width of the coating chamber [mm] Go [m] Liquid precursor Downstream width of the coating chamber[mm] Go [m] Liquid precursor Downstream width of the coating chamber [m] Go [m] Bottom layer thickness [m] Middle layer thickness [m] Top layer thickness [m] Total thickness [m] 12 0.71 II rolling microsphere 100 I 10 200 IV 10 300 63 72 139 274 13 1.5 VII rolling microsphere 80 III 10 300 IV 10 400 20 121 152 293 14 1.5 I rolling microsphere 250 SAW 10 300 - - - 210 15 1.5 I rolling microsphere 300 SAW 10 300 - - - 16 1.5 I rolling microsphere 300 V 10 300 - - - 220 17 0.71 I rolling microsphere 300 V 10 300 - - - 210 18 1.5 I rolling microsphere 250 VIII 10 300 SAW300 200
84/100
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Table 5: Opacity, loss of transmission and color change
Example Y x y Opacity Transmission loss Color change dx Color change dy 14 90.2 0.3131 0.3302 1.88 0.6% 0.0005 0.0004 15 90.27 0.3132 0.3302 2 0.6% 0.0006 0.0004 16 90.5 0.3131 0.3302 1.05 0.3% 0.0005 0.0004 17 90.41 0.313 0.3302 1.19 0.4% 0.0004 0.0004 18 90.93 0.3129 0.3301 1.04 -0.2% 0.003 0.0003 glass ref. 90.77 0.3126 0.3298 0.56 0.0% 0 0
Table 6: Reflection
Example Y 14 7.69 15 7.66 16 7.9 17 7.96 18 7.61 glass ref. 8
Examples 19 to 21 [00250] A coating apparatus comprising two coating stations was used
I and II as described above and schematically shown in Figure 1. A removable strip Hostaphan 2SLK, 75 qm, Mitsubishi was used as a substrate, and the downstream speed was established as indicated in Table 7 below. The anterior and posterior walls were each formed by cladding knives, each having a lower portion with a toroidal profile and dimensions as described above. The width of the coating chamber in the downstream direction and the gaps between the lower portion of the coating knives and the
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86/100 substrate surface as indicated in Table 7 below.
[00251] Liquid precursors I, X or XI, respectively, were measured at the front of the upstream side of the anterior wall as a rolling microsphere (coating station I) and liquid precursors IV or IX, respectively, were filled in a coating station II (coating chamber). Subsequent to the formation of the stack of two liquid precursor layers, a removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was applied to the exposed surface of the top layer of liquid precursor IV or IX, respectively through the wall upstream of the back wall of the coating knife . The removable strip used as a substrate remained attached to the bottom layer.
[00252] The stack of the two liquid precursor layers between the two removable strips was cured by passing it through the UV curing station described in the above coating apparatus to provide the multilayer film comprising an exposed polyurethane backing layer and a layer of pressure sensitive adhesive top attached to the substrate formed by the Hostaphan 2SLK release layer, 75 pm, Mitsubishi.
[00253] Subsequent to curing, the two removable strips were removed and the total thickness of the construction of the dual layer polyurethane film and pressure sensitive adhesive cured was measured.
[00254] The mechanical strength of the polyurethane top layer of the multilayer films was evaluated by measuring the abrasion and scratch resistance as described in the test section above. The results of the two tests described are summarized in Table 8.
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Table 7
Example Downstream speed [m / min] Coating station I Coating station II Multilayer film Liquid Precursor Downstream width of the coating chamber [mm] Go [m] Liquid precursor Downstream width of the coating chamber [m] Go [m] Bottom layer thickness [m] Top layer thickness [m] Total thickness [m] 19 0.71 I rolling microsphere 350 IX 10 450 AT AT 280 20 0.71 X rolling microsphere 350 IX 10 450 AT AT 280 21 0.71 XI rolling microsphere 350 IV 10 450 AT AT 280
87/100
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Table 8
Example Number of abrasive cycles tolerated without damage to the surface Maximum pencil hardness(Ericson test) 19 «500 9H 20 «600 9H 21 «700 9H
Example 22 and comparative example 1a to 1c [00255] A coating apparatus comprising two coating stations I and II as described above and schematically shown in Figure 1 was used. A removable Hostaphan 2SLK strip, 75 pm, Mitsubishi was used as a substrate, and the downstream velocity was established as indicated in Table 9 below. Each anterior wall and posterior wall were formed by cladding knives each having a lower portion with toroidal profile and dimensions as described above. The width of the coating chamber in the downstream direction and the gaps between the edge extending transversely from the coating knives and the surface of the substrate are shown in Table 9 below.
[00256] Liquid precursor X was measured at the front of the upstream side of the anterior wall as a rolling microsphere (coating station I) and liquid precursor XII was filled in a coating station II (coating chamber). Subsequent to the stacking of the two liquid precursor layers, a removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was applied to an exposed surface of the top layer of liquid precursor XII through the wall upstream of the back wall of the coating knife. The removable strip used as a substrate remained attached to the bottom layer.
[00257] The stack of two liquid precursor layers between two removable strips was cured by passing it through the UV curing station described in
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89/100 above coating apparatus for providing the multilayer film comprising a layer of polyurethane and a layer of pressure sensitive adhesive.
[00258] Subsequent to curing, the removable strips were removed and the thicknesses of the cured polyurethane layer and the pressure sensitive adhesive layer, respectively, were evaluated by microscopic evaluation of cross-sections of multilayer films. Cross sections were obtained by cutting samples with sharp razors, and the thickness measurement shown in Table 9 was performed using a light microscope (ML), Reichert Jung, Polyvar MET. Equipment configurations:
