MXPA97009538A - Articles retrorreflectores for devices of salvage in the - Google Patents

Abstract

The present invention relates to retroreflective articles for sea rescue devices, comprising a layer of a pressure-sensitive adhesive made using a solvent-free, heat-melt process that employs a non-thermoplastic, sticky elastomer as the starting material . The process employs a continuous mixing device that has a sequence of transportation and alternating processing zones

Description

RETRORREFLECTORSS ARTICLES FOR SEA SALVAGE DISCLOSURES Background of the Invention 1. Field of the Invention This invention relates to retroreflective articles comprising a layer of pressure-sensitive adhesive, lightly or non-crosslinked, made by a solvent-free hot melt process of an amorphous hydrocarbon elastomer, made sticky which is adheres to a wide variety of substrates adapted for life-saving devices at sea without the need for sizing. 2. Related Art Retroreflective articles have many uses. It is often desired to adhere the retroreflective articles to other articles, whereby a portion of the second article becomes visible at night or in inclement weather conditions. If an adhesive should be used to adhere the retroreflective article REF: 26059 To the second article, environmental conditions must be taken into consideration. Retroreflective articles can be used to reflectorize rescue devices, such as, for example, inflatable lifejackets and lifejackets used in marine equipment, i.e. high humidity conditions and / or immersion in water. In these conditions, the current technology for reflectorizing these materials is first applying a solvent-based adhesive sizing to the material. Then a retroreflective article with the back part is applied with synthetic rubber adhesive, acrylic or highly sticky, to the area with sizing. Adhesive priming is required in order for the retroreflective article to remain in the garment under conditions of high humidity and / or immersion in the water. The current adhesive sizing (for example that known under the trade designation E-44, available from the assignee) is found to work only on selected substrates, and is not preferred by the user due to its odor and additional application time (the application of the sizing on the substrate and waiting for the finished drying). For example, inflatable lifejackets, lifejackets, and liferafts may comprise a number of different materials, including one or more of the following: polymer coated fabric (such as fabric coated with plasticized polyvinyl chloride, fabric coated with rubber and the like), laminates of vinyl film / nylon cloth, strong cotton cloth, fiberglass, polyolefin film, vinyl film and the like. It would be preferred if a retroreflective article were available having a pressure sensitive adhesive thereon that would adhere to a variety of tissues of the salvage devices, without the need for a sizing.

Brief Description of the Invention According to the present invention, there is presented a retroreflective article for sea rescue devices (SOLAS) comprising a layer of pressure sensitive adhesive as described in the world patent publication of the assignee WO 94/11175 on a surface No incidence of light of the article. The articles of the invention are useful for reflectorizing SOLAS by adhering a retroreflective sheet material to a variety of materials. The adhesive allows the SOLAS to exhibit sufficient tolerance to water immersion to pass demanded tests of such items, without the help of a sizing. In particular, retroreflective articles of the invention comprise: (a) a retroreflective layer material comprising a surface with light incidence and a surface without incidence of light; and (b) a layer of pressure sensitive adhesive disposed on at least a portion of the surface without incident light, the adhesive derived from an amorphous hydrocarbon elastomer using a heat fusion process, without solvent, the adhesive comprises : (i) a rubber having a glass transition temperature ranging from about -120 ° C to about -50 ° C; and (ii) a tackifier having a ring and ball softening point that varies from about 70 ° C to 140 ° C, the adhesive comprises from about 60 to about 125 parts by weight of tackifier per 100 parts by weight. rubber weight. Preferably, the rubber is slightly reticulated (preferably by means of an electron beam) but not to the point of insolubility in toluene. A small percentage by weight of the chemical crosslinker such as phenolic resin can be used to increase the molecular weight of the rubber, as an alternative to the electron beam. Preferably, the adhesive is present in a coating weight ranging from about 20 to about 40 grams per . 16 centimeters by 15.24 centimeters (4 inches by 6 inches) (approximately 80 to approximately 170 grams per square meter (gsm)), more preferably about to about 40 grams per 10.16 centimeters per 15.24 centimeters (4 inches by 6 inches) (approximately 120 to approximately 170 gsm). Preferably an outer coating material is adhered to the adhesive so that the article can be made available in roll form. Preferably, the adhesive is used to adhere the retroreflective layer material to a variety of substrates, such as vinyl-coated nylon fabric. For the retroreflective articles of the invention the adhesive layer adheres to the surface without light incidence of the retroreflective article (i.e., the surface of the retroreflective article that receives no incident light when the article is used for its required purpose). Such a surface without incidence of light may include i) a sealing film (preferably polyester, polyolefin, polyvinyl chloride or polycarbonate) bonded to the retroreflective, transparent layer material having a substantially planar surface and a second structured surface, the second structured surface comprised of a plurality of notches (parallel or intersecting) defining a plurality of peaks, ii) a metallized surface of a retroreflective layer material having a substantially planar surface and a second structured surface, the structured surface having a metal layer thereon, or iii) a binder layer of a retroreflective layered material with spheres (ie, materials in retroreflective layers comprising a plurality of transparent microspheres.) The PSAs useful in the invention are produced in preferential way through a process that allows elast processing amorphous hydrocarbon monomers, especially amorphous hydrocarbon elastomers, of high molecular weight, without the need to use either organic solvents or low molecular weight plasticizing auxiliaries. The process produces PSAs by solvent-free mixing of amorphous, sticky hydrocarbon elastomers. The process employs a continuous mixing device and heat fusion processing techniques. The adhesive composition can be mixed without prior trituration of the batch, separated from the elastomer and without the use of significant amounts of plasticizing aids to reduce the viscosity of the composition to render it processable. Additionally, the adhesive composition can be applied to a moving fabric directly from the mixing device to provide a continuous method for manufacturing the articles of the invention. The process can supply even high molecular weight hydrocarbon elastomers, for example MWV viscosity average molecular weight of 250,000 or greater. The process can employ either aerobic or anaerobic processing. For purposes of this invention, aerobic processing means that a gas containing available oxygen (such as compressed air) is intentionally injected into the mixing device to promote oxidative decomposition of the hydrocarbon elastomer. Anaerobic processing means that gas with oxygen available in the mixing device is not intentionally injected. However, smaller amounts of air may be present in the anaerobic processing in the practice of the invention. The aerobic processing can be advantageously used when the hydrocarbon elastomer will be preferentially subjected to chain cleavage rather than cross-linking and / or chain extension. Aerobic processing allows a greater reduction in the molecular weight of the elastomer in a relatively short period of time. Additionally, aerobic processing allows processing at lower temperatures. As a result, the thermally sensitive materials can be mixed with the hydrocarbon elastomer in the process of the invention. Anaerobic processing can be used advantageously when using elastomers that crosslink under oxidative conditions. This mitigates the problem of these elastomers that crosslink during processing. Anaerobic processing can also be used with elastomers that do not cross-link under oxidative conditions to achieve a higher molecular weight than would be achieved under aerobic conditions. This increases the cohesion strength of the adhesive and minimizes the degree of the last crosslinking necessary to provide increased cohesion strength. The anaerobic processing of any type of elastomer also results in adhesives that have a low odor and lighter color.

