• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention provides a retroreflective sheet comprising a structured film having a structured member arrangement and a sealing film attached to the structured film by a plurality of riveted connections, wherein the riveted connections penetrate the sealing film. The riveted connection preferably forms a flange. The sealing film is preferably a thermoplastic polymer having a ductility of at least about 20%. The retroreflective sheet according to the present invention may comprise a seal coating located on the seal film. In some embodiments, the seal coating may be provided from a seal coating precursor having a radiation curable component. The invention also includes a method of making various embodiments of retroreflective sheets.
    公开号:KR20000005167A
    申请号:KR1019980707836
    申请日:1997-03-11
    公开日:2000-01-25
    发明作者:부르스 비 윌슨；쉐럴 엠 프레이
    申请人:스프레이그 로버트 월터；미네소타 마이닝 앤드 매뉴팩춰링 캄파니；
    IPC主号:
    专利说明:

    Structured retroreflective sheet with riveted connections
    The retroreflective sheet has the capability of reflecting incident light back to its light source. This advantageous property allows retroreflective sheets to be used in a wide variety of articles. Typical examples of retroreflective sheets are microsphere sheets and structured sheeting such as cube corner sheets.
    Microsphere sheets, which are sometimes referred to as “beaded” sheets, are well known in the art, and are usually specular or diffusely reflective materials incorporated at least partially into the binder layer and bonded to the retroreflective sheet. The majority of glass microspheres or ceramic microspheres with (eg pigment particles, metal fragments or vapor coating) are used. Examples of such retroreflectors are disclosed in US Pat. Nos. 3,190,178 (Meckenzi), 4,025,159 (Meggrass) and 5,066,098 (Kult).
    Structured retroreflectors typically include a sheet having a structured retroreflective member arrangement projecting from a flat front and back. Cube corner structured retroreflective members typically have a trihedral structure with sides that are approximately three mutually perpendicular at a single corner. In use, the retroreflector is generally arranged in front facing away from the intended position of the intended observer. Incident light is totally reflected at the face of the structured member so that it enters the sheet in front and passes through the body of the sheet and exits from the front in the direction toward the light source (ie, the incident light is retroreflected). Since structured retroreflective sheets typically have a geometric shape that is a cube corner, it is to be understood that what is mentioned below is a cube corner type retroreflective sheet and is applicable and generally referred to as a structured retroreflective sheet. Where structured retroreflective sheets are specifically cited, it is to be considered that they include cube cornered sheets, and any other structured sheet may be used in retroreflective applications.
    Light rays are typically reflected at the structured member surface by specular reflective coatings such as total internal reflection (TIR) or deposited aluminum films. Reflectors using TIR require a low refractive index interface, typically air, between the surface and the material. Examples of cube corner reflectors include U.S. Patent Nos. 3,712,706 (Stam), 4,025,159 (McGrass), 4,202,600 (Burke et al.), 4,243,618 (Ban Anam), 4,349,598 (White), 4,895,428 ( Nelson et al.) And PCT Publication No. WO 95/11469 (Benson et al.). Typically, the structured retroreflective sheet uses retroreflective brightness (ie, retroreflectivity) that is at least about 50 candela / lux / m 2 .
    If the structured retroreflective sheet is susceptible to moisture (eg, outdoors or high humidity), the structured retroreflective member may be exposed to moisture, oil, and dirt, such as moisture, oil, Protect from foreign matter. It is common to use a continuous film (also called a sealing film) attached to a structured member having individual patterns that become sealed cells, as disclosed in U.S. Patent Nos. 4,025,159 (McGreece) and 5,117,304 (Huang). Conventional sealing films can be single or multilayer thermoplastic or thermoplastic / thermosetting films attached to the structured surface. The sealing film maintains an air interface around the structuring member to maintain retroreflectivity with lower refractive index. The sealing film also protects the surface from deterioration caused by environmental exposure.
    Conventional sealing films are attached to structured members by applying heat and pressure. A cell pattern (ie, a cell) is created by continuously contacting the structured surface using an embedding mechanism in the sealing film. The contact area between the sealing film and the tip of the structured member is not retroreflective. In addition, the embedding process may deform or break the structured member. Reducing the surface area with respect to the TIR reduces the overall efficiency of the retroreflector, thereby lowering the brightness of the sheet structure.
    The durability of the structured retroreflective sheet will in part prevent the moisture and moisture in the cell from collecting. The goal is to maintain the sealing of the cells to prevent moisture from penetrating these cells. Therefore, more durable sealing is required for cube corner retroreflective sheets and other structured retroreflective sheets.
    The present invention relates to structured retroreflective sheets. More specifically, it relates to a cube corner type retroreflective sheet having a seal film and a cube corner attached with an interlock mechanism with an optional seal coating.
    1 is a top view of the back side of a cube corner retroreflective sheeting;
    FIG. 2 is a sectional view showing the cube corner member arrangement shown in FIG. 1. FIG.
    3 is a cross-sectional view of a structured retroreflective sheet according to the invention with a cube corner film, a sealing film and a riveted connection according to the invention.
    4 is a schematic view showing one pattern of a cell formed using the riveted connection according to the present invention.
    5 is a cross-sectional view of an arrangement of cube corner members in another embodiment that engages raised structures.
    FIG. 6 is a cross-sectional view of a cube corner retroreflective sheet using the cube corner film of FIG. 5. FIG.
    7 is a plan view showing a pattern of raised structures of cube corner-shaped films useful for making retroreflective sheets according to the present invention.
    8 is a schematic diagram illustrating a method of making a structured retroreflective sheet according to the present invention.
    The present invention provides a retroreflective sheet comprising a structured film having a structured member array and a sealing film, wherein the sealing film is attached to the structured film by a plurality of riveted connections. Here, the first face of the sealing film faces the structured member, and the second face faces the direction away from the structured member. The riveted connections each have holes formed in the sealing film that protrude through the portion of the structured film so that the sealing film is attached to the structured film. While the structured retroreflective sheet includes a cube corner film having a cube corner member arrangement, it is preferred that structured members having other shapes and geometries can be used to form the riveted connections of the sealing film.
    In another embodiment, the portion of the structured film that protrudes through the hole in at least one of the riveted connections extends to form a flange adjacent the second side of the sealing film. In another embodiment, the riveted connection may be located in a predetermined pattern.
    In yet another embodiment, the sealing film comprises a thermoplastic polymer and has a ductility of at least about 20%. In another embodiment, the thermoplastic polymer is ethylene-propylene grafted with a mixture of cast polyether, cast polyester, cast polyamide, ionomeric ethylene copolymer, plastic vinyl halide polymer, poly-alpha-olefin, styrene and acrylonitrile. Non-conjugated diene terpolymers as well as other styrene-acrylonitrile copolymers such as styrene-acrylonitrile graft copolymers, acrylonitrile-butadiene-styrene graft copolymers and extractable styrene-acrylonitrile copolymers And combinations or mixtures thereof.
    The retroreflective sheet according to the invention may comprise a seal coating formed on the seal film. In some embodiments, the seal coating may be provided from a seal coating precursor that includes a component that is cured by spinning, such as acrylate.
    The invention also encompasses a method for implementing various embodiments of retroreflective sheets according to the invention.
    The above and other features of various embodiments of the present invention are more fully described in the following brief description of the drawings and the description of the invention, and like reference numerals designate like parts. However, because the detailed description and drawings (not to be drawn on scale) are merely illustrative of the present invention, it does not improperly limit the scope of the present invention.
    In describing preferred embodiments of the present invention, specific terminology will be used for the sake of clarity. However, it is to be understood that the invention is not to be limited by the specific terms selected, and that each term selected includes all technical equivalents that yield similar results.
    1 and 2 schematically illustrate a portion of a typical repeated cube corner retroreflective sheet 10. Geometrically structured forms of articles of this type are disclosed, for example, in US Pat. Nos. 3,810,804 (Roland) and 4,588,258 (Hoopman). Referring to FIGS. 1 and 2, reference numeral 12 generally denotes one of the fine cube corner members of the arrangement disposed on one side of the sheet 10. Each member 12 has three exposed planes 14 substantially perpendicular to each other. The vertices 16 of the prism may be aligned perpendicular to the bottom center but are not necessary. The angle between the planes 14 is the same angle, ie about 90 °, for each cube corner member arranged. However, the angle may deviate slightly from 90 ° depending on the desired application. The vertices 16 of each cube corner member 12 may be aligned vertically with the bottom center of the cube corner member, but may be inclined away from the center of the bottom surface as disclosed in US Pat. No. 4,588,258. It may be. Therefore, the present invention is not limited to any particular cube corner shape, but is preferably used in a cube corner shape that can be used as a retro reflector. In addition, the structured retroreflective sheet of the present invention is not limited to the use of cube corner members, but other shapes are possible as long as they have retroreflective properties and can form riveted connections as described in more detail below. Of the many possible shapes, however, cube corner sheets disclosed in US Pat. No. 4,588,258 are preferred. This is because this sheet provides a wide angle of retroreflectivity among multiple viewing planes.
    As illustrated in FIG. 1, the cube corner members 12 in the sheet 10 may all have the same dimensions, exist in the same plane, and may be arranged in an array or pattern of columns and rows. However, if desired, different members on the arrangement may have various dimensions and orientations. The cube corner member 12 is disposed above the body portion 18, below or in front of the body portion 20 which is substantially smooth or flat. Body portion 18, which tends to be referred to as a "land," is typically integrated with cube corner optical member 12. The land dimension of the sheet relative to each cube corner member depends on the method selected at the time of manufacture, which in turn may depend on the end use of the sheet.
    Structured retroreflective sheets of the present invention generally have good chemical and mechanical durability, good dimensional stability and high retroreflectivity. The retroreflective sheet includes a structured retroreflective film comprising a plurality of structured members and a sealing film attached to the structured member to produce a cell pattern, such as disclosed in US Pat. No. 4,025,159. This sealing film protects the structured member from environmental degradation. The sealing film also provides a sealed air layer around the structuring member that holds the total reflection mechanism of the sheet as it is exposed to environmental conditions such as moisture, dust, or the like, leading to degradation of the optical properties.
    The retroreflective sheet of the present invention typically exhibits a retroreflective brightness, i.e., a retroreflective coefficient of at least about 50, preferably at least about 250, more preferably at least about 500 candela / lux / m 2 , these values being ASTM According to Method E810-94, measured at an angle of incidence of -4 ° and observation angle of -0.2 ° with the sheet lying flat.
    Preferred embodiments of the invention include a separation layer of a binder disposed on the sealing film that binds the sealing film to the structured retroreflective film to protect the structured member from environmental invasion. In some embodiments, the binder also provides additional mechanical strength to the retroreflective sheet. The structured retroreflective film, sealing film and / or binder may also impart color to the retroreflective sheet. Certain embodiments of the retroreflective sheet according to the present invention also include an overlay film disposed on the structured retroreflective film on a surface facing the surface of the sealing film.
    A backing layer or adhesive layer can be provided on the retroreflective sheet, if desired, to secure the retroreflective sheet to the substrate. Various heat activated adhesives, solvent activated adhesives, pressure sensitive adhesives or other adhesives may be applied or laminated to the back side of the sheet to adhere the retroreflective sheet to the substrate. In addition, the release liner may be disposed on the adhesive layer if desired.
    In one application, retroreflective sheets made in accordance with the present invention may be affixed to signs for use as, for example, traffic control, commercial advertising, information, etc. as internal or external signs.
    3, one embodiment of the structured retroreflective sheet 30 of the present invention is shown. In this embodiment, structured retroreflective sheet 30 has a cube corner film 35, a sealing film 36, a seal coating having a plurality of cube corner members 32 and a body, ie, a “land” portion 34. (38; optional) and overlay film 40 (optional). In the preferred embodiment, the overlay film 40 is the outermost layer of the front side of the sheet 30. The land portion 34 of the cube corner film 35 is distinguished from the overlay film 40 as a layer disposed very close to the bottom surface of the cube corner member 32. The sealing film 36 and the seal coating 38 generally serve to protect the cube corner member 32 from environmental degradation and / or to provide additional mechanical strength to the sheet. Selective layer 39 of adhesive is also shown with sheet 30 attached to a substrate (not shown).
    The cube corner film 35 and the optional overlay film 40 preferably each comprise a light transmissive polymeric material. For this material, the cube corner member 32 and the land portion 34 of the cube corner film 35 may be the same or different. Light enters the cube corner sheet 30 through the front face 41 of the cube corner film 35 and the optional overlay film 40. The light then passes through the land portion 34 and strikes the plane 42 of the cube corner member 32. The light then returns in the same direction as the direction in which the light was incident, as shown by arrow 43.
    In most cases, the land portion 34 is integral with the cube corner member 32. Because of being "integral", the land portion 34 and the cube corner member 32 are formed in a single process from a single polymeric material, but this means that two different polymeric layers are not continuously joined. Land portion 34 typically has a thickness of about 250 μm or less, preferably about 1200 μm. Although it is desirable to keep the land portion to a minimum thickness (in some embodiments, it may be zero without an intermediate portion between the bottom surface of the cube corner member and the overlay film), the sheet 30 may not cover some land portions 34. Including, a flat interface can be provided between the cube corner member 32 and the overlay film 40. Typically the cube corner member 32 has a height of about 20-500 μm, more typically a height of about 60-175 μm. The sealing film 36 generally has a thickness of about 10-250 μm, preferably about 10-200 μm, and most preferably about 25-80 μm. The seal coating 38 typically has a thickness of about 10-250 μm, preferably having a thickness of about 10-80 μm. Overlay film 40 typically has a thickness of about 10-200 μm, preferably about 10-100 μm. Although the embodiment of the present invention shown in FIG. 3 is a single layer of overlay film 40, it is possible to provide a multilayered overlay film if desired within the scope of the present invention.