Polyvar MET: incident light / transmitted light / dark field
Magnification: 100x
Table 9
Example Downstream speed [m / min] Coating chamber I Coating Chamber II Multilayer film Liquid precursor Downstream width of the coating chamber [mm] Go[m] Liquid precursor Downstream width of the coating chamber [mm] Go [m] Background layer thickness[m] Top layer thickness [gm] Total thickness [gm] 22 0.71 X rolling microsphere 380 XII 10 420 270 70 340
[00259] The optical qualities of the multilayer film of Example 22 were compared to the flexible and conformable 2-layer films below which comprise a layer of polyurethane or polyethylene, and a layer of adhesive sensitive to the opposite pressure. Comparative films are commercially available as follows:
• PUL 2006 3M ™ high performance protective polyurethane film, commercially available from 3M (Comparative Example 1a) • PU 5892 GA7 3M ™ high performance protective polyurethane film, commercially available from 3M (Comparative Example 1b) • P- 450 3M ™ high performance protective polyethylene film, available
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90/100 commercially with 3M (Comparative Example 1c) [00260] The optical quality of the films was determined using the Shack-Hartmann wavefront sensor system and the test method based on Siemens Star as described above. The good optical quality and low image distortion of the flexible film of Example 22 could be seen in the results mentioned in Table 10. The peak-to-valley values of the wavefront deformation summarize the film-induced wavefront deformation protective and glass-induced deformation where the film is laminated. The measurement of the glass reference without the protective film shows that the influence of the glass plate on the deformation of the wavefront is very small compared to the influence of the protective film. The peak-to-valley value of the measured wavefront deformation for the float glass plate is subtracted from the peak-to-valley value of the measured wavefront deformation for the multilayer film applied to the glass reference plate to provide the peak-to-valley value of the wavefront deformation for the multilayer film only.
[00261] Figures 9b to 9e show a photograph of the Siemens Star test for individual films. The Siemens Star test for a glass reference is shown in Figure 9a. The glass reference was a 2 mm thick clear glass plate (calcium carbonate natron silicate float glass) having a refractive index n589 nm, 23 ° c of approximately 1.52.
Table 10
Tested film Peak-to-valley wavefront [in λ = 635 nm] Peak-avale range of the wavefront[in λ = 635 nm] SiemensStar Resolving power r [lp / mm] R range[lp / mm] Example 22 2.93 *) 0.77 Figure 9b 2.9 0.0 Ex. Comp. > 10 **) - Figure 9c 1.2 0.0
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1aEx. Comp.1b > 43 **) - Figure 9d 1.0 0.2 Ex. Comp.1c (evaluation is not possible due to very intense wavefront deformation)Figure 9e 0.6 0.0 Glass reference 0.20 0.01 Figure 9a 3.0 0.3
*) Peak-to-valley value for glass reference subtracted **) Peak-to-valley value for glass reference not subtracted
Example 23 [00262] A coating apparatus comprising two coating stations I and II as described above and schematically shown in Figure 1 was used. A removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was used as a substrate, and the speed at downstream was established as indicated in Table 11 below. The anterior and posterior walls were both formed by cladding knives each having a lower portion with a toroidal profile and dimensions as described above. The width of the coating chamber in the downstream direction and the gaps between the lower portion of the coating knives and the surface of the substrate are shown in Table 11 below.
[00263] The liquid precursor X was measured at the front of the upstream side of the anterior wall as a rolling microsphere (coating station I) and liquid precursor XIII was filled into a coating station II (coating chamber). Subsequent to the formation of the stack of the two liquid precursor layers, a strip
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92/100 removable Hostaphan 2SLK, 75 pm, Mitsubishi was applied to an exposed surface of the liquid precursor top layer XIII through the wall upstream of the back wall of the coating knife. The removable strip used as a substrate remained attached to the bottom layer.
[00264] The stack of two liquid precursor layers between the two removable strips was cured by passing it through the UV curing station described in the above coating apparatus to provide the multilayer film comprising a layer of polyurethane and an upper layer of sensitive adhesive the opposite pressure.
Example 24 [00265] A coating apparatus comprising two coating stations I and II as described above and schematically shown in Figure 1 was used with the modification that a removable strip 15 was applied downstream to the coating apparatus 1 using of a downstream bar 30 having a comma shape with a diameter of 45 mm. The "open face" distance 31 between the surface downstream of the rear wall 12 and the surface upstream of the comma bar (with bar) 30 was 200 mm. The modified coating apparatus used in Comparative Example 2a is shown in Figure 10.
[00266] A removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was used as a substrate 2, and the downstream speed in a downstream direction 3 was established as indicated in Table 11 below. The front wall 11 and the back wall 12 were each formed by cladding knives each having a lower portion with toroidal profile and dimensions as described above. The width of the coating station II (coating chamber) in the downstream direction and the gaps between the lower portion of the coating knives and the substrate surface are shown in Table 11 below.