The preferred process for manufacturing the PSAs useful in the invention employs a continuous mixing device having an alternate transport sequence and processing zones. The elastomer is continuously transported from one area to the other by the device. The processing zones are capable of crushing the elastomer. These are also capable of mixing the additives in the elastomer. In the preferred process, an amorphous elastomer is fed into a first transport zone of the mixing device. This first zone transports the elastomer to a first processing zone where the elastomer is crushed. The shredded elastomer is then transported to a second transportation zone where a tackifier is added and the mixture of the two is brought to a second processing zone where the tackifier and the shredded elastomer are mixed together to form a slurry mixture. the two materials. The mixture can then be discharged from the mixing device and stored for later use. Alternatively, the mixture can be applied to a fabric, preferably a moving fabric, in the form of a thin film. In order to facilitate the description of the invention, the following terms used herein should have the following meaning: SOLAS in an acronym for the safety of life at sea and it should be understood that retroreflective articles comprise a retroreflective layer material with spheres or corner of cube that has a layer of PSA non-thermosetting on its surface without incidence of light. The PVC component includes fabrics coated with PVC and free PVC articles from the fabric. Particularly preferred are highly and monomerically plasticized PVC components, such as PVC coated fabrics. An amorphous hydrocarbon elastomer is to be understood as a hydrocarbon homopolymer or copolymer as distinguished from a block copolymer. Pressure sensitive adhesive (PSA) should be understood as an adhesive that is usually tacky at room temperature and adheres to a surface with no more than contact with the surface without the need for more than finger pressure or pressure. hand. Tackifying agent should be understood as a material that is miscible with at least one hydrocarbon elastomer, has a MWn of average molecular weight in number of 10,000 grams per mole (g / mol) or less and a glass transition temperature (Tg) -30 ° C or higher, as measured by differential scanning calorimetry (DSC). Auxiliary plasticizer should be understood as a material that has a MWn of less than 50,000 g / mol and a (Tg) of less than -30 ° C as measured by the DSC. The additional aspects and advantages of the invention will become apparent from the following description of the invention.

Brief Description of the Drawings FIGURES 1-6 are cross-sectional (elongated) views of retroreflective articles illustrative of the invention comprising an adhesive as described herein.

Description of the Preferred Modalities The invention provides retroreflective articles comprising a pressure sensitive adhesive (PSA) on a surface without incident light. The articles of the invention, mainly by virtue of the adhesive, pass a number of rigorous tests, and preferably all tests, described further herein, which are used to determine whether the articles withstand the adhesion test after soaking in water that includes salt water. Many previously known adhesives have not yet shown the ability to comply with these tests, or they can only do so with the help of an adhesive sizing. The pressure sensitive adhesives useful in the invention and the inventive articles are now described with reference to the figures of the drawings.

I. Adhesive Layer Useful PSAs in The invention is preferably produced by a process employing a continuous mixing device. A number of such devices are known. These may comprise an individual unit of a series of interconnected units for continuously processing the elastomer. The device has a sequence of alternating processing and transportation sections that interconnect. An example of a continuous mixing device useful in the present invention is a twin screw extruder or propeller having a series of sequence of transportation and processing zones. Preferably a plurality of inlet openings are provided along the length of the extruder to facilitate the addition of various materials such as tackifier resins., fillers, antioxidants, plasticizing aids (if desired), radiation boosters such as electron beam sensitizers and photoinitiators, light stabilizers and other adjuvants known in the art. Additions of the material, whether elastomer, tackifier or other adjuvants, are made through the entry holes to an area and areas partially and completely for transportation. A pump and a melt filter can be presented as either an integral part of the extruder, or as a separate unit to facilitate both the removal of the adhesive from the mixing device and the removal of unwanted contaminants from the adhesive stream. In the practice of the process, the elastomer is added to a first transport zone of the mixing device at a controlled rate so that the elastomer does not completely fill the zone. The elastomer can be formed into small pellets by grinding or forming small balls by extrusion before it is fed to the mixing device. Alternatively, it can be fed directly into the mixing device without grinding or forming small balls using a device such as a Moriyama extruder. If the elastomer is formed into small balls, it is preferably treated with a material such as talc to prevent agglomeration of the pellets. The elastomer is then transported through the first transportation zone to a first processing zone where it is crushed. The first processing zone is typically designated as being essentially and completely filled and which grinds the elastomer. Additionally, the processing zone transports the elastomer to the next zone. It may be desirable to provide the first processing zone as at least two discrete processing sections separated from each other by a transportation section. This allows the elastomer to be crushed in the steps, with the cooling of the crushed elastomer between each step. If two or more elastomers are to be processed, they can both be added to the first transportation zone and crushed in the first processing zone. Alternatively, the elastomers can be added sequentially to different transport zones with sequential grinding after each addition of elastomer. The sequential addition of the elastomer to different transport zones can also be employed when using an individual elastomer. The grinding is carried out preferentially in the absence of materials that will lubricate the elastomer and prevent the reduction of its molecular weight. However, this does not prevent the presence of small amounts of such materials, provided that the present amount does not effectively reduce the grinding ratio. Other certain solid adjuvants, such as talc, inorganic fillers, antioxidants and the like, can be fed to the mixing device such that they are present during the grinding. The crushed elastomer then passes from the first processing zone to a second transportation zone. As with the first transportation zone, the second transportation zone is not filled completely by the elastomer. The tackifier, and optionally other additives, are fed into the second transportation zone. The resulting mixture is transported to the next processing zone where they are mixed to form a mixture of the materials. A number of techniques can be used to feed these materials to the mixing device. For example, a constant proportion feeder such as a K-Tron weight loss feeder can be used to add solid materials. Small heated container dischargers, gear pumps and other suitable equipment can be used to feed liquids in a controlled proportion to feed the liquids to the mixing device. The additives present in low concentration can be pre-mixed with one or more of the other components for a more accurate addition. Although substantially all the crushing occurs in the first processing zone, there may be some grinding occurring in the subsequent processing of the elastomer through the mixing device. This additional crushing may occur in subsequent transportation or processing zones. In any case, the degree to which the elastomer must be crushed in the practice of the invention varies with each elastomer employed and the desired finished product. In general, the elastomer must be sufficiently crushed to (i) allow subsequently added tackifiers and any other adjuvants to be satisfactorily mixed into the elastomer to form a mixture and(ii) allowing the mixture to be extruded as a stream that is essentially free of both rubber particles and visually identifiable regions of a tackifier and any other unmixed adjuvant. Once the crushed elastomer, the tackifier and any other adjuvant have been formed in the mixture, the composition can now be referred to as an adhesive. This adhesive typically has a viscosity at the processing temperature in the range of 500 Poises to 5000 Poises (measured at a shear rate of 100 sec. "1). Higher viscosity adhesives can also be processed in the process. invention The adhesive processing temperature is typically in the range of 100-200 ° C. The adhesive can be discharged from the mixing device into a storage container for further processing or use, alternatively, it can be downloaded directly on a support (e.g., an outer skin, a conformation layer, or a binder layer of a retroreflective sheet material) in the form of a thin film Preferably, the support comprises a moving fabric of material in retroreflector layers.The thin adhesive film can be formed by pumping the adhesive through a coating nozzle, optionally with the xiliar of a gear pump or other suitable device to develop sufficient pressure. The nozzle is preferably of the contact variety (ie, not a drop nozzle) that smears or smears the adhesive on a moving fabric supported on a backing roller. The nozzle may have a flexible blade, a cylindrical rubber extender, or a cylindrical metal rod, rotatable on the downstream side of the nozzle opening for spraying the adhesive. The nozzle can be located at the inlet of the mixing device to allow coating in line with the mixing and extrusion operations. Alternatively, the adhesive can be discharged from the mixing device and fed to the coating nozzle using a separate extruder, a melt pump, or a combination of an extruder and a melt pump with sufficient pressure to force the mixture of adhesive through the nozzle. The adhesive can be optionally filtered before feeding the coating nozzle.

