MXPA97007754A - Materials that flow in a flowed form and a method for sealing superfic - Google Patents

Abstract

The invention provides a method for imparting topographic or protective features to a substrate, by contacting a material in the form of a sheet comprising a thermosetting layer, with a substrate, and heating the sheet material at an elevated temperature.

Description

MATERIALS THAT FLOW IN A FLOWED FORM AND METHOD FOR SEALING SURFACES FIELD OF THE INVENTION The present invention relates to a method for using a material in the form of a sheet that flows in a molten form, to provide protective and aesthetic characteristics to a surface.

BACKGROUND OF THE INVENTION There are numerous applications in the industry where it is desirable and necessary in some cases to provide protective and / or aesthetic characteristics to a surface. Such applications include the use of a dyeable sealer for automotive bodies. Historically, a variety of materials have been used as sealants to fill empty spaces in structures and exclude dust, moisture and other materials. Co-sealers or liquids or solids have been supplied depending on the application demands. In the automotive industry, paste-like plastisols have been used by REF: 25779 decades for sealing metal joints, as described in US Patent No. 4,900,771 (Gerace et al.). These materials work by having particles of PVC (polyvinyl chloride) that swell in a plasticizer, when heated, and fuse into a solid material. Typically, paint adheres poorly to PVC-based sealants, due to high levels of plasticizer. In addition, PVC sealants can not be recycled, and when burned, they give off HCl. For this reason they are not used in Europe. Hot melt sealants and adhesives are generally solid thermoplastic materials that melt rapidly when heated, and then form a firm bond upon cooling. A typical class of hot melt adhesive compositions use polyolefins which are known in the art as difficult to paint, and which have poor adhesion to non-porous metallic surfaces, such as steel and aluminum. In use, a sphere of liquid sealant is applied over the weld or joint, in the manner in which a caulking is applied and the worker must brush or level the material in a relatively uniform film. The application of a liquid sealant requires skill and frequently results in a poorly sealed joint. Liquid sealants can be used for visible applications due to non-uniform appearance. Recently, there have been tendencies toward more benign sealing systems with users, such as ropes or tapes because the handling properties of these materials make installation quick and eliminate the need for fineness of the material after application. The ribbons and ropes of the PVC-based sealing material have begun to find convenient applications. Other materials have also been supplied as a strip or tape. U.S. Patent No. 3,659,896 (Smith et al.) Discloses a curable, semi-cured polymeric sealing strip composition based on a liquid polysulfide polymer for bonding and sealing a windshield to a car body with the sealing strip. The sealing strip has adhesion to glass and metal, such that the windshield is immediately sealed at room temperature; Additional curing of the sealing material occurs with exposure to moisture at ambient conditions. U.S. Patent No. 4,490,424 (Gerace) discloses a hot melt adhesive and sealant tape in which the tape comprises a core of hot melt adhesive encapsulated in a cover or plastic resin shield. The plastic resin is compatible with the hot melt adhesive core in the liquid and solid states. There is a need in the industry for a fusible, bendable, user-friendly sealer material that can be used for visible and non-visible applications, and handled as a strip or tape. Pressure sensitive adhesives, thermosetting are known and have utility in a number of industries including the assembly of automobiles and appliances. Such adhesives are described in U.S. Patent No. 5,086,088 (Kitano et al.). These adhesives are pressure sensitive, for example, they are sticky at the bonding temperature, and are typically used in the form of a pressure sensitive adhesive transfer tape in which the adhesive layer is provided on a release liner. . The transfer belt may further include a non-woven web for reinforcing the adhesive layer. In use, the transfer belt joins a surface to another surface at room temperature. The surfaces are then heated to a temperature sufficient to cure the adhesive to a thermoset stage. In some applications, it may be desirable to have a thermosetting, pressure-sensitive adhesive tape having a non-stick surface that can be activated to an adhesive state at the use temperature. An application of this type is in some automobile assembly lines where the doors are temporarily attached to the body of the vehicle by bolting the hinges on the body before painting it. The door is placed on the vehicle by aligning the door hinges over slotted holes in the vehicle body, and then securing the hinges to the body with one or more corresponding washers and bolts. After the body of the vehicle has been painted, the doors are removed from the hinges, so that the interior parts can be installed. It might be desirable to have the washers fixed in place over the hinges, so that when the doors are retracted, they will be precisely aligned without taking time to realign them. Japanese Patent Publication (Kokai) No. 64-67417 discloses a washer attached to a door hinge with a sticky thermosetting adhesive film. The washer serves as an alignment for a bolt that is used to attach the hinge to a door. The film is sticky on both sides and is prone to contamination by dust, oil, etc., which can be found in assembly plants. The contaminated surface, in turn, must be cleaned to ensure an adequate bond. The film also tends to be very thin, so that it can be difficult to handle and remove the linings or linings, so that the film can be attached to the washers and the surfaces with bolts can be a labor-intensive operation, which prohibits the automation of the assembly line. It is known to saturate a non-woven fabric as a support with a thermosetting adhesive to increase the stiffness of the adhesive, so that it can be handled more easily, because this could add costs and does not avoid the other deficiencies of the adhesive film described. previously. Japanese Patent Publication (Kokai) No. 53-42280 discloses a composite needle having a sheet of thermosetting material that is coated with a heat fusion material. The heat fusion material is aimed at coating the thermosetting resin sheet, so that workers can avoid direct contact with the skin with the thermosetting adhesive. The thermosetting material and the heat fusion material are mutually non-reactive and compatible, and characterized by a maximum difference in melting temperatures of 50 ° C. The hot melt material is melted and mixed with the thermosetting material before it hardens. Japanese Patent Laid-Open Application JP H4-189885 discloses a thermosetting pressure sensitive adhesive made from acrylate copolymers and epoxy resin copolymers. The adhesive composition may be coated on one or both sides of a non-woven material, which acts as a pre-preg to increase the strength of the adhesive sheet.

It may be desirable to have a thermosetting, pressure-sensitive adhesive tape that is substantially free of tack at room temperature (approximately 21 ° C) on at least one surface, but both larger surfaces of the tape can be adapted for attachment to other surfaces.

BRIEF DESCRIPTION OF THE INVENTION The invention provides an adhesive composition comprising a thermosetting pressure sensitive adhesive layer, and a layer of heat fusion adhesive that is substantially free of adhesiveness at room temperature. Preferably, the hot melt adhesive has a thermal activation temperature of about 50 ° C, at the temperature used to cure the thermosetting adhesive. The invention also provides an adhesive compound for attachment to a washer, which will be attached to the washer at room temperature, and for further attachment of the washer to a surface after a heating cycle, and a washer attached to the compound .

The invention also provides a method for joining the compound to washers. The invention further provides a heat fusion sealing tape and a method for using the tape. Additional features and advantages of the invention will be described in the following description, and in part will be apparent from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention will be realized and achieved by the methods and articles particularly pointed out in the. written description and claims thereof. It is understood that the foregoing general description and the following detailed description are exemplary and explanatory, and are intended to provide a further explanation of the invention as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be described in greater detail with reference to the following drawings, in which: Figure la is a cross-sectional view showing a sheet material according to the invention, located in a car roof channel, before heating.

Figure Ib is a cross-sectional view showing the sheet material shown in Figure la, after heating.

Figure 2 is a cross-sectional view of a two-layer sheet material according to the invention.

Figure 3a is a cross-sectional view of another material in the form of a two-layer sheet, according to the invention.

Figure 3b is a cross-sectional view showing the sheet material of Figure 3a, located in a car roof channel before heating.

Figure 3c is a cross-sectional view showing the sheet material of Figure 3a, located in a car roof channel after heating.

Figure 4a is a top view of a washer having a sheet material of the invention, adhered to it.

Figure 4b is a cross-sectional view along the line 4b of Figure 4a.

Figure 4c is a cross-sectional view showing the embodiment of Figure 4a, which has a bolt inserted therein for attaching a door hinge to a door structure.

Figures 5a and 5b are referred to as examples 22 and 23.

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises the use of a sheet material, which flows in molten form, to provide protective and / or aesthetically pleasing characteristics to a substrate. In general, the method of the invention includes the placement of a sheet material, which flows in molten form, on the substrate, and heating the sheet material to cause sufficient softening of the sheet material, so that it binds to the substrate. When the sheet that flows in molten form is placed on the substrate at room temperature, this is substantially free of adhesion. As the sheet is heated it first softens and conforms to the surface of the substrate, thereby allowing trapped air to be pushed out by the flowing material. Moreover, in the heating cycle, according to the sheet material it becomes hotter, it becomes sticky or adherent, and sufficiently wet the surface to join the surface. In some applications, the sheet material will also melt and flow to plug defects, surface imperfections and / or fill in empty spaces. After the sheet has been bonded to the surface, the sheet material can remain flowable in molten form, eg, thermoplastic, where reheating will cause the material to flow again, the sheet material can be cured or reticular when it is heated, and it becomes thermoset, so that it no longer flows when it is reheated; or a portion of the sheet material can be cured or become crosslinked, for example, heat-harden, while a portion of the sheet material remains thermoplastic. The method of the present invention has a number of applications in the industry. One utility of the method is in the automotive industry, where it can be used in a process to seal joints or metal joints in automobiles. By this process, the sheet material is prepared first, such as by the process described above. Subsequently, the sheet material could be applied over the joint to be sealed. Sealing and full bonding could be obtained because the sheet material flows before hardening. As a result of the controlled flow of the edges of the sheet material, an aesthetic surface appearance is achieved. The exposed surface of the material in the form of a hardened sheet can then be painted or otherwise decorated to be attached to the body of the automobile. An alternative application of the method of the invention is in the application of emblems or insignia of design elements to surfaces, such as a car body. An example of an emblem or logo is a logo of an automobile manufacturer. An example of a design element is placed to enhance and highlight the curvature of the automobile body and to provide protection to the prepared metal substructure without the need for full metal stamping, to obtain the shape. In such a method, the sheet material is initially configured in the shape of the desired emblem or insignia or design elements, such as by die cutting. The practice of the method of the invention thereby provides an aesthetically pleasing emblem or badge having smooth transitional lines relative to the surface to which it is attached. In yet another application of the method of the invention, the substrate to which the sheet material initially adheres is a temporary substrate such as a disposable liner or coating. Subsequent to the hardening of the sheet material in a manner to provide controlled flow of its edges, the hardened sheet material can be attached (eg, adhered) to the permanent substrate through the use, for example, of a system adhesive other than sheet material itself, since the material in the form of a hardened sheet may be substantially devoid of pressure-sensitive adhesive properties. In this way, the method of the invention can be used to apply shaped, hardened sheet materials, such as printed signs to surfaces such as wooden doors. The sheet material, which can flow in molten form, can be placed in a roof channel on a car before it is painted to hide imperceptible imperfections in the metal, spot welds, and the gradual joint where the metal The leaf-shaped roof is welded to the sheet metal of the car body. In a specific embodiment, the sheet-shaped material flowing in molten form is cut into a strip having a width slightly greater than the width of the roof channel and a length equal to the length of the channel. The roof channel can be unprepared, unprepared, with a portion sealed with conventional sealants, primed with conventional primers, or primed and painted. Typically, the automobile can be sized with an electrodeposition coating as detailed hereinafter, before the application of the strip. The strip is then heated in the channel, so that the strip-shaped material flows and levels on any imperfections and gradual union in the roof channel creating an aesthetically pleasing, smooth appearance within the channel. At the same time, the strip that flows in molten form also adheres to the inner surfaces of the roof channel and provides a protective seal in the channel, to prevent rain water, dust, snow etc. enter the roof channel and cause rust or corrosion. In this application, in which the strip has a width slightly greater than the width of the roof channel, the strip material also takes a concave configuration along the length of the roof channel, to provide a channel to carry the water outside the roof of the car. The material in the form of strips is preferably compatible with the paint and allows the paint to dry and cure without wrinkling or cracking of the paint, while being hermetically joined to the paint and to the surfaces of the roof channel.