[00267] The liquid precursor X was measured on the front side of the upstream side
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93/100 of the anterior wall as a rolling microsphere I and the liquid precursor XIII was filled in a coating chamber (coating station II).
[00268] Subsequent to the formation of the pile of liquid precursor layers and after leaving this pile of layers from the coating apparatus, a removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was applied to an exposed surface of the top layer of liquid precursor XIII with the use of the bar 30. The gap between the edge extending transversely from the bar and the exposed surface of layer XIII was initially established so that a rolling microsphere was formed upstream of the bar. The span width was then adjusted by increasing the span to a value where a rolling microsphere just disappeared. This span width was used to apply the removable strip. The removable strip used as a substrate remained attached to the bottom layer.
[00269] The stack of two liquid precursor layers between the two removable strips was cured by passing it through the UV curing station described in the coating apparatus above to provide the multilayer film comprising a layer of polyurethane and an upper layer of adhesive. pressure sensitive.
Comparative example 2a [00270] A simple layer of polyurethane non-adherent, 260 pm thick, was obtained using a coating device in Figure 1, which in this case comprises only a coating knife. The liquid precursor X was measured at the front of the upstream side of such a single-coated knife as a rolling microsphere (coating station I). A removable strip Hostaphan 2 SLK, 75 pm, Mitsubishi was used as a substrate. The downstream speed in the downstream direction 3 and the span between the transversely extending edge of a coating knife and the substrate surface were established as indicated in Table 12 below.
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94/100 [00271] Subsequent to the formation of a precursor layer X, a removable strip Hostaphan 2 SLK, 75 μιτι, Mitsubishi was applied to an exposed surface of the layer through the surface upstream of the coating knife. The removable strip used as a substrate remained attached to the precursor layer X. The precursor layer X was then cured by passing through the UV curing station described in the above coating apparatus to provide a single cured non-stick polyurethane layer. 260 μιη thick X between two removable Hostaphan strips. The refractive index of the precursor layer X was n589 nm, 23 ° C = 1.5030.
[00272] Then one of the removable strips was removed. The cured layer of precursor X was fixed through the remaining removable strip to the bottom lining of the coating apparatus to coat the cured layer of precursor X with a layer of pressure sensitive adhesive from precursor XIII in a second pass. The liquid precursor XIII was measured at the front of the upstream side of such a single-coated knife as a rolling microsphere. The downstream speed in the downstream direction 3 and the span between the span extending transversely from the coating knife and the exposed surface of the cured layer X were established as shown in Table 12 below.
[00273] Subsequent to the formation of a precursor layer XIII, a removable strip Hostaphan 2 SLK, 75 μιη, Mitsubishi was applied to an exposed surface of the precursor layer XIII through the surface upstream of the coating knife. The stack of layers between the two removable strips comprising the precursor bearing layer XIII with the cured X layer was passed through the UV curing station described above.
Comparative example 2b [00274] A single cured pressure sensitive adhesive layer XIII was obtained using a coating apparatus described in Example
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95/100
Comparative 2 (b) above. The coating span and thickness of the cured single-layer film XIII are summarized in Table 12 below. The refractive index of precursor layer XIII was n589 nm, 23 ° c = 1.4734.
[00275] A removable strip was removed from the pressure sensitive adhesive film XIII of the cured single layer and the polyurethane film of the cured single layer non-stick X obtained in Comparative Example 2 (b) above was laminated against each other by passing over the stack of layers with a 200 mm wide hard cylinder and a mass of 2 kg at a speed of approximately 10 mm / s in a forward and backward direction.
[00276] The optical properties of the multilayer films of Examples 23 and 24 and Comparative Examples 2a and 2b were evaluated using the measurement methods presented above. The results are mentioned in Tables 13a and 13b. Siemens Star photographs are shown as Figures 9f - 9i. The surface of the cured top layer of the multilayer film of Example 24 showed macroscopic coating defects (bubbles with a diameter of approximately 1 mm) while the surface of the cured top layer of the multilayer film of Example 23 was essentially free of defects in coating macroscopic.
Table 11
Example Film Downstream speed [m / min] Substrate Coating station I Coating station II Multilayer film Precurs or liquid Downstream width of the coating chamber [mm] Go vm] Precurs or liquid Downstream width of the coating chamber [mm] Go vm] Thickness of bottom lady [m] Thickness of the top lady [m] Total thickness [m] 23 0.71X rolling microsphere 320 XIII 10 420 320 24 0.71X rolling microsphere 320 XIII 10 500 330
Table 12
Example Film Downstream speedSpeed [m / min] Substrate Coating station I Coating station II Multilayer film Liquid precursor Downstream width of Go [one] Liquid precursor Downstream width of Go [m] Thickness of Thickness of Total thickness
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coating chamber [mm] coating chamber [mm]bottom layer [m] top layer [m] [m] Precursor X single layer 0.71X rolling microsphere 220 260260 Single layer of precursor XIII 0.71XIII rolling microsphere 90 7070 Comp. 2 a 0.71 Cured single layer of precursor X XIII Rolling microsphere 420330
