Patent Application
20150240136
This disclosure relates to a structural adhesive film suitable, for example, for bonding a first metal part and second part, and in particular for hem flange bonding of a first metal part and a second part. More specifically, the present disclosure is directed to a structural adhesive film comprising a thermosettable composition which comprises an epoxy compound having a selected average epoxy equivalent weight, a thermoplastic resin having a selected softening point, and an epoxy curing agent. The present disclosure further relates to a thermoset structural adhesive film obtainable by thermosetting of the structural adhesive film of the disclosure, and to a two-part assembly comprising such a thermoset structural adhesive film.
The present disclosure also relates to a method for bonding a first metal part and second part, in particular for hem flange bonding of a first metal part and a second part, and doing so using such structural adhesive films.
Metal joints in vehicles may be formed through the use of an adhesive. For example, an adhesive may be used to bond a metal panel, for example a roof panel to the support structure or chassis of the vehicle. Further, an adhesive may be used in joining two metal panels of a vehicle closure panel. Vehicle closure panels typically comprise an assembly of an outer and an inner metal panel whereby a hem structure is formed by folding an edge of an outer panel over an edge of the inner panel. Typically, an adhesive is provided there between to bond the panels together. Further, a sealant typically needs to be applied at the joint of the metal panels to provide for sufficient corrosion resistance. For example, U.S. Pat. No. 6,000,118 (Biernat et al.) discloses the use of a flowable sealant bead between the facing surfaces of the two panels, and a thin film of uncured paint-like resin between a flange on the outer panel and the exposed surface of the inner panel. The paint film is cured to a solid impervious condition by a baking operation performed on the completed door panel. U.S. Pat. No. 6,368,008 (Biernat et al.) discloses the use of an adhesive for securing two metal panels together. The edge of the joint is further sealed by a metal coating. Patent application WO 2009/071269 (Morral et al.) discloses an expandable epoxy paste adhesive as a sealant for a hem flange. A further hemmed structure is disclosed in U.S. Pat. No. 6,528,176 (Katsuhiko et al.).
Further efforts have been undertaken to develop adhesive compositions whereby two metal panels, in particular an outer and an inner panel of a vehicle closure panel, could be joined with an adhesive without the need for a further material for sealing the joint. Thus, it became desirable to develop adhesive systems that provide adequate bonding while also sealing the joint and providing corrosion resistance. A partial solution has been described in e.g. WO 2007/014039 (Lamon et al.), which discloses a thermally expandable and curable epoxy-based precursor of an expanded thermoset film toughened foamed film comprising a mixture of solid and liquid epoxy resins, and claimed to provide both favorable energy absorbing properties and gap filling properties upon curing. Another partial solution has been described in WO 2011/141148 (Czaplickl et al.), which describes a heat activated structural adhesive that is solid and dry to the touch at ambient temperature, that can be activated to develop adhesive properties at an elevated temperature and which can be molded without curing.
Without contesting the technical advantages associated with the adhesive compositions and systems disclosed in the art, there is still a need for a high performance structural adhesive film that combines excellent physical properties such as form stability, flexibility, robustness and handling properties in uncured state; as well as excellent bonding and sealing performance after curing.
The structural adhesive film of the present disclosure is particularly suitable for automated handling and application, in particular by fast robotic equipments. More particularly, the structural adhesive film of the present disclosure enables efficient automation of the process of forming a metal joint between metal plates. Other advantages of the structural adhesive films, thermoset structural adhesive films, assemblies and methods of the disclosure will be apparent from the following description.
According to one aspect, the present disclosure relates to a structural adhesive film comprising a thermosettable composition, which comprises:
According to another aspect, the present disclosure relates to a method for bonding a first metal part and a second part, the method comprising:
According to still another aspect of the present disclosure, it is provided a two-part assembly, comprising:
In another aspect, the present disclosure is directed to a thermoset structural adhesive film obtainable by thermosetting of the thermosettable composition as defined above, wherein the thermosetting of the thermosettable composition is performed at a temperature comprised between 140° C. and 200° C.
According to still another aspect, the present disclosure is directed to the use of a structural adhesive film as described above for bonding a first metal part and a second part, preferably for hem flange bonding of a first metal part and second part.
According to one aspect, the present disclosure relates to a structural adhesive film comprising a thermosettable composition, which comprises:
The term “film” used throughout the present description relates to two-dimensional articles which are usually referred to as strips, foils, bands, sheets, sheeting or the like. The softening point of the thermoplastic resin is typically defined as its Tg value (Glass Transition Temperature), as measured e.g. by Differential Scanning calorimetry (DSC).
In the context of the present disclosure, it has been surprisingly discovered that uncured structural adhesive films provided with an elongation at break of at least 60%, when measured according to tensile test DIN EN ISO 527, are particularly suitable for automated handling and application (in particular by fast robotic equipments), in particular when used for bonding metal parts, more in particular for hem flange bonding of metal parts. Advantageously, the structural adhesive films according to the disclosure allows high-speed robotic application.
In a preferred aspect, the present disclosure relates to a structural adhesive film comprising a thermosettable composition, wherein the thermosettable composition comprises:
The structural adhesive film according to the present disclosure, comprises a thermosettable composition that comprises an epoxy compound having an average epoxy equivalent weight of less than 250 g/equivalent. Suitable epoxy compounds for use herein will be easily identified by those skilled in the art, in the light of the present description.
In a preferred aspect, the epoxy compound for use herein has an average epoxy equivalent weight of less than 230 g/equivalent, preferably less than 220 g/equivalent, more preferably less than 200 g/equivalent. Preferably, the epoxy compound for use herein has an average epoxy equivalent weight comprised between 100 and 200 g/equivalent, preferably between 150 and 200 g/equivalent, more preferably between 170 and 200 g/equivalent. Preferably still, the epoxy compound for use herein has a weight average molecular weight of not more than 700 g/mol, preferably not more than 500 g/mol, more preferably not more than 400 g/mol. Advantageously, the epoxy compound for use herein has a weight average molecular weight comprised between 200 and 400 g/mol, preferably between 300 and 400 g/mol, more preferably between 350 and 400 g/mol. The epoxy compound for use herein is preferably selected from the group of epoxy compounds having an average epoxy functionality, i.e. an average number of polymerizable epoxy groups per molecule, of at least 2 and, more preferably, from 2 to 4.