The car, with the strip in place, can then be painted and brought to an oven curing cycle at approximately 170 ° C for approximately 20 minutes. A clear protective coating can also be applied and cured. It is recognized that the curing times and furnace temperatures will vary depending on the paint line, and the curing requirements of the clear coating and paint. Typical cycles may be in the range of about 20 to 40 minutes at temperatures of about 120 ° C and 200 ° C. In a preferred embodiment, the paint also typically reacts with the strip-shaped material flowing in molten form to improve adhesion between the paint and the strip flowing in molten form. The reaction of the paint with the strip material causes the strip material to become thermoset at and near the interface of the strip with the paint, while the strip material remains thermoplastic below the strip. the interfacial layer. In another preferred embodiment, the same strip that flows in fluid form is a thermosetting material that reacts with the paint during the curing cycle, and also undergoes cure to provide a strip that is thermoset. Healing can be achieved by thermal or radiation means, as discussed below in the present. In an alternative mode, the strip can be placed in the roof channel after the car has been painted. The area of the roof channel can then be heated with conventional heaters, such as an infrared heater or by a quartz halogen lamp, to melt and bond the strip to the roof channel without further processing. In this embodiment, the strip may be composed of pigments to provide a complementary contrasting color. The material in the form of a sealing strip in molten form can remain thermoplastically, become thermoset throughout the thickness of the strip, or become thermoset only on the surface of the strip. Leaf-shaped materials that flow in molten form are preferably solids, and may or may not be tacky at room temperature. In some embodiments, the material in the form of a sealing sheet in molten form will also function as a hot melt adhesive. The hot melt adhesive materials preferably have a melting point above about 50 ° C. As used herein, a "hot-melt adhesive composition" refers to a composition that is solid and non-tacky at room temperature (about 21 ° C) but which, after heating, melts sufficiently to wet a surface and adhere to it. Adhesives that have melting temperatures below 50 ° C may melt prematurely in storage in hot climates, and may not work well in applications that require a part to be die cut or punched on a punch press as described further ahead. The sheet material can be formed into a sheet using conventional sheeting techniques, including extruding the material from a hot die; heating the sheet material to an appropriate melting temperature and cutting with knives on a release liner or liner; the curtain coating of molten material; or the dispersion of the material in a solvent, coating on a release liner, and drying the solvent. For environmental reasons, the preferred methods are solvent-free systems. The thickness of the sheet material, which flows in molten form will vary depending on its intended end use. For sealing applications, it is desirable to have sufficient sheet thickness to provide sufficient material to flow and level over indentations, voids, and other surface imperfections., or to fill empty spaces between the joints. It has been found that useful thicknesses are in the range of about 0.05 mm (millimeters) to 25 mm. For typical sealing and casting applications where a protective seal is desired, the thicknesses may be in the range of 0.10 to 25 mm, preferably 0.20 to 10 mm, and more preferably 0.34 to 6 mm. The material in the form of sheet that can flow in molten form can be packaged in the form of rolls of sheet material, rolls of tapes, for example, lengths of materials in narrow widths, or stacks of sheets cut to a desired dimension or a desired shape for the final use. If the compositions of the sheet material flowing in molten form are sticky or adherent, a release liner or coating may be interleaved between the adjacent sheets or wraps of a roll. In some two-layer sheet constructions in which a layer that is adherent, the non-adherent layer can serve as the liner or coating without requiring a separate liner. The sheet material includes a latent catalyst activated by light in the sheet, the sheet is preferably packaged and transported in the absence of actinic radiation until ready for use. The compositions for the sheet material flowing in molten form can also be packaged for use in an applied hot melt system, with the use of small container dischargers, dispensers per cartridge, and the like. The compositions can then be heated at the point of use and applied in the molten state to the substrate. This method may require specialized equipment to apply the composition. Materials that flow in molten form can be applied and bound to most substrates including plastics, metals, ceramics, glass and cellulosic materials; metal substrates prepared, bare or painted such as aluminum, cold rolled steel, galvanized steel, and porcelain steel, which are particularly preferred.

The sheet that can flow in molten form can include one or more other layers for various purposes, as detailed hereinafter. Such layers include a thermosettable melt-sealing layer, a thermosetting pressure sensitive adhesive layer, a pressure-sensitive adhesive layer, a second layer flowing in a molten form, eg, one having a different glass transition temperature. in the first layer flowing in molten form, a layer capable of crosslinking with the flowing layer in molten form at the interface between the two layers, an expandable layer, a non-woven layer, or a polymeric film, eg, a film thermoplastic which is preferably dimensionally stable at the application and use temperatures. The various methods of joining the additional layers to the flowing layer in molten form include techniques known in the industry such as thermal lamination, bonding with a pressure sensitive adhesive, coexisting the second layer with the layer that it flows in molten form, hot melt coating, direct coating of the second layer to the first, and the like.

The sheet material flowing in molten form, useful in the practice of the invention, comprises thermoplastic polymeric materials having functional groups that can react with typical paints used in the industry, such as those based on melamine or epoxide. Preferred thermoplastic polymers are functionalized semicrystalline or amorphous polymers having a glass transition temperature of greater than -30 ° C, and functionalized semicrystalline polymers having a glass transition temperature below -30 ° C. Useful polymers are those having functional groups including -OH, -NH, -CONH, -COOH, -HN2, -SH, anhydrides, urethanes and oxirane. Preferred functional groups are -OH, -COOH, and -NH. Examples of useful polymers include functionalized polyesters, polyamides, ethylene (meth) acrylates, such as those functionalized with -OH groups, ethylene-acrylic acids, polysulfides, polyacetals such as polyvinyl butyral, olefinic polymers having appropriate functional groups such as ethylene acid. - (meth) acrylic, propylene- (meth) acrylic acid, ethylene- (meth) acrylic ester, propylene (meth) acrylic ester, polycaprolactones, epoxy polycaprolactone compositions and epoxy polyester hot melt compositions described in the parent application North American No. Ser 08 / 047,862, filed on April 15, 1993, and compatible mixtures thereof. Preferred materials for the sheet material flowing in molten form include polycaprolactones and polyesters having hydroxyl and carboxyl termination and can be amorphous or semi-crystalline at room temperature. More preferred are the hydroxyl terminated polyesters which are semi-crystalline at room temperature. A material that is "amorphous" has a vitreous transition temperature but does not show a measurable crystalline melting point, as determined in a differential scanning calorimeter (DSC). Preferably, the vitreous transition temperature is lower than the photoinitiating decomposition temperature if one is used as described hereinafter, but not being greater than about 120 ° C. A material that is "semi-crystalline" shows a crystalline melting point as determined by DSC, preferably with a maximum melting point of about 200 ° C.

The crystallinity of a polymer is also observed as a clouding or opacification of a sheet that had been heated to an amorphous state as it cooled. When the polyester polymer has been heated to a molten state and is coated by knives on a liner or coating to form a sheet, it is amorphous and it is observed that the sheet is clear and perfectly transparent to light. As the polymer in the sheet-like material cools, crystalline domains are formed, and crystallization is characterized by clouding of the sheet to a translucent or opaque state. The degree of crystallinity can be varied in the polymers by mixing in any compatible combination of amorphous polymers and semicrystalline polymers having various degrees of crystallinity. It is generally preferred that the material heated to an amorphous state be allowed sufficient time to return to its semicrystalline state before painting it, so that the paint is applied to a uniformly consistent surface. The clouding of the sheet provides a convenient non-destructive method for the determination that crystallization has occurred to some degree in the polymer.

The polymers may include nucleating agents to increase the rate of crystallization at a given temperature. Useful nucleating agents include microcrystalline waxes. An appropriate wax is one comprising an alcohol of more than 14 carbon atoms (CAS # 71770-71-5) and an ethylene homopolymer (CAS # 9002-88-4) sold by Petrolite Corp as Unilin 700. The catalysts for Paints such as paratoluenesulfonic acid can be added to the polyester, as well as melamines to improve the adhesion of the flowing layer in molten form, to the paint of the coatings. Preferred polyesters are solids at room temperature. Preferred polyester materials have a number average molecular weight of from about 7500 to 200,000, more preferably from about 10,000 to 50,000, and more preferably from about 15,000 to 30,000. The polyester components useful in the invention comprise the reaction product of dicarboxylic acids (or their diester equivalents) and diols. The diacids (or diester equivalents) can be saturated aliphatic acids containing from 4 to 12 carbon atoms (including branched, unbranched or cyclic materials having 5 to 6 carbon atoms in a ring) and / or aromatic acids containing 8 to 15 carbon atoms. Examples of suitable aliphatic acids are succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, 1, 12-dodecanedioic, 1,4-cyclohexanedicarboxylic, 1,3-cyclopentanedicarboxylic, 2-methylsuccinic, 2-methylpentanedioic, 3 -methylhexanedioic acid and the like. Suitable aromatic acids include terephthalic acid, isophthalic acid, italic acid, 4,4'-benzophenone-dicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylthioether-dicarboxylic acid, and 4,4'-acid. diphenylaminodicarboxylic. Preferably, the structure between the two carboxyl groups in the diacids contain only carbon and hydrogen, and more preferably, the structure is a phenylene group. Mixtures of the above diacids can also be used. The diols include branched, unbranched and cyclic aliphatic diols having from 2 to 12 carbon atoms. Examples of suitable diols include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1, 6-hexanediol, cyclobutan-1,3-di (2'-ethanol), cyclohexan-1, -dimethanol, 1,10-decanediol, 1, 12-dodecanediol, and neopentyl glycol. Long chain diols including poly (oxyalkylene) glycols in which the ethylene group contains from 2 to 9 carbon atoms, preferably 2 to 4 carbon atoms, can also be used. Mixtures of the above diols can also be used. Commercially available, useful hydroxyl-terminated polyester materials include various semi-crystalline, linear, saturated copolyesters available from Hüls America Inc such as Dyna? Ol® S1401, Dynapol®? 1402, Dynapol * S1358, Dyna? Ol® S1359, Dynapol®S1227, and Dynapol®S1229. The amorphous linear, saturated, useful copolyesters available from Hüls America Inc include Dyna? Ol® S1313 and Dyna? Ol® S1430. The above polyesters can be cast in sheets by melting the polyester resin at temperatures of about 100 ° to 150 ° C, to form a melted material and knife coating over a liner or coating such as a paper coated with silicone release . The polyester materials may also include fillers as described below for an epoxy polyester composition.