The coated adhesive can optionally be crosslinked by exposure to ionization radiation, such as an electron beam or ultraviolet radiation, or a phenolic resin can be added as a chemical crosslinker, to increase the cohesion strength of the material. The crosslinking can be carried out in line with the coating operation or it can occur as a separate process. The degree of crosslinking should not result in the rubber being insoluble in toluene. A release liner can optionally also be applied to the fabric, either before or after the application of the adhesive. The release liner may be continuous or discontinuous on the fabric and is usually on the surface of the fabric opposite to that which the adhesive ultimately carries. The release coating can be applied either in line with the coating or crosslinking operations, or as a separate process. A twin screw or propeller extruder is preferably used as a mixing device. The screw or propeller of the extruder must be configured to crush the elastomer in the first processing zone before the addition of the tackifier. Additionally, if a mixture of elastomers is used in the adhesive, the first processing zone preferably allows the grinding and mixing of the elastomer components. The portion of the extruder and the screw or helix after the first processing zone must be designed to allow the addition of the tackifier and other additives to the elastomer and good mixing of the elastomer with these materials. Preferentially, the screw or propeller is designed so as to result in a homogeneous adhesive composition. The design of the screw or propeller to achieve crushing, transportation and mixing follows normal practices known in the art. Specifically, the screw or helix has a sequence of transportation and processing zones. The flow restriction and mixing elements are provided to achieve proper flow along the screw or helix and to obtain proper grinding and mixing. The transportation zones may contain ordinary Archimedes screw or helix elements. The processing zones may contain kneading blocks, rod mixers or other elements designed for grinding, composition and mixing. Flow restriction elements, such as kneading blocks arranged with an inverted pitch, reverse pitch transportation screws, a disc element or other device designed to restrict the flow of material, may also be present in the area of processing to ensure that the portion of the processing area that precedes these elements contributes to run the total material while the transportation area after these contributes to run only a part of the total. A wide variety of amorphous hydrocarbon elastomers can be employed in the present invention. These materials can be used individually or mixed together in the practice of the invention. Examples of these elastomers include, natural rubber, butyl rubber, synthetic piliisoprene, ethylene-propylene rubber, ethylene-propylenediene monomer rubber (EPDM), polybutadiene, polyisobutylene, poly (alpha-olefin) and styrene random copolymer rubber -butadiene. These elastomers are distinguished from thermoplastic elastomers of the block copolymer type such as styrenic diene block copolymers having glassy end blocks attached to an intermediate rubbery block. The adhesives useful in the present invention preferably contain a "non-phenolic" tackifier wherein "non-phenolic" means that the tackifier is selected from turpentine resins, terpenes, and tackifier of the hydrocarbon resin type. Certain tackifiers of the terpene type can actually have a minor portion of phenolic comonomer. Non-phenolic tackifiers are useful since they make it easy to control the elastic modulus and tackiness of the adhesive to the desired ranges. Suitable non-phenolic tackifiers include one or more types of abietic acid such as abietic acid, neoabietic acid, palustric acid, dihydroabietic acid, tetrahydroabietic acid and dehydroabietic acid, esters of all these; and types of pimaric acid, such as pimaric acid and isopimaric acid, dehydrated versions thereof, and esters thereof. The esters of the abietic acid types and types of pimaric acid are typically reacted and preferably by the acid with a polyol, such as pentaerythritol, glycerin, ethylene glycol, and the like. Representative commercial examples include those known under the trade designations ESTER GUM 8D (an ester of rosin), HERCOFLEX 400 (an ester of rosin), HERCOLYN D (a hydrogenated methyl ester), FORAL 85 (an ester of a resin of glycerin, hydrogenated turpentine), ESTER R-95 (an ester of pentaerythritol rosin), and FORAL 105 (an ester of pentaerythritol rosin, hydrogenated), all available from Hercules Chemical Co. The tackifiers do not Suitable phenolics of the terpene type include monomers of polymerized versions such as α-pinene, β-pinene and dipentene (limonene), and the like, optional commutation with C 9 monomers such as styrene monomer. The typical molecular weights of these tackifiers vary from about 300 to about 2000. The monomers are typically derived from turpentine and other natural sources, such as citrus peels, although the synthetic versions are equally operative. Commercially available non-phenolic, terpene-type tackifiers include those known under the trade designations ZONAREZ A-25 (based on a-pinene, Tg = -22 ° C), ZONAREZ A-100 (based on a -pinene, Tg = 55 ° C), both available from Arizona Chemicals; PICCOLYTE SIO (based on ß-pinene, Tg = -37 ° C), PICCOLYTE S115 (based on ß-pinene, Tg = 64 ° C), PICCOLYTE A115 (based on α-pinene, Tg = 64 ° C ), PICCOFYN A-135 (phenolic polyterpene, Tg = 84 °), and PICCOLYTE HM-85 (styrenated terpene, Tg = 35 ° C), all available from Hercules Chemical. Suitable non-phenolic, hydrocarbon-type tackifiers are low molecular weight polymers derived from either aliphatic or aromatic hydrocarbon monomers using a Lewis acid catalyst (cationic polymerization) or heat and pressure (addition polymerization initiated of free radicals). Examples of suitable aliphatic resins include those derived from cis-piperylene, trans-piperylene, isoprene, 2-methylbutene-2, dicyclopentadiene, and the like having molecular weights in preferred form ranging from about 800 to about 1500. Commercially available versions include those known under the trade designations WINGTACK 10 (Tg = -28 ° C) and WINGTACK 95 (Tg = 50 ° C), both available from Goodyear Chemical Co .; ESCOREZ 1310 (Tg = 40 ° C) and ESCOREZ 5300 (Tg = 50 ° C), both from Exxon Chemical Co .; and PICCOTAC 95 (Tg = 41 ° C), available from Hercules Chemical Co. Examples of suitable aromatic resins include those derived from indene, styrene, methylindene (s), methylstyrene (s), and the like, preferably having a molecular weight ranging from about 300 to about 1200. The aromatic resins can be hydrogenated to give better stability and / or compatibility. Commercially available versions include those known under the trade designations PICCOVAR AP-25 (type C9, Tg = -50 ° C) and REGALREZ 1094. { hydrogenated α-methyl styrene, Tg = 37 ° C), both commercially available from Hercules Chemical Co .; ARKON P90 (hydrogenated type C9, Tg = 36 ° C), available from Arakawa Co .; and ESCOREZ 7105 (hydrogenated type C9, Tg = 52 ° C), available from Exxon Chemical Co. The terpene type tackifiers are optimal because they exhibit high compatibility with the rubber component and provide high adhesion, and makes stickiness control more easily. The tackifiers useful in the invention preferably have a low molecular weight relative to the hydrocarbon elastomer, a Tg greater than that of the hydrocarbon elastomer, and are preferably completely miscible with the rubber component. Typically the tackifier comprises from about 60 to about 125 parts by weight per 100 parts by weight of rubber. A particularly preferred tackifier is ß-pinene, available from Hercules Chemical Co., Inc. under the trade designation PICCOLYTE S-115. A number of adjuvants can also be used in the adhesive. Examples of such adjuvants include antioxidants, such as hindered phenols, hindered amines and disintegrators of sulfur and phosphorus hydroperoxide.; inorganic fillers such as talc, zinc oxide, titanium dioxide, aluminum oxide and silica; plasticizing auxiliaries such as those materials described as plasticizers in the Dictionary of Rubber, K.F. Heinisch, pp. 359, John Wiley & Sons, New York (1974), oils, elastomer oligomers and waxes; and similar. Typically, any antioxidant present comprises up to 5 parts by weight per 100 parts by weight of elastomer; the inorganic filler may comprise up to 50 parts by weight per 100 parts by weight of elastomer, and plasticizer auxiliaries up to 10 weight percent of the total adhesive. Preferably, the use of plasticizing auxiliaries is unnecessary.