Table 13a
Tested film Picoa-Vale wavefront[in λ = 635 nm] SiemensStar Resolving power r [lp / mm] R range[lp / mm] Example 23 3.13 *) Figure 9f 2.5 0.6 Example 24 4.18 *) Figure 9g 1.9 0.1 Comp. Ex.2a 7.03 *) Figure 9h 2.7 0.2 Comp. Ex.2b 8.86 *) Figure 9i 2.3 1.0
*) Peak-to-valley value for glass reference subtracted
Table 13b
Movie Thickness[mm] StreamingT [%] ReflectionR [%] T + R[%] Absorption[%] Reflection without speculating [%] Opacity Clarity Example 0.32 90.74 7.68 98.42 1.58 0.5 1.94 94.9 23 Example 0.33 90.34 8.02 98.36 1.64 0.47 2.08 94.7 24
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Comp.Ex. 2a 0.34 90.14 8.04 98.18 1.82 0.51 2.22 94.9 Comp. 0.33 90.04 8.05 98.09 1.91 0.46 2.43 94.7 Ex. 2b
Example 25 and comparative example 3 [00277] A coating apparatus was used which comprises two coating stations I and II as described above and schematically shown in Figure 1. A removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was used as a substrate, and the downstream speed was established as indicated in Table 14 below. The anterior and posterior walls were each formed by cladding knives, each having a lower portion with toroidal profile and dimensions as described above. The width of the coating chamber in the downstream direction and the gaps between the lower portion of the coating knives and the surface of the substrate as indicated in Table 14 below.
• liquid precursor X was measured at the front of the upstream side of the anterior wall as a rolling microsphere (coating station I) and liquid precursor XIII was filled into a coating station II (coating chamber). Subsequent to the formation of the stack of the two liquid precursor layers, a removable strip Hostaphan 2SLK, 75 pm, Mitsubishi was applied to an exposed surface of the top layer of liquid precursor XIII through the wall upstream of the back wall of the coating knife. The removable strip used as a substrate remained attached to the bottom layer.
[00278] The stack of the two liquid precursor layers between the two liners was cured by passing it through the UV curing station described in the above coating apparatus to provide the corresponding multilayer film comprising a layer of polyurethane and a layer of sensitive adhesive. the pressure.
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98/100 [00279] Subsequent to curing, the removable strip applied to the urethane bottom layer was removed and the thicknesses of the pressure sensitive adhesive and cured polyurethane layers, respectively, were evaluated by microscopy of the cross sections of the multilayer films . Cross sections were obtained by cutting the samples with sharp razors and the thickness measurement shown in Table 14 was performed using a light microscope (ML), Reichert Jung, Polyvar MET. Equipment configurations:
Polyvar MET: incident light / transmitted light / dark field
Magnification: 100x [00280] T-peel strength and 90 ° adhesion to glass were evaluated according to the test method described above and the result is reported in Table 16 below.
Comparative example 3 [00281] The single 270 pm thick non-stick polyurethane layer and a single 70 pm thick pressure sensitive adhesive layer were obtained by curing precursors X and XIII, respectively, each between two ceilings with the use of curing conditions as presented in the “coating device” section above.
[00282] The thicknesses of the single layer adhesive films were summarized in Table 15 below.
[00283] A removable strip was removed from the pressure-sensitive adhesive film of the single layer and the non-stick polyurethane film, respectively, and these were then laminated against each other by passing over the pile of layers with a hard cylinder. with a width of 200 mm and a mass of 2 kg at a speed of approximately 10 mm / s in a forward direction and
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99/100 back.
[00284] T-peel strength and 90 ° adhesion to glass were evaluated according to the test method described above and the result is recorded in Table 16 below.
Table 14
Example Downstream speed [m / min] Coating station I Coating station II Multilayer film Liquid precursor Downstream width of the coating chamber [mm] Go[m] Liquid precursor Downstream width of the coating chamber [mm] Go [m] Bottom layer thickness [m] Top layer thickness [m] Total thickness [m] 25 0.71 X rolling microsphere 320-330 XIII 10 420 270 70 340
Table 15
Laminated protective film Polyurethane layer thickness [m] Thickness of a pressure sensitive adhesive layer [m] Total thickness[m] Comp. Ex. 3 Two-layer laminated protective film (unprepared) 270 70 340
Table 16
Example Detachment resistance T (T-peel strength) [N] Failure mode observed with detachment measures T (T-peel) Detachment resistance 90 ° [N] 25 > 6.38 Sudden detachment from the substrate 6.6 Comp. Ex.3 3.50 Slip separation fault at interface 6.2
List of reference numbers
1 Coating device 2 Substrate 3 Downstream steering 10 Multilayer film precursor 11 Previous wall 12 Back wall 13 Intermediate wall 14 Solid film 15 Release film
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100/100
I - IV
19th
19b
100
101
200
201
202
203
204
205
206
207
210
Coating chamber
Rolling microsphere
Consecutive numbering of coating stations starting from the rolling microsphere (if present) as the coating station further upstream with the following coating chamber numbered in a downstream direction Lower portion of the coating knife
Upstream surface of the coating knife Downstream surface of the coating knives Cured multilayer film Downstream cylinder or bar Open face distance
Go
Coating chamber width Wavefront sensor system Fiber-coupled layer diode Spherical wavefront Aspherical collimation lens Flat wavefront Glass plate
Deformed wavefront
Kepler telescope
Shack-Hartmann sensor device