The sheets formed from the above polyesters are particularly useful for sealing and bonding to surfaces having voids and imperfections, such as in the molding of the roof channel described above, on a car. In addition, it has been found that these polyesters provide surfaces compatible with the paint for epoxy melamine paints, and will withstand at least two typical paint cure cycles (for example 20-30 minutes at 120 ° C, and 20-30 minutes at 200 ° C). It has also been found that these polyesters, when coated with epoxy and melamine paints, will react with the paint at the interface between the flowing sheet in molten form and the paint. Also preferred for the sheet material flowing in molten form are epoxy polycaprolactone compositions and epoxy polyester hot melt compositions. Polycaprolactones are biodegradable in the soil. Especially preferred are epoxy polyester hot melt compositions which are cured with exposure to radiation, to provide high strength sealing materials that have good adhesion to the substrate to which they adhere. The epoxy containing material contributes to the final strength and thermal resistance of the composition, while the polyester component allows the sheet material to conform to the substrate and provide initial adhesion to the substrate, and the photoinitiator allows the composition be cured (for example, cross-linked covalently) after exposure to radiation. Optionally, the hot melt compositions of the invention may also include a hydroxyl-containing material to impart flexibility and rigidity to the hot melt compositions. Preferred polyesters for the sheet, epoxy / polyester material are those hydroxyl and carboxyl terminated functional materials, described above. Especially preferred are the hydroxyl terminated polyesters that have a certain degree of crystallinity. The epoxy-containing materials useful in the compositions of the invention are any organic compounds having at least one oxirane ring (e.g., (polymerizable by a ring opening reaction.) Such materials, broadly referred to as epoxides, include monomeric and polymeric epoxides and may be aliphatic, cycloaliphatic or aromatic.These materials generally have, on average, at least two epoxy groups per molecule (preferably more of two epoxy groups per molecule) The "average" number of the epoxy groups per molecule is defined as the number of epoxy groups in the epoxy-containing material, divided by the total number of epoxy molecules present.The polymeric epoxides include linear polymers having terminal epoxy groups (for example, a diglycidyl ether of a polyoxyalkylene glycol), polymers having oxirane units in the backbone (for example, polybutadiene polyepoxide), and polymers having protruding epoxy groups (for example, polymer or copolymer of glycidyl methacrylate) The molecular weight of the material it contains Epoxy can vary from 58 to approximately 100,000 or more.

Mixtures of various epoxy-containing materials can also be used in the hot melt compositions of the invention. Useful epoxy-containing materials are those containing cyclohexene oxide groups such as epoxycyclohexanecarboxylates, exemplified by 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-. methylcyclohexanecarboxylate; and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate. For a more detailed list of useful epoxides of this nature, reference may be made to U.S. Patent No. 3,117,099. Additional epoxy-containing materials, which are particularly useful in the practice of this invention, include glycidyl ether monomers of the formula where R 'is alkyl or aryl and n is an integer from 1 to 6. The examples are glycidyl ethers of the polyhydric phenols obtained by the reaction of a polyhydric phenol with an excess of chlorohydrin such as epichlorohydrin (for example, diglycidyl ether) of 2, 2-bis- (2, 3-epoxypropoxyphenol) propane). Additional examples of epoxides of this type that can be used in the practice of this invention are described in U.S. Patent No. 3,018,262. There are a number of commercially available materials that contain epoxy, which can be used in this invention. In particular, epoxides that are readily available include octadecylene oxide, epichlorohydrin, styrene oxide, vinyl cyclohexene oxide, glycidol, glycidyl methacrylate, diglycidyl ether of Bisphenol A (for example, those available under the trade designations EPON 828, EPON 1004, and EPON 1001F from Shell Chemical Co., and DER-332 and DER-334, from Dow Chemical Co.), diglycidyl ether from Bisphenol F (for example ARALDITE GY281 from Ciba-Geigy), vinylcyclohexene dioxide (e.g. ERL 4206 from Union Carbide Corp.), 3,4-epoxyloxyhexylmethyl-3,4-epoxycyclohexene carboxylate (e.g. ERL-4221 from Union Carbide Corp.), 2- (3,4-epoxycyclohexyl-5,5-spiro- 3, 4-epoxy) -cyclohexane-methadioxane (e.g. ERL-4234 from Union Carbide Corp.), bis (3-epoxycyclohexyl adipate) (e.g. ERL-4299 from Union Carbide Corp), dipentene dioxide (e.g. ERL-4269 from Union Carbide Corp.), epoxidized polybutadiene (e.g. OXIRON 2001 from FMC Cor p.), silicone resin containing epoxy functional groups, epoxy silanes (e.g., beta- (3,4-epoxycyclohexyl) ethyltrimethoxy-silane and gamma-glycidoxypropyltrimethoxysilane, commercially available from Union Carbide) epoxy fire retardant resins ( for example DER-542, an epoxy brominated bisphenol resin available from Dow Chemical Co. ), diglycidyl ether of 1,4-butanediol (for example ARALDITE RD-2 of Ciba-Geigy), epoxy resins based on epichlorohydrin of hydrogenated bisphenol A (for example EPONEX 1510 of Shell Chemical Co.) and novolac polyglycidyl ether of phenol formaldehyde (for example DEN-431 and DEN-438 from Dow Chemical Co.). The photoinitiators which are useful in the compositions of the invention are cationic and include in these three types, i.e. aromatic iodonium complex salts, aromatic sulfonic complex salts and metallocene salts. Useful complex aromatic iodonium salts have the formula: where Ar1- and Ar2 are aromatic groups containing from 4 to 20 carbon atoms, and are selected from the group consisting of the phenyl, thienyl, furanyl and pyrazolyl groups. Z is selected from the group consisting of oxygen; sulfur; where R is aryl (from 6 to 20 carbon atoms, such as phenyl) or acyl (from 2 to 20 carbon atoms, such as acetyl, benzyl, etc.); a carbon-carbon bond; or where Ri and R2 are selected from hydrogen, alkyl radicals of 1 to 4 carbon atoms, and alkenyl radicals of 2 to 4 carbon atoms. The value of m is zero or 1 and X is a complex anion containing halogen, selected from tetrafluoroborate, hexafluorophosphate, pentafluorohydroxyantimonate, hexafluoroarsenate, and hexafluoroantimonate. The aromatic groups Ar1 and Ar2 may optionally have one or more benzofunctional rings (for example, naphthyl, benzothienyl, dibenzothienyl, benzofuranyl, dibenzofuranyl, etc.). The aromatic groups can also be substituted, if desired, by one or more non-basic groups if they are essentially unreactive with the epoxide and the hydroxyl functional groups. Useful, aromatic iodonium complex salts are more fully described in U.S. Patent No. 4,256,828. Preferred aromatic iodonium complex salts are diaryliodonium hexafluorophosphate and diaryliodonium hexafluoroantimonate.

The aromatic iodonium complex salts useful in the compositions of the invention are photosensitive only in the ultraviolet region of the spectrum. These, however, can be sensitized in the near ultraviolet and visible spectrum range by sensitizers for known photolyzable organic halogen compounds. Illustrative sensitizers include aromatic amines and colored aromatic polycyclic hydrocarbons. The aromatic sulfonium complex salt photoinitiators, suitable for use in the compositions of the invention, can be defined by the formula wherein R3 and R4 and R5 may be the same or different, with the proviso that at least one of the groups is aromatic. These groups can be selected from the aromatic portions having 4 to 20 carbon atoms (for example, substituted and unsubstituted phenyl, thienyl and furanyl) and alkyl radicals having from 1 to 20 carbon atoms. The term "" alkyl "" includes substituted alkyl radicals (eg, substituents such as halogen, hydrsyl, alkoxy, aryl). Preferably, R3 R and R5 are each aromatic, Z, m and X are all as defined above with respect to the complex iodonium salts. If R3 R or R5 is an aromatic group, it may optionally have one or more benzofused rings (for example, naphthyl, benzothienyl, dibenzothienyl, benzofuranyl, dibenzofuranyl, etc.). Such aromatic groups may also be substituted, if desired, with one or more non-basic groups that are essentially unreactive with the epoxide and hydroxyl functional groups. Triaryl substituted salts such as triphenylphosphonium hexafluoroantimonate are preferred. Useful sulfonium complex salts are described more fully in U.S. Patent No. 4,256,828. The aromatic sulfonium complex salts, useful in the invention, are inherently photosensitive only in the ultraviolet region in the spectrum. These, however, are sensitized to the near ultraviolet and visible spectrum range by a select group of sensitizers such as described in US Pat. No. 4,256,828. Useful metallocene salts may have the formula: wherein Mp represents a metal selected from Cr, Mo, W, Mn, Re, Fe, and Co; L1 represents 1 or 2 ligands contributing with p-electrons which can be the same or different ligand selected from h3-allyl, h5-cyclopentadienyl, and substituted and unsubstituted h7-cycloheptatrienyl, and h-cycloheptatrienyl and h6-aromatic compounds selected from h ° -benzene and substituted compounds of hb-benzene and compounds having from 2 to 4 fused rings each capable of contributing 3 to 8 electrons for the valence layer of Mμ. L "represents zero or 1 to 3 ligands that contribute an equal number of sigma electrons that can be the same or different selected carbon monoxide or nitrosonium ligand; with the proviso that the total charge contributed to Mp by. L and L2 plus the ionic charge on the metal Mp, resulting in a net positive residual charge of q for the complex, and q is an integer having a value of 1 to 2, the residual electrical charge of the complex cation; Y is a halogen-containing complex anion, selected from AsF6-, SbF6_, and SbF5OH-; and r is an integer having a value of 1 to 2, the numbers of the complex anions required to neutralize the charge q on the complex cation. Useful metallocene salts are described more fully in U.S. Patent No. ,089,536 (Palazzotto et al.). An example of a useful salt is (? 5-cyclopentadienyl) (? B-xylenes) Fe + SbF6 ~, also denoted as Cp (xylenes) Fe + SbFfi ". Useful amounts of the metallocene catalyst are in the range from about 0.05. to 20 parts by weight of the epoxy resin, preferably from about 0.07 to about 10 parts, more preferably from about 0.09 to about 3 parts.The metallocene salts can be used in conjunction with a reaction accelerator such as an oxalate ester of a tertiary alcohol Useful commercially available photoinitiators include FX-512, a complex salt of aromatic sulfonium (3M Company), a complex salt of aromatic sulfsnium (Union Carbide Corp.), UVI-6974, a complex salt of aromatic sulfonium ( Union Carbide Corp) and IRGACURE®261, a complex metallocene salt (Ciba-Geigy) Optionally, the hot melt compositions of the invention may also comprise a the one that contains hydroxyl. The hydroxyl-containing material may be any liquid or solid organic material having hydroxyl functionality of at least 1, preferably 2, more preferably of about 3. The hydroxyl-containing organic material must be free of other groups containing "active hydrogen" such as the amino and mercapto portions. The hydroxyl-containing organic material must also be substantially free of groups that can be thermally or photolytically unstable so that the material will not decompose or release volatile components at temperatures below about 100 ° C, or when exposed to actinic radiation by beam of electrons during healing. Preferably, the organic material contains two or more primary or secondary aliphatic hydroxyl groups (for example, the hydroxyl group is directly attached to a non-aromatic carbon atom). The hydroxyl group may be terminally located, or it may be protruding from a polymer or copolymer. The average number-equivalent weight of the hydroxyl-containing material is preferably from about 31 to 2250, more preferably from about 80 to 1000, and more preferably from about 80 to 350. Representative examples of suitable organic materials having a hydroxyl functionality of 1. , include alkanols, monoalkyl ethers of polyoxyalkylene glycols, and monoalkyl ethers of alkylene glycols.