II. Materials in Retruereflective Layers For Solas A. Articles incorporating the cube corner retroreflector layer material A preferred embodiment of the articles of the present invention relates to. a retroreflective article comprising a retroreflective, transparent layered material having a first substantially planar surface and a second structured surface, the second structured surface comprised of a plurality of notches defining a plurality of peaks (in the layered corner material) cube at least two notches intersect, while in the prism films the notches are parallel), a layer of sealing film (colored or colorless) disposed on, and attached to a first portion of the notches, a second portion of the notches. notches prevents contact with the sealing film layer, and a layer of pressure-sensitive adhesive (as described herein) disposed between the sealing film layer and a substrate, such as a highly monomerically plasticized PVC component. As used herein, the term "peak" means a projection having at least two planar facets, such as prisms, pyramidal protrusions, cube corner protrusions, and the like. The phrase does not include protrusions that do not include planar facets, such as protrusions present in holographic films.

The term "transparent, retroreflective layer material" means a material in plastic layers that transmits at least 50% of the incident light in the visible spectrum (approximately 400-700 nanometers wavelength), as determined by a standard spectrophotometer . Referring now to FIGS. 1-6, where similar numbers are used to represent similar elements from figure to figure, a preferred embodiment of a transparent cube corner retroreflector article of the invention is illustrated in cross section (elongated) in FIGURE 1. In FIGURE 1, the layered material 100 comprises a transparent layer 50 having a smooth, flat surface 54 and a structured surface 56 comprised of a plurality of peaks 58. The layer 50 can be extremely thin to increase the flexibility, or coating layer 64 may have a low modulus as described in co-pending assignee patent application serial number 08 / 326,696, issued October 20, 1994, incorporated by reference herein. In the '696 application, the layer 50 is formed of a thermoplastic coating film 64 and decoupled thermosetting hub corner elements. A sealing film layer, thermoplastic 60 is disposed over the peaks 58, and a plurality of air spaces 62 are defined between the cube corners and sealing film layer 60 to grant retroreflectivity to the article. The sealing film layer 60 adheres to the layer 50 to a plurality of sealing areas 66, where the thermoplastic sealing film material has flowed between the individual corner corner elements to reach and fuse with the film of thermoplastic coating layer 64. The seal prevents water, oil and the like from entering between the sealing film layer 60 and the layer 50. In FIGURE 1, the reference number 68 represents an optional chemical finishing layer or a corona treatment layer positioned between the sealing film layer 60 and a PSA 70 layer. Chemical and / or physical sizing is preferred but is not necessary for the invention. The layer combination consisting of the layer 50, the sealing film layer 60, and the sizing layer or the corona treatment layer 68 is designated as a retroreflective, layered material substrate. An outer coating (not shown) is preferably placed on the surface of the PSA layer 70 to protect its surface before adhering to a fabric, such as a highly monomerically plasticized PCV component 72. FIGURE 2 illustrates another embodiment of the inventive article, respectively. FIGURE 2 illustrates a retroreflector, cube corner material 200, comprising a layer 50 as in the embodiment illustrated in FIGURE 1. However, the embodiment 200 comprises a metal layer 51, which serves to reflect light incident in layer 50. The sealing layer does not appear. FIGURE 2 illustrates a layer of PSA 70 which adheres a substrate, such as a plasticized PVC component 70 to the metal layer 51. This embodiment eliminates the need for a sealing film, but requires that the non-thermosettable PSA be capable of join a plasticized PVC component to a metal surface. The layer 50 can be any of the materials in substantially and substantially internal or cube corner reflectance layers, described in U.S. Patent Nos. 3,140,340 3,648,348 4,576,850; 4,588,258; 4,775,219 4,801,193 4,805,984; 4,895,428; 4,906,070 4,938,563 5,056,892; 5,138,488; 5,175,030; and 5,183,597, all of which are incorporated herein by reference. More specifically, the layer 50 preferentially comprises a large number of precisely formed elements (preferably pyramidal, cube corner or a series of parallel prisms) defined by notches defining the elements. The pyramids, cube corners, or prisms substantially and totally reflect light in a direction opposite to the incident direction. The precisely formed elements define a plurality of bags 11 (FIGURES 1 and 2), filled with air or another fluid. "Reflex substantially and entirely internal" pertains to the optical quality of the film, and means that the film has a Test Value T of 5% or less, where Test T is described as follows. The optical quality of a retroreflective film can be evaluated with an apparatus that includes a laser beam (such as a Spectra-Physics Inc. Model 117A) with a spatial filter, a beam expansion mechanism and a collimator. Two diaphragms or irises are placed 18 and 38 cm from the laser, and a sample holder, annular with an opening of 6.35 cm in diameter is placed 84 cm from the laser. Directly behind the sample holder is an integration sphere (with an opening of 3 cm in diameter) and a LABSPHERE ML-400 radiometer. Using the diaphragms or irises, the laser is focused through the aperture to obtain a clean circle of light approximately 3 mm in diameter on a black surface mounted on the sample holder. A 100% source intensity measurement is taken without a sample in place. The TIRF to be tested is then mounted on the sample holder with its flat surface facing the laser and its indentations that extend vertically. Unless reported otherwise, the T-Test Values are measured at room temperature. The readings are then made from 12 to 15 different points in the TIRF within an area of 5 cm in diameter while ensuring that no light hits the structure of the sample holder. The readings are averaged and multiplied by 100 to give the percent transmission that is the T-Test Value of the TIRF sample. The Value of the T Test is a criterion of replication fidelity of the TIRF. The percentages of the lower Test Value T indicate better replication fidelity than the higher percentages, and a Test Value T of 5% or less indicates that the film is substantially and completely internally reflective. The layer 50 preferably comprises an acrylic material having excellent durability, such as poly (methyl) methacrylate, polyester (such as polyethylene terephthalate), polyamide, polycarbonate, poly (vinyl chloride), poly (polyvinylidene chloride), cellulose acetate butyrate, cellulose acetate propionate, poly (ether sulfone), polyurethane, ionomer resins (such as polyethylene / acrylic acid ionomers, crosslinked with metal ion, known under the trade designation SURLYN), and the like, and in Preferably, it also comprises a UV light absorber. Of the aspects of mechanical strength and light reflectivity, the layer 50 preferably has a refractive index of about 1.6, which is possible if the layer is made of a polycarbonate resin, an ionomeric resin such as that just described, or an acrylic resin The structured layered material or layer 50 can be made as an integral material, for example, by embossing a preformed layer material with a described arrangement of cube corner elements, or emptying a fluid material in a mold; or these can be made as a layered product, for example, by emptying the elements against a preformed film as taught in U.S. Patent No. 3,684,348, or by laminating a preformed film on the front face of individual molded elements. Polycarbonates and ionomers are materials in integral layersPreferred The thickness of the layer 50 preferably varies from about 50 to about 500 microns in terms of the height of the apex of the pyramid or prism to the base of the base portion. If the thickness is less than 50 micrometers, the mechanical strength is not sufficient and it is difficult to obtain a predetermined height for the pyramids or cousins, so that retroreflectivity decreases. On the other hand if the thickness exceeds 500 micrometers, the total thickness of the retroreflective layered material becomes too thick that handling becomes difficult and the amount of the adhesive required is increased. In the present invention, the sealing film layer 60 (FIGURE 1) is involved in the retroreflectivity display by forming an air layer 62 between the sealing film layer 60 and the layer 50. In other words, in order to that the layer 50 exhibits retroreflectivity, there must be an air layer below the precisely formed elements to produce a change in the refractive index. The sealing film layer 60 is laminated to the structure surface of the layer 50, and the sealing film layer 60 is bonded thereto with heat and / or radiation at a plurality of locations, thereby forming a plurality of sealed airbags. It is understood that "air" is used only as an example and that other fluids may be used, depending on the atmosphere in which the articles of the invention are produced, and provided that the fluid used is significantly different in the index of refraction of layer 50 (a difference in refractive index of 0.5 is preferred). The processes of US Patent No. 4,025,159 (incorporated by reference herein) can be used to effect bonding of the sealing film layer 60 to the second structured surface of the layer 50. If water, oil similar between the layer 50 and the sealing film layer 60, the refractive index changes and retroreflectivity decreases. Accordingly, the sealing film layer has the sealed effect for water and the like. The sealing film layer 60 is preferably an article similar to a plastic film comprising a plastic resin, talc such as polyurethane, polyester, polyvinyl chloride and the like, which may contain a predetermined amount of one or more pigments such such as titanium dioxide (white), silica, red oxide, and the like, added to the resin. Particularly, the blank is suitable for the present invention because the recognition of the retroreflective articles of the invention is high.