Any organic compound having at least one oxirane ring polymerizable by a ring opening reaction may be used as an epoxy compound in the thermosettable composition of the structural adhesive film according to the disclosure, provided they have an average epoxy equivalent weight of less than 250 g/equivalent. Such materials, broadly called epoxies, include monomeric epoxy compounds and polymeric epoxy compounds and can be aliphatic, cycloaliphatic, aromatic or heterocyclic. Useful materials generally have at least two polymerizable epoxy groups per molecule and, more preferably, from two to four polymerizable epoxy groups per molecule.
These epoxy compounds are generally liquid, or semi-liquid, at room temperature and are frequently also referred to as reactive epoxy thinners or reactive epoxy diluents. These compounds are preferably selected from the group of optionally substituted di- and polyglycidyl ethers of di- and polyphenols or aliphatic or cycloaliphatic hydroxyl compounds. Suitable epoxy compounds for use herein are commercially available from Momentive under tradename Epikote™ 828; from Dow Chemical Co. under tradename DER 331, DER 332 and DER 334; from Resolution Performance Products under tradename Epon® 828; from Polysciences, Inc. under tradename Epon® 825/826/830/834/863/824; from Hexion under tradename Bakelite® EPR 164; from Huntsman under tradename Araldite® GY 250/260; or from Leuna Harze under tradename EPILOX® A 1900.
Epoxy compounds which are useful in the structural adhesive film are preferably derived from bisphenol A, bisphenol E, bisphenol F, bisphenol S, aliphatic and aromatic amines, such as methylene dianiline and aminophenols, and halogen substituted bisphenol resins, novolacs, aliphatic epoxies, and combinations thereof and/or therebetween. More preferably, the organic epoxies are selected from the group comprising diglycidyl ethers of bisphenol A and bisphenol F and epoxy novolacs.
The amount of epoxy compound in the thermosettable composition of the structural adhesive film is typically comprised between 30 and 60 wt %, preferably between 40 and 60 wt %, more preferably between 50 and 60 wt %, based on total weight of the thermosettable composition.
The thermosettable composition of the structural adhesive film according to the disclosure further comprises a thermoplastic resin having a softening point comprised between 60° C. and 140° C. Suitable thermoplastic resins for use herein will be easily identified by those skilled in the art, in the light of the present description. Thermoplastic resins may also frequently be referred to as film forming agents.
In a preferred aspect, thermoplastic resins for use herein have a softening point comprised between 70° C. and 120° C., preferably between 80° C. and 100° C., more preferably between 85° C. and 95° C.
Suitable thermoplastic resins for use herein are preferably selected from the group consisting of polyether thermoplastic resins, polypropylene thermoplastic resins, polyvinyl chloride thermoplastic resins, polyester thermoplastic resins, polycaprolactone thermoplastic resins, polystyrene thermoplastic resins, polycarbonate thermoplastic resins, polyamide thermoplastic resins, and any combinations of mixtures thereof.
Suitable thermoplastic resins for use herein may be advantageously selected from the group of polyether thermoplastic resins, and preferably polyhydroxyether thermoplastic resins. In a preferred aspect, thermoplastic resins for use herein are selected from the group of polyhydroxyether thermoplastic resins, which are preferably selected from the group consisting of phenoxy resins, polyether diamine resins, polyvinylacetal resins, in particular polyvinyl butyral resins, and any combinations or mixtures thereof. Examples of suitable polyvinylacetal resins for use herein include Vinyl Chloride/Vinyl Acetate Copolymers, Carboxyl-Modified Vinyl Copolymers, and Hydroxyl-Modified Vinyl Copolymers, commercially available from Dow Chemicals. In a very preferred aspect of the disclosure, the thermoplastic resin for use herein is selected from the group of phenoxy resins. Suitable thermoplastic resins for use herein are commercially available from InChem Corporation under trade designation PKHP, PKHH, PKHA, PKHB, PKHC, PKFE, PKHJ, PKHM-30 or PKHM-301.
The amount of thermoplastic resin in the thermosettable composition of the structural adhesive film is typically comprised between 10 and 50 wt %, preferably between 15 and 30 wt %, more preferably between 20 and 30 wt %, based on total weight of the thermosettable composition.
The thermosettable composition of the structural adhesive film according to the disclosure, further comprises an epoxy curing agent. Any epoxy curing agent, commonly known in the art, may be used in the thermosettable composition of the structural adhesive film of the disclosure. Suitable epoxy curing agents for use herein are materials that react with the oxirane ring of the organic epoxide to cause substantial cross-linking of the epoxide. These materials contain at least one nucleophilic or electrophilic moiety (such as an active hydrogen atom) that causes the cross-linking reaction to occur. Epoxy curing agents are distinct from epoxide chain extension agents, which primarily become lodged between chains of the organic epoxide and cause little, if any cross-linking. Epoxy curing agents as used herein are also known in the art as epoxy hardeners, epoxide hardeners, catalysts, epoxy curatives, and curatives.
Sometimes, differentiation is made between epoxy curing agents and accelerators which are used to increase the rate of the epoxide curing reaction. Accelerators typically are multifunctional materials which can also be classified as epoxy curing agents. Therefore, in the present specification, no differentiation is made between curing agents and accelerators.
Epoxy curing agents for use herein include those which are conventionally used for curing epoxy resin compositions and forming crosslinked polymer networks. Suitable epoxy curing agents may also be referred to as latent curing agents, which are typically chosen so that they do not react with the epoxy resin until the appropriate processing conditions are applied. Such compounds also include aliphatic and aromatic tertiary amines such as dimethylaminopropylamine and pyridine, which may act as catalysts to generate substantial crosslinking. Further, boron complexes, in particular boron complexes with monoethanolamine, imidazoles such as 2-ethyl-methylimidazole, guanidines such as tetramethyl guanidine, dicyanodiamide (often referred to as DICY), substituted ureas such as toluene diisocyanate urea, and acid anhydrides such as the 4-methyltetrahydroxyphthalic acid anhydride, 3-methyltetrahydroxyphthalic acid anhydride and methylnorbornenephthalic acid anhydride, may be employed. Still other useful epoxy curing agents include polyamines, mercaptans and phenols. Other epoxy curing agents for use herein include encapsulated amines, Lewis acids salts, transition metal complexes and molecular sieves. Preferably, the epoxy curing agent is selected from the group consisting of amines, acid anhydrides, guanidines, dicyandiamide and mixtures thereof. More preferably, the epoxy curing agent contains dicyandiamide. Suitable epoxy curing agents for use herein are commercially available from Air Products under tradename Amicure® CG-1200.