    The polymeric material of the structured film and overlay film of the present invention is light transmissive (if no colorant is added). This means that the polymer transmits at least 70% of the incident light at a given wavelength. The light transmittance of the polymer is preferably at least about 80%, more preferably at least about 90%. Thus, particularly preferred light transmitting polymers are almost transparent. The polymeric material of the sealing film and seal coating of the present invention may or may not be light transmissive, but is generally impermeable to materials that may degrade the structured member.
    One or more of the structured film, sealing film, seal coating and overlay film may be modified to include colorants such as dyes and / or pigments. In general, retroreflective sheets may be formed of the first color in daylight or any other nearly collimated light (ie, non-reflected light) and generally collimated light, such as automotive headlights (ie, generally retroreflected). And a second color when irradiating light). For example, if the structured film is colored and the sealing film is colored differently, the daylight color will be the combined color of the sealing film and the structured film, but the retroreflected color will be the color of the structured film. In addition, both the structured film and the sealing film are colorless, light transmissive, and the seal coating can be colored to diffuse more color in this configuration. It is known to introduce colorants into the components of the retroreflective sheet 30.
    Sealing film 36 is attached to a structured member, such as cube corner member 32, through a unique " riveted " connection 50. This connecting portion 50 is preferably located in a pattern forming an array of cells 24 as shown in FIG. The cells 24 are each bonded by a sealing leg 26 which generally corresponds to the pattern formed on the embossing rolls. This connection part 50 is arranged along the sealing leg 26 at irregular intervals based on the sealing film 36 being penetrated by the cube corner member 32.
    It should be appreciated that the pattern shown in FIG. 4 may be provided for attaching the sealing film 36 and the cube corner film 30 (or other structured film) to any suitable pattern of connections 50. The sealing legs 26 preferably cross to define individual cells 24, and in some cases the sealing legs 26 may not cross. Further, the contacts 50 need not be aligned along any sealing leg or any other pattern, but are preferably provided in a pattern that is spaced irregularly or does not define the cell 24 as shown in FIG. 4.
    The connecting portion 50 preferably has the sealing legs 26 each forming a seal in the sealing cell 24. It will be appreciated, however, that the sealing legs 26 are each sealed and do not need to be sealed in some structures where, for example, no sealing protection is required in the structuring member in the cell 24.
    The "riveted" connection 50 is formed by destructive interference between the sealing film 36 and a structured film such as cube corner film 35. Essentially, the structured film allows the structured film to pass through the sealing film through the area of each connection 50 under temperature and pressure resulting in the structure passing through the sealing film and expanding (ie flattening) horizontally. As shown in FIG. 3, each connection 50 is more conventional than at least one shank portion 52 extending through the aperture of the sealing film 36 and the aperture formed through the sealing film 36. It is common to include a larger flange 54. The larger flange portion 54 typically results in the diffusion of material from the cube corner member 32 through the sealing film 36. This means that the material from the cube corner is flattened and the flange portion is at least slightly larger than the hole so that the flange portion cannot pass back through the hole again without deforming or twisting the hole. Since the flange portion 54 is larger than the corresponding hole through the sealing film 36, the flange portion is positioned to push the opposing surface of the sealing film. This is an interlocking bond between the shank 52, the flange 54 and the sealing film 36 providing a mechanical connection between the sealing film 36 and the cube corner film 35.
    The flange 54 need not be formed through every hole in the sealing film 36, but a black hole will accompany the flange 54. When the holes of the sealing film 36 are formed closely, the flanges 54 from adjacent holes can be in the same direction as each other, which makes the bond between the cube corner film 35 and the sealing film 36 more firm. Can be. Here, "flange" and "flange" are used in the same sense, and "shank" and "shank" are also used in the same sense.
    If the cube corner film 35 was simply laminated to the sealing film 36 as disclosed, for example, in US Pat. No. 4,025,159, this mechanical connection 50 was absent. However, it is the interlocking connection that contributes to the durability of the connection between the structured film and the sealing film of the present invention.
    In one preferred method, the heat and pressure used to form the contacts 50 are applied through the sealing film 36 using a patterned embossing roll heated to a temperature higher than the temperature at which the sealing film 36 melts. . It will be appreciated that there are other ways of providing the necessary energy that can be used to form the connection 50, such as ultrasonic welding or the like. In addition, although the cube corner member 32 will penetrate the sealing film 36 and form a connection 50 through heat and / or pressure, the sealing film 36 may be chemically reacted or mechanical (eg, thermal). Through a combination of energy and chemical reactions, holes may be formed in each region of the connection 50.
    In a conventional thermal / mechanical method of forming a connection via embossing, the temperature of the embossing roll is at least about 10 ° C. above the temperature at which the sealing film melts. This temperature is preferably above the glass transition temperature of the polymer of the structured film (eg, cube corner film). Typically, the temperature of the embossing roll is at least about 50 ° C. above the glass transition temperature of the polymer of the structured film. During the process, the sealing film 36 is melted and formed with holes by a structured member such as cube corner member 32. The tip of the cube corner member 32 will melt and extend to form the flange portion 54 of the riveted connection 50. The structured member may therefore have a different shape or geometry than the cube corner member, as long as there are other features that can form holes in the tip or sealing film and form riveted connections.
    The connection 50 is additionally protected and sealed by a sealing coating 38 provided on the sealing film 36. The seal coating 38 helps to prevent moisture from penetrating into the volume formed between the seal film 36 and the cube corner member 32. The material for the seal coating 38 and the method of applying the seal coating 38 are described in detail below.
    Another embodiment of a cube cornered sheet 130 is shown in FIGS. 5 and 6. An embodiment of the cube corner member sheet 130 includes a cube corner film 135 composed of a plurality of cube corner members 132 and land portions 134 to which the members 132 are attached. In addition, the sheet 130 may include an overlay film 140 as described above with respect to the embodiment shown in FIG. 3. The main difference between the cube cornered film 30 (shown in FIG. 3) and the cube cornered film 130 (shown in FIGS. 5 and 6) is that the film 130 is formed of a cube cornered film 135. And a raised structure 137 extending from the land portion 134. The raised structure 137 is shaped to penetrate the sealing film 136 to form the riveted connection 150 in the same manner as described for the structuring member 32 of the cube corner film 30. It is preferable to include the penetrating member 133 on the top.
    As shown in FIG. 6, when the sealing film 136 and the cube corner film 130 are forced together at a suitable temperature and pressure, the member 133 penetrates the sealing film 136, and FIG. 3. A " riveted " connection 150 is formed having a through portion similar to that formed in the embodiment shown in FIG. 3 and a shank portion 152 extending through the flange portion 154.
    Referring to FIG. 7, raised structure 137 may be provided as ridge 170 as shown, where ridge 170 defines region 172 in which the structured member is not located.
    Although the repeating pattern of raised ridge 170 is in the preferred embodiment of raised structure 137, it should be noted that raised structure 137 may be provided as a ridge that can be arbitrarily oriented without intersecting. do. In addition, the raised structure 137 may be provided as a plateau riser that is unconnected on the land portion 134. In such embodiments, the plateaus may be located in a patterned arrangement or distributed randomly on the surface of the cube corner film 135. Structured retroreflective sheets with raised structures and methods for making them are disclosed, for example, in US Pat. No. 3,924,929 (Holmen et al.) And PCT Publication No. WO 95/11469 (Benson et al.). The penetrating member 133 on the raised structure 137 must be able to form a riveted connection and may be retroreflective.
    One advantage of including the raised structure 137 in the cube corner film 130 is that additional space is provided between the cube corner member 132 and the raised structure 137. This additional space may ensure that the peak of the cube corner member 132 does not contact the sealing film 136. If such a peak is in contact with the sealing film 136, the difference in refractive index required for total reflection may be lost in the contact area, thereby reducing the efficiency of the retroreflective sheet 130 by causing light to be refracted out of the cube corner member 132. Drop.
    8 illustrates one method of making retroreflective sheets in accordance with the present invention using web-fed equipment. In the method shown, the sealing film 62 is attached to the organized film 64 by passing two films between the nip roller 66 and the embossing heat roller 68. The textured film is adjacent to the nip roller 66 with the organized member tip (eg, cube corner peak) interviewing the embossing roller 68. The sealing film 62 is adjacent to the structured member tip. Suitable pressure is applied to the components on the raised embossing pattern 70 carried on the surface of the embossing roller 68. Counterforce nip rollers are preferred for rollers with fairly solid rubber smooth surfaces, such as 40-80 durometer rollers. For example, the embossing roller is tightly patterned, which is used to apply pressure to the material to be welded at only one point of the raised pattern 70. Embossing roller 68 and rigid durometer roller 66 are both heated with suitable heat depending on the composition of the polymer used in the two layers.
    The sealing film 62 is melted while being pierced by the peak of the structured member and melted to form a riveted connection 50 as shown in FIG.
    In order to protect the embossing roller 68, a separation film 72 can be disposed between the sealing film 60 and the embossing roller 68. Typically, the separator film 72 is polyethylene terphthalate at least about 5-200 micrometers and 10-20 micrometers thick. This arrangement allows heat and pressure to be transferred through the polyethylene terphthalate, resulting in a riveted connection of the sealing film and the cube corner peak. The thickness of the other film can be used as long as heat and pressure can be transferred through the material from the embossing roller to the sealing film without melting the separation film. For example, poly (tetrafluorethylene) may be used, as well as other materials having a melting temperature of about 230 ° C. or higher.
    In a preferred method of making the sheet of the invention, the film can be pre-heat treated before embossing. The embossing roller surface temperature is about 150-325 ° C., about 170-270 ° C. is preferred. The rubber roller surface temperature is about 70-120 ° C, preferably about 85-100 ° C. The nip force between the rollers is about 100-200 Pascals, with about 130-170 Pascals being preferred. Under the above conditions, the web speed may be about 10 meters per minute. However, it should be noted that preheating the film or adjusting the roll temperature or nip force results in faster processing.
    In addition, one of ordinary skill in the art will understand that the exact temperature, pressure and web speed will depend on the materials used.
    Structured retroreflective film
    The polymeric material (eg cube corner member) and the land portion of the structured member are preferably thermoplastic and have a very high refractive index such that the end product has sufficient durability and weathering as well as high efficiency retroreflective properties (relative to other polymers). Having a solid and hard material. Here, "thermoplastic" means a material that becomes soft when heated and returns to its original state when cooled.
    Suitable polymeric materials of the structured member have a relatively high refractive index, a relatively high glass transition temperature (Tg), as well as a higher melting temperature (Tm) than that of the material of the sealing film. Typically, the refractive index of the polymer of the structured member is at least about 1.5. Typically, Tg is greater than about 100 ° C, preferably greater than about 120 ° C. Typically, the Tm of the polymer of the structured member is higher than about 30 ° C. than the Tm of the polymer of the sealing film as described below. The difference in the melting temperature of the sealing film and the structured member is necessary for the formation of the riveted connection as described above. It is preferred to be about 50 ° C. larger than the Tm of the polymer of the sealing film, more preferably about 80 ° C. larger. Typically the polymer used in the sealing film has a melting temperature (Tm) of greater than about 25 ° C, preferably about 80 ° C. Even more preferably, the Tm of the polymer used in the sealing film is about 80-200 ° C., most preferably 80-140 ° C.
    In general, the thermoplastic polymer used in the structured member is amorphous or semicrystalline. In embodiments without an overlay film or seal coating, the thermoplastic polymer, preferably the land portion, used in the structured member is chemically and mechanically durable to prevent degradation from environmental factors. As described above, the polymeric material used for the land portion of the structured film may be the same as the polymer used for the structured member.
    Examples of thermoplastic polymers that can be used in the structured member include, but are not necessarily limited to, acrylic polymers such as poly (methyl methacrylate), polycarbonates, polyamides, cellulose acetates, cellulose (acetate co butyrates) ), Celluloses such as cellulose nitrate, polyesters such as poly (butylene terephthalate) and poly (ethylene terephthalate), and fluoros such as poly (chlorofluoroethylene) and poly (vinylidene fluoride) Polymers, polyamides such as poly (caprolactam), poly (amino caproic acid), poly (hexamethylene diamine coadipic acid), poly (amide coimide), poly (ester coimide), and polyether Polyolefins such as ketones, poly (etherimide), poly (methylpentene), poly (phenylene ether), poly (styrene coacrylonitrile), Poly (styrene) and poly (styrene) copolymers, such as li (styrene coacrylonitrile cobutadiene), and silicone modified polymers such as silicone polyamides and silicone polycarbonates (i.e., at least 10 weight percent of silicone Polymers), and mixtures of the above-described polymers such as polyamide and acrylic polymer mixtures and fluorine modified polymers such as perfluoropoly (ethylene terephthalate) and poly (methylmethacrylate) and fluoropolymer mixtures It includes.
    Preferred thermoplastic polymers for the structured member include acrylic polymers, polycarbonates, polyamides, and mixtures thereof. Such polymers are preferred for one or more of the following reasons. Advantages of impact resistance, dimensional stability, thermal stability, environmental stability, transparency, excellent recoverability from tooling or casting, and high refractive index. Most preferred polymers for the structured member are polycarbonates such as bisphenol A polycarbonate, which are available under the trademark MOBAY MAKROLON 2407 from LEXAN 123R and Pittsburgh Movey, Pennsylvania, from General Electric, Pittsfield, Massachusetts.
    The polymeric material used in the structured film of the present invention may include additives such as acid fungicides and UV absorbers. This is particularly useful to prevent degradation of the polymeric material upon treatment or when exposed to environmental conditions (ie UV radiation). Examples of acid fungicides for polycarbonates include phosphite stabilizers. Examples of UV absorbers include derivatives of benzotriazoles such as TINUVIN 327, 328, 900, 1130, and TINUVIN-P from Shiva Gegi, Adslay, NY, and the registered trademark UVINUL- from BASF, Clifton, NJ. Chemical inducers of benzophenones such as M40, 480 and D-50, and SYNTASE800 (2-hydroxy-4-n-octyl benzophenone) from Great Lakes Chemicals, West Lafayette, Indiana, and Clinton, NJ Chemical derivatives of diphenyl acrylates such as the registered trademarks UVINUL-N35 and 539 from BASF. Optional polymeric materials include phosphite stabilizers and / or UV absorbers and are purchased from the manufacturer.
