Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
  • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
  • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
  • B29C65/4805—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the type of adhesives
  • B29C65/481—Non-reactive adhesives, e.g. physically hardening adhesives
  • B29C65/4825—Pressure sensitive adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/201—Adhesives in the form of films or foils characterised by their carriers characterised by the release coating composition on the carrier layer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
  • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/29—Laminated material
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
  • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C09J7/385—Acrylic polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/40—Adhesives in the form of films or foils characterised by release liners
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2675/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, for preformed parts, e.g. for inserts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
  • B29L2031/3091—Bicycles
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/306—Applications of adhesives in processes or use of adhesives in the form of films or foils for protecting painted surfaces, e.g. of cars
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2433/00—Presence of (meth)acrylic polymer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2475/00—Presence of polyurethane
  • C09J2475/005—Presence of polyurethane in the release coating
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2475/00—Presence of polyurethane
  • C09J2475/006—Presence of polyurethane in the substrate

Definitions

• the present invention relates generally to defect-free polymer films useful for protecting surfaces, related protective sheets, methods of making and using the same, and articles comprising the defect-free polymer films.
• a variety of protective sheets are known. Many of those are based on one or more polyurethane layers. Polyurethane chemistries generally provide one or more properties including the following: environmental resistance, chemical resistance, abrasion resistance, scratch resistance, optical transparency, and other often desirable properties.
• WO 02/28636 describes a finishing film comprising a flexible polymeric sheet material having a first major surface and a second major surface and a pressure sensitive adhesive layer covering at least a portion of the first major surface of the sheet material.
• the finishing film is described as being commercially available from 3M Co. under the trade designation, SCOTCHCAL PAINT PROTECTION FILM PUL 0612, and comprising a 6 mil polymer film comprising an aliphatic polycaprolactone- based thermoplastic urethane elastomer. Examples of methods for formation of the polymer film described therein are extrusion, calendaring, wet casting, and the like. Thereafter, a waterborne polyurethane coating is formed on one side of the polymer film, with the other side of the polymer film being laminated to an acrylic pressure sensitive adhesive.
• WO 03/002680 describes an adhesive sheet comprising a flexible base material, an adhesive layer disposed on a back surface of said base material, and a protective layer disposed on a front surface of the base material.
• the protective layer described therein is made of a hydrophilic film containing a curing resin and a hydrophilic agent of an inorganic oxide.
• the base material contains a layer containing a first polyurethane resin having a reaction product of polyester polyol and a polyfunctional isocyanate compound.
• the base material comprises a lower layer containing the first polyurethane resin and an upper layer disposed between the lower layer and the protective layer that adheres to the protective layer and contains a second polyurethane resin having a reaction product of a
• the upper layer preferably comprises a hard polyurethane resin in comparison with the first polyurethane resin of the lower layer to enable adhesion between the entire base material and the protective layer to be effectively increased through the upper layer, even if the curing resin in the protective layer is comparatively hard and has a low- temperature elongation differing to a large extent from that of the lower layer of the base material.
• the polyester polyol forming the first polyurethane resin of the lower layer may be formed from a diol having caprolactonediol in the main chain.
• U.S. Patent No. 8,765,263, assigned to 3M Innovative Properties Co. describes a multilayer protective film comprising a first layer, a second layer and a pressure sensitive adhesive (PSA) layer.
• the first layer at least comprises a polyester-based polyurethane, a polycarbonate-based polyurethane, or a
• the second layer at least comprises a
• polycaprolactone-based thermoplastic polyurethane One major surface of the first layer is bonded to one major surface of the second layer, and the PSA layer is bonded to an opposite major surface of the second layer such that the second layer is sandwiched between the first layer and the PSA layer.
• the predominant method of forming the second layer is described as extruding the polycaprolactone-based thermoplastic polyurethane at an elevated temperature through a die, although casting and injection molding are also described.
• polycaprolactone-based polyurethanes Due to their superior rheological and viscoelastic properties over other aliphatic polyester polyurethanes in the genus of which they are a part, as well as its ability to impart good water, oil, solvent, and chlorine resistance to the polyurethane produced, polycaprolactone-based polyurethanes are often used in protective sheets.
• the polycaprolactone-based polyurethane layer is positioned adjacent the adhesive layer. It is known, however, that commercially available paint protection film products are prone to leaving a less than desirable amount of adhesive residue on a surface when removed therefrom after use. The presence of adhesive residue on a surface to be protected is counter to the concept of a protective sheet.