The amount of epoxy curing agents in the thermosettable composition of the structural adhesive film is typically comprised between 2 and 15 wt %, preferably between 2 and 8 wt %, more preferably between 2.5 and 4 wt %, based on total weight of the thermosettable composition.
In a particular aspect, the thermosettable composition of the structural adhesive film may further comprise one or more toughening agents. Any toughening agent, commonly known in the art, may be used in the thermosettable composition of the structural adhesive film of the disclosure. The toughening agents are preferably selected from a group comprising core-shell toughening agents, CTBNs (carboxyl and/or nitrile terminated butadiene/nitrile rubbers) and high molecular weight amine terminated polytetramethylene oxide.
Core-shell toughening agents which are especially preferred, usually comprise different materials in the inner core region and the outer shell region, respectively. Preferably, the core may be harder than the shell but this is not required. The shell may comprise harder material and/or the shell may be layered in its construction. Most preferably, the inner hard core component is comprised of a single and/or a plurality of organic polymers and inorganic oxides from the first, second and/or third transition series of the periodic table such as silica, alumina, zirconia, and/or naturally occurring minerals such as feldspars, silicates, aluminates, zirconates, and/or other hardened materials such as carbides, nitrides, silicides, aluminides, and/or some combination thereof and therebetween. The outer soft shell component may be comprised of rubbers such as diene, olefin rubbers, natural rubber, polyisoprene, copolymers thereof, ethylene propylene monomer rubber, diene-acrylonitrile copolymers, copolymers of vinyl aromatic monomers, styrene-butadiene copolymers known as SBR rubbers, and terpolymers of dienes with acrylonitrile or unsaturated esters and styrene or vinyl toluene. The soft shell preferably includes modifications with functionalities such as carboxyl, hydroxyl, epoxy, cyanates, isocyanates, amino, and thiol which can react with the epoxy components of the precursor. Core-shell toughening agents which are useful in the thermosettable composition are commercially available, for example, from Rohm and Hass under the trade designation Paraloid™.
CTBN toughening agents react through their carboxyl and/or nitrile functional groups with the epoxide component of the precursor during curing thereby introducing their butadiene/nitrile rubber portion as a soft, shock-absorbing segment into the epoxy network forming a hard segment. CTBN toughening agents which are useful in the present disclosure are commercially available, for example, from Hanse Chemie AG, Hamburg, Germany, under the trade designation Albipox™,
A high molecular weight amine terminated polytetramethylene oxide useful in the thermosettable composition is commercially available, for example, from 3M Company, St. Paul/Minn., USA, under the trade designation “3M EPX™ Rubber”.
The amount of the one or more toughening agents present in the thermosettable composition is typically comprised between from 10 to 40 wt %, preferably between 10 and 30 wt %, more preferably between 10 and 20 wt %, based on total weight of the thermosettable composition.
In a particular aspect of the structural adhesive film according to the present disclosure, the weight ratio of the toughening agent and the thermoplastic resin is advantageously comprised between 1 and 4, preferably between 1 and 3, more preferably between 1.5 and 2.5, even more preferably between 1.8 and 2.2.
In a particular aspect, the thermosettable composition of the structural adhesive film may further comprise one or more blowing agents. Any blowing agent, commonly known in the art, may be used in the thermosettable composition of the structural adhesive film of the disclosure.
By including a blowing agent in the thermosettable composition of the structural adhesive film, the structural adhesive film becomes heat expandable and may be referred to as an expandable structural adhesive film. Accordingly, by heating, for example during the heating to cause thermosetting of the adhesive sheet, the structural adhesive film expands which helps sealing of any gap in the metal joint. As a result, corrosion resistance may be improved. The one or more blowing agents are preferably selected from the group of non-encapsulated and encapsulated blowing agents.
Non-encapsulated blowing agents, which are sometimes also referred to as chemical blowing agents, release a gaseous compound such as nitrogen, nitrogen oxide, hydrogen or carboxide dioxide during heating. Chemical blowing agents which are useful in the present disclosure include, for example, azobisisobutyronitriles, azodicarbonamides, carbazides, hydrazides, non-azo chemical blowing agents based on sodium borohydride or sodium bicarbonate/citric acid and dinitrosopentamethylenetetramine. The amount of the one or more chemical blowing agents is typically comprises between 0.2 and 2 wt %, preferably between 0.5 and 1.5 wt %, based on the total weight of the thermosettable composition.
Encapsulated blowing agents usually comprise liquified gases such as, for example, trichlorofluoromethane or hydrocarbons such as n-pentane, iso-pentane, neo-pentane, butane and/or iso-butane encapsulated in a polymeric thermoplastic shell. Upon heating the liquified gas expands and enlarges or blows up the thermoplastic shell like a “micro-balloon”. Typically, the amount one or more encapsulated blowing agents may be advantageously comprised between from 0.5 to 10 wt %, preferably from 1 to 5 wt %, more preferably from 1 to 2 wt %, based on the total weight of the thermosettable composition. Encapsulated blowing agents, which are useful in the thermosettable composition, are commercially available, for example, from Pierce & Stevens Chemical Corp under the trade designation Micropearl™, from Matsumoto under the trade name Microsphere™ or from Akzo Nobel under the trade name Expancel™.
In a particular aspect, the amount of one or more blowing agents is selected such as to provide the structural adhesive film with a free expansion rate upon curing of not more than 50%, preferably not more than 40%, more preferably not more than 30%, when subjecting the structural adhesive film to a curing temperature above the activation (onset) temperature of the curing reaction, and when measured as described in the Test Methods section. More in particular, the amount of one or more blowing agents is selected such as to provide the structural adhesive film with a free expansion rate upon curing of between 10 and 40%, preferably between 10 and 30%, more preferably between 15 and 25%.