B. Items that Use Layered Material Retruerefector with Spheres FIGURE 3 is a cross-sectional (elongated) view of one embodiment of illustrated article 300 of the invention comprising a retroreflective, embedded lens material adhered to a substrate using an adhesive according to the invention . In this embodiment, the retroreflective layer material comprises a layer of polyvinyl butyral 80 in which a plurality of glass microspheres 82 are embedded. Other organic layers, such as copolymers of acrylic acid of glyptal, alkyd, ethylene and / or propylene, ethylene methacrylic acid copolymer, ionomers, crosslinked and / or uncrosslinked aliphatic polyurethanes, vinyl, PMMA, and the like may also comprise the layer 80. A cover material 86 is illustrated on the printed signs for abrasion resistance, resistance to chemical deterioration, and the like, which would be desired by the users of the inventive articles in outdoor use, prolonged (ie greater 1 year), such as liferafts, inflatable lifejackets, and the like. A reflective layer 84, a PSA 90 layer, and a substrate (for example a plasticized PVC component 92) complete the structure. Preferred retroreflective, embedded lens materials include those known under the trade designation SCOTCHLITE, available from Minnesota Mining and Manufacturing Co., St. Paul, MN, subsequently 3M). Retroreflective, enclosed lens materials can also be used and are described in U.S. Patent Nos. 2,407,680, 4,664,966 and 4,511,210, all incorporated herein by reference. Materials in retroreflective layers also useful are the encapsulated lens layer materials described in U.S. Patent Nos. 3,190,178; 4,025,159; 4,896,943; 5,064,272; 5,066,098 and 5,069,964, all incorporated herein by reference. FIGURES 4 and 5 are illustrative (elongated) cross sections of two encapsulated, retroreflective lens materials, useful materials 400 and 500, respectively as described in detail and illustrated as FIGURES 1 and 2 in U.S. Patent No. 5,069,964 .

FIGURE 4 is a cross-sectional illustration of a complete portion 400 of a microsphere-based embodiment of the retroreflective layer material of the invention. The layered material 400 comprises in part a face member 112, (sometimes referred to as a cover film or a cover sheet), and the encapsulation member 114 comprising the binder layer 116, the intermediate adhesive 118. The adhesive pressure sensitive or mounting adhesive layer 131 is in direct contact on the face with the intermediate adhesive 118. The face tensile strength relief member 112 and the encapsulation member 114 are arranged in spaced relation and sealed by a network of intersecting links 122. The layered material 400 also comprises retroreflective elements 124 disposed between the face member 112 and the encapsulation member 114. The retroreflective elements 124 are substantially arranged in a monolayer and have an air gap, that is, the front surfaces of the same are exposed. In this embodiment, the retroreflective elements 124 are partially embedded in the binder layer 116 of the encapsulation member 114 and protrude partially from the front surface 130 thereof, and comprise microspheres 126 having reflectors 128 disposed behind the rear surfaces of the reflector. the same. Typically, the mounting adhesive 120 will be covered by the protective, removable outer liner 132 during handling. FIGURE 5 is a cross-sectional illustration of a completed portion 500 of another microsphere-based embodiment of the retroreflective layered material of the invention wherein the barrier layer 120 adheres directly to the back side of the binder layer 116 of the barrier member. 114 'encapsulation, that is, it "self-adheres" to it without the use of an intermediate adhesive. As illustrated in FIGURE 5, the retroreflective layer materials of the invention comprise the mounting adhesive 131 on the back side of the encapsulation member 114 'to be used to fix the layered material 500 to a substrate (not shown). Typically the mounting adhesive 131 will be covered by the protective, removable outer liner 132 during handling. FIGURE 6 is a cross-sectional illustration of a complete portion 600 of yet another microsphere-based embodiment of the retroreflective material of the invention wherein the mounting adhesive 131 adheres directly to the back side of the binder layer 116 of the encapsulation member 114", ie, it" adheres directly "thereto without the use of a barrier layer, to be used to fix the material in layers 600 to a substrate (not shown). The mounting adhesive 131 will also be covered by the protective, removable outer covering 132 during handling.The modalities 400, 500 and 600 of FIGURES 4, 5 and 6, respectively, are particularly useful as mentioned for SOLAS applications.In particular, the United States Coast Guard specifies that the substrates of inflatable lifejackets are preferably one of the following materials: rubber coated fabric, vinyl film, laminated vinyl nylon, "denim" cotton coat with pigment, or fiberglass. In addition, the highly monomeric plasticized PVC and the polyolefin film and the coated fabric can also be useful.

This invention is illustrated by the following examples, but the particular materials and amounts thereof cited in these examples, as well as other conditions and details should not be constructed to limit the claims indefinitely.