    Other additives, such as colorants, light stabilizers, free radical disinfectants or antioxidants, and processing aids such as antiblocking agents, releasing agents, lubricants and the like may be added to the polymeric material of the structured layer. Such additives may be included in the polymeric material of the structured layer as an amount that can be readily determined by one skilled in the art to achieve the desired result.
    Of course, the particular pigment selected depends on the desired color of the sheet. If a pigment is used, it should not impair the transparency of the retroreflective sheet. Pigments may include dyes and / or pigments. They are typically used in amounts of about 0.01-2.0 wt-%, based on the total weight of the structured film, preferably about 0.01-0.5 wt-%.
    Light stabilizers that can be used may include hinder amines, which are typically used at about 0.5-2.0 wt-% based on the total weight of the structured film. A wide range of hinder amine light stabilizers can be advantageously used. Examples may use the trademarks TINUVIN-144, 292, 622, 770 and CHIMASSORB-944 from Adslay Chiba, Ltd., as well as 2,2,6,6-tetraalkyl piperidine compounds.
    Typically, free radical sterilizers or antioxidants may be used at about 0.01-0.5 wt-% based on the total weight of the structured film. Suitable antioxidants include IRGANOX-1010, 1076, and 1035 from New York Adsleigh Chiba Ltd. as well as hindered phenolic resins such as MD-1024.
    Small amounts of other processing aids that are at least one weight percent of the polymer resin can be added to improve the processing capacity. Useful processing aids include fatty acid esters, or fatty acid amides available from Glycosa, Norwalk, Connecticut, as well as metal stearates available from Henkel, Hoboken, NJ.
    Various techniques and methods are known for the production of structured retroreflective articles. For example, the structured film of the retroreflective sheet of the present invention is made by forming a plurality of structured members from a light transmitting material using a tool having a casting surface composed of a plurality of cavities suitable for forming the structured member. Can be. If desired, the overlay film may be secured to land portions of structured members that serve as lands, or may be secured to land portions of structured film formed of lands. This step involves the structured retroreflective sheets disclosed in US Pat. Nos. 3,689,346 (Roland), 3,811,983 (Roland), 4,332,847 (Roland), 4,601,861 (Pricon et al.) And 5,450,235 (Smith et al.). It can be carried out according to various methods of preparation.
    Sealing film
    In the structured spinning sheet of the present invention, a sealing film 36 (FIG. 3) is used behind the structured film. This sealing film 36 maintains space around most structured members. Since the refractive index of air is lower than the refractive index for the material used in the structured member, total reflection is encouraged to provide the desired reflectance. In addition, the sealing film 36 serves as a barrier to foreign materials such as water, oil, dust, and the like, and can provide mechanical strength to the structure.
    Suitable polymeric materials used in the sealing film are thermoplastics that prevent degradation by weathering (ie, UV radiation, moisture) so that the retroreflective sheet can be used as an over-the-counter device. In addition, the thermoplastic polymer material should be chosen to adhere well to the seal coating or adhesive because it serves as an adhesive for mounting the substrate and / or structure covering the seal coating to the bottom surface of an aluminum plate or the like. If an opaque or colored sealing film is desired, the polymeric material used for the sealing film must be matched with various pigments and / or dyes.
    Suitable thermoplastic polymers used as sealing films retain physical integrity at the temperature at which the sealing film is applied to the structured film. This means that the sealing film melts and / or penetrates only at the bonding position between the sealing film and the structured film. In addition, it is preferred to have a ductility of at least about 20%, and more preferably about 50%, prior to the final fail (eg, permanent deformation). In particular, preferred materials have a ductility of at least about 70% prior to the final fail. That is, upon final failing, the sealing film expands and becomes permanently deformed as a result of the force generated when it expands. As a result, the sealing film of the present invention has a poor contact force with more structured member peaks in a structure having a low ductility sealing film. Reduced contact maintains space around the structured member to promote total reflection and reduce leakage through the member. This provides an even more effective retroreflector, as evidenced by the increased "brightness" of the sheet structure. It also provides an increase in transparency in the sealing base. Such a sealing film may be referred to as a "yielding" sealing film. In comparison, an example of an inflexible sealing film is a biaxially oriented polyethylene terephthalate film.
    Examples of thermoplastic polymers suitable for use in flexible sealing films include mold polyethers; Template polyester; Template polyamides; Ionomeric ethylene copolymers such as poly (ethylene-co-methacrylic acid) with sodium or zinc ions, sold under the trade names SURLYN-8920 and SURLYN-9910 from E.I DuPont de Nemours, Wilmington, Delaware; Plastic vinyl halide polymers; Poly-alpha-olefins; Polymers of ethylene-propylene-diene monomers (“EPDM”) containing ethylene-propylene-non-conjugated diene terpolymers (acrylonitrile EPDM styrene or “AES”) grafted with a mixture of styrene and acrylonitrile; Crosslinkable acrylate rubber substrates grafted with styrene-acrylonitrile ("SAN") copolymers containing graft rubber components such as styrene and acrylonitrile or derivatives thereof (e.g. alpha-methylstyrene and methacrylonitrile) (E.g., also known as "ASA" or acrylate-styrene-acrylonitrile copolymers) containing butyl acrylate, and styrene or acrylonitrile or derivatives thereof (e.g. alpha methyl styrene and methacryl) Nitrile) and grafted butadiene and styrene copolymers or copolymers containing butadiene and acrylonitrile copolymers or butadiene substrates (also known as "ABS" or acrylonitrile-butadiene-styrene copolymers) as well as extractable styrene-acrylics Ronitrile copolymers (ie, non-grafted copolymers) (also known as "ABS"); And materials from the group consisting of combinations or mixtures thereof.
    Preferred polymers for use in the sealing film are the styrenics of the aforementioned multi-phase copolymer resins (ie, multiphase styrenic thermoplastic copolymers of immiscible monomers) mentioned as AES, ASA and ABX, and combinations or mixtures thereof. in the family). Such polymers are disclosed in US Pat. Nos. 4,444,841 (Willer), 4,202,948 (Piscoe) and 5,306,548 (Zabrocky et al.). The mixture may be a physical mixture of polymers in which each layer is injection molded into a multilayer film of different resins or subsequently into a single film. For example, ASA and / or AES resin can be co-injection molded on ABS. Polyphase AES, ASA, and ABS resins can be used individually or together or in various combinations with other resins, such as those used to produce moldable products such as garden furniture, ship hulls, window frames, and parts of vehicle bodies. It can be used for various applications.
    Particularly preferred polymers used in sealing films for the provision of riveted connections are polyphase AES and ASA resins, combinations and mixtures thereof. Such a polymer can maintain the tensile strength of the retroreflective sheet over time. AES resins containing atrylonitrile, EPDM and styrene are particularly preferred because they can adhere to a wide variety of polymer types in the molten state, and examples thereof include polycarbonate, polymethylmethacrylate, polystyrene, urethane acryl, and the like. Can be mentioned. Commercially available AES and ASA resins or combinations thereof include, for example, the trade name ROVEL available from DOW Chemical Company, Midland, Mich., Trade names LORAN S 757 and 797, available from BASF Aktiengesellschaft, Ludwigshafen, Germany, Connecticut, USA Trade names CENTREX 83 and 401 sold by Bayer Plastics, Springfield, trade name GELOY sold by General Electric Company of Selkirk, NY, USA, and trade name VITAX sold by Hitachi Chemical Company, Tokyo, Japan. Some commercially available AES and / or ASA materials also have ABS mixed with them. Commercially available SAN resins include the trade name TYRIL available from DOW Chemical, Midland, Mich., USA. Commercially available ABS includes the trade name CYOLAC, such as CYOLAC GPX 3800, available from General Electric, Pittsfield, Massachusetts.
    The sealing film may be made from a mixture of one or more of the aforementioned materials forming a flexible film and one or more thermoplastic polymers that themselves produce a non-flexible film (ie, a non-combustible sealing film of elastic or brittle material). . Examples of thermoplastic polymers that can be mixed with the aforementioned flexible materials include biaxially stretched polyethers; Biaxially stretched polyester; Biaxially oriented polyamides; Acrylic polymers such as poly (methyl methacrylate); Polycarbonate; Polyimide; Celluloses such as cellulose acetate, cellulose (acetate-co-butyrate), cellulose nitrates; Polyesters such as poly (butylene terephthalate), poly (ethylene terephthalate); Fluoropolymers such as poly (chlorofluoroethylene), poly (vinylidene chloride fluoride); Polyamides such as poly (caprolactam), poly (amino caproic acid), poly (hexamethylene diamine-co-adipic acid), poly (amide-co-imide), and poly (ester-co-imide ); Polyether ketones; Poly (etherimide); Polyolefins such as poly (methylpentene); Aliphatic and aromatic polyurethanes; Poly (phenylene ether); Poly (phenylene sulfide); Atactic poly (styrene); Template rule array polystyrene; Polysulfones; Silicone modified polymers (ie, polymers containing small weight percent (up to 10 weight percent) of silicone) such as silicone polyamides and silicone polycarbonates; Acid functional polyethylene copolymers such as poly (ethylene-co-acrylic acid) poly (ethylene-co-methacrylic acid), poly (ethylene-co-maleic acid) and poly (ethylene-co-fumaric acid); Fluorine modified polymers such as fluorinated poly (ethylene terephthalate); And materials from the group consisting of mixtures of the foregoing polymers, such as mixtures of polyimide and acrylic polymers, and mixtures of poly (methylmethacrylate) and fluorinated polymers. Such “non-flexible” thermoplastic polymers are thermoplastics in any desired amount so long as the final film preferably has a ductility of at least about 20%, more preferably at least 50%, prior to the final failure. It can be mixed with the polymer. Examples of combinations for flexible / non-flexible materials are polycarbonate / ABS resins such as the trade names PULSE 1350 and 1370 available from DOW Chemical Company, Midland, Mich., USA.
    These polymer compositions include UV stabilizers such as the trade name IRGANOX, commercially available from Ciba-Geigy Corp., Adslay, NY, fillers such as antioxidants, talc, reinforcements such as MICA or glass fibers, fire retardants, antistatic agents, Release agents such as the trade name LOXIL G-715 or LOXIL G-40 sold by Henkel Corp. of Hoboken, NJ, or the trade name WAXE sold by Hoechst Celanese Corp. of Carotette, NC It may contain other components, including fatty acid ester of. Colorants such as pigments and dyes may also be mixed in the polymer composition of the sealing film. Examples of colorants include rutile TiO 2 pigments, iron oxide pigments, carbon black, carboxide sulfides, and copper phthalcyanine, sold under the trade designation R960 from Dupont de Nemours, Wilmington, Delaware. Often the aforementioned polymers are commercially available, especially with one or more of these additives such as pigments and stabilizers. Typically, such additives are used in amounts that provide the desired characteristics. They are preferably used by about 0.02-20% by weight, more preferably 0.2-10% by weight, based on the total weight of the polymer composition.
    For efficient formation of riveted connections, the thickness of the sealing film is not greater than the height of the structured retroreflective member. The height of the structured member is usually about 500 μm or less, preferably 200 μm or less. Typically, the thickness of the sealing film is about 250 μm or less, preferably 200 μm or less, and more preferably about 25-80 μm or less. The minimum thickness of the sealing film is typically greater than about 10 μm, preferably greater than about 25 μm. Such thin films may be prepared, for example, using the extrusion molding process disclosed in pending US patent 08 / 626,709 filed "EXTRUDING THIN MULTIPHASE POLYMER FILMS, filed April 1, 1996" (representative reference number 52496USA3A). Can be.
    Sealing coating
    Seal coating 38 (FIG. 3) is an oligomeric or polymeric material used to coat seal film 36 (FIG. 3). The seal coating is provided from a seal coating precursor that is provided as a fluid capable of flowing enough to be coatable and then condensed to form a film. The condensation can be accomplished by curing (ie, polymerization and / or crosslinking) and / or drying (eg removing the liquid phase) or simply by cooling. The seal coating precursor may be an organic solvent based, water based or 100% solid (substantially solvent free) composition. That is, the seal coating is formed by a formulation with 100% solids or coated by removing the solvent (eg ketone, tetrahydrofuran or water) with continuous drying or curing. Preferably the seal coating precursor is a formulation having 100% solids that is substantially free of solvent (ie less than 1% by weight). For this reason, the non-reactive diluent (described below) is present in the seal coating precursor at less than 1% by weight. Thus, the seal coating precursor may be dried simply to form a coating, or the components of the seal coating precursor may have various curing mechanisms (oxidative curing with oxygen, thermal curing, moisture curing, high energy radiation curing, condensation polymerization, addition polymerization and their Combination) to polymerize or crosslink.
    Preferred seal coating precursors are those capable of irreversibly forming cured oligomer / polymer materials and are often used interchangeably under the term " heat curable " precursor. As used herein, the term “thermally curable” precursor is irreversible when applying heat and / or other energy sources such as E-beams, ultraviolet light, visible light, or the like, or by addition of chemical catalysts, moisture, etc. over time. Used to refer to reactive systems that cure. The term "reactive" means that the components of the seal coating precursor react with one another (or with themselves) by polymerizing and crosslinking, or by using the mechanisms described above.