• alternative protective sheet is positioned adjacent the adhesive layer.
• the system is solventborne or waterborne, it must first be coated onto a desired substrate and then dried to remove solvating or dispersing medium (i.e., organic solvent or water, respectively) in order to form a polymer film.
• solvating or dispersing medium i.e., organic solvent or water, respectively
• formation of polymer films of sufficient thickness can be problematic using wet casting methods.
• some polymer chemistries are not capable of being formed into polymer films using wet casting methods due to the lack of adequate solubility of such polymers or their constituents in conventional solvents and dispersing mediums.
• Gelation results in the presence of gel particles (also referred to as “gel”) in the final product.
• gel particles also referred to as “gel”
• a “gel” is generally understood to be a viscous
• composition which in polymer processing can be, for example, an at least partially polymerized composition, one having a relatively high molecular weight, and/or one containing significant amounts of entrapped gas (e.g., air or reaction by-products, such as carbon dioxide).
• entrapped gas e.g., air or reaction by-products, such as carbon dioxide.
• Gels may manifest themselves in various forms and often result from overheating during processing of polymerized compositions into polymer films. For example, gels may take a crosslinked form, result from catalyst or other organic or inorganic residue in stagnating and/or dead regions of resins during extrusion, result from degraded oxidation-related occurrences (e.g., carbon dioxide bubbles resulting from moisture), or have their roots in the supply chain. Gelation can make formation of uniform layers of polymeric material (e.g., films) difficult.
• defects can lead to weak points and rupturing in polymer films and generally compromise suitable of polymer films for many applications. As such, exhaustive efforts are conducted throughout the supply chain to determine the presence and extent of defects. Many defects are readily detectable when viewed with an unaided human eye. Other methods for detection of defects can also be used, including spectroscopy. When detected, defect-laden polymer film must often be scrapped, leading to considerable waste.
• Multi-layer protective sheets of the invention include at least an improved carrier layer and are useful in a range of indoor and outdoor applications in, for example, the transportation, architectural and sporting goods industries.
• the protective sheets can advantageously be applied to at least a portion of a surface of any article where protection is desired.
• Such articles include, for example, motorized vehicles and non-motorized vehicles (e.g., conventional bicycles) amongst a multitude of other applications.
• the surface to be protected can be painted or unpainted.
• a multi-layer protective sheet comprises a defect- free carrier layer.
• protective sheets of the present invention do not include such a layer adjacent the adhesive layer, the result being an unexpected improvement in one or more desired properties in addition to the processing efficiencies imparted thereby.
• the improved polyurethane- based carrier layer in protective sheets of the invention is polymerized in-situ. It is to be understood that, as used herein, when a polymerizable composition is
• polymerized into a desired polymer film “in-situ,” polymerization of the polymer comprising the film begins just before, while, or shortly after the polymerizable composition is being positioned into the desired film format and polymerization is essentially completed during such positioning or shortly thereafter.
• "just before” and “shortly after,” as used in reference to timing of when polymerization begins refer to time periods of no more than about thirty seconds.
• loss factor refers to the ratio of loss modulus to storage modulus for a carrier layer so tested. The loss factor is ultimately an indication of the effectiveness of a material's damping qualities.
• peak loss factor refers to the highest loss factor value determined when the carrier layer is so tested. The higher the loss factor of a material, the more efficient the material will be in effectively accomplishing energy absorption and dispersal.
• polyurethane-based carrier layer in protective sheets of the invention has a peak loss factor of at least about 0.5, at least about 0.8, or even at least about 1 .2 when tested as a standalone film according to the Loss Factor Test Method described below.
• a multi-layer protective sheet of the invention comprises the improved polyurethane-based carrier layer and an adhesive layer on one major surface thereof.
• a multi-layer protective sheet comprises sequential layers as follows: a topcoat layer; the improved polyurethane-based carrier layer; and, an adhesive layer.
• Figure 1 is a graph of Loss Factor (also referred to as Tan Delta) versus Temperature for polyurethane-based carrier layers used in protective sheets of the invention and conventionally formed polyurethane carrier layers used in conventional protective sheets.
• Figure 2 is a graph of Storage Modulus versus Temperature for polyurethane-based carrier layers used in protective sheets of the invention and conventionally formed polyurethane carrier layers used in conventional protective sheets.
• the present invention is directed toward improved multi-layer protective sheets, including at least one defect-free polymer film layer therein.