EXAMPLES Example A The PSA of natural rubber resin was made using the process described above. The following adhesive formulation was anaerobically compounded and coated on the released, differential outer coating. A natural Mooney controlled viscosity rubber (SMR CV60) (available from The Ore and Chemical Company, Inc.) was ground and sprinkled with talcum powder. This rubber is fed to Zone 1 of a twin-screw extruder or co-rotating screw (ZSK-90 Werner-Pfeiderer Co.) in the proportion of 45.2 kg / hr (99.5 lbs / hr). The tackifier, Piccolyte ™ S-115, ß-pinene, was added with the rubber stream in Zone 1 at a rate of 6.8 kg / hr (14.9 lbs / hr): The screw or propeller of the extruder was operated at 150 rpm. The temperatures in Zones 1-3 were adjusted to approximately 90 ° C. The tackifier was added to zone 4 at a rate of 11.3 kg / hr (24.9 lbs / hr). The additional tackifier was added to Zone 5 at the rate of 27.1 kg / hr (59.7 lbs / hr). The temperature in Zones 4 and 5 was adjusted to 66 ° C. The antioxidant was added to the sticky agent stream of Zone 5 at a rate of 0.45 kg / hr (1.0 lbs / hr). The adhesive was applied at a rate of 90.8 kg / hr (200 lbs / hr) and coated to a width of 35.6 cm (14 inches). The line speed was automatically adjusted to maintain a coating thickness of 177 μm (7 mils). The adhesive was exposed on the 2 Mrad line of the electron beam radiation at an acceleration voltage of 192 kV.

Example 1 A paper carrier coated with polyethylene was heated to about 105 ° C and then immersed with glass microspheres having an average diameter of about 65 microns and a refractive index of about 1.91. Excess microspheres were removed from the surface of the carrier by substantially producing a monolayer of microspheres thereon, and the carrier and the monolayer were then heated to about 140 ° C to soften the polyethylene coating such that the microspheres were partially embedded in the same by gravity and capillary forces according to normal techniques. The carrier and the monolayer were then placed inside a vacuum chamber and an aluminum layer deposited therein at a thickness of 100 manometers. A binder material of the solvent-borne urethane / vinyl system comprising 18.0 parts of aromatic urethanes, 6.0 parts of vinyl, 8.30 parts of titanium dioxide, 0.5 parts of Irganox 1010 (heat stabilizer from Ciba-Geigy), 0.5 parts of UVINOLN35 (BASF's vinyl stabilizer), 0.5 parts of stearic acid, and 66.5 parts of solvents were coated on the aluminum-coated microspheres and the assembly was dried in an oven at 121 ° C (250 ° F) to remove the solvents, which form the binder layer. An acrylate PSA transfer film was then hot rolled to the exposed surface of the binder, such that the surface of the PSA was in contact with the binder material. This PSA transfer film comprises a PSA layer of acrylate having a thickness of about 1.5 mils and a polyester film coated with polyethylene having a total thickness of about 1.0 mil. This PSA layer was formed by the bar coating of a solvent solution of a 90:10 copolymer of pressure sensitive base, of 2-methyl butyl acrylate: acrylate acid in a polyester carrier coated with polyethylene and drying Heat in an oven to remove most solvents. The paper carrier coated with polyethylene was then removed to expose the front surface of the microspheres embedded in the binder material, to leave the material in base layers in this way. The layering material made in exactly the same manner as described in U.S. Patent No. 5,069,964, Example 1, was then contacted with the base layer material such that the inner layer was in contact with the microspheres. protruding from the base layer material and sealing them together with a network of interconnection links according to normal procedures. After the interconnection bonds were formed, the polyethylene coated polyester carrier was then removed from the base layer material, i.e., used only as a sealing film, to thereby leave an intermediate acrylate PSA Adhere to the binder material. The PSA of natural rubber resin, without solvent, coated on the outer coating of Example A, was then applied directly to the exposed surface of the intermediate acrylate PSA layer adhering to the binder, and the outer coating was removed . This PSA layer is called a mounting PSA substrate or layer because the retroreflective material is adhered to the substrates after the outer coating is removed. Finally the carrier is removed from the front surface of the cover film.

EXAMPLE 2 The retroreflective sheet material was made using the same materials and conditions as described in U.S. Patent No. 5,069,964, Example 1, except that the PSA of natural rubber resin, without solvent of Example A, is used as the substrate of PSA. In this example, the PSA substrate was applied directly to the exposed sealing film that adheres to the binder material.

Example 3 The retroreflective sheet material was made in exactly the same manner as Comparative Example A in U.S. Patent No. 5,069,964, except that the PSA of natural rubber resin, without solvent of Example A, is used as the PSA substrate. In this example, the PSA substrate is applied directly to the exposed binder layer.

Comparative Example 1 Example 1 was repeated, except that PSA ROBOND PS-67 substrate layer, a latex acrylic PSA layer (available from Rohm &Haas) formed on an outer coating having a thickness is used as the substrate layer of PSA ROBOND PS-67. of 5 mils adhesive This PSA layer of substrate was formed by a bar coating of the PSA solution (containing 35% solid by weight) in an outer coating released at an aperture grading of 14 mils and dried by heating for 5 hours. minutes in an oven at 93 ° C (200 ° F) after 5 minutes of air drying to remove most solvents.

Comparative Example 2 Example 1 was repeated, except that a PSA layer of thermoplastic acrylic (available from Asland Chemical, Inc.) formed on an outer coating, having a thickness, is used as a PSA substrate AROSET 1081-Z-45. of 5 mils adhesive This PSA layer of substrate was prepared in exactly the same manner as described in Comparative Example 1, except that the graduation of the aperture was adjusted to obtain 5 mils of thickness of the PSA layer on the outer coating after drying because the PSA solution has a different solids percent.

Comparative Example 3 Example 1 was repeated using as substrate PSA AROSET 1085-Z-45, a cross-linked acrylic PSA layer, heat activated (available from Asland Chemical, Inc.) formed in an outer coating having a thickness of 5 mils. This PSA layer of substrate was prepared in exactly the same manner as described in Comparative Example 1, except that the graduation of the aperture was adjusted to obtain 5 mils of thickness of the PSA layer in the outer coating after drying due that the PSA solution has a different solids percent.

Comparative Example 4 Example 1 was repeated using UP 309 as the substrate PSA, acrylic PSA transfer tape (adhesive coated on an outer release coating, differential which is available from Coating Science Inc.).

Comparative Example 5 Example 1 was repeated except that the substrate PSA 8768A, latex rubber-based adhesive layer (available from Bostik) formed on the outer coating having an adhesive thickness of 7 mils is used as the PSA of the substrate. This PSA substrate was prepared in exactly the same manner as described in Comparative Example 1, except that the graduation of the aperture was adjusted to obtain 7 mils of the PSA layer thickness on the outer coating after drying because the solution of PSA has a different solids percent.

Comparative Example 6 Example 1 was repeated, except that a PSA substrate of the 6 mils thick acrylate PSA containing 90 parts by weight of isooctyl acrylate and 10 parts by weight of acrylic acid is used. This PSA of the substrate was prepared in exactly the same manner as described in Comparative Example 1, except that the graduation of the aperture was adjusted to obtain 6 mils of thickness of the PSA layer on the outer coating after drying because the solution of PSA has a different solids percent.

Comparative Example 7 Encapsulated lens layer material, Scotchlite SOLAS Grade 31501, commercially available. This layered material was manufactured in the same manner as described in Example 1, except that the PSA substrate of Comparative Example 6 is used and has an adhesive thickness of 3 mils.