The thermosettable composition may optionally comprise further components, additives and/or agents. Other optional ingredients that may advantageously be incorporated into thermosettable composition include wetting agents, such as those selected from the group consisting of titanates, silanes, zirconates, zircoaluminates, phosphoric ester(s) and mixtures thereof. The wetting agent improves the mixability and processability of the composition and can also enhance the composition's handling characteristics. Useful wetting agents are disclosed in U.S. Pat. No. 5,019,605. An especially useful wetting agent is commercially available as Coatex DO-UP6L from Coatex, Gene, France.
Other optional ingredients which may be used include additives, agents or performance modifiers such as e.g. flame retardants, impact modifiers, heat stabilizers, colorants, processing aids, lubricants, and reinforcing agents.
In a particular aspect, the thermosettable composition may comprise one or more fillers which may be used to regulate rheological properties of the precursor and adjust its viscosity to improve and adjust its processability for specific applications. Preferred fillers for use herein are selected from the group consisting of filler particles, microspheres, expendable microspheres, preferably pentane filled expendable microspheres or gaseous cavities, glassbeads, glass microspheres, hydrophobic silica type fillers, hydrophilic silica type fillers, fibers, electrically and/or thermally conducting particles, nano particles, and any combinations thereof. Preferred fillers for use herein are selected from the group of inorganic fillers, including silica. One preferred filler for use herein is hydrophobic fumed silica, which is commercially available as AerosilTM from Degussa or CAB-O-SIL™ from Cabot. Another preferred filler for use herein is expanded perlite, which is commercially available under the trade designation Eurocell® from Europerl, Germany. Typically, the amount of filler may be advantageously of not more than 10 wt %, based on the total weight of the thermosettable composition.
In another particular aspect, the thermosettable composition may comprise one or more incompressible particulate material, such as e.g. solid glass beads commercially available from Kominex Mineralmahlwerk, GmbH. In the context of the present disclosure, it has been found that when incompressible particulate material is comprised in the thermosettable composition of the structural adhesive film according to the disclosure, undesirable squeezing-out of the structural adhesive film before curing may be advantageously avoided during compression step, when the structural adhesive film is used for bonding metal parts.
In a preferred aspect of the structural adhesive film according to the disclosure, the weight ratio of the epoxy compound and the thermoplastic resin, and optionally the amount of the toughening agent are selected such as to provide the structural adhesive film with an elongation at break of at least 100%, preferably at least 200%, more preferably at least 500%, even more preferably at least 700%, still more preferably at least 900%, when measured according to tensile test DIN EN ISO 527. Advantageously, the structural adhesive film is provided with an elongation at break of not more than 3000%, preferably not more than 2500%, more preferably not more than 2000%, in particular not more than 1500%, when measured according to tensile test DIN EN ISO 527.
The structural adhesive film according to the disclosure may be readily prepared by a number of techniques. For example, the various components may be added under ambient conditions to a suitable internal mixing vessel, such as a Mogul mixer. The mixing temperature is not critical and the mixing of the first and second epoxy components and the optional toughening agent component is typically performed at a temperature of 80-85° C. When the epoxy curing agent component and the optional blowing agent component is added the temperature may preferably be decreased to not more than 70° C. Mixing is continued until the components form a homogeneous mixture, after which time the thermosettable composition is removed from the mixer. Due to their excellent processability the thermosettable composition can be processed as a film by conventional application equipment such as extruders or hot-melt coaters. The thermosettable composition may be processed as a self-supporting film or may alternatively be coated/laminated onto a suitable liner, such as e.g. a siliconized liner. The structural adhesive film of the disclosure may be applied to various substrates such as, for example, metals (for example, Al, Al alloys, titanium or stainless steel) or other substrates comprising, for example, glass, boron, carbon, Kevlar fibers, epoxy, phenols, cyanate esters and polyester matrices.
The structural adhesive film according to the disclosure is typically a soft conformable film, and may or may not be tacky at room temperature. Prior to curing, the structural adhesive film is preferably deformable and drapable so that it can applied to curved surfaces and assume any two-dimensional shape. The thickness of the structural adhesive film material may vary widely. Useful thicknesses have been found to be in the range of about 0.05 mm (millimeters) to 25 mm. For typical joining of metal panels, thicknesses may range from 0.1 to 5 mm, for example from 0.1 to 3 mm, or from 0.3 to 1 mm.
The structural adhesive film may be packaged in the form of rolls of film material, rolls of tapes, i.e., lengths of material in narrow widths, or stacks of sheets cut to a desired dimension or shape for the end use. If the adhesive film is tacky, a release liner may be interleaved between adjacent sheets or wraps of a roll. In the context of the present disclosure, it has been surprisingly found that where the structural adhesive film is packaged in the form of rolls of film material, the corresponding roll of film material is particularly resistant to oozing (i.e. the diffusing of epoxy resin out if the roll of film) upon storage. Without wishing to be bound by theory, it is believed that the long polymeric chains comprised in the thermoplastic resin participate in retaining the epoxy resin into the structural adhesive film upon storage. In particular, the structural adhesive film of the disclosure remains oozing-resistant when packaged in the form of rolls of film material having a length of above 100, preferably above 200, more preferably above 300, even more preferably above 500, still more preferably above 700, yet more preferably above 800 meters, and having a width typically comprised between 5 and 40 mm, in particular between 10 and 30 mm, more in particular between 10 and 20 mm.
The structural adhesive film of the disclosure may include one or more layers. The adhesive film may also include a netting. A suitable netting includes an open cloth or fabric of a polymeric material. Generally, the netting will be soft and may be stretchable. A particular example includes a heat set, soft and stretchy open nylon knitted cloth. The netting may have a thickness of 1 to 15 g/m2, for example 5 to 12 g/m2. A useful material includes 3M™ Scotch-Weld™ 3336 available from 3M Co. The structural adhesive film may also include a open non-woven layer such as a scrim.