    Preferred embodiments of the invention include both sealing films and sealing coatings. The sealing film uses a thermoplastic to form a substantially mechanical bond with the structured film and seals the air to increase total reflection, and the seal coating preferably employs a reactive system to increase the bonding mechanism to provide better sealing. do. Both mechanisms occur in one layer of material, although a heat seal mechanism can be combined with a reactive seal mechanism to form a more durable bond, such as in US Pat. No. 4,025,159 (Meggrass). This separates the heat sealing mechanism into individual layers from the reactive sealing mechanism, thereby making the invention infeasible in a variety of applications. That is, by optimizing the formulation of the sealing film and the seal coating separately, the opacity, flexibility, durability, strength, etc. of the retroreflective sheet can be altered in the desired end use. However, binding agents used in U.S. Patent No. 4,025,159 (Meggrass), such as thermoplastic acrylic trimers (methyl methacrylate / ethylacrylate / isooctyl acrylate) and tetraethylene glycol diacrylate, are particularly preferred for thermoplastic sealing films. As long as the flexible sealing film is used for bonding with the sealing coating, it can be used to form the sealing coating in the present invention.
    Thus, the seal coating can perform various functions when used in bonding with the seal film. For example, the seal coating can provide additional durability, strength and opacity to the seal film. The sealing coating precursor preferably has a viscosity that allows it to flow into and around the riveted connections in the sealing leg, thereby increasing the opacity in this area as well as the bond to the structured member tip (eg, the cub tip). Thereby increasing the hermetic sealing of the structure. When the flexible sealing film forms an airtight seal with the structured film, the sealing coating flows into adjacent cube regions without leaking through the penetration of the sealing film. The seal coating also helps to fill in the recesses created by embossing the seal film with the structured film and provides a better blending layer for the adhesive composition. Depending on the sealing coating rate relative to the sealing film, additional flexibility or strength to the sheet structure can be provided.
    By flattening and filling all recesses formed in the sealing film 36, the sealing coating 38 helps to reduce moisture-induced structural buckling at the bond between the sheet 30 and the aluminum sign. Although structural buckling does not affect the performance of the retroreflective sheet, it can cause partial peeling between the sheet and the bottom surface. However, when the backside is flattened by the seal coating 38, the adhesive used to bond the sheet 30 to the backing film and / or signpost is reduced or eliminated the path used for the film having recesses in the sealant film. Moisture penetration can be substantially suppressed in between. This may occur, in particular, when the adhesive used to bond the sheet 30 to the backside is substantially cured (ie, the adhesive does not fill the recess or fails to fill because it does not conform to this recess). Moreover, the seal coating provides strength to the sheet, and this additional strength can also help to prevent mechanical deformation of the sheet to prevent moisture induced structural buckling.
    The components selected for use in the seal coating precursor can be used to increase the durability and weather resistance of the retroreflective sheet. In addition, the seal coating precursor preferably has uniform rheology appropriate for both seal coatings and seal films and flows around the riveted connections. Additional opacity can be obtained by the present invention because the components of the seal coating precursor suspend or disperse various dyes at useful concentrations. Depending on the structure of the sheet, the various components of the seal coating, in particular in the seal leg, preferably interact with the seal film and / or overlay film material to form a durable bond. The term "interaction" refers to various mechanical interactions, such as surface roughness, dissolution, penetration, or the like, of polymers used in sealing films and / or structured films. This term also applies to covalent interactions (eg, polymerization and / or crosslinking) between components of the seal coating precursor and the seal film and / or the structured film. However, the degree of interaction cannot be large enough to destroy the integrity of the retroreflective sheet.
    The seal coating precursor may comprise a reactive or non-reactive component. Non-reactive seal coating precursors typically include polymers or oligomers dissolved or degraded in non-reactive volatile liquids, although 100% solids systems may also be used. This may include, for example, thermoplastics coated with a solvent or coated as a hot melt and latex coated with water. However, although they may be used, non-reactive seal coating precursors are not preferred. Typically, the non-reactive sealing coating precursor should include additional processing steps, such as removal of all liquids used to form the sealing coating. This can cause the sheet to be subjected to undesirable thermal stresses, producing undesirable emissions. In addition, since the non-reactive seal coating precursor does not irreversibly interact with the sheet (eg, structured film or seal film), it may not increase the strength of the structure as desired.
    Suitable materials for forming the seal coating include materials that can be crosslinked or polymerized with reactive components, i.e. a wide variety of mechanisms (oxidative curing, condensation, moisture curing, radiation or thermal curing of free radical systems, or combinations thereof). Sealing coating precursors comprising are preferred. Examples include amino resins (ie aminoplast resins) such as alkylating urea-formaldehyde resins; Melamine-formaldehyde resins and alkylated benzoguanamine-formaldehyde resins; Acrylate resins (containing acrylates and methacrylates) such as vinyl acrylates, acrylated epoxy, acrylated urethanes, acrylated polyesters, acrylated acrylic resins, acrylated polyethers, acrylated oils and acrylated silicones; Alkyd resins such as urethane alkyd resins; Polyester resins; Reactive urethane resins; Phenol formaldehyde resins (ie, phenol resins) such as resol and novolac resins; Phenol / latex resins; Epoxy resins such as bisphenol epoxy resins; Isocyanate; Polysiloxane resins containing alkylalkoxysilane resins; Reactive vinyl resins, and the like. As used herein, "resin" or "resin system" means a polydisperse system containing monomers, oligomers, polymers or combinations thereof.
    Such reactive seal coating precursors can be cured by various mechanisms (eg, condensation or further polymerization) using, for example, thermal energy, radiation energy, and the like. Particularly preferred is a form of action of rapid (eg, requiring up to 5 minutes, preferably up to 5 seconds) of radiation energy. Electron beam (E beam) radiation can penetrate a thickly colored coating and is desirable because of the speed and efficient use of applied energy and its ease of control. Other useful forms of radiation energy include ultraviolet / visible light, nuclear radiation, infrared and microwave radiation. Depending on the specific curing mechanism, the seal coating precursor may further comprise a catalyst, initiator, or curing agent to facilitate initiating or accelerating the curing and / or crosslinking treatment.
    Reactive seal coating precursor components that can be cured by the passage of time after addition of thermal energy and / or catalysts include phenolic resins such as resol and novolac resins; Epoxy resins such as bisphenol A epoxy resins; And amino resins such as alkylated urea-formaldehyde resins, melamine-formaldehyde resins and alkylated benzoguanamine-formaldehyde resins. Sealing coating precursors containing the aforementioned reactive components may include thermal free radical initiators, acidic catalysts, and the like, depending on the resin system. Thermal free radical initiators include peroxides such as benzol peroxide and azo compounds. Typically, such reactive seal coating precursor components require temperatures higher than room temperature (ie, 25-30 ° C.) for curing, although curable systems are known at room temperature.
    In the resol phenol resins, formaldehyde and phenol have a molar ratio of greater than about 1: 1 by weight, typically from about 1.5: 1.0 to 3.0: 1.0. Novolac resins have a molar ratio of formaldehyde to phenol of about 1: 1 or less by weight. Examples of commercially available phenolic resins include the trade names DUREZ and VARCUM available from Occidental Chemicals Corp., Dallas, Texas; RESINOX, available from Monsanto, Lewis Street, Montana, USA; AEROFENE and AEROTAP available from Ashland Chemical Co., Columbus, Ohio.
    The epoxy resin contains oxirane and is polymerized by ring opening. They can vary considerably in the nature of their backbone and substituents. For example, the main chain may be of any type usually associated with an epoxy resin, and the substituent may be any substituent that does not contain a reactive hydrogen atom that reacts with the oxirane ring at room temperature. Alternative examples of acceptable substituents include halogens, ester groups, ether groups, sulfonate groups, siloxane groups, nitro groups and phosphate groups. Most commonly marketed epoxy resins include diphenylol propane (to form 2,2-bis [4- (2,3-epoxypropoxy) phenyl] propane (diglycidyl ether of bis phenol A) That is, it is a reaction product of bisphenol A) and epichlorohydrin. Such materials are commercially available under the trade names EPON (eg, EPON 828, 1004 and 1001F) from Shell Chemical Co. and DER from DOW Chemical Co., Midland, Michigan, USA. Other suitable epoxy resins are the glycidyl ethers of phenol formaldehyde novolacs available under the trade names DEN (e.g., DEN 431 and 428) from DOW Chemical Co.
    Amino resins (ie aminoplast resins) are reaction products of formaldehyde and amines. The amine is typically urea or melamine. Most common amino resins include alkylated urea-formaldehyde resins and melamine-formaldehyde resins, and alkylated benzoguanamine-formaldehydes are also known. Melamine-formaldehyde resins are typically used where durability and chemical resistance are required outdoors. However, amino resins are not usually used alone because they tend to break easily. Therefore, they are often combined with other resin systems. For example, they can be combined with alkyd resins, epoxy resins, acrylic resins and other resins containing functional groups that react with amino resins to exhibit the advantageous properties of both resin systems combined.
    As a more preferable sealing coating precursor, it can harden | cure using radiation. This is referred to herein as a radiation curable material. As used herein, "radiation cured" or "radiation curable" is optionally combined and / or crosslinked using an appropriate catalyst or initiator when exposed to infrared radiation, visible radiation, electron beam radiation or combinations thereof. By hardening mechanism involving bonding. Typically, there are two forms of radiation curing mechanisms that generate free radical cure and cationic cure. These are generally associated with one stage of curing or one type of curing system. Free radical and cationic materials can also be cured to impart proper properties from both systems. In addition, dual and hybrid curing systems are also possible, as described below.
    In cationic systems, cationic photoinitiators degrade in response to exposure to ultraviolet / visible light to generate an acidic catalyst. This acidic catalyst propagates the crosslinking reaction via an ionic mechanism. Although oligomeric aromatic epoxy resins and vinyl ethers can be used, epoxy resins, in particular cycloaliphatic epoxy resins, are the most common resins used for cationic curing. In addition, polyol resins can be used with epoxy resins as chain-transfer agents and softeners for cationic curing. Eckberg et al., "UV Cure of Epoxysiloxanes," Radiation Curing in Polymet Science and Technology: Volume IV, Practical Aspects and Applications, Fouassier and Rabek, eds., Elsevier Applied Science, NY, Chapter 2, 19-49 (1993) Epoxysiloxanes such as those disclosed in can be cured using cationic photoinitiators. This cationic photoinitiator includes salts of onium cardion such as allylsulfonium salts and organometallic salts. Examples of such cationic photoinitiators are disclosed in US Pat. Nos. 4,751,138 (Tumey et al.) And 4,985,340 (Palazzotti) and European Patent Applications 306,161 and 306,162. Suitable photoinitiators for epoxysiloxanes are photoreactive iodonium salts sold under the trade name UV9310C from GE Silcones, Waterford, NY.
    In free radical systems, radiation provides a very rapid and controlled generation of materials of highly reactive species that initiate polymerization of unsaturated materials. Examples of free radical curable materials include acrylate resins, aminoplast derivatives having at least one side group alpha, beta-unsaturated carbonyl groups, isocyanurate derivatives having at least one side group acrylate groups, at least one side group Isocyanate derivatives with acrylate groups, unsaturated polyesters (e.g., condensation products of organic diacids and glycols), polyene / thiol / silicone systems and other ethylenically unsaturated compounds, and mixtures and combinations thereof, It is not limited to this. Such radiation curable systems are described in Allen et al., "UV and Electron Beam Curable Pre-Polymers and Diluent Monomers: Classification, Preparation and Properties," Radiation Curing in Polymer Science and Technology: Volume I, Fundamentals and Methods, Fouassier and Rabek, eds Elsevier Applied Science, NY, Chapter 5, 225-262 (1993); Federation Series on Coatings Technology; Radiation Cured Coatings, Federation of Socienties for Coatings Technology, Philadelphia, PA, pages 7-13 (1986); and Radiation Curing Primer I; Inks, Coatings, and Adhesives, RadTech International North America, Northbook, IL, pages 45-53 (1990).
    Although free radical curable systems can be cured using thermal energy, they can be cured using radiation energy as long as there is a source of free radicals in the system (peroxide or azo compound). Thus, the terms "radiation curable" and more specifically "free radical curable" may be cured using thermal energy and are included within the scope of the system associated with the free radical curing mechanism. On the other hand, the term "radiation cured" refers to a system cured by exposure to radiation energy.
    Suitable acrylate resins for use in the present invention include acrylated urethanes (e.g. urethane acrylates), acrylated epoxies (e.g. epoxy acrylates), acrylated polyesters (e.g. polyester acrylates), acrylated acrylic resins, acrylated silicones, Acrylated polyethers (eg, polyether acrylates), vinyl acrylates and acrylated oils, but are not limited to these. As used herein, "acrylates" and "acrylate-functional groups" include acrylates and methacrylates regardless of whether they are monomers, oligomers or polymers.
    Acrylated urethanes are diacrylate esters of hydroxy terminated NCO expanded polyesters or polyethers. Although acrylated aliphatic urethanes are preferred because they are less affected by weathering, they may be acrylated aliphatic or aromatic. Examples of commercially available acrylated urethanes include the trade name PHOTOMER (eg PHOTOMER 6010) available from Henkel Corp. of Hoboken, NJ; 1200 molecular weight aliphatic urethane diacrylate diluted with UCBE Radcure Inc., Smyrna, GA, EBECRYL 220 (molecular weight 1000 hexaaromatic urethane acrylate), EBECRYL 284 (1,6-hexanediol diacrylate) ), EBECRYL 4827 (1600 molecular weight aromatic urethane diacrylate), EBECRYL 4830 (1200 molecular weight aliphatic urethane diacrylate diluted with tetraethylene glycol diacrylate), EBECRYL 6602 (trimethylolpropane epoxy triacrylate diluted) Trifunctional aromatic urethane acrylate of 1300 molecular weight), and EBECRYL 8402 (aliphatic urethane diacrylate of 1000 molecular weight); Trade names SARTOMER (eg, SARTOMER 9635, 9645, 9655, 963-B80, 966-A80), available from Sartomer Co., West Chester, Pennsylvania; And the trade name UVITHANE available from Morton International of Chicago, Illinois, USA.