• Protective sheets of the invention are advantageously not only capable of protecting a surface with improved properties, but also capable of being more cleanly removed therefrom than conventional protective sheets including conventionally formed polyurethane carrier layers.
• adhesive residue remaining on a surface from which the protective sheet is removed after use is minimized or eliminated by providing a polyurethane-based carrier layer adjacent the adhesive layer that is capable of absorbing more energy during stretching and/or impact than that associated with conventionally formed polyurethane carrier layers typically used in conventional protective sheets. That is, the improved polyurethane-based carrier layer used in protective sheets of the invention is capable of exhibiting more effective damping qualities (as evidenced by its "peak loss factor" described herein) than those associated with conventionally formed polyurethane carrier layers. Including such a layer adjacent the adhesive layer facilitates better continued anchorage of the adhesive layer during application of the protective sheet and, hence, less residual adhesive on a surface after removal of the protective sheet therefrom.
• properties of individual layers within a multi-layer protective sheet are better balanced according to the invention when using such a polyurethane-based carrier layer.
• a polyurethane-based carrier layer having a relatively high loss factor adjacent such a topcoat layer facilitates a more uniform rate and degree of recovery across thickness of the protective sheet when the protective sheet is stretched and/or impacted.
• multi-layer protective sheets of the invention are provided.
• multi-layer protective sheets are capable of recovering to essentially their original state when stretched ⁇ i.e., elongated) to a length of up to about 1 25% of their initial length.
• multi-layer protective sheets are capable of recovering to essentially their original state when stretched to a length of up to about 150% of their initial length.
• multi-layer protective sheets are capable of elongating to a length of up to more than about 200% of their initial length before breaking.
• a multi-layer protective sheet of the invention comprises the improved polyurethane-based carrier layer and an adhesive layer on one major surface thereof.
• a multi-layer protective sheet comprises sequential layers as follows: a topcoat layer; the improved polyurethane-based carrier layer; and, an adhesive layer. Each of those layers is described in further detail below.
• multilayer protective sheets of the invention may include a resilient layer sandwiched between the improved polyurethane-based carrier layer and the adhesive layer as described in U.S. Patent Application No. 62/306,645, entitled "Protective Sheets, Articles, and Methods," and incorporated by reference in its entirety herein.
• carrier layer is used herein to refer to the layer(s) of polymer film adjacent to the adhesive layer.
• a carrier layer may also be referred to as a "base layer,” “support layer,” or a similar designation.
• the carrier layer of protective sheets of the invention is referred to as a "mid-ply layer” when it contains multiple layers (i.e., "n” number of individual layers).
• the carrier layer of protective sheets of the invention can be a single film layer according to other embodiments of the invention.
• each of the "n” individual layers can be the same or different chemistries.
• each of the "n” individual layers has essentially the same chemistry.
• carrier layers used in protective sheets of the invention are polyurethane-based.
• polyurethane as used herein includes polymers containing urethane (also known as carbamate) linkages, urea linkages, or combinations thereof (i.e., in the case of poly(urethane-urea)s).
• polyurethane-based carrier layers contain at least urethane linkages, urea linkages, or combinations thereof.
• polyurethane-based carrier layers are based on polymers where the polymeric backbone has at least 40%, preferably at least 60%, and more preferably at least 80% urethane and/or urea repeat linkages formed in-situ during the polymerization process.
• Polyurethane-based carrier layers are prepared according to methods of the invention by reacting components, which include at least one isocyanate- reactive (e.g., hydroxy-functional, such as polyol) component and at least one isocyanate-functional (e.g., polyisocyanate) component.
• components of exemplary polymerizable compositions that are useful in the formation of polyurethane-based carrier layers according to methods of the invention are described in U.S. Patent No. 8,828,303, entitled “Methods for Polymerizing Films In- Situ Using a Radiation Source,” incorporated herein by reference in its entirety.
• polymerization of the polymerizable composition is initiated using at least one radiation source selected from ultraviolet radiation, thermal radiation, and electron beam radiation.
• Radiación of the invention can utilize continuous processing or batch processing.
• continuous processing such as web-based, in-situ polymerization of the polyurethane-based carrier layer using relatively low energy ultraviolet radiation (e.g., having an energy of less than about 100 mW/cm 2 ), can be used in one embodiment of the invention.
• batch processing such as coating an ultraviolet-curable
• polyurethane-based carrier layer in-situ can be used in another embodiment of the invention.
• the polymerizable composition for formation of the polyurethane-based carrier layer is essentially free of solvents.
• solvent-based processing typically entails use of elevated temperatures for effective removal of excess solvent from the polymerized composition.