The structural adhesive film according to the present disclosure is suitable to provide any benefit selected from the group consisting of form stability, flexibility, robustness, handling properties, suitability for automated handling and application, wash-out resistance with warm water, in uncured state; excellent bonding and sealing performance, high mechanical strength, water barrier properties, gap filling properties, controlled expansion behaviour, and smooth finish after curing.
According to another aspect, the present disclosure relates to a method for bonding a first metal part and a second part, the method comprising:
According to still another aspect, the present disclosure relates to a method of making a two-part assembly, the method comprising:
In a preferred aspect of the methods according to the disclosure, the parts, in particular metal parts, are automobile panels joined together at an edge, so as to form a so-called hemmed structure or a hem flange.
Accordingly, in one preferred aspect of the method according to the disclosure, it is provided a method for hem flange bonding of a first metal part and a second part, wherein:
Preferably, the structural adhesive film is adhered to the second panel with the structural adhesive film being adhered to the second flange of the second metal panel and folded around the second end of the second metal panel such that the structural adhesive film is adhered to opposite sides of the second flange of the second metal panel.
In one preferred aspect of the method for bonding a first metal part and a second part or the method of making a two-part assembly or the method for hem flange bonding of a first metal part and a second part, as described above, the second part is a metal part and the second panel is a metal panel.
Any metals commonly known in the art, may be used in the methods of the present disclosure. Suitable metals for use herein may be easily identified by those skilled in the art in the light of the present disclosure. Exemplary metals for use herein include, but are not limited to, steel, aluminum, magnesium, and any combinations, alloys or mixtures thereof.
In another preferred aspect of the method for bonding a first metal part and a second part or the method of making a two-part assembly or the method for hem flange bonding of a first metal part and a second part, as described above, the second part is a composite part and the second panel is a composite panel.
Any composite material commonly known in the art, may be used in the methods of the present disclosure. Suitable composite material for use herein may be easily identified by those skilled in the art in the light of the present disclosure.
In a particular aspect, the composite material for use herein is selected form the group consisting of epoxy-based materials, phenolic-based materials, polyamide-based materials, polyethylene-based materials, polypropylene-based materials, polybutylene terephthalate-based materials, and any combinations or mixtures thereof.
In another aspect, the composite material for use in the composite part and/or the composite panel comprises a resin matrix and reinforcing fibers. Exemplary resin matrices for use herein comprise a base material preferably selected from the group consisting epoxy-based materials, phenolic-based materials, polyamide-based materials, polyethylene-based materials, polypropylene-based materials, polybutylene terephthalate-based materials, and any combinations or mixtures thereof. In a particular aspect, the reinforcing fibers are selected from the group consisting of carbon fibers, glass fibers, ceramic fibers, and any combinations or mixtures thereof.
According to another aspect of the present disclosure, it is provided a two-part assembly, comprising:
In one particular aspect, the two-part assembly is such that:
In one preferred aspect of the two-part assembly according to the present disclosure, the second part is a metal part and the second panel is a metal panel, thereby forming a metal assembly.
In another preferred aspect of the two-part assembly, the second part is a composite part and the second panel is a composite panel, thereby forming the so-called hybrid (metal-composite) assemblies.
Suitable composite materials for use in the two-part assembly according to the present disclosure, may be identical to those described above in the context of the method for bonding a first metal part and a second part or the method of making a two-part assembly or the method for hem flange bonding of a first metal part and a second part.
In a particular aspect, one of the metal parts is a roof panel and the other metal part is a support structure, for example the chassis of the vehicle. The metal parts and panels are typically steel parts and panels but other metal parts and panels such as aluminum parts and panels may be used as well in connection with the disclosure. In a particular embodiment, the metal parts are unpainted, i.e. they are body in white parts as they are known or called in the automotive industry.
Typically the joint of the metal panels for a vehicle closure panel is formed early in the manufacturing process where the panels are often contaminated for example with grease or oil. The structural adhesive film used in connection with the method typically allows bonding of the metal parts and panels to an adequate level while also providing good sealing properties on the joint thereby providing corrosion resistance.
Further, the structural adhesive film can generally be applied to metal parts and panels that may be contaminated to some extent with for example oil and generally there will be no need for cleaning of the parts or panels prior to applying the adhesive sheet. Application of the structural adhesive film through automated equipment such as robot heads is conceivable as well. Moreover, an initial adhesive bond of sufficient strength can be formed such that the metal parts can be held together without the need for clamping during further handling of the joint or manufacturing steps such as for example painting, and prior to thermosetting and forming of the final and permanent bond.
The final adhesive bond advantageously has good crash resistance and preferably has a good elongation at break such that stress that might be created at the joint can be adsorbed without causing failure of the bond. Further, the structural adhesive film according to the disclosure is sufficiently resistant to washing out and accordingly, the metal parts joint together by the adhesive sheet can be subjected to a washing operation, for example as may be necessary prior to painting.
The disclosure will be further described with reference to the following schematic figures without the intention to limit the disclosure thereto:
In accordance with one aspect illustrated in
The outer panel 10 may then be folded such that the flange 12 of the outer panel is folded over the flange 22 of the inner panel 20 and over portion 34 of the structural adhesive film 30. Accordingly, outer panel 10 will be folded over inner panel 20 with the structural adhesive film located between the two panels and thus a metal joint is obtained. In case the structural adhesive film 30 was adhered to the outer panel 10 instead of inner panel 20, the structural adhesive film 30 will be folded in-between the panels during folding of the outer panel 10 over flange 22 of the inner panel 20.
The metal joint obtained is then heated to cause thermosetting of the thermosettable composition of the structural adhesive film, thereby forming a permanent adhesive bond between the panels and sealing the joint. This heating step can conveniently be performed whilst the panel assembly is being painted and baked as part of a usual vehicle manufacturing process. However, as desired, a separate heating or baking step of the metal joint may be provided as well. Typically, the temperature for heating the metal joint and to cause adhering and sealing, is between 60 and 200° C., for example between 100 and 150° C. Heating may be carried out in one or more steps. For example two or more heating cycles at different temperatures in the aforementioned range may be carried out. For example in a particular aspect, a first heating step may heat the metal joint to a temperature between 60 and 100° C. and in a further heating step a higher temperature of between 80 and 200° C. may be used. The heating time may vary but is typically between 5 minutes and 60 min, for example between 10 and 30 min. When several heating steps are used, the time for each of the heating steps may vary and may be within the aforementioned ranges.