Comparative Example 8 The retroreflective material of SOLAS, commercially available, sold under REFLEXITE under the designation REFLEXITE SOLAS / UK -D.O.T. which employs the adhesive of the substrate has the same composition as the adhesive of the substrate of Comparative Example 4.

Adhesion Strength Retroreflective back-layered materials with PSA of Examples 1-3 and Comparative Examples 1-8 were tested without the aid of a sizing, in accordance with the USCG adhesion test method (Guadacosta de United States) listed in subpart 164.018"Retroreflective materials for rescue equipment" of 46 CFR Ch.I (10-1-93 Edition), which is described in Federal Specification LS-300. In this test, a rigid backing is used, to which the test substrate is adhered with a contact adhesive, except that once the test substrate is attached to the rigid backing, the assembly is cut into a substrate panel of 50 mm. mm x 90 mm. The retroreflective layer material, coated with PSA with a size of 25 mm x 100 mm, would then be applied to the substrate panel (with a handling ease at the end and not adhered to the test substrate) where the PSA in contact with the surface Testing the substrate panel. This assembly was called as the test panel. When the retroreflective material with the backside with PSA is tested in accordance with this adhesion test, the material should be tested using a test weight of 0.75 kg (1.75 lb) and using each of the materials including aluminum (listed in Table A) as a test substrate, and the material should not be peeled for a distance of more than 5 cm (2 pg) in 5 minutes.

(A) Aluminum panel (B) Vinyl film joins L-P-375 (C) Cured polyester lamination resin is bonded to MIL-R-21607 (D) laminated vinyl-nylon fabric joins MIL-C-43006 (E) Denim is joined to CCC-C-443 (F) Rubber coated fabric meets MIL-C-17415 For each test substrate, identical test panels were prepared, and one was immersed in distilled water in a covered vessel for 16 hours before the test weight 0.75 kg (1.75 Ib) was attached to the loose end of the retroreflective layer material with the back with PSA (where the test panel was placed on a stand so that the test weight was manipulated vertically below the test panel), and the other test panel was immersed in a salt water (4% NaCl) by weight) in a covered container for 16 hours before the test weight was applied. If a particular test panel used in the test results in a test failure, the retroreflective material will not be approved by the US Coast Guard. to attach to the substrate of the type used in the test panel. The retroreflective material with the backside with PSA can nonetheless be approved for use with other types of substrates depending on the test results with other panels. The test of the layered materials of Examples 1-3 and Comparative Examples 1-8 for the strength of the adhesive without the need for sizing, in accordance with this USCG adhesion test method against the substrates listed in the Table A, produced the results shown in Table 1. In addition, retroreflective materials with the PSA backing of Examples 1-3 and Comparative Examples 1-8 were tested without the aid of a sizing for adhesive strength in accordance with the IMO (Intentionk Maritime Organization) adhesion test method listed in section 4.6 of the Technical Specification for Retruereflector Material for Use in Salvage Applications, against the test surface materials listed in Table B.

Table B Identification Substrate DK.l Denmark / Life raft awning Viking DK.2 Denmark / Viking life raft 1. 1. Germany / Paul Merten / IMO - Lifejacket IV.1 Germany / DSB / IMO - Liferaft raft bottom IV.2 Germany / DSB / IMO- Top of the life raft Vl Germany / Kadematic / CEN - Lifejacket UK .l United Kingdom - Beaufort UK.2 survival suit UK - Beaufort UK.4 lifejacket - Beaufort UK5 life raft UK - Crew life jacket AL Aluminum GRP Polyester cured In this test, the The test was prepared and tested in exactly the same conditions as described in the USCG adhesion test method, except that the adhesion strength of the retroreflective layer material with the backside with PSA was measured by a manufactured "Peeling Tester". by Instron Co., in a 180 degree recoil with a speed of 300 mm / min. The retroreflective layered material was designed for use with a tested adhesive according to this test, it must have an average adhesion strength of not less than 16 Newtons by 25 mm wide. If the particular test panel used in the test results in a test failure, the retroreflective material will not be approved for joining the material of the type used as the test panel. The test results of the retroreflective layer materials of Examples 1-3 and Comparative Examples 1-8 without the aid of a sizing for the adhesive strength against the salvage materials (listed in Table B), in accordance with this IMO adhesion test method are shown in table 2.

Table 1 (Resistance of USCG Adhesion against the test substrates listed in Table A) * RESISTANCE OF ADHERENCE BY USCG - HANDLING WEIGHT AT 90 DEGREES, DISTANCE OF PEEL, CM (INCHES) IN 5 MINUTES. DISTILLED WATER Substrate A B D F Example 1 0.51 (0.20) 0.18 (0.20) 0.51 (0.20) 0.53 (0.21) 1 .27 (0.50) or Example 2 1 .02 (0.40) 1.02 (0.40) 1.14 (0.45) 1.02 (0.40) 3.18 (1.25) Example 3 0.76 (0.30) 0.51 (0.20) 0.51 (0.20) 1.91 (0.75) 2.79 (1.10) Comparative Example 1 > 5.0 (2.0) 3.81 (1.50) 1 .40 (0.55) > 5.0 (2.0) > 5.0 (2.0) Comparative Example 2 1 .27 (0.50) 2.16 (0.85) 0.64 (0.25) 0.89 (0.35) 3.30 (1.30) Comparative Example 3 1.52 (0.60) 1.14 (0.45) 1 .02 (0.40) 1 .40 ( 0.55) 3.81 (1.50) Comparative Example 4 3.81 (1.50) 0.51 (0.20) 1.02 (0.40) 1.27 (0.50) > 5.0 (2.0) Comparative Example 5 > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) Comparative Example 6 0.38 (0.15) 0.64 (0.25) > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) Comparative Example 7 0.64 (0.25) 1.14 (0.45) > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) Comparative Example 8 1.02 (0.40) 1.02 (0.40) 0.89 (0.35) 1.02 (0.40) > 5.0 (2.0) SALT WATER AT 4% SUBSTRATE A B C D F G Example 1 0.24 (0.10) 0.18 (0.20) 0.33 (0.13) 0.33 (0.13) 0.18 (0.20) > 5.0 (2.0) Example 2 0.51 (0.20) 0.51 (0.20) 0.89 (0.35) 0.64 (0.25) 2.79 (1.10) > 5.0 (2.0) Example 3 0.51 (0.20) 0.51 (0.20) 0.38 (0.15) 1.30 (0.51) 2.03 (0.80) > 5.0 (2.0) Comparative Example 1 4.83 (1.90) 3.18 (1.25) 0.64 (0.25) > 5.0 (2.0) > 5.0 .0) > 5.0 l 2.0) or Comparative Example 2 0.51 (0.20) 0.51 (0.20) 0.64 (0.25) 0.64 (0.25) 2.79 1.10) > 5.0 [2.0) Comparative Example 3 1.27 (0.50) 0.89 (0.35) 0.64 (0.25) 0.89 (0.35) > 5.0 [2.0) > 5.0 [2.0) Comparative Example 4 3.05 (1.20) 0.51 (0.20) 0.64 (0.25) 0.76 (0.30) > 5.0 (2.0) > 5.0 (2.0) Comparative Example 5 > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) Comparative Example 6 0.51 (0.20) 0.25 (0.10) 4.57 (1.80) > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) Comparative Example 7 0.64 (0.25) 0.84 (0.33) > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) > 5.0 (2.0) Comparative Example 8 1.02 (0.40) 1.02 (0.40) 0.89 (0.35) 1.02 (0.40) > 5.0 (2.0) > 5.0 (2.0) Tested after 16 hours of immersion in water, within 5 minutes remove from water. Number in () indicates inches.