Representative examples of useful monomeric polyhydroxy organic materials include alkylene glycols (eg, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 2-ethyl-1,6-hexanediol, bis (hydroxymethyl) cyclohexane, 1,18-dihydroxyoctadecane, and 3-chloro-1,2-propanediol), polyhydroxyalkylene (for example glycerin, trimethylolethane, pentaerythritol and sorbitol) and other polyhydroxy compounds such as N, N-bis (hydroxyethyl) benzamide, 2- buten-l, 4-diol, castor oil, etc. Representative examples of useful hydroxyl-containing polymeric materials include polyoxyalkylene polyols (for example, polyoxyethylene and polyoxypropylene glycols, and triols of equivalent weight of 31 to 2250 for diols, or 80 to 350 for triols), glycols of polytetramethylene oxide of varying molecular weight, hydroxyl-terminated polyesters, and hydroxyl-terminated polylactones. Commercially available, useful hydroxyl-containing materials include the POLYMEG series (available from QQ Chemicals, Inc.) of polytetramethylene oxide glycols such as POLYMEG 650, 1000 and 2000; TERATHANE series (from E.

I. duPont de Nemours an Company) and polytetramethylene oxide glycols such as TERATHANE 650, 1000 and 2000; POLYTHF, a polytetramethylene oxide glycol from BASF Corp.); BUTVAR series (available from Monsanto Chemical Company) of polyvinylacetal resins such as BUTVAR B-72A, B-73, B-76, B-90 and B-98; the TONE series (available from Union Carbide) of the polycaprolactone polyols such as TONE 0200, 0210, 0230, 0240 and 0260; the DESMOPHEN series (available from Miles Inc.) of saturated polyester polyols such as DESMOPHEN 2000, 2500, 2501, 2001KS, 2502, 2505, 1700, 1800 and 2504; the RUCOFLEX series (available from Ruco Corp.) of saturated polyester polyols such as S-107, S = 109, S-1011 and S-1014; VORANOL 234-630 (a trimethylolpropane) from Dow Chemical Company; VORANOL 230-238 (an adduct of glycerol-polypropylene oxide) from Dow Chemical Company; the SYNFAC series (from Milliken Chemical) of the polyoxyalkylated bisphenols A such as SYNFAC 8009, 773240, 8024, 8027, 8026 and 8031 and the ARCOL series (from Arco Chemical Co.) of polyoxypropylene polyols such as ARCOL 425, 1025, 2025 , 42, 112, 168 and 240. The amount of hydroxyl-containing organic material used in the compositions of the invention can vary over a wide range, depending on factors such as the compatibility of the hydroxyl-containing material with the material containing epoxy and the polyester component, the equivalent weight and functionality of the hydroxyl-containing material, and the physical properties desired in the final cured composition. The optional hydroxyl-containing material is particularly useful in designing the flexibility of the hot melt compositions of the invention. As the equivalent weight of the hydroxyl-containing material increases, the flexibility of the hot-melt composition increases correspondingly, although there may be a consequent loss in cohesive strength. Similarly, the decrease in equivalent weight can result in a loss of flexibility with a consequent increase in cohesive strength. In this way, the equivalent weight of the hydroxyl-containing material is selected to balance these two properties, the appropriate balance depending on the particular application. Flexible, molten seal compositions are useful in the formation of flexible sheets for sealing performance at lower temperatures, for example, below about 0 ° C. If the hydroxyl-containing material is used to design the flexibility of the sealing composition in molten form, the polyoxyethylene glycols and triols having an equivalent weight of about 31 to 2250 for the glycols, and 80 to 350 for the triols, are particularly preferred. Even more preferred are polyoxypropylene glycols and triols having an equivalent weight of about 31 to 2250 for the glycols, and an equivalent weight of about 80 to 350 for the triols. The flowing compositions in molten form of the invention comprise from 0.01 to 95 parts per 100 parts total of the epoxy-containing material and, correspondingly, from 99.99 to 5 parts of the polyester component. More preferably, the flowing compositions in molten form of the invention comprise from 0.1 to 80 parts of the epoxy-containing material and, correspondingly, from 99.9 to 20 parts of the polyester component. More preferably, the hot melt compositions of the invention comprise from 0.5 to 60 parts of the epoxy-containing material, and, correspondingly, from 99.5 to 40 parts of the polyester component. By increasing the amounts of the epoxy-containing material relative to the polyester component, it generally results in compositions that flow in molten form, which have higher final strength and higher thermal resistance, but less flexibility, and lower viscosity. Increasing the amounts of the polyester component generally results in flowing compositions in molten form having lower final strength, lower thermal resistance and higher viscosity, but greater flexibility and greater strength build-up prior to firing. In this way, the relative amounts of these two ingredients are balanced depending on the properties sought in the final composition. The photoinitiator, if used, is included in an amount in the range of about 0.01 to 4% based on the combined weight of the epoxy-containing material and the polyester component. Increasing the amounts of the photoinitiator can result in an accelerated healing rate. The increased amounts of the photoinitiator can result in a reduced requirement for energy exposure. The amount of the photoinitiator is determined by the rate at which the composition must be cured, the intensity of the radiation source, and the thickness of the composition. In some applications, it is useful to initially cure the composition flowing in molten form, only on the surface of the sheet, and subsequently thermally cure the final complete sheet. For example, a material in the form of epoxy polyester sheet curable by actinic radiation, is exposed to actinic radiation to cure the surface of the sheet material, and then it is placed in the aforementioned roof channel, such that the material in Leaf shape forms a concave surface along the roof channel as shown in Figure Ib. The strip is then heated to sufficient temperature to bond the strip to the surface within the channel, and cure the full thickness of the sheet. The result is a surface with coatings on the sheet material that helps provide a smooth surface for visual and functional reasons. Compositions flowing in molten form, which include in a polyether polysil, can be useful in allowing the molten flowing sheet to conform to the surface and displace entrapped air prior to the formation of a permanent bond to the substrate. In addition, and optionally, up to 50% of a total composition (based on the epoxy-containing material, the polyester component, the photoinitiator and the hydroxyl-containing material, optional), can be provided by various fillers, adjuvants, additives and the like, such as silica, glass, clay, talc, pigments, dyes, glass spheres or bubbles, glass or ceramic fibers, antioxidants, and the like, to reduce the weight or cost of the composition, to adjust the viscosity, and provide additional reinforcement. Fillers and the like, which are capable of absorbing the radiation used during the curing process, must be used in an amount that does not adversely affect the healing process. Flowing compositions in molten form comprising the above polyester and epoxy polyester materials are prepared by mixing the various ingredients in an appropriate container, preferably one that is not transparent to actinic radiation if a photoinitiator is used, a high temperature sufficient to liquefy the components, so that they can be efficiently mixed with agitation until the components are perfectly mixed in molten form but without thermally degrading the materials. The components can be added simultaneously or sequentially, although it is preferred to first mix the epoxy-containing material and the polyester component, followed by the addition of the hydroxyl-containing material and then the photoinitiated. The compositions flowing in molten form must be compatible in the molten phase, for example, there should be no visually evident phase separation between the components. The sheet that flows in molten form, made with the epoxy polyester compositions, may be adherent or non-adherent. A mixture of liquid and solid materials containing epoxy is useful in providing an adherent or sticky sheet. In use, the sheet-shaped materials that flow melted, which contain a photoinitiator, can be exposed to a radiation source to activate the catalyst, to cure the epoxy-containing material before, during or after the sheet material has been applied to the substrate. Activation of the catalyst occurs after exposure of the sheet materials to any source that emits actinic radiation (for example, radiation having a wavelength in the visible ultraviolet spectral regions). Suitable sources of radiation include mercury, xenon, carbon arc, tungsten filament, quartz halogen lamps, fluorescent lights, sunlight, etc. Exposure times must be sufficient to activate the catalyst and may vary from less than about 1 second to 20 minutes or more, depending on the amount and time of reagents involved, the radiation source, the distance from the source of radiation, and the thickness of the leaf. The time necessary to achieve complete healing can be accelerated by curing the leaf-like materials with heat, such as in an oven. The temperature of the cure will vary depending on the vitreous transition temperature of the polyester component, the concentration of the photoinitiator, the conditions at radiation exposure, and the like. Typical cyclic cure conditions are in the range of 5 to 30 minutes, with temperatures that are in the range of about 50 ° C to 200 ° C. More than one heating cycle can be used to cure sheet materials. The compositions can also be cured by exposure to electron beam radiation. The necessary dose is generally less than 1 megarad to 100 megarads or more. The rate of cure tends to increase with the increasing amounts of the photoinitiator at a given light or irradiation exposure. The rate of healing also increases with the increase in the intensity of the radiation or the dose of electrons. Other layers may be included in the sheet that flows in molten form, for various purposes. A second layer flowing in molten form can be adhered to a larger surface of the first molten flowing sheet, to improve the topographic and aesthetic characteristics of a surface. A second layer of the sheet material that flows in molten form can be included to improve the environmental resistance of the tape in exteriors. The second layer of the ribbon flowing in molten form can include thermal expansion agents such as blowing agent, foaming agents, expandable polymeric microspheres and the like, to impart a convex shape to a surface. A net or woven or non-woven mesh can be included in the sheet material that flows in molten form. The network can be laminated to the melt flowing layer using an adhesive or by heat lamination techniques, and can be inserted between two melt flowing layers. The addition of a non-woven network has been found to be useful in controlling the flow of the flowing layer in molten form. The woven or nonwoven web can also be used to impart strength in sheet material to improve handling properties. Other materials that can be included as part of the sheet material that flows in molten form are thermoplastic films. Preferably, the films are dimensionally stable at the temperatures at which they can be exposed either on application to a substrate of the melt flowing sheet material, for example, when the sheet material is heated to a temperature necessary for cause the flow and / or thermosetting of the sheet material, or after it has been applied, for example, exposure to cold ambient temperatures, sunlight, etc. Useful films include polyurethane films, oriented polyester films, polyimide films, polyolefin films, and the like. The films can be used to provide smooth surfaces for painting or as the finished surface after the sheet flowing in molten form has been bonded to a surface. Thermosetting films can also be used. Examples of thermosetting films include films made from the above-described epoxy polyester materials that have been crosslinked, crosslinked epoxy films, and the like. Preferred films include films made from the above-described epoxy polyester materials, polyester films including polyethylene terephthalate films, ultra-high molecular weight polyethylene films, ultra-high molecular weight polyethylene microporse films, polypropylene films of ultra-high molecular weight, ultra-high molecular weight microporous polypropylene films, and polyimide films. Ultra-high molecular weight polyolefin films are preferred in some embodiments, because the very long chains of these polyolefins can be smoothed after heating without showing the typical molten liquid flow of the thermoplastic materials. Useful ultra-high molecular weight polyethylene films have an intrinsic viscosity of at least about 18 deciliters per gram (dl / g), a typical intrinsic viscosity range between about 18 and 39 dl / g, and a range preferred between 18 and 32 dl / g. Useful polypropylene films of ultra-high molecular weight have an intrinsic viscosity of at least 6 dl / g. A typical range of intrinsic viscosity is from 6 to about 18 dl / g, and a preferred range is from 6 to 16 dl / g. Thermoplastic thermosetting films must be dimensionally stable at the temperatures at which they are exposed. By dimensionally stable, it is understood that the films have sufficient integrity at the temperatures of use, and particularly, during the heat cure cycle of the melt-seal layer at about 120 ° C to 200 ° C for 20 to 40 minutes, so that they do not melt and do not flow. Also, the films do not show wrinkling when they are heated to the melt seal temperature and subsequently cooled. The films also have sufficient integrity to prevent air bubbles trapped in the pre-melt seal layer from blowing through the film, and causing a defect. Preferably, the films, after they have been laminated to a melt-sealing layer and heated to the temperature necessary to bond the melt-seal layer to a surface, will show a shrinkage in the direction of the network and transverse to the network of less than about 5%, more preferably, less than about 3%, and more preferably, less than about 2%. In the highly preferred embodiments, the films will show less than 1% shrinkage in the direction of the network, and less than 0.5% in the direction transverse to the network. Depending on the application, it may be desirable to have a certain amount of shrinkage in the film to help control the flow of underlying melt-seal material. The films may contain additives to improve or impart various properties such as paint adhesion and thermal stability. Useful materials for these purposes include siliceous fillers such as silica, talc, zeolites, kaolinite, mica, alumina-silica gels, glass, and the like, carbonaceous materials, inorganic metal oxides, sulphides, sulfates and carbonates. Examples include carbon black, iron oxide, titanium oxide, zirconia, zinc sulphide, barium sulfate, calcium carbonate, and magnesium carbonate. Preferred fillers are silicas and clays, and the preferred siliceous fillers are precipitated silica, silica gel and fumed silica. Fillers may be used in amounts of about 5% to 90% by weight, based on the total weight of the film. In a preferred embodiment, the film is a microporous ultra-high molecular weight microporous polyolefin film, having 50 to 90% by weight of the total weight of the film of a siliceous filler and a network of pores that are interconnected to all throughout the film, with the pores constituting 35 to 80 percent by volume of the film. Useful commercially available films include microporous films sold by PPG Industries under the trade name Teslin®, and polyester films sold by ICI Americas under the trade name Melinex *. Suitable microporous films are described in U.S. Patent Nos. 4,861,644 (Young et al.) And 4,439,256 (Shipman). The dimensionally stable film can be used alone or in combination. For example, a suitable construction could include a 76.2 μ (0.003 inch) thick polyester film as the dimensionally stable film, and having a 12.7 μ (0.0005 inch) thick film of the thermosetting epoxy polyester material, laminated to the polyester film. A film having good dimensional stability at a higher temperature such as polyester can also be laminated to a film having less dimensional stability at the same temperature. An example of such a construction could be an ethylene-vinyl alcohol film of . 4 μ (0.001 inches) of thickness laminated on the 76.2 μ polyethylene terephthalate film (0.003 inches) thick. Films in combination can be formed by conventional means such as adhesive lamination of the films in conjunction with, for example, a hot melt adhesive or a lamination adhesive, coextruding the films, and extrusion coating of the films on the film plus stable and optionally curing the coating. The films may be heat stabilized by conventional means to improve the thermal stability of the films. Typically, such a process includes heating the film without tension to a temperature above the maximum use temperature. The stable dimensional film can be treated to improve the adhesion of the film to either or both of the melt-sealing layer and a paint or primer. Such treatments may include corona treatment, flame treatment, chemical preparation, chemical grafting, and the like. The treatments are especially useful for polyolefin films. In a preferred embodiment, the dimensionally stable film is coupled to a second film which can provide a surface that will readily accept standard paints and primers, such as those used in the automotive industry. Examples of such films include films made from ethylene vinyl alcohol and the above-described epoxy polyester. Two or more layers flowing in molten form having different flow properties in molten form can be laminated together to form a molten flowing sheet material. For example, the top layer can be formulated to have greater flow properties than the inner layer while the bottom layer is formulated to have greater strength for better handling properties, so that with heating, the top layer will flow and encapsulate the inner layer. In another embodiment, a layer of pressure sensitive adhesives (PSA) can be coupled to the flowing layer in molten form, so that the molten flowing sheet can be placed on a surface before the molten flowing layer is heated The molten flowing layer may also flow slightly to provide rounded edges on the molten flowing sheet, without flowing around the PSA, or may flow sufficiently to encapsulate the PSA so that none of the PSA edges are exposed.