In another particular aspect, one of the first metal part or the second part is a roof panel and the other part is a support structure, for example the chassis of the vehicle.
In still another particular aspect, the first metal part is a car body structure, in particular the outer metal structure of a vehicle door, and the second part is an inner module (or panel) of a car body structure, in particular the inner module of a vehicle door.
According to the particular aspect wherein the second part comprises a composite material, particularly lightweight structures, in particular car body structures, more in particular vehicle door constructions may be obtained.
In accordance with still another aspect, the present disclosure relates to a thermoset structural adhesive film obtainable by thermosetting of the thermosettable composition as defined above, wherein the thermosetting of the thermosettable composition is performed at a temperature comprised between 140° C. and 200° C.
In yet another aspect of the present disclosure, it is provided a structural adhesive film as described above, in the form of a tape which has been wound to form a roll. In one particular aspect, the structural adhesive film of the disclosure is packaged in the form of rolls of film material having a length of above 100, preferably above 200, more preferably above 300, even more preferably above 500, still more preferably above 700, yet more preferably above 800 meters, and a width typically comprised between 5 and 40 mm, in particular between 10 and 30 mm, more in particular between 10 and 20 mm. According to still another aspect, the present disclosure relates to the use of a structural adhesive film as described above for the manufacturing of two-part assemblies, in particular assemblies comprising a first metal part and a second part.
The present disclosure further relates to the use of a structural adhesive film as described above for bonding a first metal part and a second part, preferably for hem flange bonding of a first metal part and a second part.
In one preferred aspect of the uses according to the present disclosure, the second part is a metal part and the second panel is a metal panel.
In another preferred aspect of the uses according to the present disclosure, the second part is a composite part and the second panel is a composite panel. Suitable composite materials for use in the uses according to the present disclosure, may be identical to those described above in the context of the method for bonding a first metal part and a second part or the method of making a two-part assembly or the method for hem flange bonding of a first metal part and a second part.
Embodiment 1 is a structural adhesive film comprising a thermosettable composition, which comprises:
Embodiment 2 is the structural adhesive film of embodiment 1, wherein the thermosettable composition comprises:
Embodiment 3 is the structural adhesive film according to any of the preceding embodiments, wherein the epoxy compound has a weight average molecular weight of less than 700 g/mol, preferably less than 500 g/mol, more preferably less than 400 g/mol. Preferably, the epoxy compound has a weight average molecular weight comprised between 200 and 400 g/mol, more preferably between 300 and 400 g/mol, even more preferably between 350 and 400 g/mol.
Embodiment 4 is the structural adhesive film according to any of the preceding embodiments, wherein the epoxy compound has an average epoxy equivalent weight of less than 230 g/equivalent, preferably less than 220 g/equivalent, more preferably less than 200 g/equivalent. More preferably, the epoxy compound has an average epoxy equivalent weight comprised between 100 and 200 g/equivalent, preferably between 150 and 200 g/equivalent, more preferably between 170 and 200 g/equivalent.
Embodiment 5 is the structural adhesive film according to any of the preceding embodiments, wherein the thermoplastic resin has a softening point comprised between 70° C. and 120° C., preferably between 80° C. and 100° C., more preferably between 85° C. and 95° C.
Embodiment 6 is the structural adhesive film according to any of the preceding embodiments, wherein the thermoplastic resin is selected from the group consisting of polyether thermoplastic resins, polypropylene thermoplastic resins, polyvinyl chloride thermoplastic resins, polyester thermoplastic resins, polycaprolactone thermoplastic resins, polystyrene thermoplastic resins, polycarbonate thermoplastic resins, polyamide thermoplastic resins, and any combinations of mixtures thereof.
Embodiment 7 is the structural adhesive film according to any of the preceding embodiments, wherein the thermoplastic resin is selected from the group of polyhydroxyether thermoplastic resins, which are preferably selected from the group consisting of phenoxy resins, polyether diamine resins, polyvinylacetal resins, in particular polyvinyl butyral resins, and any combinations or mixtures thereof.
Embodiment 8 is the structural adhesive film according to any of the preceding embodiments, wherein the thermoplastic resin is selected from the group of phenoxy resins.
Embodiment 9 is the structural adhesive film according to any of the preceding embodiments, wherein the thermosettable composition comprises a toughening agent preferably selected from the group consisting of core-shell tougheners.
Embodiment 10 is the structural adhesive film of embodiment 9, wherein the thermosettable composition comprises a toughening agent in an amount comprised between 10 and 40 wt %, preferably between 10 and 30 wt %, more preferably between 10 and 20 wt %. Embodiment 11 is the structural adhesive film according to any of the preceding embodiments, wherein the thermosettable composition further comprises a blowing agent, preferably selected from the group consisting of non-encapsulated and encapsulated blowing agents.
Embodiment 12 is the structural adhesive film of embodiment 11, wherein the thermosettable composition comprises a blowing agent, in an amount comprised between 0.5 and 10 wt %, preferably between 1 and 5 wt %, more preferably between 1 and 2 wt %.
Embodiment 13 is the structural adhesive film according to any of the preceding embodiments, wherein the thermosettable composition further comprises a filler, preferably in an amount of less than 10 wt %, wherein the filler is preferably selected from the group of inorganic fillers comprising silica.
Embodiment 14 is the structural adhesive film according to any of the preceding embodiments, wherein the weight ratio of the epoxy compound and the thermoplastic resin, and optionally the amount of the toughening agent are selected such as to provide the structural adhesive film with an elongation at break of at least 100%, preferably at least 200%, more preferably at least 500%, even more preferably at least 700%, still more preferably at least 900%, when measured according to tensile test DIN EN ISO 527.
Embodiment 15 is the structural adhesive film according to any of embodiments 11 to 14, wherein the amount of the blowing agent is selected such as to provide the structural adhesive film with a free expansion rate upon curing of between 10 and 40%, preferably between 10 and 30%, more preferably between 15 and 25%, when subjecting the structural adhesive film to a curing temperature above the activation temperature of the curing reaction, and when the free expansion rate is measured as described in the Test Methods section.