    The acrylated epoxy is a diacrylate ester of an epoxy resin, such as a diacrylate ester of a bisphenol A epoxy resin. Examples of commercially available acrylated epoxy include the trade names EBECRYL 600 (525 molecular weight bisphenol A epoxy diacrylate), EBECRYL 629 (550 molecular weight epoxy novolac acrylate, available from UCB Redcure Inc., Smyrna, GA, USA. ) And EBECRYL 860 (1200 molecular weight epoxidized soybean oil acrylate); And the trade names PHOTOMER 3038 (epoxy acrylate / tripropylene glycol diacrylate mixture), PHOTOMER 3071 (modified bisphenol A acrylate) sold by Henkel Corp, Hoboken, NJ, and the like.
    The acrylated polyester is the reaction product of acrylic acid and dibasic acid / aliphatic / diol based polyester. Examples of commercially available acrylated polyesters include the trade names PHOTOMER 5007 (2000 molecular weight hexa group acrylate), PHOTOMER 5018 (1000 molecular weight tetrafunctional acrylate), and PHOTOMER 5000 available from Henkel, Hoboken, NJ, USA. Other acrylated polyesters of the series; Trademarks EBECRYL 80 (1000-functional tetrafunctional modified polyester acrylate), EBECRYL 450 (fatty acid-modified polyester hexaacrylate) and EBECRYL 830 (1500 molecular weight hexacyclic polyester) sold by UCB Radcure, Smyrna, GA, USA Acrylates).
    The acrylated acrylic resin is a silicone-based oligomer or polymer having acrylic acid groups of reactive side groups or end groups capable of forming free radicals for subsequent reaction. These and other acrylates are described in Allen et al., "UV and Electron Beam Curable Pre-Polymers and Diluent Monomers: Classification, Preparation and Properties," Radiation Curing in Polymer Science and Technology: Volume I, Fundamentals and Methods, Fouassier and Rabek, eds., Elsevier Applied Science, NY, Chapter 5, 225-262 (1993); Federation Series on Coating Technology: Radiation Cured Coatings, Federation of Societies for Coatings Technology, Philadelphia, PA, pages 7-13 (1986); Radiation Curing Primer I: Inks, Coatings, and Adhesives, RadTech International North America, Northbrook, IL, pages 45-53 (1990).
    Isocyanurate derivatives having at least one side group acrylate group and isocyanates having at least one side group acrylate group are also disclosed in US Pat. No. 4,652,274 (Boetcher et al.). The isocyanurate resin having an acrylate group contains a triacrylate of tris (hydroxy ethyl) isocyanurate.
    The radiation curable aminoplast resin has at least one side group alpha, beta-unsaturated carbonyl group per molecule or oligomer. These unsaturated carbonyl groups are groups in the form of acrylate, methacrylate or acrylamide. Examples of the resin having an acrylamide group include N- (hydroxymethyl) -acrylamide, N, N'-oxydimethylenebisacrylamide, ortho- and para-acrylamide methylated phenol, acrylamidomethylated phenol novolac, Glycoluril acrylamide, acrylamidomethylated phenols, and combinations thereof. Such materials are also disclosed in US Pat. Nos. 4,903,440 (Larson et al.), 5,055,113 (Larson et al.) And 5,236,472 (Kirk et al.).
    Other suitable ethylene-based unsaturated resins generally include compounds of monomers, oligomeric polymers containing ester groups, amide groups and acrylate groups. Such an ethylenically unsaturated compound has a molecular weight of about 4000 or less. These are preferably esters consisting of reactive compounds containing aliphatic monohydroxy groups or aliphatic polyhydroxy groups and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid and the like. Representative examples of acrylate resins are listed later. Other ethylenically unsaturated resins include monoallyl, polyallyl and polymetharyl esters and amides of carboxylic acids such as diallyl phthalate, diallyl adipate and N, N-diallyl adipamide, as well as styrene divinyl benzene, Vinyl toluene. The other ethylenically unsaturated resins include tris (2-acryloyl-oxyethyl) -isocyanurate, 1,3,5-tri (2-methacryloxyethyl) -s-triazine, acrylamide, methylacryl Amide, N-dimethylacrylamide, N, N-dimethylacrylamide, N-vinylpyrrolidone and N-vinylpiperidone.
    In dual cured resin systems, polymerization or crosslinking occurs in each of the two stages through the same or different reaction mechanisms. In hybrid cured resin systems, two mechanisms of polymerization or crosslinking occur simultaneously when exposed to electron beam radiation, which is ultraviolet / visible light. Chemical curing mechanisms occurring in these systems include radical polymerization of acrylic double bonds, radical polymerization of unsaturated polyesters of styrene or other monomers, air drying of allyl groups, cationic curing of vinyl ethers or epoxies, condensation of isocyanate salts, and There is thermal curing by acid-catalyst, but not limited thereto. Thus, dual curing and hybrid curing systems can combine radiation curing with thermal curing, or radiation curing with moisture curing. It is also possible to combine electron beam curing with ultraviolet / visible radiation curing. For example, a combination of curing mechanisms can be achieved by mixing two types of functional groups with a material on one substrate or by mixing different materials with one type of functional groups. Such systems include Peeters, "Overview of Dual-Cure and Hybrid-Cure Systems in Radiation Curing," Radiation Curing in Polymer Science and Technology: Volume III, Polymer Mechanisms, Fouassier and Rabek, eds., Elsevier Applied Science, NY, Chapter 6 , 177-217 (1993).
    Among the radiation curable materials, free radical curable materials are advantageous. Because acrylates are particularly preferred for use in the seal coating precursors of the present invention. Examples of such materials include monofunctional or multifunctional acrylates (ie acrylates and methacrylates), acrylated epoxies, acrylated polyesters, acrylated aromatic or aliphatic urethanes, acrylated acrylic resins, acrylated silicones and combinations thereof, and There is a mixture, but is not limited thereto. These may be monomers or oligomers having a variety of molecular weights (eg, 100-2000 average molecular weights) (ie, low molecular weight polymers suitably containing typically 2-100 monomer units or often 2-20 monomer units). Preferred seal coating precursors include acrylated epoxy, acrylated polyester, acrylated aromatic or aliphatic urethanes and acrylated acrylic resins. More preferred seal coating precursors are acrylated aromatic or aliphatic urethanes and most preferred seal coating precursors are acrylated aliphatic urethanes.
    Free radical radiation curable systems often include oligomers and / or polymers (also called film formers) that form the backbone of the cured material and reactive monomers (also called reactive diluents) for controlling the viscosity of the curable composition. Film formers are typically monomeric or polymeric materials, but some monomer materials may also form a film. Typically, such systems require the use of ultraviolet / visible or electron beam radiation. Ultraviolet / visible light curable systems typically include a photoinitiator. Aqueous or organic solvents (acting as non-reactive diluents) can also be used to reduce the viscosity of the system, which is typically synonymous with heat treatment. Thus, the seal coating precursor of the present invention preferably does not contain an aqueous or organic solvent. In other words, the seal coating precursor is preferably a formulation having 100% solids.
    Preferred seal coating precursors of the present invention include reactive diluents and film formers. This reactive diluent contains at least one monofunctional or multifunctional monomer compound. As used herein, a single functional group means that the compound contains one carbon-carbon double bond, and the multi-functional group contains other chemically reactive groups capable of crosslinking through one or more carbon-carbon double bonds or condensation. Means that. Examples of resins having carbon-carbon double bonds and chemically reactive groups include isocyanatoethyl methacrylate, isobutoxymethyl acrylamide and methacryloxy propyl trimethoxy sirane. Suitable reactive diluents are those typically used in radiation curable systems that control viscosity. Although non-acrylates such as n-vinyl pyrrolidone, limonene and limonene oxide can be used as these, it is preferred that they are acrylates as long as the monomer is an ethylenically unsaturated compound that provides its reactivity. Film formers include at least one radiation curable material, such as monofunctional or multifunctional oligomeric compounds commonly used in radiation curable systems, although thermoplastic polymers may also be used. These thermoplastic polymers may or may not react with reactive or self-reactive (eg internally crosslinkable) diluents.
    Preferably, the seal coating precursor comprises at least one single functional monomer compound and at least one multifunctional oligomeric compound. Most preferably, the seal coating precursor has at least one monofunctional monomer acrylate having a molecular weight of about 1000 (preferably about 100-1000) and a molecular weight of about 500, preferably 500-7000, more preferably 1000- At least one multifunctional oligomeric acrylated urethane that is 2000.
    Single functional monomers typically lower the viscosity of the mixture and quickly penetrate into the sealing film and / or the structured film. Multifunctional monomers and oligomers (eg, diacrylates and triacrylates) typically have greater crosslinking and stronger bonding between the layers and within the seal coating. Also, depending on the structure, the multifunctional monomers and oligomers can provide flexibility or strength to the seal coating. An acrylated oligomer, preferably an acrylated urethane oligomer, provides the coating with desirable properties such as roughness, hardness and flexibility.
    Examples of suitable monofunctional monomers include ethyl acrylate, methyl acrylate, isooctyl acrylate, octaethylated phenol acrylate, isobornyl acrylate, 2-ethylhexyl acrylate, 2-phenoxyethyl acrylate, 2- (ethoxyethoxy) ethyl acrylate, ethylene glycol acrylate, tetrahydroxy furpril acrylate (THF acrylate), caprolactone acrylate, and methoxy tripropylene glycol mono acrylate Do not. Examples of suitable multifunctional monomers include triethylene glycol diacrylate, pentaerythritol triacrylate, glycerol triacrylate, glycerol trimethacrylate, glyceryl propoxylate triacrylate, trimethylolpropane trimethacrylate , Trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, tetramethylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol dimethacrylate, ethylene glycol Diacrylates, polyethylene glycol diacrylates, pentaerythritol tetraacrylates, pentaerythritol tetraacrylates, and 1,6-hexane diacrylates. Other monofunctional and multifunctional monomers include vinyl acetate, n-vinyl formamide and those disclosed in Table 1 below. The monomers include the trade name EBECRYL, available from UCB Inc. of Smyrna, GA, trade name PHOTOMER, available from Henkel Corp., Hoboken, NJ, and SARTOMER, available from Sartomer Co., West Chester, Pennsylvania, USA. Is available. Limonene oxide is commercially available from Aldrich Chemical Co., Milwaukee, Wisconsin. n-vinyl pyrrolidinone is commercially available from Kodak, Rochester, NY.
    Examples of suitable acrylated oligomers are acrylated epoxy, acrylated polyesters, acrylated aromatic or aliphatic urethanes, acrylated silicones, acrylated polyethers, vinyl acrylates, acrylated oils, acrylated acrylic resins. Of these, acrylated aromatic or aliphatic urethanes are preferred, of which acrylated aliphatic urethanes are more preferred due to their flexibility and weather resistance. Some examples of some acrylated aliphatic urethanes (ie, aliphatic urethane acrylates) include the trade name PHOTOMER 6010 (MW = 1500) available from Henkel Corp., Hoboken, NJ; Trade names EBECRYL 8401 (MW = 1000) and EBECRYL 8402 (MW = 1000, urethane diacrylate), available from UCB Radcure Inc., Smyrna, GA; S-9635 and S-9655, available from Sartomer Co., West Chester, Pennsylvania, and containing 25% by weight of isobornyl acrylate; S-963-B80, available from Sartomer Co. and containing 20% by weight of 1,6-hexanediol diacrylate; And S-966-A80, available from Sartomer Co. and containing 20% by weight of tripropylene glycol diacrylate.
    Preferred reactive monomers (ie reactive diluents) are those which interact (dissolve or soak) with the overlay film or sealing film. More preferred monomers are those which interact with both films of the structured film (eg polycarbonate) and the sealing film (eg AES and / or ASA film). Certain monomer / film interactions can be readily indicated for interaction by providing monomer solution to the surface of the film. Priola et al., Proceedings of the International Conference in Organic Coations Science and Technology, Athens, Greece, July 7-11,1987, pp.308-318, disclose appropriate timepiece testing for this purpose. A positive response indicates that the substrate is diluted or dissolved upon exposure to the appropriate amount of monomer, indicating that the monomer penetrates or swells the substrate or otherwise reacts with the substrate. Examples of monomers which interact with films made of polycarbonate or AES materials obtainable under the trade name CENTREX 833 are shown in Table 1 below.
    Classification of monomers for compatibility with polycarbonates and AES / ASA MonomerType of substanceCENTREX 833Polycarbonate EBECRYL 110Octaethylated phenol acrylateyesyes PHOTOMER 4028Bisphenol A ethoxylate diacrylatenoneyes PHOTOMER 4072Trimetholol Propane Propoxylate Triacrylatenonetrace PHOTOMER 4149Trimethylol propane ethoxylate triacrylatetracetrace PHOTOMER 8061Methoxy Tripropylene Glycol Monoacrylatetraceyes PHOTOMER 8149Methoxy ethoxylated trimethylpropanediacrylateyesyes SARTOMER 2131,4-butanediol diacrylateyesyes SARTOMER 2381,6-hexanediol diacrylateyesyes SARTOMER 2562 (ethoxy-ethoxy) ethyl atylateyesyes SARTOMER 268Tetraethylene Glycol Diarylateyestrace SARTOMER 272Triethylene Glycol Diacrylateyesyes SARTOMER 285Tetrahydroxyfurfuryl acrylateyesyes SARTOMER 306Tripropylene Glycol Diacrylatetracetrace SARTOMER 497n-vinyl formamideyesyes SARTOMER 506Isobornyl acrylatenoneyes SARTOMER 9008Alkoxylated trifunctional acrylatestracenone + Limonene oxideLimonene oxideyesyes -Limonene oxideLimonene oxideyesyes NVPn-vinyl pyrrolidinoneyesyes
    As shown in the table above, thermoplastic polymers may be used as film formers in addition to or instead of mono- or multi-functional oligomers. Thus, many of the sealing film materials described above (eg, AES and / or ASA materials) can be used as sealing coating precursors. Preferably, they can be used in addition to single or multifunctional oligomers to control the viscosity and flowability of the seal coating precursor and to help reduce the amount of stretch of the film. For example, various granular ASA and / or AES resins sold under the trade name CENTREX are preferred because they are soluble in various monomers (ie, reactive diluents) and are radiation curable (eg, crosslinked upon exposure to ultraviolet / visible radiation). . However, other thermoplastic polymers may also be used that do not react with or react with the reactive diluent. For example, almost non-reactive thermoplastic acrylate trimers used in the binders of US Pat. No. 4,025,159 (Meggrass) can be used in the seal coating precursor of the present invention.