Useful PSAs include PSAs of block copolymers, such as styrene-isoprene-styrene block copolymers which can be hot-melt or solvent-coated; Acrylonitrile PSAs; Acrylate PSAs, such as acrylic or methacrylic ester copolymers of non-tertiary alcohols having from about 4 to 12 carbon atoms in the alcohol moiety, and optional copolymerizable reinforcing monomers, which are polymerized using known techniques including solvent polymerization, emulsion polymerization, and radiation polymerization; PSAs made of natural rubber, PSAs made of silicone and PSAs made of vinyl acetate. The PSAs can be attached to the sheet flowing in molten form, by any known techniques including coating the PSA directly on the sheet, and curing the PSA or drying the solvent, rolling the PSA transfer ribbon to the sheet, coextruding a PSA hot melt with the flowing layer in molten form, and the like. In a preferred embodiment, the PSA is an acrylate copolymer. Useful esters for the copolymer include N-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isooctyl acrylate, decyl acrylate, dodecyl acrylate, and mixtures thereof. The copolymerizable reinforcing monomer, if used, is a monomer which has a vitreous transition temperature of the homopolymer greater than the glass transition temperature of a homopolymer prepared from the acrylic or methacrylic ester. Useful reinforcing monomers include acrylic acid, isobornyl acrylate, N-vinyl-pyrrolidone, acrylonitrile, N = vinyl-caprolactane N-vinyl-piperidine, and N, N-dimethylacrylamide, and itaconic acid. When a reinforcing monomer is used, the acrylic or methacrylic ester will generally be present in an amount of about 50 to 100 parts by weight, and the reinforcing comonomer will be present in a corresponding amount of about 50 to 0 parts by weight. The pressure sensitive adhesives described above can be prepared by known processes by mixing an initiator such as azobisisobutyronitrile in an organic solvent such as ethyl acetate, adding the monomers in the desired proportions, and then heating at an elevated temperature such as at 80 ° C, until the polymerization is completed. The adhesives can also be prepared by ultraviolet light polymerization and E-beam polymerization by processes known in the art. Pressure sensitive adhesives are also commercially available from a number of suppliers as adhesive transfer tapes. Such tapes include the product numbers 465, 476 and 468 all commercially available from Minnesota Mining and Manufacturing Co. In another embodiment, the sheet material flowing in molten form may include a layer of a thermosettable PSA, which is sticky and pressure sensitive at room temperature, and which is cured to a thermoset adhesive after heating . This type of molten flowing sheet material has utility in joining two surfaces to the sheet which is bonded to a first surface on the side of the PSA thermoset at a lower temperature, for example, at about room temperature, and then joining a second surface on the side flowing in molten form, at a higher temperature, for example, the melting temperature of the molten flow layer.

When the substrates are heated to the higher temperature, the PSA is also cured to form a thermoset adhesive having very high bond strengths. In this application, the molten flowing layer can be selected for minimum flow at the higher temperatures, so that the molten flowing material does not flow out of the joint. Preferred flowing layers melted for this embodiment include the aforementioned polyesters and functionalized olefinic polymers. Suitable thermosettable PSAs include a thermosetting component and a pressure sensitive adhesive component. The thermosetting component will generally be present in an amount of about 25 to 150 parts by weight based on 100 parts by weight of the PSA component. Coatable compositions for thermosettable PSA can be formed by various methods including the co-mixing of a solvent-based PSA, a thermosetting resin, and thermosetting curatives; the dissolution of a pressure-sensitive elastomer, such as a nitrile-butadiene rubber, in a solvent, and mixing with thermosetting resins and curing agents; and mixing the monomers or prepolymers useful for the preparation of a PSA, such as the monomers for the preparation of the aforementioned acrylate copolymers, with thermosetting resins and curing agents, and photopolymerizing the mixtures. Useful materials for the PSA component include those described above for a PSA. Preferred materials include acrylonitriles and acrylates, especially preferred are acrylates. The thermosetting components are thermosetting resins such as epoxy resins, urethane resins, and phenolic resins. Preferred thermosetting resins are epoxies and urethanes, and epoxides are most preferred. Useful epoxy resins are described above. The epoxy resin can be solid, liquid or a mixture thereof, as long as the epoxide can be mixed with the PSA component. Preferred epoxides include phenolic epoxy resins, epoxy bisphenol resins, hydrogenated epoxy resins, epoxy bisphenol resins, aliphatic epoxy resins, halogenated bisphenol epoxy resins, novolac epoxies, and mixtures thereof, and the most preferred epoxides include bisphenol diglycidyl A. In a preferred embodiment, the thermosettable PSA is the reaction product of a photopolymerized polymer of a composition having (i) a prepolymer syrup (eg, partially polymerized to a viscous syrup typically between about 100 and 10,000 centipoise). ) or a monomeric syrup of an ester of acrylic or methacrylic acid C as described above; (ii) optionally, a reinforcing comonomer as described above; (iii) an epoxy resin; (iv) a photoinitiator; (v) a heat activatable hardener for the epoxide. The adhesives can be prepared according to the procedures found in US Pat. No. 5,086,088. Useful photoinitiators for polymerizing the prepolymer or monomeric syrup can be any conventional free radical initiator C activable by, for example, ultraviolet light. An example of a suitable photoinitiator is 2,2-dimethoxy-2-phenyl-acetophenone (Irgacure®651 available from Ciba-Geigy Corporation). The photoinitiator is used in an amount sufficient to polymerize the monomers, typically from about 0.01 to 5 parts by weight per 100 parts of the prepolymer or monomeric syrup. The heat activatable curing agent is added to the composition to effect the curing of the epoxy resin when heated. The hardener may be of any type but preferably, it is an amine type hardener such as dicyandiamide and polyamine salts. Suitable commercial curing agents are available under the brand Omicure * from Omicron Chemical, and under the Ajicure® brand of Ajinomoto Chemical. The curing agent is used in an amount sufficient to cure the epoxy resin, typically, in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight per 100 parts of the epoxy resin. It is useful to also add an accelerator to the adhesive composition, because the heat to which the composition is exposed may be insufficient to fully activate the curing agents to cure the epoxy resin. The accelerator allows the adhesive to cure at a lower temperature and / or for shorter periods of exposure to heat. Imidazole and urea derivatives are particularly preferred in the practice of the present invention, and useful compounds include 2,4-diamino-6- (2'-methyl-imidazole) -ethyl-s-triazine isocyanurate, 2- phenyl-4-benzyl-5-hydroxymethylimidazole, hexakis phthalate (imidazole) nickel, and toluene-bis-dimethylurea. The accelerator can be used in an amount of up to 20 parts by weight per 100 parts by weight of the epoxy resin. In making the melt flowing sheet with a thermosettable PSA, the aforementioned solvent-based compositions are coated on a flexible network, preferably a liner or release coating coated with silicone, at the desired adhesive thickness and the solvent is removed by heating the adhesive to a temperature below the hardening temperature. The adhesive is then laminated to the sheet that flows in molten form, for later use. Alternatively, the compositions can be coated directly onto the melt flowing sheet, dried at temperatures below the heat fusion activation temperature. In an alternative embodiment, a photopolymerized syrup composition having the thermosetting PSA ingredients described above, is prepared by coating the syrup composition on a silicone release coating and photopolymerizing in an inert atmosphere, for example, a substantially free atmosphere. of oxygen, for example, a nitrogen atmosphere, and irradiating the composition with ultraviolet light. A sufficiently inert atmosphere can be achieved by covering the coating with a second polymeric film, which is substantially transparent to UV radiation, and irradiating through the film. The adhesive is then laminated to the melt flowing layer. Alternatively, the sheet of the flowing layer in molten form may be used in place of the upper or lower release liner. In addition, a non-woven or reinforcement mesh may be inserted between the layers, or embedded within the thermoset PSA layer to provide additional strength for handling purposes. The aforementioned molten flowing sheet having a thermosetting PSA is particularly useful for joining washers in automobile assembly. The washer is prepared by laminating the washer to a piece of thermosetting PSA that has been cut, for example, die cut or punch-pressed, to the size and shape of the washer. The cut thermosetting PSA is then laminated to the washer manually or by robotic machinery, with the side flowing in molten form exposed and available for attachment at higher temperatures. Alternatively, the thermosettable PSA is bonded to a sheet of metal suitable for making washers. The layer flowing in molten form of the sheet is free of tack at room temperature. The washers of the desired dimension are then stamped from the metal sheet. In use, the washer is used to tighten a bolt to a door hinge, as the door is aligned and attached to the chassis or car frame. The car is then painted and put through oven curing cycles to dry and cure the paint. The flow side in molten form of the sheet, it also melts sufficiently in the furnace to aggressively join the metal surface of the chassis by frame. The doors are then removed to install the interior parts, and the doors can be retracted in the aligned position as indicated by the position of the washers. The washer joining method allows for the automatic assortment of the washers in the assembly, as well as the removal of coatings and adhesive contamination problems associated with the previously known methods of the joint washers. In the washer attachment application the flowing sheet in molten form is preferably about 10 to 250 micrometers thick, more preferably 25 to 100 micrometers. Thicknesses greater than about 250 microns can result in weakening of the molten flowing material, from the washer, during the heat setting operation, which can affect the strength of the bond between the washer and the car frame. The thermosetting, pressure sensitive adhesive layer should be in the range of about 10 to 300 microns, and preferably, about 30 to 200 microns.