权利要求:
Claims (9)
[1]
1. Continuous self-measured process to form a multilayer film that comprises at least two overlapping polymeric layers, CHARACTERIZED by the fact that it comprises the steps of:
(i) providing a substrate;
(ii) providing two or more coating knives that are moved, independently of each other, from said substrate to form a normal gap on the surface of the substrate;
(iii) moving the substrate in relation to the coating knives in a downstream direction, (iv) providing liquid polymer curable precursors on the upstream side of the coating knives, thereby coating with two or more precursors through the respective spans as overlapping layers on the substrate;
(v) supplying one or more solid films and applying them simultaneously to the formation of the adjacent lower polymeric layer, and (vi) curing the precursor of the multilayer film that was obtained in this way;
a lower layer of a curable liquid precursor being covered by an adjacent upper layer of a curable liquid precursor or a film, respectively, without exposing said lower layer of a curable liquid precursor.
[2]
2. Process, according to claim 1, CHARACTERIZED by the fact that a removable strip is fixed in step (v) to the exposed surface of the upper layer of the multilayer film precursor simultaneously with the formation of such an upper layer.
[3]
3. Process according to claim 1 or 2, CHARACTERIZED by the fact that the coating knife has an upstream surface, a downstream surface and a lower portion facing the substrate at the distance of the span.
[4]
4. Process according to any one of claims 1 to 3,
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2/3
FEATURED by the fact that liquid precursors have a Brookfield viscosity of at least 1,000 mPa.s at 25 ° C.
[5]
5. Multilayer film CHARACTERIZED by the fact that it is obtainable by the process as defined in claim 2, in which a removable strip is attached to the exposed surface of the upper layer of the precursor of the multilayer film simultaneously with the formation of such an upper layer.
[6]
6. Light-transmitting multilayer film according to claim 5, CHARACTERIZED by the fact that it comprises at least two overlapping polymeric layers, each having a transmission of at least 80% in relation to visible light, with the multilayer film exhibiting a transmission in relation to visible light that is greater than the transmission of a comparative multilayer film obtained by a method that differs from the above method in that the removable strip is attached to the exposed surface of the upper layer in a position downstream of the formation of the top layer of the multilayer film precursor.
[7]
7. Multilayer film, according to claim 6, CHARACTERIZED by the fact that the ratio between the transmission of the multilayer film and the transmission of the comparative multilayer film is at least 1.002.
[8]
8. Light-transmitting multilayer film according to claim 6 or
7, CHARACTERIZED by the fact that it comprises: at least two overlapping polymer layers, in which one of the outer layers comprises a polyurethane polymer obtainable from the polymerization of a liquid precursor comprising at least one ethylenically unsaturated urethane compound and in which the another opposite outer layer comprises an adhesive, the multilayer film having a maximum wavefront aberration of a wavefront resulting from a planar wavefront of a wavelength of λ = 635 nm, normally affecting the outer layer opposite the adhesive outer layer and transmitted through the multilayer film, measured as the peak-to-valley value of the wavefront
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3/3 transmitted less than 6 λ (= 3,810 nm).
[9]
9. Light-transmitting multilayer film according to claim 8, CHARACTERIZED by the fact that the ethylenically unsaturated polyurethane compound is a methacrylate urethane compound.