    The seal coating precursor may contain various solvents in addition to the diluent monomers described above to assist in solubilizing the high molecular weight reactive resin (eg, acrylated oligomer) and / or the thermoplastic polymer of the structured film and / or the seal film. Such solvents are referred to as non-reactive diluents and / or non-reactive monomers, for example, because they hardly polymerize or crosslink with the reactive resin of the seal coating precursor under the curing conditions of the process of the invention. In addition, these solvents are typically removed completely by heat even though complete removal is not required. Suitable solvents for this purpose include ketone solvents, tetrahydrofuran, xylene and the like. Optionally, however, preferably the seal coating precursor may be a 100% solid composition as described above.
    If desired, the seal coating precursor may contain colorants (ie pigments and dyes). Examples of suitable colorants include TiO 2 , phthalocyanine blue, carbon black, basic carbonate white lead, zinc oxide, zinc sulfide, antimony oxide, zirconium oxide, lead sulfochromate, bismuth vanadate, bismuth molybdate, as well as other pigments, in particular Opaque pigments disclosed in US Pat. No. 5,272,562 (Cotter). Colorants can be used in amounts that can provide a desired color and can be added to the seal coating precursor in a variety of ways. For example, colorants may be included in commercially available granular ASA and / or AES. Commonly and preferably pigments are used in the form of dispersion in, for example, neopentyl glycol diacrylate (tradename 9WJ available from Penn Color, Doylestown, Pa.).
    Preferably, the seal coating precursor comprises about 5% to 25% by weight reactive diluent based on the total weight of the seal coating precursor. The amount of film former and optional pigment in the seal coating precursor depends on the desired opacity, flexibility, viscosity, and the like. Preferably, the seal coating precursor contains from about 25 wt% to 95 wt% film former and up to 50 wt% pigment relative to the total weight of the seal coating precursor.
    Photoinitiators are typically contained in the ultraviolet / visible curable sealing coating precursor of the present invention. Illustrative examples of photopolymerization initiators (ie, photoinitiators) include organic peroxides, azo compounds, quinones, benzophenones, nitroso compounds, acryl halides, hydrozones, mercamto compounds, pyryllium compounds, triacrylimidazoles, bis Imidazoles, chloroalkytriazines, benzoin ethers, benzyl ketals, thioxanthones and acetophenone derivatives and mixtures thereof, but are not limited thereto. Specific examples include benzyl, methyl o-benzoate, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone tertiary amine, acetophenone such as 2,2-diethoxyaceto Phenone, benzyl methyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 2-benzyl-2-N, N-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide 2-methyl-1-4 (methylthio), phenyl-2-morpholino-1-propanone, bis (2,6-dimethoxybenzoyl) (2,4,4-trimethylpentyl) phosphine oxide and the like Can be mentioned. Such photoinitiators include the trade names DAROCUR 265 (2-hydroxy-2-methyl-1-phenylpropan-1-one and 2,4,6-trimethylbenzoyl, available from Ciba-Geigy Corp., Adsley, NY, USA. 50:50 mixture of diphenylphosphine oxide) and CGI1700 (bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine and 2-hydroxy-2-methyl-1-phenylpropane- 25-75 mixture of 1-one). Typically, the photoinitiator is used in an amount sufficient to provide the desired reaction rate. Such photoinitiators are preferably used in amounts of about 0.01-5% by weight, more preferably 0.1-1% by weight, based on the total weight of the seal coating precursor.
    Other additives that may be contained in the seal coating precursor include fillers, antifoams, adhesion promoters, levelers, wetting agents, lubrication aids, stabilizers, plasticizers, and the like. They may be reactive or non-reactive, but are usually non-reactive. Examples of reactive plasticizers are the trade names SARBOX SB-600 and SB-510E35 available from Sartomer Co. Typically, such additives are used in amounts to achieve the desired properties. Preferably the additive is used in an amount of about 0.01-5% by weight, more preferably 0.1-1% by weight, based on the total weight of the seal coating precursor.
    Suitable methods of applying the seal coating precursor to the seal film can be used in connection with the present invention. Preferably, however, the coating method is a method that allows the sealing coating precursor to contact the structured film and further "fills" the settlement caused by the sealing legs. The choice of coating method depends on the viscosity of the seal coating precursor, the depth of settlement, the desired coating thickness, the coating speed and the like. Suitable coating methods include, for example, knife coating, rod coating and notch bar coating. The thickness of the seal coating depends on the viscosity and film structure of the seal coating precursor, the type of coating means used and the desired final properties. Typically a wet coating thickness of about 10-250 μm is used. Several suitable methods for providing a layer of seal coating for use in the present invention are described in US Pat. No. 4,327,130; No. 4,345,543; No. 4,387,124; And 4,442,144 (all assigned to Pipekin).
    Once the seal coating precursor is coated onto the seal film / structured film / overlay film structure, it is desirable to be exposed to an energy source for initial cure. Examples of suitable and preferred energy sources are thermal energy and radiation energy. The amount of energy depends on the chemistry of the resin, the dimensions of the seal coating precursor after coating and the type and amount of any additives, in particular the pigment load. In thermal energy, the temperature is about 30 ° C to 100 ° C. The exposure time is about 5 minutes to 24 hours, and the lower the temperature, the longer it takes.
    Suitable radiation energy sources for use in the present invention are electron beams, ultraviolet light, visible light or combinations thereof. Electron beam radiation, known as ionizing radiation, has an energy level of about 0.1-10 Mrad, preferably 3-8 Mrad, more preferably about 5-6 Mrad, and an acceleration voltage level of about 7.5 KeV to about 5 meV, preferably Can be used at an acceleration voltage level of 100-300 KeV. Ultraviolet radiation refers to nonspecific radiation having a wavelength of about 200-400 nm. Ultraviolet light of 118-236 w / cm is preferably used. Visible light refers to non-specific radiation having a wavelength in the range of about 400-800 nm. Using radiation energy, some pigment particles and / or other optional additives may absorb the radiation energy and interfere with the polymerization of the sealing coating precursor to the resin. If this is observed, the level of radiation energy or photoinitiator can be raised to the level necessary to compensate for this radiation absorption. In addition, the electron beam acceleration voltage is increased by increasing the penetration of ionizing radiation energy.
    Overlay material
    The overlay film 40 (FIG. 3) of the present invention is used as a barrier to prevent foreign substances such as organic solvents, water, oil, dust, and the like from penetrating into the structured film. Thus, the polymeric material used in the overlay film must have resistance to degradation due to weathering (eg, UV light) or environmental penetration so that the retroreflective sheet can generally be used in outdoor devices for extended periods of time. They must have good adhesion to the polymeric material of the structured film and must be light transmissive. Preferably, the polymeric material used in the overlay film is substantially transparent. In some devices it is necessary for the overlay to have good adhesion to the ink so as to provide graphics or messages to the display. In addition, the polymeric materials used in the overlay film preferably retain their material integrity at the temperature applied to the structured film.
    The overlay for the thermoplastic structured material is thermally cast and then bonded to the structured film. Typically, the overlay film is a thermoplastic. Examples of polymers that can be used in the overlay film include, but are not necessarily limited to, fluorinated polymers such as poly (chlorotrifluoroethylene), available under the registered trademark KEL_F800 from 3M of Sao Paulo, Minnesota, and Bram, Massachusetts. Poly (tetrafluoroethylene-co-hexafluoropropylene), available under registered trademark EXAC FEP from Pfton, and poly (vinylidene fluoride, available under registered trademark KYNAR, from Penwalt, Philadelphia, PA. ) Or poly (vinylidene fluoride-co-hexafluoropropylene) and VFFL (ethylene-co-meta) with sodium or zinc ions available under the broad trademarks SURLYN-8920 and SURLYN-9910 from Delaware Wilmington Dupont Ionomer ethylene copolymers such as krylic acid), low density polyethylene, linear low density poly Low density polyolefins such as styrene and very low density polystyrene, plasticized vinyl halide polymers such as plasticized poly (vinylchloride), poly (ethylene-co-acrylic acid) and poly (ethylene-co-met Polyethylene copolymers containing acidic polymers such as acrylic acid), poly (ethylene-co-maleic acid), and poly (ethylene-co-fumaric acid), and polymethylmethacrylate, methyl, ethyl, propyl, butyl, and the like, or acryl group polymers such as poly (ethylene-co-alkyl acrylate) and polymethyl methacrylate having n 3 of CH 3 (CH 2 ) N and poly (ethylene-co-butyl acetate) and dicyclohex; Diisocyanates, such as thymethane-4,4'-diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, cyclohexyl diisocyanate, diphenylmethane diisocyanate and combinations of these diisocyanates Update; Polydiols such as polypentylene adipate glycol, polytetramethylene ether glycol, polyethylene glycol, polycaprolactone diol, poly-1,2-butylene oxide glycol and combinations with these polydiols, and chains such as butanediol or hexanediol Alipa and aromatic polyurethanes extracted from the weighting agent.
    Commercially available urethane polymers include registered trademarks PN-03 or 3429 from Morton International, Seabrook, New Hampshire, and X-4107 from Cleveland B.F Goodrich, Ohio. Combinations of the above polymers can also be used as overlay films.
    Good polymers for the overlay film include fluorinated polymers such as poly (vinylidene fluoride) (PVDF) and acrylic group polymers such as polymethylmethacrylate (PMMA). Particularly better polymer groups include mixtures of PVDF and PMMA, which include about 60-95 weight percent (wt-%) PMMA and about 5-40 wt-% PVDF. In such mixtures, PMMA contributes to the flexibility of the overlay film, while PVDF contributes to the chemical (eg organic solvent) stability and flexibility of the overlay film. PMMA can also be impact-modified with butyl acrylic rubber, but not deformed. An example of an impact modified PMMA can use the registered trademark CP924 from Delaware Wilmington ICI Polymers, which can be obtained with the Benzontriazole UV absorber TINUVIN 900. Non-impact modified PMMA materials are referred to as "straight" PMMA. A suitable source of "straight" PMMA can use the registered trademark VO-45 from Atohas North America, Bristol, Pennsylvania, and CP81 from ICI Polymers, Walmington, Delaware. PVDF materials may utilize KYNAR from El Patocham North America, Philadelphia, Pennsylvania, and SOLVEY and SOLEF from Sorex Polymers, Huxton, Texas. Such polymers are good in terms of suitable mechanical properties, good adhesion to structured films, clarity, improved solvent durability and environmental friendliness.
    The overlay film may be a single layer or a plurality of layers having a thickness of about 10-200 micrometers if desired. In addition, the adhesion between the overlay film and the structured film can be improved by placing a thin bonding layer (not shown in FIG. 3) between the structured film and the overlay. As another method for improving the adhesion, a surface treatment method may be used.
    Example
    The features and advantages of the retroreflective sheet according to the invention are explained by way of examples. However, while describing the examples, the scope of the present invention should not be unduly limited to other conditions and details and the specific components and materials used. The following tests are used to examine the examples for retroreflective sheet structures of the present invention.
    Z-peel inspection
    Tension Adhesion Z-peel test is based on ASTM D 952-93. The instance to be examined is attached between two metal fixtures. For the next example, the test is started using a top fixture which is a 25.4 mm metal cube on each edge of 6.5 cm 2 . The bottom fixture is an aluminum plate 1.6 cm thick, 5 cm x 30.5 cm. For inspection, the retroreflective sheet of the present invention, which is 30 mm 2 , is manufactured under the trade name SCOTCH Adhesive Tape No. The top is covered with a suitable pressure sensitive tape, such as 419 (available from 3M, St. Paul, Minn.), And the bottom is ASTM D446 prior to crosslinking with the isooctyl acrylate-acrylic acid copolymer at a 93: 7 ratio. -93 group of bisamide crosslinks having an inherent viscosity of 1.5 to 1.7 when measured with a modified Ostward 50 viscometer at 20 ° C. using the test method (referred to as 93: 7 adhesive below) (US Pat. And a pressure sensitive adhesive crosslinked with the same). No. 419 adhesive tapes are inspected by storage in a dryer containing calcium carbonate for at least 24 hours prior to use. The sheet is placed and sealed with a film on the center of the aluminum plate, and the metal blocks are laminated on the upper side of the sheet. The sheet is then trimmed around the edge of the top block to inspect 25.4 x 25.4 mm 2 of sample. Next, it is compressed in a force of 1900 Newtons for 60 seconds and combined into a sandwich shape. The steel cube is secured to the upper jaws of the standard tension test device, and the aluminum plate is secured along the two sides to the fixture of the lower grip of the tester. The upper and lower jaws quickly separate at 50 cm / min, record the movement curve for force, and record the highest force.
    90 ° peeling test
    The 90 ° peel test (or referred to as the T-peel test) is based on ASTM D 1876-93. One piece of adhesive is laminated to the bottom of the sample of the structural retroreflective sheet. The adhesive used is a pressure sensitive adhesive using a 93: 7 adhesive. A sample of approximately 3.8 to 5.1 cm is applied to form a tab at one end of the sample using an adhesive tape folded up (adhesive tape (No. 898) under the trade name SCOTCH available from 3M, Minnesota, St. Paul)). The sample is then mounted on a 7 x 30.5 cm aluminum plate with a normal thickness of approximately 1 mm. Hand rollers are used to make good contact between the substrate and the adhesive exposed on top of the sample.