TEST PROCEDURES RESISTANCE OF THE CUT BY TRANSLAPE Two panels of 2.5 cm by 5 cm of PPG ED-11 (steel prepared by electrodeposition available from Advance Coating Technologies, Inc., also referred to herein as ED-11 panels) were joined with a 2.54 cm x 1.27 cm overlap area using a strip of flowing tape in molten form, which measured 2. 54 cm x 1.27 cm. The sample is heated to join the two panels together at the temperatures indicated in the specific examples, and then cooled to room temperature by at least 16 hours. The panels are then tested on an Instron® tensile test machine using a crosshead speed of 5 cm per minute. The force to the failure of the adhesive is recorded in Mega Pascals (MPa).

CUTTING EFFORT OF ADHESIVE FOR THE UNION OF THE WASHER The shear stress of the adhesive was measured according to JISK6850. Two 1.6 mm thick steel panels were used as the substrates. The adhesive was placed between the panels and then cured at a temperature of 140 ° C with a pressure of 500 g / cm2 for 60 minutes. The panels were then cooled to room temperature before the test. Using a tension tester, the constant stress of the adhesive was measured at a jaw separation speed of 50 mm / min.

Preferred adhesives have a shear stress greater than 50 kgf / cm2.

PUNCHING ABILITY A pressure operated punch press was used to punch the bonding materials in the form of a circle corresponding to the hole in a washer with a pressure of 30 kgf / cm2. The number of samples per bond material was five. The samples were evaluated under the following criteria.

Good: no failure or defect in the punching. The pressure-sensitive thermoset adhesive does not leak out of the hot melt film. The section in cross section looks good.

Relatively hard for punching: one or two samples were punctured imperfectly. The thermosetting adhesive slightly leaks out of the hot melt film.

LEAK FROM AN ADHESIVE AGENT The samples used in the measurement of the shear stress of the adhesive were used to visually verify the leakage of a pressure-sensitive thermosetting adhesive or the hot melt film from the steel panels. The criteria are presented below: No Leakage: Perfect Light Leakage Amount: Good Large Leakage Quantity: Poor The specific embodiments of the invention are illustrated by the following non-limiting examples. The parts refer to parts by weight, unless indicated otherwise.

EXAMPLES 1-2 For Example 1 (EJ-1), a flowing sheet was prepared in molten form, prepared by heating 100 parts of a semicrystalline polyester resin, hydroxyl functional group (Dynapol8> 1402 available from Hüls America) approximately 110 ° C to form a molten mixture. The molten mixture was coated on a knife bar coater (heated to 127 ° C) on a silicone coated paper to form a 1.0 mm thick sheet. The sheet was cooled to room temperature and became opaque after about 2 hours indicating that crystallization had occurred.

For Example 2 (EJ-2), a molten flowing sheet was prepared by mixing 10 parts of a diglycidyl ether of bisphenol A (EPON®828, available from Shell Chemical Company) with 89 parts of DYNAPOL®S1402 and 1 part of triphenyl sulfonium hexafluoroantimonate (described in U.S. Patent No. 4,321,951, column 5, line 48, to column 7, line 48), and mixed at about 110 ° C for about one hour. The resulting mixture was coated on a knife bar coater (heated to 127 ° C) on a silicone-coated paper to form a 1.0 mm thick sheet. The leaf was cooled to room temperature.

PROOF OF EXAMPLES 1 and 2 The sample tapes of Examples 1 and 2 measuring approximately 2.5 cm by 7.6 cm were placed through a 2.5 cm wide strip of anodized aluminum placed through a larger anodized aluminum panel (hereinafter referred to in FIG. present as a stepped panel), and heated in an oven at 177 ° C for 30 minutes. Both ribbons flowed out and provided smooth aesthetically pleasing surfaces with rounded corners and smooth transitions between the aluminum strip and the panel. The tapes also flowed beyond the original dimensions of the strips on the panels, and they adhered tenaciously to the panels. Each sample was then cut into strips 1.9 cm wide and approximately 25.4 cm long and placed in U-channels that had an internal width of 1.9 cm. Each U-channel was formed by bending two pieces of cold-rolled steel at 90 ° angles and welding the pieces together, so that a stepped joint was formed in the U. U-shaped channels, with the coupled strips were tilted at an angle of about 15 ° and heated in an oven at 177 ° C for 30 minutes, and cooled to room temperature. Both strips had flowed outward to effectively seal the joint and impart a smooth surface in the channel, without appearance of the stepped or gradual joint on the surface. The lower edge of both strips was marked on the U-shaped channel and both U-shaped channels were then placed in an oven at 120 ° C at an angle of 15 ° for 30 minutes, and then cooled. The flow from the subsequent heating was approximately 3.2 mm in the EJ-1 and approximately 25.4 mm in the EJ-2. An additional sample of each of the EJ-1 and EJ-2 was tested on the staggered panels as described above, and heated for 30 minutes at 177 ° C. The four samples (the two original samples exposed to previous heating cycles and the two new samples without exposure to the subsequent heating cycles) were painted with a water-based, white basecoat (H B90934 available from PPG Industries) and heated by 5 minutes at 121 ° C. A clear two part coating (CNCT2AH part A and CNCT2BE part B, both available from PPG Industries), was mixed according to the manufacturer's instructions and spray-painted on all four panels. The panels were then heated for 30 minutes at 140 ° C and cooled. The finish of the paint on the strips that flow in molten form, was identical in luster or brightness, color and image distinction (which is an indication of its mirror-like qualities) that the metal surface surrounds. The transition of the paint between the strip flowing in molten form and the metal surface is smooth and showed no evidence of a dividing line or separation of the edge of the paint. Samples that had been heated once flowed melted from the tapes before painting, were then placed in an oven at 120 ° C for 30 minutes. After cooling, no additional flow was observed on any panel and the surface remained smooth and aesthetically pleasing. The panel with the molten strip of the EJ-2 showed slight wrinkling on the surface at oven temperatures, but the wrinkles disappeared with cooling at room temperature. The following test examples illustrate the preferred embodiments of the invention, wherein sealed, aesthetically pleasing and paintable surfaces are imparted to a metallic surface.

EXAMPLE 3 The molten flowing layer of the EJ-1 was placed on a strip measuring 2.5 cm by 7.6 cm, placed on an ED-11 panel, and heated in an oven at 177 ° C for 30 minutes. The panel was then cooled, painted with the white basecoat and the clearcoat paints described above, and placed in an oven at 121 ° C for 3Q minutes to cure the paint. The melt flowing ribbon produced a protrusion that had rounded edges on the panel. Subsequent heating of the panel placed horizontally in an oven at 177 ° C for 30 minutes, did not affect the surface of the paint with any distortion to the protrusion. The panel was then placed in an oven at 177 ° C for 30 minutes at an angle of 75 ° from the horizontal. As the panel became heated, a bulge formed in a tear shape with the surface of the paint remaining intact. The panel was cooled to room temperature in the position at an angle of 75 ° and the protrusion returned to its original shape. The same panel was heated to an angle of 75 ° except that a small hole was punched through the paint layer in the molten flowing layer. After heating, the underlying molten flowing layer was still thermoplastic and exuded out of the small orifice. The following example illustrates the formation of a reaction interface between the paint and the molten flowing sheet material.

EXAMPLE 4 A strip of molten flowing sheet of EJ-1, which measured approximately 2.5 cm by 7.6 cm, was placed on a polyester film coated with silicone release and placed in an oven at 177 ° C until the tape became clear, indicating that it had become amorphous. The strip was removed from the oven and cooled to room temperature (between 21 ° C and 23 ° C). The strip still clear, had enough tack to adhere to an ED-11 at room temperature. The panel was then heated to adhere the strip to the panel at 120 ° C for 10 minutes, and then reheated to 177 ° C for 30 minutes. The sample was then painted and cured in an oven at 140 ° C for 30 minutes. This example illustrates how a mode of the invention can be temporarily placed on a substrate, before permanently binding to the substrate.