Embodiment 16 is a method of making a two-part assembly, the method comprising:
Embodiment 17 is a method for bonding a first metal part and a second part, the method comprising :
Embodiment 18 is the method of embodiment 17 for hem flange bonding of a first metal part and a second part, wherein:
Embodiment 19 is the method of embodiment 18, wherein the structural adhesive film is adhered to the second panel with the structural adhesive film being adhered to the second flange of the second panel and folded around the second end of the second panel such that the structural adhesive film is adhered to opposite sides of the second flange of the second panel.
Embodiment 20 is a method according to any of embodiments 16 to 19, wherein the second part is a metal part and the second panel is a metal panel.
Embodiment 21 is a method according to any of embodiments 16 to 19, wherein the second part is a composite part and the second panel is a composite panel.
Embodiment 22 is a method according to embodiment 21, wherein the composite part and/or the composite panel comprises a resin matrix and reinforcing fibers.
Embodiment 23 is a method according to embodiment 22, wherein the resin matrix comprises a base material selected from the group consisting epoxy-based materials, phenolic-based materials, polyamide-based materials, polyethylene-based materials, polypropylene-based materials, polybutylene terephthalate-based materials, and any combinations or mixtures thereof.
Embodiment 24 is a method according to any of embodiment 22 or 23, wherein the reinforcing fibers are selected from the group consisting of carbon fibers, glass fibers, ceramic fibers, and any combinations or mixtures thereof.
Embodiment 25 is a two-part assembly, comprising:
Embodiment 26 is the metal part assembly according to embodiment 25, wherein:
Embodiment 27 is an assembly according to embodiment 25 or 26, wherein the second part is a metal part and the second panel is a metal panel.
Embodiment 28 is an assembly according to embodiment 25 or 26, wherein the second part is a composite part and the second panel is a composite panel.
Embodiment 29 is an assembly according to embodiment 28, wherein the composite part and/or the composite panel comprises a resin matrix and reinforcing fibers.
Embodiment 30 is an assembly according to embodiment 29, wherein the resin matrix comprises a base material selected from the group consisting epoxy-based materials, phenolic-based materials, polyamide-based materials, polyethylene-based materials, polypropylene-based materials, polybutylene terephthalate-based materials, and any combinations or mixtures thereof.
Embodiment 31 is an assembly according to any of embodiment 29 or 30, wherein the reinforcing fibers are selected from the group consisting of carbon fibers, glass fibers, ceramic fibers, and any combinations or mixtures thereof.
Embodiment 32 is an assembly according to any of embodiments 25 to 31, wherein one of the first metal part and the second part comprises a roof panel and the other part comprises a support structure.
Embodiment 33 is a thermoset structural adhesive film obtainable by thermosetting of the thermosettable composition as defined in any of embodiments 1 to 15, wherein the thermosetting of the thermosettable composition is performed at a temperature comprised between 140° C. and 200° C.
Embodiment 34 is a structural adhesive film according to any of embodiments 1 to 15, in the form of a tape which has been wound to form a roll.
Embodiment 35 is the use of a structural adhesive film according to any of embodiments 1 to 15 for the manufacturing of two-part assemblies, in particular assemblies comprising a first metal part and a second part.
Embodiment 36 is the use of a structural adhesive film according to any of embodiments 1 to 15 for bonding a first metal part and second part, preferably for hem flange bonding of a first metal part and a second part.
Embodiment 37 is the use according to any of embodiment 35 or 36, wherein the second part is a metal part, preferably comprising a metal panel.
Embodiment 38 is the use according to any of embodiment 35 or 36, wherein the second part is a composite part, preferably comprising a composite panel.
Embodiment 39 is the use according to embodiment 38, wherein the composite part and/or the composite panel comprises a resin matrix and reinforcing fibers.
Embodiment 40 is the use according to embodiment 39, wherein the resin matrix comprises a base material selected from the group consisting epoxy-based materials, phenolic-based materials, polyamide-based materials, polyethylene-based materials, polypropylene-based materials, polybutylene terephthalate-based materials, and any combinations or mixtures thereof.
Embodiment 41 is the use according to any of embodiment 38 or 39, wherein the reinforcing fibers are selected from the group consisting of carbon fibers, glass fibers, ceramic fibers, and any combinations or mixtures thereof.
The disclosure is further illustrated by the following examples. These examples are merely for illustrative purposes only and are not meant to be limiting on the scope of the appended claims.
1. Tensile Test according to DIN EN ISO 527 (DIN 53 455). Tensile Test for the determination of the elongation at break of the uncured structural adhesive film.
The adhesive films are conditioned 24 h under normal conditions. Strips of the adhesive film, 25 mm broad×100 mm long, are cut. Right and left sizes are protected with masking tape so that 50 mm free tape in the middle of the length is able to be measured. The masked areas permit the clamping of the sample in the tensile machine.
The test is performed on a tensile test machine, Zwick testing machine Z05, 200N measuring Head, equipped with pneumatic clamping jaws. The sample is clamped in the jaws of the tensile machine, with an gap of 50 mm, the upper jaw first, followed by the lower one. The strip is carefully vertically fixed. The testing speed is 300 mm/min. Audit End is set on Fmax drop 94%. The elongation at break of the sample is then measured.
2. Overlap Shear Strength according to DIN EN 1465.
Overlap shear strength is determined according to DIN EN 1465 using a Zwick Z050 tensile tester (commercially available by Zwick GmbH & Co. KG, Ulm, Germany) operating at a cross head speed of 13 mm/min on hot dipped galvanized steel strips (commercially available as Etalon steel, reference GC 300500AA from Societee Etalon; France) having the following dimension 100 mm×25 mm×0.8 mm and coated with 3 g/m2 Oil (PL 3802-39S commercially available from Fuchs Petrolub AG, Germany). For the preparation of an Overlap Shear Strength test assembly the epoxy film to be tested (having a thickness of 0.7 mm) is applied on one end of a first steel strip and covered by a second steel strip forming an overlap joint of 10 mm. The overlap joints are then clamped together using two binder clips and the test assemblies placed into an air circulating oven for 30 minutes at 180° C. Hereby the test assemblies are heated up and cooled down using 3° C./minute ramps. Test assemblies are then conditioned for 24 hours at ambient condition 23 +/−2° C. and 50 +/−% % relative humidity before testing. As the test temperatures for measuring Overlap Shear Strength are varied from −40° C. to room temperature up to +80° C., the tests assemblies are placed prior to testing on the Zwick tensile tester into an environmental chamber (commercially available by RS Simulatoren, Oberhausen, Germany) and the Overlap shear strength measured at −40° C., room temperature (23° C. +/−2° C.) and +80° C. 3 samples are measured for each of the examples at the three different test temperatures and results averaged and reported in MPa.