Table 2 (Resistance of the adhesion of IMO against the test substrates listed in Table B) * RESISTANCE OF THE ADHERENCE BY IMO - REVERSAL OF LAYER A180 DEGREES, Newton by 25 mm wide SALT WATER SUBSTRATE To GRP DK1 DK2 M! Y. i \? 2 V. UK1 UK2 UK4 UK5 Example 1 32.7 34.0 38.2 34.0 19.8 39.0 32.3 23.8 33.4 28.7 29.6 29.9 Example 2 34.9 38.4 37.7 31.8 22.5 37.2 25.9 17.1 28.4 23.6 24.8 30.0 Example 3 31.4 32.7 36.5 30.5 19.2 35.4 22.5 17.5 26.7 22.8 24.1 29.8 Comparative Example 1 26.2 43.6 30.1 < 16.0 < 16.0 27.6 < 16.0 < 16.0 < 16.0 < 16.0 19.7 < 16.0 Comparative Example 2 43.6 24.0 31.1 20.8 < 16.0 34.6 < 16.0 < 16.0 26.4 25.6 13.9 31.8 Comparative Example 3 28.3 19.6 30.6 < 16.0 < 16.0 30.2 < 16.0 < 16.0 18.9 16.9 < 16 22.5 Comparative Example 4 30.5 33.1 32.3 < 16.0 < 16.0 33.7 < 16.0 21.1 29.5 32.7 16.1 31.2 Comparative Example 5 34.9 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 Comparative Example 6 37.1 16.5 17.2 < 16.0 < 16.0 17.1 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 21.2 Comparative Example 7 28.3 < 16.0 < 16.0 < 16.0 < 16.0 17.1 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 Comparative Example 8 43.6 34.9 43.8 < 16.0 < 16.0 45.7 < 16.0 < 16.0 33.5 40.9 < 16.0 44.6 DISTILLED WATER SUBSTRATE To GRP DK1 DK2 Ll IV.1 IV.2 V.1 UK1 UK2 UK4 UK5 Example 1 30.1 34.2 38.2 35.1 22.4 38.9 35.3 20.7 28.3 27.1 32.8 29.8 Example 2 32.4 35.1 35.5 32.1 31.1 39.5 25.2 17.9 23.8 20.1 24.9 29.7 Example 3 31.2 31.9 34.6 30.0 20.2 34.5 20.6 17.5 25.1 19.5 23.8 28.4 Comparative Example 1 26.7 35.8 28.7 < 16.0 < 16.0 30.8 < 16.0 < 16.0 < 16.0 < 16.0 18.2 < 16.0 s ON Comparative Example 2 41.2 21.2 31.6 16.7 < 16.0 33.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 33.2 Comparative Example 3 25.4 17.9 23.6 < 16.0 < 16.0 31.6 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 16.2 Comparative Example 4 29.5 27.8 32.3 < 16.0 < 16.0 32.1 < 16.0 < 16.0 < 16.0 28.7 < 16.0 32.4 Comparative Example 5 30.9 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 Comparative Example 6 34.6 16.5 16.8 < 16.0 < 16.0 18.5 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 20.1 Comparative Example 7 25.8 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 < 16.0 Comparative Example 8 41.2 31.5 44.6 < 16.0 < 16.0 45.7 < 16.0 < 16.0 < 16.0 20.9 < 16.0 39.8 * Tested after 16 hours of immersion in water, within 5 minutes remove from water.

Based on the results in Tables 1 and 2, the materials in retroreflective layers designed for use with the adhesives of the invention subjected to USCG and IMO adhesion tests on more substrates without the aid of sizing. Although the present invention has been described with respect to the specific embodiments, the invention is not intended to limit those embodiments. Preferably, the invention is defined by the claims and equivalents thereof.

It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates.

Having described the invention as above, property is claimed as contained in the following:

Claims (14)

1. A retroreflective article for life-saving devices at sea, characterized in that it comprises: (a) a retroreflective layer material comprising a surface with incidence of light and a surface without incidence of light; and (b) a layer of pressure-sensitive adhesive disposed on at least a portion of the surface without incident light, the adhesive is derived from an amorphous hydrocarbon elastomer by using a heat fusion process without solvent, the adhesive comprises : (i) a rubber having a glass transition temperature ranging from about -120 ° C to about -50 ° C; and (ii) a tackifier having a ring and ball softening point which varies from about 70 ° C to 140 ° C, the adhesive comprises from about 60 to about 125 parts by weight of tackifier per 100 parts by weight. rubber weight.

2. The article according to claim 1, characterized in that the tackifier is completely miscible with the rubber.

3. The article according to claim 1, characterized in that the rubber is lightly crosslinked by an electron beam to provide an additional molecular weight but not to the point of insolubility in toluene.

4. The article according to claim 1, characterized in that the rubber is crosslinked with a chemical crosslinker to provide an additional molecular weight but not to the point of insolubility in toluene.

5. The article according to claim 1, characterized in that the adhesive is present in a coating weight ranging from about 80 to about 170 grams per square meter.

6. The article according to claim 1, characterized in that the adhesive is present in a coating weight ranging from about 120 to about 170 grams per square meter.

7. The article according to claim 1, characterized in that the adhesive layer has an outer coating material removably adhered to the adhesive.

8. The article according to claim 1, characterized in that the retroreflective layered material is selected from the group consisting of the group consisting of layered materials of embedded lenses, layered encapsulated lens materials and structured layered materials.

9. The article according to claim 1, characterized in that the light-free surface of the retroreflective sheet material is selected from the group consisting of i) a sealing film comprised of polymeric material selected from the group consisting of polyester, polyvinyl chloride and polycarbonate, the sealing film bonded to a retroreflective, transparent layered material has a substantially flat surface and a second structured surface, the second structured surface comprised of a plurality of notches defines a plurality of peaks, ii) a metallized surface of a The retroreflective layer material has a substantially flat surface and a second structured surface, the second structured surface has a metal layer therein, and iii) a binder layer of an embedded retroreflective layer material.

10. The article according to claim 1, characterized in that the light-free surface of the retroreflective layer material further contains a layer of intermediate adhesive in contact with the layer of binder material of the embedded retroreflective layer material.

11. The article according to claim 1, characterized in that the rubber is selected from at least one of the following: natural rubber, polyisoprene, polybutadiene, polyisobutylene, butyl rubber, ethylene-propylene rubber, ethylene-propylene monomer rubber diene, poly (alpha-olefin) and styrene-butadiene random copolymer and mixtures thereof.

12. The article according to claim 1, characterized in that the rubber is natural rubber.

13. The article according to claim 1, characterized in that the tackifier is selected from at least one of the following: terpenes and phenolic derivatives of terpene, turpentine resin and turpentine resin derivatives, and hydrocarbon resins of 5 and 9 carbon atoms.

14. The article according to claim 1, characterized in that the tackifier is ß-pinene.