EXAMPLE 5 The melted flowing sheet material of the EJ-1 was laminated to an acrylate PSA transfer tape (Adhesive Transfer Tape 467 available from Minnesota Mining &Manufacturing Co.). The strips measuring 2.5 cm by 7.6 cm were laminated to an anodized aluminum panel, and 2.54 cm by 1.27 cm strips were laminated to the ED-11 overlap cut panels described above. The samples were placed in an oven for 15 minutes at 177 ° C and then cooled to room temperature until they were opaque (approximately 90 minutes). The sample on the anodized aluminum panel adhered perfectly, and the molten flowing sheet had encapsulated the PSA. Samples cut in flap were tested and had a shear stress in overlap, average, of 17.84 kg / cm2 (253.8 pounds per square inch). It was observed that the faults were cohesive between the PSA and the molten flowing sheet. The above example illustrates the utility of a PSA layer on the molten flowing sheet to keep the sheet in place until it is heated to seal a surface.

EXAMPLE 6-10 Two polyesters with hydroxyl functional group having different amounts of crystallinity were mixed and coated to form sheets as described in EJ-1. The time required for the sheets to become opaque was measured as an indication of the rate of crystallization. The polyester materials used were Dynapol®1402, a highly crystalline polyester resin and Dynapol®1359, a polyester resin with higher crystallinity. The amounts of each resin are shown in Table 1. The details shown in Table 1 indicate that the rate of crystallization can be varied.

EXAMPLES 11-18 AND C1-C3 Various thermoplastic materials were evaluated for the flow and adhesion of the paint. The materials were provided in sheets of 1 mm to 3 mm in thickness. Example 11 was prepared as in EJ-1, except that a sheet of 1 mm thickness was prepared, and example 12 was prepared as in EJ-2, except that with a thickness of 1 mm. The remaining sheets were prepared by placing spheres of the materials between the lining or polyester coatings coated with release liner and heating with a plate until the materials were fused into sheets between approximately 0.08 mm and 0.15 mm in thickness. Multiple sheets were folded together to form thicker sheets measuring between about 1 and 3 m.

The samples were placed on staggered panels (described above) at 177 ° C for 20 minutes, and the flow properties were observed. The samples were then painted with a white base coat, which possessed water (HWB90934 available from PPG Industries) and heated for 5 minutes at 140 ° C. A clear two part coating (CNCT2AH part A and CNCT2BE part B both available from PPG Industries) was mixed according to the manufacturer's instructions and spray-painted onto the panels. The panels were then heated for 30 minutes at 140 ° C and cooled overnight. The panels were then reheated to 140 ° C for 20 minutes. The materials were tested as follows: (1) for the flow after heating, but before painting (OK indicates that the material flowed but remained viscous; L indicates that the material was liquefied); (2) quality of paint after painting, curing of the paint and overheating (OK indicates very good surface appearance; FAIL indicates that the paint cracked or was not cured); (3) after reheating (OK indicates no change in appearance; EDGE indicates that the paint cracked around the perimeter of the sheet and FAIL indicates that the paint cracked and the polymer flowed out of the cracks); and (4) for the adhesion of transverse paint reported as a percentage of the paint still adhering to the melt flowing sheet, the test by ASTM D3359-90 to obtain (100% is desired, FAIL indicates that the sample failed before the test could be done). The test results are shown in Table 2.

A - TS-1502 available from Sherex Co. B - BUTVAR®B79 polyvinyl butyral from Monsanto Co. C - Surlyn ^ lGOd ethylene-acrylic acid film from DuPont Co. D - Primacors3440 ethylene-acrylic acid from Dow Chemical Co. E - Elvax®260 ethylene vinyl acetate from DuPont Co. F - SCX 8008 polyolacrylic from J.C. Johnson Co. G - Carbowax®8000 by Union Carbide H - Carbowax * 20M by Union Carbide I - TMP (trimethylolpropane) from Aldrich Chemical * Wrinkled paint surface when hot; surface smoothed with cooling ** The paint film was fragile EXAMPLES 19-21 Example 19 is a melt flowing sheet, made as in EJ-1, except with a thickness of about 2 mm. Example 20 was prepared using two sheets prepared as in EJ-1, at a thickness of 1.27 mm with a non-woven nylon between the two sheets. The non-woven fabric was 10.29 g / m2 (0.3 oz / square yard) (CEREX® available from Fiberweb N.A.) and laminated to the first sheet between two silicone-coated polyester release liners or liners, with a hot iron. The second sheet was then laminated in a similar manner. The sheets became transparent during the rolling process. Example 21 was treated as in Example 20, except that a non-woven polyester 17.16 g / m2 (0.5 oz / square yard) Reemay 2250 available from Reemay) was used. Examples 19-21 were tested by cutting strips of 2.54 cm by 20.3 cm and placed longitudinally on a curved metal surface that was formed by bending a metal panel prepared with ED-11, such that it swept at an angle starting at approximately 30 ° from the horizontal. The flexed panel was placed in an oven at 177 ° C for 10 minutes. After cooling, it was observed that Example 19 had significant flow down the sides of the panel. Example 20 had a slight amount of flow, but shrinkage of about 8% due to nylon shrinkage. Example 21 also had a slight amount of flow but no shrinkage. The following examples illustrate how a non-woven mesh can be used to control the flow of the molten flowing sheet.

EXAMPLES 22 AND 23 Leaves were prepared as in EJ-2 at a thickness of 0.076 mm. The sheet for Example 22 was exposed to UV radiation (low intensity black light) for 5 minutes. The leaves for each example were then cut and placed to make 0.72 mm thick sheets. The leaves were then cut into 2.54 cm by 7.62 cm strips placed on two overlapping metal panels, and then heated to 177 ° C for 30 minutes. Figures 5a and 5b describe the panels and a sheet before (Figure 5a) and after the heating (Figure 5b). The panels were 'cooled and both examples showed sufficient flow to seal the joint. Example 23, the sample that was not irradiated, had a smoother profile over the staggering in the overlapping panels, and the staggering in the panels was more pronounced in Example 22. The panels were coated with a black BASF overlay Cured, overcoated with a clear two-part coating, and cured. Both samples were painted well and adhesion to the transverse cleft was 100%.

The above examples illustrate how the irradiation of the sheet material can change the shaping capacity of the surface.

EXAMPLE 24 A molten flowing, crosslinkable sheet was prepared as in EJ-2, except that the composition for a preparation by mixing 10 parts of a cycloaliphatic epoxide (ERL-4221 available from Union Carbide) with 89 parts of a saturated linear copolyester weakly crystalline (DYNAPOL® S1402) and a part of triphenyl-sulfonium haxafluoroanti onate and coating to a thickness of 2 mm. A second molten flowing sheet, prepared as in EJ-1, was prepared, except that the thickness was 2 mm. The two sheets were placed on top of each other and between the polyester liners coated with silicone release, and heated at 177 ° C for 10 minutes to form a 4 mm thick sheet. A strip to a width of about 2.54 cm was cut and placed in a roof channel prototype having a width of 1.25 cm and a depth of approximately 1.9 cm, with the sheet crosslinkable on top. The prototype with the strip was placed in an oven at 177 ° C for 20 minutes. After cooling, the strip had maintained a concave surface, aesthetically pleasing, along the length of the prototype. The lower layer had melted and flowed into the joint in the prototype and the sides of the belt had been tenaciously joined to the sides of the channel to effectively seal the channel. Some trapped air bubbles were observed and these may have been related to the thickness of the tape.

EXAMPLE 25 A cross-linked molten flow sheet, 2 mm thick, of example 24 was exposed to UV black light for 20 seconds, to photolyze the surface with a total energy of 160 mj / cm2 (milijoules per square centimeter) using a Uvirad radiometer (Model No. VR365CH3) from E.I.T (Electronics Instrumentation &Technology, Inc.

Sterling, VA.). A strip was cut as in the example 24, was folded longitudinally with the photolized side inward, and then placed in a roof channel, prototype, as described in example 24, with the photoslide side facing up. The prototype was then heated like this by 177 ° C for 20 minutes. The thinner strip provided a smoother transition line between the strip and the sides, and the prototype channel for roof, while the provision while providing a tenacious bond to the sides of the prototype. Some air trapped between the strip and the prototype was observed, but the bubbles did not affect the aesthetically pleasing surface characteristics of the strip.

EXAMPLE 26-34 The molten flowing sheets were prepared as described in EJ-2, except that the compositions and materials were changed as shown in Table 3. Examples 26-31 were 2 mm thick and Examples 32-34 They were 1 mm thick. All the Examples showed good flow properties and adhesion to the paint was 100% for all samples.

PET - Dynapol®S1402 Epoxy 1 - diglycidyl ether oligomer of bisphenol A (Epon®1001, available from Shell Chemical Co.) Epoxy 2 - Epon®1002 Epoxy 3-diglycidyl ether of bisphenol A (Epon®828, available from Shell Chemical Co.) Catalyst 1 - triphenyl sulfonium hexafluoroantimonate Catalyst 2 - described in US Patent No. 5,089,536 (eta-xylenes (mixed isomers)) (eta 5 -cyclopentadienyl) iron (1+) -hexafluoroantimoniates.

EXAMPLE 35 A molten flowing sheet of 0.254 mm thick was prepared as in Example 1. The second layer was prepared as follows: A 50/50 mixture of butyl acrylate and N-vinyl caprolactam was mixed to form a solution. A molten flowing composition (57.7% acrylate and 42.3% epoxy) was prepared by mixing 75 parts of butyl acrylate, 75 parts of the butyl acrylate / N-vinyl-caprolactam solution, 50 parts of a copolymer of butyl methacrylate / methyl methacrylate (Acryloid * B-60, available from Rohm and Hass, Co.) and 110 parts of a diglycidyl ether oligomer of bisphenol-A (Epon®1001) in a container on a roller mill until the epoxide and copolymer were in solution. To the solutions were added 0.5 parts of 2,2-dimethoxy-2-phenyl-acetophenone (Irgacure®651, available from Ciba-Geigy), 0.15 parts of antioxidant (Irganox®1010, available from Ciba-Geigy), 1.0 parts of carbon tetrabromide, 3.86 parts of dicyandiamide (DYHARD®100, available from SKW Chemical), 1.38 parts of hexakis phthalate (imidizole) nickel, 2 parts of glass spheres (Glass Spheres C15-250 available from Minnesota Mining and Manufacturing Co .) and 7 parts silica (Cab-o-sil8M-5, available from Cabot Corp). The composition was mixed with a high shear mixer and then mixed on a roller mill for approximately 24 hours. The composition was then degassed and covered by a blade to a thickness of approximately 2.0 mm between 0.05 mm thick polyester linings which had been coated with silicone. The coated composition was then exposed to ultraviolet light sources having 90% emissions between 300 and 400 nm with a maximum at 351 nm. The luminous intensity above the network was 1.88 m / cm2 (milliwatts / square centimeter) and 1.29 mW / cm2. The total energy used was 653.8 millijoules. The resulting melt flowing tape was substantially free of tack at room temperature (approximately 21 ° C).

One of the polyester liners or liners was removed from each of the sheets, and the first and second sheets flowing molten were laminated together with an iron lying at approximately 65.6 ° C to form a melt flowing composite sheet. A strip of the composite sheet was placed on a metal panel having a slight depression on the surface, with the first layer of the sheet on the metal surface, heated at 177 ° C for 30 minutes, and then cooled to room temperature. Example 38 showed no surface defects from the depression. As a comparison, a sheet having only the second layer described above was tested in the same way. The surface of the second leaf had a visible crater in the leaf, superimposed on the depression.