• polyurethane-based carrier layers are essentially free of unreacted solvent. Accordingly, it is preferred that the polymerizable compositions from which they are formed are essentially free of solvents.
• any suitable additives can be present in the carrier layer.
• Other additives are selected as known to those skilled in the art based on the intended application. Those skilled in the art are readily able to determine the amount of such additives to use for the desired effect.
• the carrier layer has a thickness of about 5 microns to about 1 ,250 microns.
• Each of the "n" number of individual film layers therein can be as thin as about 5 microns and up to about 50 microns in thickness, the presence of thicker layers being particularly useful in, for example, ballistic applications.
• a carrier layer having a thickness of about 220 microns or less is used according to one aspect of the invention.
• the carrier layer has a thickness of about 180 microns or less.
• the carrier layer can have a thickness of about 120 microns to about 180 microns. Not only is recoverability of the carrier layer, and hence overall protective sheet, enhanced by using a thinner carrier layer, overall cost of the sheet is reduced in this manner.
• protective sheets of the present invention do not include such a layer adjacent the adhesive layer, the result being an unexpected improvement in one or more desired properties in addition to the processing efficiencies imparted thereby.
• the improved polyurethane- based carrier layer in protective sheets of the invention is polymerized in-situ.
• U.S. Patent No. 8,828,303 and U.S. Patent Publication No. US-201 1 - 0137006-A1 both incorporated herein by reference, describe methods and films formed by such in-situ polymerization.
• use of an in-situ polymerized polyurethane-based carrier layer was found to facilitate improvements in physical properties desired in addition to the processing efficiencies imparted thereby.
• in-situ polymerized carrier layers of the invention are not generally thermoplastic in nature. ln-situ polymerized carrier layers of the invention look and feel very similar to conventional extruded carrier layers. An improved polymer architecture, however, provides in-situ polymerized carrier layers of the invention with some significantly different properties.
• solvent resistance is solvent resistance.
• the solvent resistance of preferred in-situ polymerized carrier layers of the invention approximates that associated with conventional crosslinked ⁇ i.e., thermoset) materials.
• thermoset thermoplastic materials
• extruded materials will generally dissolve completely when immersed in a solvent, e.g., tetrahydrofuran, while the in- situ polymerized materials of the invention exhibit only minor swelling when immersed in the same solvent.
• Another significantly different property is storage modulus.
• extruded materials generally exhibit a continual drop in storage modulus with increasing temperature.
• the storage modulus of preferred in- situ polymerized carrier layers of the invention is significantly different, however, in that it exhibits a rubbery plateau region, a characteristic that is consistent with lightly crosslinked elastomers.
• the storage modulus of preferred in-situ polymerized polyurethane-based carrier layers is about two orders of magnitude higher than that of thermoplastic polyurethane at conventional extrusion
• polyurethane-based carrier layer in protective sheets of the invention has a peak loss factor of at least about 0.5, at least about 0.8, or even at least about 1 .2 when tested as a standalone film according to the Loss Factor Test Method described below.
• ARGOTEC 49510 was significantly lower than those according to the invention, which had a peak loss factor of greater than 0.5 (i.e., as illustrated by the data curves labeled 1 and 2).
• the peak loss factor tested for extruded polyurethane carrier films occurred at about 25 °C.
• the peak loss factor tested for polyurethane-based carrier films used in protective sheets of the invention occurred at about a temperature of at least about 35 °C.
• the half-height loss factors occurred across a temperature span of less than about 40 °C, less than about 30 °C. in some embodiments, and even less than about 20°C. in some embodiments, for tested polyurethane-based carrier films used in protective sheets of the invention as opposed to occurring across a temperature span of greater than about 40 °C, and even greater than about 45 °C. in the exemplified embodiments, for extruded polyurethane-based carrier films.
• the half-height loss factor was measured to be 53 °C.
• the half-height loss factor was measured to be 49 °C.
• the half-height loss factor was measured to be 18°C.
• the half-height loss factor was measured to be 22°C.
• the carrier layer is also defect-free.
• a "defect” is understood to be a visual imperfection such as, for example, a gel particle, a die line, or a gauge line.
• “defect-free” refers to polymer films with no more than the maximum allowable defects shown in Table 1 , as set forth in terms of the maximum defect diameter.
• no defects are detectable within the polymer film when viewed by an unaided human eye. More preferably, no defects are detectable within the polymer film when viewed with magnification up to about 50x.