    The finished set of samples, ie the composite, is set in a constant temperature (20 ° C.) and constant and relative humidity (50%) chamber for 24 hours before testing. The replaced set of compounds is placed in a distilled water bath at 21 ° C. for 24 hours and 10 days at constant temperature (20 ° C.) and humidity (50% relative humidity). Each compound is mounted on a constant strain test device (for example, a device made under the trade name SINTECH or INSTRON) for inspection to separate the sample from the substrate at an angle of approximately 90 °. The sample and the substrate are carried out by a jig to move to the side while both jaws of the machine move vertically, thus maintaining the drop edge of the sample / substrate composite at the center between both jaws of the tension test device.
    A jig consisting of a "ball slide" (available from McMaster-Carr, Chicago, Ill.) With a moving bed attached to the floor is preferred. The column extends at right angles from the bottom of the floor. The composite, i.e., the sample, fired on the substrate, is attached to the moving bed, and the upper jaw of the tension test device is filled with the tab formed at one end of the sample while the pillar is clamped to the lower jaw so as not to move. Thus both jaws are separated at 30.5 cm / min and force is required to influence the separation between the sample and the substrate. This measures the force required to peel off the sealed film / sealing coating composite from the structural film.
    Water resistance
    This inspection method is an immersion method that is emptied to measure the calculated degree of sealing under processing conditions. The device has a PYREX glass dryer, a vacuum pump, a (0 to 1.0 x 10 5 Pascal) vacuum gauge, a valve and associated vacuum tube, a liquid dish soap (slow surfactant) and an approximate 50 g weight with an internal diameter of 200 to 250 mm.
    The dryer adds 4-6 drops of liquid dish soap and fills half with tap water. The test is performed at room temperature (approximately 20-25 ° C.). The dryer is closed and the vacuum pump is attached to the nozzle of the dryer lid using a vacuum hose that includes a gauge and a bleeder valve. The pressure in the dryer is reduced to 85 x 10 3 Pascals less than the ambient pressure and held for 1 minute. The vacuum pump is then turned off and the bleeder valve applies air to the dryer until the pressure is equal to atmospheric pressure. Open the dryer and remove the sample. Record the amount of water entering the rescue cell. The “good” grade is filled with water only in the open cells on the periphery where the water enters.
    Improved weather resistance
    After exposure to ultraviolet (UV) radiation, the sample was subjected to ASTM procedure No. 1 using a UV lamp with a maximum emission of 340 nm to measure the amount of retroreflective brightness and retention of exfoliation coalescence. Placed in a fluorescent UV concentrator (available from Q-Panel Co., Westlake, OH) according to G-53, circulated for 20 hours in bright conditions at 75 ° C., circulated in dark for 4 hours at 50 ° C. Repeat with different exposure times.
    Luminance
    The sheet is luminescent according to ASTM Method E 810-94 with an angle of incidence of -4 ° and an angle of observation of -0.2 ° when using a 553 backlight meter (serial number 474764) to form a flat plate (e.g. stacking plates). Measure
    Humidity and Temperature Circulation (Blue M Cycle Chamber)
    In order to measure the peel strength maintained during repeated exposure to temperature and humidity cycles, a sample of retroreflective sheet is prepared 5 cm wide and 15 cm long and is mounted sticky using a pressure sensitive adhesive with a 93: 7 adhesive. . The sample is placed in a panel support with holes to keep the panel at 90 ° from horizontal. The panel support is placed in a blue M cycle chamber produced by General Signal Corporation of Stamford, Connecticut. The Blue M cycle chamber is programmed to circulate for 8 hours from 60 ° C to -40 ° C. At 60 ° C., this Blue M Cycle chamber is maintained at 92% relative humidity (RH) for 1 hour. Samples were removed from the chamber after 1000 hours and 90 ° peel adhesion was measured.
    Example 1
    Retroreflective sheet for riveting between cube corner components and sealing film
    The cube corner film adhered to the top is made of the following components: The cast polycarbonate resin (MAKROLON 2407, made by Mobay Corp., Pittsburgh, Pennsylvania) has a microcube prism recess with a depth of approximately 175 μm. It is cast on a heated microstructured nickel tool. Micro cube recesses are formed in matching pairs of cube corner components that are inclined 9.2 ° from the main groove or inclined to the optical axis and are disclosed in US Pat. No. 4,588,258. The nickel tool thickness is 508 μm and the tool is heated to 216 ° C. The polycarbonate dissolved at a temperature of 288 ° C. to fold the microcube recess was cast on the tool for 0.7 seconds at a pressure of approximately 1.03 × 10 7 Pascals to 1.38 × 10 7 Pascals. While filling the microcube recesses, the polycarbonate places the tool in successive layers to form lands with a thickness of approximately 150 μm. The entire cube corner film is approximately 330 μm thick.
    Pre-extruded 50 μm thick impact modified, continuous poly (methylmethacrylate) overlay film (60% PLEXIGLASS VO-45 poly (methylmethacrylate)) from AtoHaas North America Inc. of Bristol, Pennsylvania Modified with 40% DR-100 cross-linked impact particles made from the butyl acrylate rubber produced) are deposited on the top surface of the continuous land layer when the surface temperature is approximately 190.6 ° C. The combined tool with laminated polycarbonate and poly (methylacrylate) overlap is cooled to solidify the laminated material at 71-88 ° C. for 18 seconds at ambient room temperature. The laminated sample is removed from the microstructured tool.
    Films sealed to a standard thickness of 50 μm are made by a method known in US Pat. No. 08 / 626,709, entitled EXTRUDING THIN MULTIPHASE POLYMER FILMS, filed Apr. 1, 1996 (Agent Control Number 52496USA3A). Four sealing films (“SF1” to “SF4”) were obtained by the following method and shown in Table 2 below.
    Sealing film Sealing filmResin trade destinationchemical substance SF1CENTREX 833 (marine white)ASA / AES Terpolymer Blend SF2CENTREX 401 (neutral)AES SF3PULSE 1350Polycarbonate / ABS Blend SF4CYOLAC GPX 3800ABS
    The cube core film with attached overlap is fed to a 60 durometer rubber roller with a steel embossing roller and a pre-extruded seal film. The sealing film is protected by a 13 μm polyethylene terephthalate film neighboring the steel embossing roll furnace. The embossing roller surface temperature is approximately 220 ° C and the rubber nip roller surface temperature is approximately 200 ° C. The pressure of the nip is provided by two 7.6 cm hydraulic poystones, and it is possible to compress one at each end of the rubber roller in the range of approximately 3.5 x 10 4 pascals to approximately 17.24 x 10 4 pascals. Rubber nip rollers are approximately 25 cm in diameter and steel embossing rollers are 40 cm in diameter. The pressure is distributed across the width of the sample and becomes 30.5 cm wide.
    The treatment web speed and force on the nip are varied to obtain the desired water resistance. In SF1, the processing web speed is 3 m / min, the display pressure of the nip is 8.08 x 10 5 Pascals, and the rubber nip roller surface temperature is 216 ° C. In SF2, the processing web speed is 4 m / min, the display pressure of the nip is 6.99 × 10 5 Pascals, and the rubber nip roller surface temperature is 216 ° C. In SF3, the treatment web speed is 3 m / min, the display pressure of the nip is 1.19 × 10 6 Pascals, and the rubber nip roller surface temperature is 216 ° C. In SF4, the treatment web speed is 4 m / min, the display pressure of the nip is 1.05 × 10 6 Pascals, and the rubber nip roller surface temperature is 216 ° C.
    Following lamination, the structure is cooled to approximately 10 ° C. using cold rollers. The polyethylene terephthalate protective layer is removed from the sample and the thickness of the finished structure is determined. Luminance, water resistance and 90 ° peel adhesion are calculated. In each structure, the initial water resistance is excellent. The luminance for each structure is shown as an average of 6 to 8 trials in units of candela / lux / m 2 (SF1, 1088; SF2, 1205; SF3, 1000; SF4, 899). A summary of weather, external weather in Florida and Arizona, humidity and temperature cycling using Blue M Cycle seals, and maintenance of 90 ° peel adhesion after 10 days of water uptake is given in Table 3.
    Retention rate of 90 ° peel adhesion and outdoor weather resistance after accelerated Suture film3000 hours12 months Arizona12 Months Florida3000 hours blue em cycle10 days water absorption SF1114%94%88%96%118% SF2120%122%126%87%133% SF33%---- SF42%----
    The structure using the sealing films SF1 and SF2 well retains the adhesive strength in this inspection. Some of these data indicate an increase of 90 ° peel adhesion over time (ie, having a retention of at least 100%). This is manifested by an increase in the molecular weight of the sealing film with respect to the crosslink concentration and time.
    The configurations using the sealing films SF3 and SF4 are known to have poor contact strength (i.e., retained peel adhesion while weathering resistance is enhanced and has not been examined in other exposures). Although the sealing films SF3 and SF4 are not weather resistant and the sealing films SF1 and SF2 are the same, their weatherability can be improved by various adhesives such as UV stabilizers and / or by the use of sealing coatings.
    Example 2
    Retroreflective sheet with riveted connections between the cube corner member and the sealing film with a solvent seal coating
    A cube corner film to which the top layer was attached was prepared as described in Example 1. The sealing film SF1 was extruded and thermally embossed to obtain a cube corner film described in Example 1. Two samples are prepared, one for applying a seal coating and the other for comparison testing.
    Seal coating solutions were prepared according to Example 2 of US Pat. No. 4,025,159 to McGrath. The solution contains 150 parts by weight of thermoplastic acrylic terpolymer (52.5% methyl methacrylate, 43% ethyl acrylate, 4.5% isooctyl acrylate), 33 parts by weight of tetraethylene dissolved in 33.3% solids in xylene. Glycol diacrylate (SARTOMER 268), 42 parts by weight of rutile TiO 2 (R960) pigment sold by DuPont de Nemours, and 0.45 parts by weight of stearic acid.
    The seal coating solution was coated onto the sealing film side of the sheet using a notch bar coater. The coated sample was dried at 150 ° C. for 10 minutes and passed through an electron beam processor at a rate of 6 meters / minute. Curing conditions are as follows. 175 ㎸, 5.88 ㎃ (This is intended to provide 5 Mrad emissions using the "Electro Curtain Model CB 300/45/380" manufactured by "Energy Sciences Inc.", Wilmington, Massachusetts, USA. ).
    The final result was glued to the aluminum test plate and subjected to the harsh climate test described above. The percentage of maintaining the initial 90˚ Peel Adhesion is shown in Table 4 below.
    sample1000 hours2000 hours3000 hours4000 hours No sealing coating97%78%101%78% Sealing coating107%103%92%102%
    Example 3
    Retroreflective sheet with riveted connections between sealing film with 100% solid sealing coating and cube corner member
    A cube corner film with a top layer attached was prepared as described in Example 1. The sealing film SF1 was extruded and thermally embossed to obtain a cube corner film described in Example 1. Various fatty urethane diacrylates (UDAs) were used in the seal coating configurations listed in Table 5 below. The fatty urethane acrylates used are as follows. "UDA-1" is "PHOTOMER 6010" (MW = 1500, sold by "Henkel Corp." in Hoboken, NJ), "UDA-2" is "S-9635" (25% by weight Isobonyl acrylate, sold at "Sartomer Co." in West Chest, Pennsylvania, USA, "UDA-3" is "S-9645" (25% by weight of isobonyl acrylate, above "Sartomer Co. ")," UDA-4 "is" S-9655 "(25% by weight of isobonyl acrylate, sold by" Sartomer Co. "above)," UDA-5 "is" S-963 -B80 "(20% by weight 1,6-hexanediol diacrylate, sold by" Sartomer Co. "above)," UDA-6 "means" S-966-S80 "(20% by weight tripropylene Glycol diacrylate, sold under "Sartomer Co." above, "UDA-7" contains "EBECRYL 284" (MW = 1200, containing 12% by weight of 1,6-hexanediol diacrylate, USA, "UCB Radcure Inc.", "Smyrna", Georgia), "UDA-8" is "EBECRYL 8402" (MW = 1000, sold by "UCB Radcure Inc." above). The units of the values in Table 5 are grams (g). The compositions also include CENTREX 833 ("833") AES / ASA terpolymers, SARTOMER 285 ("285) tetrahydroxy fufuryl acrylate and" DRAOCURE 4265 "(2-hydroxy-2-methyl-1-phenylpropane A mixture of 1-one and 2,4,6-trimethylbenzoyldiphenylphosphine oxide at 50:50, sold by "Ciba-Geigy Corp." in Hawthorne, NY, USA. Contains 1% by weight of photoinitiator on sale No dye other than what is contained in "CENTREX 833".
    Sealing coatingUDA-1UDA-2UDA-3UDA-4UDA-5UDA-6UDA-7UDA-8"833""S-285" SC-1 5012.537.5 SC-2 4314.342.7 SC-3 3316.850.2 SC-4 1022.567.5 SC-5 10 22.567.5 SC-6 10 22.567.5 SC-710 22.567.5 SC-833 16.850.2 SC-943 14.342.7 SC-10 1022.567.5 SC-11 3316.850.2 SC-12 10 22.567.5 SC-13 33 16.850.2 SC-14 43 14.342.7 SC-15 10 22.567.5 SC-16 33 16.850.2 SC-17 43 14.342.7 SC-1810 22.567.5
    The sealing film side of the sheet was coated with various sealing coating compositions using a wire winding coating rod 3 to provide a wet coating caliper of about 12 μm. The seal coating was then applied to the "American Ultraviolet UV Processor Model C38 / 300 / 2W" (two sold at "American Ultraviolet" in "Murray Hill", NY) with two medium pressure Hg bulbs of 300 watts each. Pass through several times and dry. The speed of the above processor was 33 meters / minute.