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JP2021084931A|2021-06-03|Adhesive sheet

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JP2021120449A|2021-08-19|Adhesive composition, adhesive layer, and adhesive sheet

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JP2019196468A|2019-11-14|Adhesive layer, method for producing same, adhesive sheet, adhesive layer-attached optical film, and image display device

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JP2021059618A|2021-04-15|Adhesive composition and adhesive sheet

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TW202128934A|2021-08-01|Adhesive sheet, flexible image display device member, optical member, and image display device

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JP2009299078A|2009-12-24|Pressure-sensitive adhesive sheets

同族专利:

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公开号 | 公开日

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EP2632608B1|2017-01-18|

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KR101852208B1|2018-04-25|

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EP2632608A1|2013-09-04|

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CN102821871A|2012-12-12|

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WO2011094385A1|2011-08-04|

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KR20120139703A|2012-12-27|

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JP2015205268A|2015-11-19|

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JP5898096B2|2016-04-06|

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JP2016135482A|2016-07-28|

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EP2353736A1|2011-08-10|

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CN102821871B|2015-04-08|

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US20130004694A1|2013-01-03|

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JP6105666B2|2017-03-29|

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JP2013517942A|2013-05-20|

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BR112012018982A2|2017-01-24|

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DE112011105079T5|2014-02-06|

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法律状态:
2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: B05D 1/42 (2006.01), B05D 7/00 (2006.01), C08G 18/ |

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2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-01-29| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2019-08-13| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2019-11-26| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-02-04| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/01/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP10152185A|EP2353736A1|2010-01-29|2010-01-29|Continuous process for forming a multilayer film and multilayer film prepared by such method|

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PCT/US2011/022685|WO2011094385A1|2010-01-29|2011-01-27|Continuous process for forming a multilayer film and multilayer film prepared by such method|

---