• conventional p-gels cannot form as the polymer film is not formed in a conventional reactor.
• conventional e-gels cannot form as the polymer film is not formed using a conventional extruder.
• processing aids e.g., slip and antiblock additives - that are known to contribute to gel formation and that would conventional be required and used in such methods of formation need not be, and are preferably excluded from, methods for formation of polymer films according to the invention.
• the resulting polymer films are defect-free.
• the adhesive layer is present adjacent and on a major planar side of the carrier layer opposite from that on which the optional topcoat layer is present.
• Any suitable adhesive can be used for the adhesive layer according to the invention.
• the adhesive layer comprises a pressure-sensitive adhesive.
• (meth)acrylate - i.e., acrylate and methacrylate - chemistry is preferred.
• suitable chemistries are known to those skilled in the art and include, for example, those based on synthetic and natural rubbers,
• polybutadiene and copolymers thereof polyisoprene and copolymers thereof, and silicones (e.g., polydimethylsiloxane and polymethylphenylsiloxane).
• silicones e.g., polydimethylsiloxane and polymethylphenylsiloxane. Any suitable additives can be present in conjunction with the base polymer in the adhesive layer.
• an adhesive based on 2-ethyl hexyl acrylate, vinyl acetate, and acrylic acid monomers polymerized as known to those skilled in the art was found useful in one embodiment of the invention.
• the adhesive can be crosslinked, for example, using conventional aluminum or melamine crosslinkers.
• the adhesive layer has a thickness of about 5 microns to about 150 microns. In a further embodiment, the adhesive layer has a thickness of about 30 microns to about 100 microns. However, the thickness of the adhesive layer can vary substantially without departing from the spirit and scope of the invention.
• the adhesive layer can be protected using, for example, a conventional release liner.
• the sheet can be stored and shipped easily in roll or other forms until its application.
• any outwardly exposed non-adhesive layer on a side of the in-situ polymerized polyurethane-based carrier layer opposite the adhesive layer in protective sheets of the invention is referred to as the "topcoat layer.”
• the optionally present topcoat layer is an outwardly exposed, exterior layer of the protective sheet as applied to an article. Any suitable type of material can be used for the topcoat layer in protective sheets of the invention.
• the topcoat layer can comprise as its base polymer a polycarbonate, a polyvinyl fluoride, a poly(meth)acrylate (e.g., a polyacrylate or a polymethacrylate), a polyurethane, modified (e.g., hybrid) polymers thereof, or combinations thereof.
• a polycarbonate e.g., a polycarbonate or a polymethacrylate
• a polyurethane modified (e.g., hybrid) polymers thereof, or combinations thereof.
• U.S. Patent No. 4,476,293 for a description of exemplary polycarbonate-based polyurethanes useful for the topcoat layer of the invention.
• U.S. Patent Publication No. US-2008-0286576-A1 incorporated herein by reference, for a description of further exemplary topcoat layers.
• the topcoat layer is of relatively high molecular weight. That is, while the topcoat layer can be formed by extrusion according to some embodiments of the invention, the topcoat layer is preferably of a sufficient molecular weight that extrusion thereof is not practical ⁇ i.e., if a polyurethane, the polyurethane is not considered extrusion-grade polyurethane by those of ordinary skill in the art). In a preferred embodiment, the topcoat layer is in-situ polymerized in addition to the polyurethane-based carrier layer of the invention.
• a polymer liner e.g., a clear polyester liner
• a polymer liner e.g., a clear polyester liner
• each of the individual layers of the protective sheet is formed and assembled into a multi-layer protective sheet according to the invention according to the knowledge of those skilled in the art.
• the carrier layer can be formed on a separate carrier film (e.g., polyester film), resulting in a supported carrier layer, after which time the adhesive layer of the multilayer protective sheet may be formed on the carrier layer.
• the supporting carrier film is then removed at some point in time, so that the underlying side of the carrier layer is outwardly exposed and can be, optionally thereafter, assembled with a topcoat layer thereon.
• any suitable method can be used.
• an adhesive film of the desired thickness can be cast onto a release film according to one embodiment and as known to those skilled in the art.
• the adhesive film supported on the release film can then be assembled with the carrier layer, with the release film being removed before adherence of the multi-layer protective sheet to a surface of an article.
• each of the other individual layers of the protective sheet is prepared before assembly into the final multi-layer protective sheet. Any suitable method for formation of each of the other individual layers can be used as known to those skilled in the art.
• any suitable method can be used.