    The seal coated sample was mounted on an aluminum plate for 90 ° peel adhesion test. The increase in 90 ° peel adhesion of the seal coated sample relative to the control sample (sample without seal coating) is shown in Table 6 below.
    Seal coating composition% Increment for control sampleSeal coating composition% Increment for control sample SC-1267%SC-10108% SC-2267%SC-11220% SC-3170%SC-12188% SC-4180%SC-13265% SC-5111%SC-14202% SC-6113%SC-15126% SC-7129%SC-16239% SC-8221%SC-17237% SC-9275%SC-18130%
    As a result of the experiment, it was observed in all samples that the use of the seal coating significantly increased the adhesion to the cube corner film compared to the one sealed film.
    Example 4
    Retroreflective sheet with riveted connections between the sealing film with colored sealing coating (100% solids) and the cube corner member
    A cube corner film with an upper layer was prepared in the same manner as in Example 1 except that the fluorescent dye was included. The sealing film SF1 was extruded and thermally embossed to obtain a cube corner film described in Example 1. The seal coating described in Table 7 below was made by mixing the listed components (UDA-8 was already described in Example 2, "833" refers to CENTREX 833 AES / ASA terpolymer, and "S- 285 "refers to SARTOMER 285 trihydroxy full furic acrylate, and TiO 2 grinds are sold under the name" 9WJ "from" Penn Color "in" Dolyestown, Pennsylvania, USA, and are used with neopentyl glycol diacrylate and " Rutile TiO 2 (R960) sold by DuPont ”, coated on the sealing film side of the sheet as described in Example 3, and 16 meters / minute using“ Fusion V Bulb (400 Watts) ” It is cured by passing four times at a rate of
    Sealing coatingUDA-8 (% by weight)TiO 2 grind (% by weight)"833" (% by weight)"S-285" (wt%) SC-190.60.150.000.25 SC-200.60.050.030.33 SC-210.60.250.030.13 SC-220.60.250.000.15 SC-230.30.250.050.40 SC-240.30.250.050.40 SC-250.50.250.000.25 SC-260.60.250.060.29 SC-270.60.050.060.29 SC-280.450.050.060.44 SC-290.450.050.060.24 SC-300.60.250.050.32 SC-310.530.050.050.39 SC-320.60.1750.050.19 SC-330.530.250.050.19 SC-340.40.250.030.33 SC-350.530.050.060.37 SC-360.530.180.060.24 SC-370.40.190.050.36 SC-380.50.180.040.30
    Seal coated samples were mounted on aluminum plates and 90 ° peel adhesion, Z-peel and brightness were examined. The test results are shown in Table 8 below. The 90 ° peel tack, Z-peel test showed an increase in percentage for control samples that did not include a seal coating. The luminance test result was expressed in candela / lux / m 2.
    Sealing coating% Increment for control sample Furtherance90˚ peelZ-peelbrightness SC-19137%142%358 SC-20147%139%372 SC-21103%127%413 SC-22133%145%432 SC-2385%117%394 SC-2498%114%334 SC-25140%139%424 SC-26147%149%420 SC-27166%144%391 SC-28129%133%370 SC-29161%150%329 SC-30154%136%375 SC-31144%139%368 SC-32152%154%383 SC-33150%144%386 SC-34123%135%450 SC-35126%134%417 SC-36151%144%347 SC-37104%124%400 SC-38146%122%384 Control sample--393
    The patents, patent documents, and patent publications mentioned herein are all included as part of this specification, which is equivalent to the expression that said documents are each included as part of this specification. Those skilled in the art to which the present invention pertains will readily be able to make various modifications and variations to the present invention without departing from the scope and spirit of the invention, and the various implementations described herein. It is to be understood that, by way of example, the present invention is not unduly limited.
    权利要求:
    Claims (47)
    [1" claim-type="Currently amended] a) a structured film comprising a structured member array,
    b) a sealing film attached to said structured film by a plurality of riveted connections,
    A first side of the sealing film facing the structured member, a second side facing away from the structured member, the riveted connecting portions each comprising a hole formed in the sealing film, the portion of the structured film A retroreflective sheet protruding through the hole to adhere the sealing film to the structured film.
    [2" claim-type="Currently amended] The retroreflective sheet of claim 1, wherein a portion of the structured film that protrudes through a hole formed in at least one of the riveted connections extends to form a flange.
    [3" claim-type="Currently amended] The retroreflective sheet according to claim 1, wherein the riveted connecting portion is positioned in a predetermined pattern.
    [4" claim-type="Currently amended] The retroreflective sheet of claim 1, wherein the structured film further comprises a land portion.
    [5" claim-type="Currently amended] The structure of claim 1, wherein the structured film further comprises an elevated structure extending between itself and the sealing film,
    And said riveted connection is formed on said raised structure.
    [6" claim-type="Currently amended] 6. The retroreflective sheet of claim 5, wherein a portion of the structured film that protrudes through a hole formed in at least one of the riveted connections extends to form a flange.
    [7" claim-type="Currently amended] 6. The retroreflective sheet of claim 5, wherein the raised structure further comprises one or more ridges.
    [8" claim-type="Currently amended] 6. The retroreflective sheet of claim 5, wherein the raised structure further comprises one or more ridges positioned in a predetermined pattern.
    [9" claim-type="Currently amended] 6. The retroreflective sheet of claim 5, wherein the raised structure further comprises a member for forming a hole in the sealing film.
    [10" claim-type="Currently amended] The retroreflective sheet of claim 1, wherein the sealing film comprises a thermoplastic polymer.
    [11" claim-type="Currently amended] The retroreflective sheet of claim 1, wherein the sealing film has a ductility of at least about 20%.
    [12" claim-type="Currently amended] The method of claim 11, wherein the sealing film is cast polyether, cast polyester, cast polyamide, ionomeric ethylene copolymer, plasticized vinyl halogenated polymer, styrene-acrylonitrile copolymer, poly-alpha-olefin, ethylene- A retroreflective sheet comprising a thermoplastic polymer selected from the group consisting of propylene-diene copolymers and combinations or mixtures thereof.
    [13" claim-type="Currently amended] 13. The method of claim 12, wherein the sealing film is an ethylene-propylene-nonconjugated diene terpolymer, a styrene- atrylonitrile graft copolymer, an acrylonitrile-butadiene-styrene graft grafted with a mixture of styrene and acrylonitrile. A retroreflective sheet comprising a thermoplastic polymer selected from the group consisting of copolymers, extractable styrene-acrylonitrile copolymers, and combinations or mixtures thereof.
    [14" claim-type="Currently amended] 13. The retroreflective sheet of claim 12, further comprising a seal coating formed on the second side of the seal film.
    [15" claim-type="Currently amended] 15. The retroreflective sheet of claim 14, wherein the seal coating is provided from a seal coating precursor comprising a thermally cured component.
    [16" claim-type="Currently amended] 15. The retroreflective sheet of claim 14, wherein the seal coating is provided from a seal coating precursor comprising a component that is cured by spinning.
    [17" claim-type="Currently amended] 17. The retroreflective sheet of claim 16, wherein the component cured by spinning comprises a resin cured by a cation, a resin cured by free radicals, or a mixture thereof.
    [18" claim-type="Currently amended] 17. The retroreflective sheet of claim 16, wherein the component cured by spinning comprises a dual cured resin or a hybrid cured resin.
    [19" claim-type="Currently amended] 17. The retroreflective sheet of claim 16, wherein the component cured by spinning comprises acrylate.
    [20" claim-type="Currently amended] 20. The inverse of claim 19 wherein the acrylate is selected from the group consisting of acrylated epoxy, acrylated polyester, acrylated aromatic or aliphatic urethanes, acrylated acrylics, acrylated silicones, acrylated polyethers, vinyl acrylates and acrylated oils. Reflective sheet.
    [21" claim-type="Currently amended] 21. The retroreflective sheet of claim 20, wherein the acrylate is an acrylated aromatic or fatty urethane.
    [22" claim-type="Currently amended] 22. The retroreflective sheet of claim 21, wherein the acrylate is an acrylated aromatic urethane.
    [23" claim-type="Currently amended] 23. The retroreflective sheet of claim 22, wherein the seal coating precursor further comprises a monofunctional or multifunctional reactive monomer.
    [24" claim-type="Currently amended] 24. The retroreflective sheet of claim 23, wherein the monofunctional or multifunctional reactive monomer is an acrylate monomer.
    [25" claim-type="Currently amended] 17. The retroreflective sheet of claim 16, wherein the seal coating precursor comprises a reactive diluent and a film former.
    [26" claim-type="Currently amended] 26. The retroreflective sheet of claim 25, wherein the reactive diluent comprises a monofunctional or multifunctional acrylate monomer.
    [27" claim-type="Currently amended] 27. The retroreflective sheet of claim 25, wherein the film former comprises a thermoplastic polymer.
    [28" claim-type="Currently amended] 27. The retroreflective sheet of claim 25, wherein the film former comprises a monofunctional or multifunctional acrylate oligomer.
    [29" claim-type="Currently amended] 27. The retroreflective sheet of claim 25, wherein the seal coating precursor further comprises a polyphase styrene thermoplastic copolymer.
    [30" claim-type="Currently amended] a) a cube corner film comprising a cube corner member arrangement;
    b) a sealing film attached to said cube corner film by a plurality of riveted connections,
    (Iii) the riveted connecting portions each include a hole in the sealing film that attaches the sealing film to the cube corner film by protruding through a portion of the cube corner film,
    (Ii) the sealing film comprises a polyphase styrene thermoplastic copolymer.
    [31" claim-type="Currently amended] 31. The retroreflective sheet of claim 30, wherein the sealing film has a thickness of less than about 250 microns.
    [32" claim-type="Currently amended] 31. The ethylene-propylene-non-conjugated diene terpolymer, styrene-atrylonitrile graft copolymer, acryl, wherein the polyphase styrene thermoplastic copolymer is grafted with a mixture of styrene and acrylonitrile. A retroreflective sheet, characterized in that it is selected from the group consisting of ronitrile-butadiene-styrene graft copolymers, extractable styrene-acrylonitrile copolymers, and combinations or mixtures thereof.
    [33" claim-type="Currently amended] 32. The retroreflective sheet of claim 30, further comprising a seal coating on the second side of the seal film.
    [34" claim-type="Currently amended] 34. The retroreflective sheet of claim 33, wherein the seal coating is provided by a seal coating precursor having a component that is cured by spinning.
    [35" claim-type="Currently amended] 35. The retroreflective sheet of claim 34, wherein the seal coating comprises a reactive diluent and a film former.
    [36" claim-type="Currently amended] 36. The retroreflective sheet of claim 35, wherein the reactive diluent comprises a monofunctional or multifunctional acrylate monomer.
    [37" claim-type="Currently amended] 36. The retroreflective sheet of claim 35, wherein the film former comprises a monofunctional or multifunctional acrylate oligomer.
    [38" claim-type="Currently amended] 38. The retroreflective sheet of claim 37, wherein the seal coating precursor cured by spinning further comprises a multiphase styrene thermoplastic copolymer.
    [39" claim-type="Currently amended] a) providing a structured film comprising a structured member array,
    b) attaching the sealing film to the structured film by forming a plurality of riveted connections between the structured film and the sealing film,
    And said structured film forms a hole in said sealing film to form each said riveted connecting portion.
    [40" claim-type="Currently amended] 40. The method of claim 39, wherein said attaching step further comprises forming a flange on at least one of said riveted connections.
    [41" claim-type="Currently amended] 40. The method of claim 39, wherein said attaching step further comprises forming said riveted connection in a predetermined pattern.
    [42" claim-type="Currently amended] 40. The method of claim 39, wherein the sealing film comprises a thermoplastic polymer.
    [43" claim-type="Currently amended] 40. The method of claim 39, wherein the sealing film has a ductility of at least about 20%.
    [44" claim-type="Currently amended] 40. The method of claim 39, wherein the sealing film comprises cast polyether, cast polyester, cast polyamine, ionomeric ethylene copolymer, plasticized vinyl halide polymer, styrene-acrylonitrile copolymer, poly-alpha-olefin, ethylene-propylene A diene copolymer and a thermoplastic polymer selected from the group consisting of combinations or mixtures thereof.
    [45" claim-type="Currently amended] 45. The method of claim 44, further comprising providing the seal coating precursor on the second side of the seal film.
    [46" claim-type="Currently amended] 46. The method of claim 45, wherein the seal coating precursor comprises a component that is cured by radiation.
    [47" claim-type="Currently amended] 46. The method of claim 45, further comprising curing the seal coating precursor using electron beam radiation.
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    同族专利:
    公开号 | 公开日
    AU2580797A|1997-10-22|
    DE69705214D1|2001-07-19|
    CA2250749A1|1997-10-09|
    ES2158545T3|2001-09-01|
    EP0891568A1|1999-01-20|
    AU709520B2|1999-09-02|
    DE69705214T2|2002-05-02|
    EP0891568B1|2001-06-13|
    JP2000508090A|2000-06-27|
    BR9708415A|1999-08-03|
    CN1220011A|1999-06-16|
    AT202216T|2001-06-15|
    WO1997037251A1|1997-10-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1996-04-01|Priority to US62585796A
    1996-04-01|Priority to US08/625,857
    1996-11-08|Priority to US08/747,105
    1996-11-08|Priority to US08/747,105
    1997-03-11|Application filed by 스프레이그 로버트 월터, 미네소타 마이닝 앤드 매뉴팩춰링 캄파니
    2000-01-25|Publication of KR20000005167A
    优先权:
    申请号 | 申请日 | 专利标题
    US62585796A| true| 1996-04-01|1996-04-01|
    US08/625,857|1996-04-01|
    US08/747,105|US5754338A|1996-04-01|1996-11-08|Structured retroreflective sheeting having a rivet-like connection|
    US08/747,105|1996-11-08|
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