3. Adhesive peel strength according to DIN EN 1464.
The Adhesive Peel strength is measured on hot dipped galvanized steel strips (commercially available by Etalon steel, reference GC 300500AA from Societee Etalon; France) having the following dimension 150 mm×25 mm×0.8 mm and coated with 3 g/m2 Oil (PL 3802-39s commercially available from Fuchs Petrolub AG, Germany) according to DIN EN 1464 using a Zwick Z050 tensile tester (commercially available by Zwick GmbH & Co. KG, Ulm, Germany). The cross head speed is set for all measurements to 100 mm/min and adhesive peel strength measured at 23° C. +/−2° C. and a relative humidity of 50+/−5% . For test assembly preparation a masking tape (Scotch™ 2610 Masking Tape, commercially available from 3M, USA) is applied to a first steel strip. Hereby the masking tape is applied to visualize the bond area. The bond area has a dimension of 100 mm×25 mm. The example material to be tested is then applied to the marked bond area and covered by a second steel strip having the same dimension as the first one. The two strips are hereafter first manually pressed together and then clamped together using 2 binder clips along the bond line, in order to hold the test assembly in place. The test assemblies are cured for 30 minutes at 180° C. in an air circulating oven. Hereby the test assemblies are heated up and cooled down using 3° C./minute ramps. Test assemblies are then conditioned for 24 hours at ambient condition 23 +/−2° C. and 50 +/−5% relative humidity before testing. Per example material, 3 adhesive peel strength test assemblies are prepared and the test results averaged. Test results are reported in N/25 mm.
To illustrate a vehicle door, small sized hem flanges are fabricated.
Hereby a hem flange is formed by using two steel panels (commercially available as Etalon steel, reference GC 300500AA from Societe Etalon; France) having a dimension of 200 mm×200 mm ×1 mm and in a first step applying an example film sheet having a dimension of 200 mm×20 mm×0.7 mm on the edge of the first steel panel. In a second step, the extended edge portion of the first steel panel (the length of the extended portion was between 7-8 mm) is folded back over the edge portion of the second steel panel positioning the example film sheet directly between the two steel panels. The resulting test assemblies are then dipped for 15 minutes into a to 55° C. pre-warmed watery solution comprising 3 wt. % cleaner (commercially available as LKW Reiniger from Chemische Fabrik Dr. Stocker GmbH; Duisburg; Germany). All test assemblies are then cured for 30 minutes at 180° C. in an air circulating oven. Hereby, the test assemblies are heated up and cooled down using 3° C./minute ramps. Test assemblies are then conditioned for 24 hours at ambient condition 23 +/−2° C. and 50 +/−5% relative humidity before testing. All test assemblies are then inspected visually. Test assemblies delivering porously cured bond lines are considered as a FAIL and test assemblies showing well sealed bond lines without noticeable bubbles are rated as a PASS.
5. Free expansion rate of expandable structural adhesive films. The free expansion rate (in %) of expandable structural adhesive films is determined according to EN 2667-3. Test specimens are prepared by first cutting out square aluminium alloy sheets 2024-T3 in accordance with EN 2090 having the dimension of 120 mm×120 mm and a sheet thickness of 1 to 2 mm. In a next step square adhesive film samples are cut out having the dimension of 100 mm×100 mm. The adhesive squares are then adhered to the centre of the aluminium alloy sheets. Prior to curing the uncured precursor test specimens are measured with a flat edge micrometer calliper with a precision of 0.01 mm at a temperature of 4° C. or lower (measurement is performed in a lower temperature that ambient in order to avoid tack of the film to adhere to the thickness measurement tooling). The precursor specimens are then cured for 30 minutes at 180° C. +/−3° C. using a heating air-circulating oven available from MPC and run at a heat-up ramp of 3° C./min. Prior to the cured thickness measurement all test specimen are stored at room temperature of 23 +/−2° C. and a relative humidity of 50 +/−5% until the cured specimens have returned to ambient temperature. The expansion rate is then calculated according to the following formula :
Expansion rate (%)=((Thicknesscured−Thicknessuncured)/Thicknessuncured)×100
The epoxy-based compositions of the present disclosure are prepared by combining the ingredients from the list of materials of Table 1 in a high speed mixer (DAC 150 FVZ Speedmixer, from Hauschild Engineering) stirring at 3000 rpm. In Table 2, all concentrations are given as wt. %. Comparative example C-1 does not comprise any thermoplastic resin.
In a first step the epoxy resin, the thermoplastic phenoxy resin and the core shell toughening agent are mixed together for 2 min. The mixture is then placed into an air-driven oven at temperature of 95° C. for about 1 h. The hot mixture is again stirred for 2 min at 3000 rpm in the speed mixer to ensure complete dispersion of the three ingredients. Then the mixer temperature is reduced to 60° C. and the two curatives (Amnicure CG1200 and Omnicure U52M) together with the physical blowing agent, and optionally the filler material and/or the glass beads, are added to the mixture, followed by mixing for an additional 2 minutes under vacuum. The resulted mixture is a paste having a uniform consistency. By using a knife coater the mixer is hot coated to a film having thickness of 0.4 mm. The formed film is soft and homogenous when cooled down.
As can be seen from the results shown in Table 3, the structural adhesive film according to the present disclosure, is provided with an elongation at break which is much higher than that of an adhesive film not according to the disclosure. Comparative adhesive film C-2 is obtained as a very brittle material and is unsuitable for the Tensile Test as described above.
| Number | Date | Country | Kind |
|---|---|---|---|
| 12181578.1 | Aug 2012 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2013/056161 | 8/22/2013 | WO | 00 |