• a film comprising a topcoat layer of a desired thickness can be cast onto a smooth film (e.g., polyester film) according to one embodiment and as known to those skilled in the art to form a supported topcoat layer.
• a smooth film e.g., polyester film
• the supported topcoat layer is then assembled onto the outwardly exposed side of the carrier layer - i.e., a major surface of the carrier layer opposite from that on which the adhesive layer is assembled.
• the smooth film used for formation of the topcoat layer can remain in the assembly until application of the multi-layer protective sheet to a surface of an article in order to provide extra protection during shipping and storage of the sheet.
• any suitable method can be used to assemble the topcoat layer with the carrier layer.
• the topcoat layer is formed by direct coating the topcoat layer onto the carrier layer according to conventional methods.
• the above-described processes entail formation of individual layers and then adherence of those layers together to form the multi-layer protective sheet
• some of the sheet's layers can be formed simultaneously by, for example, co-extrusion of the polymerizable compositions starting in their liquid form, which step is typically performed at a temperature below about 40 °C - e.g., about room temperature in one embodiment.
• layers other than the carrier layer may be polymerized in-situ into a film format as described in, for example, U.S. Patent No. 8,828,303 and U.S. Patent Publication No. US-201 1 -0137006-A1 . No matter what method is used, the process can be a continuous or batch process.
• Protective sheets of the invention are useful in a range of indoor and outdoor applications in, for example, the transportation, architectural and sporting goods industries. Exemplary applications including adherence of the protective sheets to articles, including motorized vehicles and non-motorized vehicles (e.g., conventional bicycles) amongst others.
• protective sheets can include components influencing their color and/or transparency
• preferably protective sheets of the invention have smooth, glossy surfaces and a substantially uniform thickness throughout in order to maximize their capability of providing seemingly invisible protection to a surface.
• a protective sheet is applied to a surface, preferably in such a way as to conform to the shape of the surface.
• recoverability is important and preferred. If a sheet is not very recoverable, micro-cracking can occur when the film is stretched too far.
• Relief cuts may be needed in that case in order to apply such sheets to substrates, particularly those having a complex surface of convex and concave features.
• relief cuts are not necessary when applying protective sheets of the invention to complex surfaces.
• Such multi-layer protective sheets are readily conformable due to their recoverability.
• Multi-layer protective sheets of the invention can be readily and easily applied to a surface of an article based on knowledge of those skilled in the art.
• the adhesive layer is generally adhered to the surface to be protected after removal of any release liner present thereon to expose the adhesive.
• the multi-layer protective sheet can be more easily repositioned before being firmly adhered to a surface.
• Dissolution and/or swelling of the discs of each example was evaluated after five minutes. To evaluate each sample, if the disc was no longer intact, the contents of the jar were poured through a 200 mesh stainless steel filter. If no solid or gel residue was retained on the screen, this verified that the material of the disc had completely dissolved and had not simply broken up into fine pieces. If the disc was intact still at five minutes, the disc was allowed to remain immersed in the THF for six hours total. After six hours total of immersion, the disc was still was removed from the jar and the diameter thereof was measured immediately. Thereafter, the disc was allowed to air dry. After about twenty-four hours, the diameter of the disc was measured again. [00077] Comparative Example C1
• a disc of ARGOTEC 49510 thermoplastic polyurethane film commercially available from Argotec, LLC (Greenfield, MA), was evaluated according to the Solvent Resistance Test Method described above. After five minutes, the disc was no longer intact and confirmed to have completely dissolved.
• a disc of ARGOTEC 46510 thermoplastic polyurethane film commercially available from Argotec, LLC (Greenfield, MA), was evaluated according to the Solvent Resistance Test Method described above. After five minutes, the disc was no longer intact and confirmed to have completely dissolved.
• a disc of Film 3 prepared according to the Exemplary Formulations below was evaluated according to the Solvent Resistance Test Method described above. After immersion for six hours, the diameter of the disc was measured to be 160% of its original size. After air drying, the disc had returned to its original 25-mm diameter, confirming evaporation of the THF.
• UV Stabilizer entrochem inc., Columbus, Heat and light stabilizer system
• An acrylic-based polyurethane topcoat layer for multi-layer protective sheets of the invention was formed from aliphatic acrylic polyols and aliphatic polyisocyanate polymer, which components were polymerized on the carrier layer in- situ after being coated to a thickness of 1 -28 microns, preferably 5-15 microns. In a preferred embodiment, the polymerizable components were coated to a thickness of about 10 microns.

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• 2017
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