EXAMPLE 36 A molten flowing sheet was prepared by extruding a 0.076 mm thick layer of an ethylene-acrylic acid having an acrylic acid content of 9% (PRIMACOR 3440, available from Dow Chemical Co.) on a T-die. plane adjusted to approximately 250 ° C.

A 50/50 mixture of butyl acrylate and N-vinyl caprolactam at approximately 50 ° C was heated to form a solution. A molten flowing composition (50% acrylate and 50% epoxy) was prepared by mixing 120 parts of butyl acrylate, 80 parts of the butyl acrylate / N-vinyl caprolactam solution, 50 parts of a copolymer of butyl methacrylate / methyl methacrylate (Acryloid®B-60, available from Rohm and Hass, Co.) and 200 parts of a diglycidyl ether oligomer of bisphenol-A (Epon®1001), available from Shell Chemical Co. ) in a container on a roller mill until epoxide and copolymer were in solution. To the solution were added 0.2 parts of 2,2-dimethoxy-2-phenyl-acetophenone (KB-1, available from Sartomer), 0.2 part of antioxidant (Irganox®1010, available from Ciba-Geigy), 0.8 part of tetrabromide of carbon, 7.0 parts of dicyandiamide (DYHARD®100, available from SK Chemical), 3.0 parts of hexakis phthalate (imidizol) nickel, 4 parts of glass spheres (Glass Spheres C15-250, available from Minnesota Mining and Manufacturing Co. ) and 14 parts of silica (Cab-o-sil®M-5 available from Cabot Corp) to form a mixture. The mixture was mixed, coated and cured according to the procedure of Example 38, to form a melt flowing ribbon.

An adhesive composite was prepared by laminating the hot melt adhesive layer to the melt flowing thermosetting tape, with a plate as described above.

EXAMPLE 37 A pressure-sensitive adhesive composition is prepared by mixing 76 parts of butyl, 24 parts of N-vinyl pyrrolidone, and 0.04 parts of Irgacure®651 photoinitiator (2, 2-methoxy-2-phenyl-acetophenone available from Ciba -Geigy) and light-curing with a source of ultraviolet (UV) light under a constant nitrogen purge to form a syrup having a viscosity of approximately 2000 cps. With constant mixing, the following materials were added to 100 parts of the acrylate syrup and mixed for about 2 hours. 0.1 part of Irgacure®651, 40 parts of diglycidyl ether oligomer of bisphenol-A (Epikote®1001 available from Shell Chemical Co.), 50 parts of diglycidyl ether of bisphenol-A (ELA 128 available from Shell Chemical Co.), 6.0 parts of dicyandiamide (CG1200 from Omicron Chemical Co.) 3.5 parts of isocyanurate adduct of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-S-triazine (2MA-OK available from Shikoku Chemical Co., Ltd.), 5.0 parts of fumed silica (Aerosil®972 available from DeGussa), and 0.03 parts of hexanediol diacrylate. The mixture was then degassed, and coated by a blade to a thickness of 10.29 g / m '(0.3 ounces per square inch) over the top of a non-woven polyamide net (CEREX from Fiberweb NA) placed on the top of a Polyester release liner coated with transparent silicone that has a thickness of approximately 0.05 mm. A similar release liner was placed on top of the coated composite, and the coated mixture was light-cured with ultraviolet lamps at an average intensity of approximately 1.1 mW / cm2, above and below the grid, such that an energy of 500 mJ / cm2 was used. The lamps used had approximately 90% of the emission between 300 and 400 nm, with a maximum of 351 nm. The resulting thermosetting pressure-sensitive adhesive tape layer (TPSA) had a thickness of about 0.3 mm. A layer of hot melt adhesive (HMA) was prepared by extruding an ethylene-acrylic acid polymer having an acrylic acid content of 6.5% (PRIMACOR®3330, available from Dow Chemical, Ltd) at a temperature of about 250 ° C using a T-die. The thickness of the layer was 50 micrometers. An adhesive tape composite was prepared by removing one of the linings from the pressure sensitive adhesive tape, and laminating the hot melt adhesive layer thereto. The compound was tested for the shear stress of the adhesive, for the punching ability, and the leakage. The test results are shown in Table 4.

EXAMPLE 38 A thermosetting pressure-sensitive adhesive was prepared by dissolving 150 grams of an acrylonitrile rubber (Nippol 1001 available from Nippon Zeon Co., Ltd.) in 400 grams methyl ethyl ketone. The following materials were then added to the solution and mixed for 24 hours to obtain a homogeneous mixture: 100 grams of Epikote®828, 100 grams of Epikote®1001, 20 grams of dicyandiamide, 235 grams of Amicure PN (curable epoxide available from Ajinomoto Co., Inc.), and 20 grams of silica powder (Aerosil®A-200 available from Nippon Aerosil Co. Ltd). The mixture was then coated by knife on a polyester liner coated with silicone, and dried for 15 minutes at 70 ° C. The resulting thermosetting pressure sensitive adhesive layer had a thickness of 100 micrometers. An adhesive composition was prepared by laminating the thermosetting pressure sensitive adhesive layer to a 50 micron hot melt adhesive layer prepared as described in Example 37. The test results are shown in Table 4.

EXAMPLES 39-42 Adhesive compounds were prepared as described in Example 38 having varying thicknesses of each layer as shown in Table 4. The test results are also shown.

TABLE 4 EXAMPLES 43-46 The thermosetting pressure sensitive adhesives of Example 37 were laminated to several layers of hot melt adhesive as shown in Table 5. The thermosetting pressure sensitive adhesive layer was 100 micrometers thick. The hot melt adhesive layers were prepared by extruding the hot melt adhesive resins shown in Table 5. The test results are shown in Table 6.

TABLE 5 TABLE 6 EXAMPLE 47 A first radiation curable epoxy polyester composition was prepared by mixing 88.9 parts by weight of a semicrystalline polyester resin with hydroxyl functional group (Dynapol®S1359 available from Huís America) and 1 part of microcrystalline wax (Unilin®700 available of Petrolite Corp). A liquid mixture having 10 parts of epoxy resin (Epon®828), and 1 part of triphenyl-sulfonium haxafluorsantomonate was pumped into the extruder at about the midpoint of the barrel and mixed with the polyester resin mixture. A vacuum of less than 635 mm Hg (25 inches Hg) was applied in the extruder barrel in the same area in the extruder barrel, to remove air from the mixture. The temperatures of the extruder barrel were in the range of 65 ° C to 110 ° C with the feed gate temperature at about 25 ° C. The flat die was maintained at a temperature of 82 ° C. The extrudate was coated on an untreated polyester film of 73.9 μ (0.00291 inches) in thickness, and the coated film was wound onto a roll after cooling. The thickness of the extrudate was in the range of 12.7 to 17.8 μ (0.005 to 0.0007 inches). The coating on the polyester film was then exposed to an ultraviolet (UV) light processor (Model QC250244ANIR supplied by Aetek International, Planfield IL) with a medium pressure UV lamp having an energy yield of 0.201 J / cm2 at a linear speed of 9.14 m / min. (30 feet per minute). The resulting coating on the polyester film was thermoset and had excellent adhesion to the polyester film. The other surface of the polyester film was then coated with a second epoxy polyester composition prepared in the same manner as the first epoxy polyester composition, except that the dry composition was 77.9 parts of Dynapol® S1359, a part of microcrystalline wax (Unilin®700) and the liquid mixture contained 20 parts of epoxy resin (Epon®828), a part of polyol (Voranol®230-238 Polyol available from Dow Chemical Co.) and 0.1 part Cp (xylenes) Fe + SbF6" The second epoxy polyester composition was coated to a thickness of 1 mm (0.040 inches) on the polyester film to form a sheet material.

EXAMPLE 48 The second epoxy polyester composition of Example 47 was coated to a thickness of 1 mm (0.040 inches) on an ultra-high molecular weight, filled, 177.8 μ (0.007 inch) thick polyolefin film (Teslin®sp 700 available from PPG Industries Inc.) to form a sheet material. A 6.35 cm (2.5 in) wide by 25.4 cm (10 in) length strip of sheet material was applied to an anodized aluminum panel and heated at 177 ° C for 15 minutes. After cooling, the shrinkage of the web transversely was determined which was 0%, and the shrinkage longitudinally to the network was 1.5%.

EXAMPLE 49 A film layer was prepared by laminating a 67.3 μ (0.00265 inch) thick polyester film (Melinex 054 polyester film, 67.3 μ (2.65 mils), from ICI Films West Chester, PA) to a 0.025 mm thick ethylene-vinyl alcohol film having 44 mole percent ethylene (EVAL E-25) with a polyester / isocyanate laminating adhesive (Adcote 76T3A / lyst F, available from Morton) diluted to a 30% solids content using ethyl acetate. The adhesive was applied to the ethylene-vinyl alcohol film at a dry coating weight of about 32 grams per square meter using an engraved hole coater. The adhesive was dried at approximately 63 ° C to evaporate the solvent. The polyester film was then corona treated and hot rolled to the side coated with ethylene-vinyl alcohol film adhesive, using pressure rollers at about 93 ° C. The laminated polyester side of the film was then coated with a 1 mm (0.040 inch) thick layer of the second epoxy polyester composition as described in example 47.

It will be apparent to those skilled in the art that various modifions and variations in the method and article of the present invention may be made, without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifions and variations of this invention, with the proviso that they fall within the scope of the appended claims and their equivalents.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, property is claimed as contained in the following:

Claims (5)

1. A method for imparting topographic or protective features to a substrate, characterized in that the method comprises the steps of: (a) providing a material in the form of a sheet having a top surface and a bottom surface, comprising two or more layers, comprising an upper layer and a lower layer, the upper layer is a microporous polyolefin film of ultra-high molecular weight, and the lower film comprises a thermosetting composition flowing in a molten form, comprising one or more thermosetting polymers; (b) contacting the inner surface of the sheet material with the substrate, leaving the upper surface of the material in the form of an exposed sheet; (c) heating the sheet material at an elevated temperature; and (d) allowing the sheet material and the substrate to cool, wherein the sheet material remains adhered to the substrate.

2. A method according to claim 1, characterized in that one or more of the thermosetting polymers comprise a polyester and a thermosetting component.

3. A method according to claim 2, characterized in that the thermosetting component comprises an epoxy resin and, optionally, a curing agent for polymerizing the epoxy resin.

4. A method according to claim 1, characterized in that the polyolefin film is a polyethylene film.

5. A method for imparting topographic or protective features to a substrate, characterized in that the method comprises the steps of: (a) providing a material in the form of a sheet having a top surface and a bottom surface, comprising two or more layers, comprising an upper layer and a lower layer, the upper layer is a polyester film with an epoxy / polyester cured dressing layer, wherein the finishing layer forms the upper surface of the sheet material, and the lower layer comprises a molten flowing thermosetting composition, comprising one or more thermosetting polymers; (b) contacting the inner surface of the sheet material with the substrate, exposing the upper surface of the sheet material; (c) heating the sheet material at an elevated temperature; and (d) allowing the sheet material and the substrate to cool, wherein the sheet material remains adhered to the substrate.