GB2376660A - Bonding material for bonding a first moulding material to a further moulding material - Google Patents

Bonding material for bonding a first moulding material to a further moulding material Download PDF

Info

Publication number
GB2376660A
GB2376660A GB0207709A GB0207709A GB2376660A GB 2376660 A GB2376660 A GB 2376660A GB 0207709 A GB0207709 A GB 0207709A GB 0207709 A GB0207709 A GB 0207709A GB 2376660 A GB2376660 A GB 2376660A
Authority
GB
United Kingdom
Prior art keywords
bonding
moulding
resin
layer
resin material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
GB0207709A
Other versions
GB0207709D0 (en
Inventor
Matthew Dennis Searle
Derek Simon Richard Ness
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gurit UK Ltd
Original Assignee
Gurit UK Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gurit UK Ltd filed Critical Gurit UK Ltd
Publication of GB0207709D0 publication Critical patent/GB0207709D0/en
Publication of GB2376660A publication Critical patent/GB2376660A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0025Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
    • B29C37/0028In-mould coating, e.g. by introducing the coating material into the mould after forming the article
    • B29C37/0032In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied upon the mould surface before introducing the moulding compound, e.g. applying a gelcoat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06Fibrous reinforcements only
    • B29C70/08Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/086Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers and with one or more layers of pure plastics material, e.g. foam layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/38Layered products comprising a layer of synthetic resin comprising epoxy resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/10Interconnection of layers at least one layer having inter-reactive properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2063/00Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00Use of polyesters or derivatives thereof, as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00Ancillary operations in connection with laminating processes
    • B32B2038/0052Other operations not otherwise provided for
    • B32B2038/0076Curing, vulcanising, cross-linking
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04Impregnation, embedding, or binder material
    • B32B2260/046Synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00Condition, form or state of the layers or laminate
    • B32B2305/08Reinforcements
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2363/00Epoxy resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00Polyesters, e.g. PET, i.e. polyethylene terephthalate

Abstract

A bonding material (10) adapted to improve the bonding between a first moulding material (22) and a second moulding material (24), the first moulding material comprising for example an epoxy resin or vinyl ester resin material and the further moulding material comprising for example a polyester or vinyl ester resin material, the respective resin materials comprising dissimilar polymerisation chemistries which prevent the first and farther moulding materials from forming a strong bond between them comprises a bonding resin material for example epoxy resin and one or more layers of reinforcement material (14,16). The bonding reinforcement material may comprise a venting structure for venting gases out of the bonding layers during processing of the bonding material The first moulding material may comprise a reinforcement resin and the further moulding material may comprise a gel coat.

Description

BONDING MATERIAL
The present invention relates to a bonding material for bonding a first moulding material to a further moulding 5 material, particularly but not exclusively to a bonding material for bonding an epoxy laminate structure to a polyester gel coat.
Moulding materials comprising epoxy resin materials are widely used for the production of high quality lightweight 10 structural components. One of the problems associated with epoxy resin based mouldings is that, for a lot of applications, it is not possible to produce an epoxy moulding with a high quality cosmetic surface directly in the mould. Therefore additional surface treatments such as 15 coating are necessary to arrive at the desired cosmetic surface quality. High cosmetic quality surfaces are however relatively easy to produce directly in the mould using polyester moulding materials, as there are a wide number of excellent polyester in mould coatings (generally known as 20 gel coats) available. However, polyester materials technology is not as good mechanically as epoxy materials technology. Polyester mouldings are generally heavier than epoxy mouldings for mouldings with similar mechanical properties. 25 In the past, attempts were made to combine different types of moulding materials, but the combined moulding materials had an unsatisfactory bond. For example, polyester gelcoats were combined with epoxy laminate systems. The formed bond between the gelcoat and the laminate was however 30 unreliable and mechanically weak. This rendered the application of combined polyester laminates and epoxy laminates unsuitable for many applications.
Since the chemistries of the various resin systems are essentially different, the resin materials are both 35 chemically and mechanically incompatible, thus strong bonds between the respective resin material can not be readily
formed. This is also observed in combined epoxy and polyester resin systems, for example in the bond between an epoxy laminate and a polyester gelcoat. The bond between polyester resin systems and epoxy resin systems may be 5 affected by a phenomenon known as air inhibition. Without wishing to be bound by any theory, we believe that the oxygen in the air interferes with the free radical cross linking mechanism of the polyester resin. This results in a thin layer of uncured polyester resin material which is 10 situated on the surface of the polyester laminate or gel coat. If an epoxy laminate or epoxy system is applied to this surface, the epoxy resin will not satisfactorily adhere to the surface. As the surface is only partially cured due to the air inhibition, the bond between the polyester 15 laminate or polyester gelcoat and the epoxy laminate or epoxy system is weak.
Another problem that arises particularly in combined epoxy laminates and polyester laminates or polyester gelcoats is that the cured polyester laminate or gelcoat has 20 a higher shrinkage than the cured epoxy laminate. This causes interracial stress between the laminates which results in loss of bonding between the laminates. A further problem of the combined laminates is that air can be trapped between the laminates which again results in poor bonding.
25 GB-A-1 291 160 (Hauk Manufacturing Company) discloses a process for moulding laminated articles composed of an elastomeric surface layer and a backing layer of a reinforced synthetic resin. Generally, elastomers are chemically classified as non-polar and completely saturated 30 substances. Synthetic resins which have a highly polar chemical structure, such as polyester resins, are difficult to adhere directly to layers of elastomer because the chemical dissimilarity of the resin and the elastomer prevents the formation of strong interracial bonds. The 35 elastomeric surface layer is bonded to the backing layer by
applying a coating of elastomer to the surface layer, depositing bonding fibres to the coating which is part cured, rolling the fibres to remove entrapped air and to form a substantially continuous fibrous coating near the 5 surface of the elastomer coating, and applying a layer of catalyzed synthetic resin backing followed by the backing layer. The method as disclosed in GB-A-1 291 160 is laborious since it requires the various layers to be applied 10 separately in order to bond the elastomer coating and the synthetic resin backing. Also, any entrapped air must be removed. If entrapped air is not removed from between the interfaces of the various layers, this affects the quality of the bond. Air inhibition or oxidation of the surface of 15 the elastomer layer still occurs as air interferes with the elastomer surface. The mechanical properties of the backing layer and the elastomer layer further cause interracial stresses which affect the bond between the layers.
The present invention aims to obviate ox at least 20 mitigate the above described problems and/or to provide improvements generally.
According to the invention there are provided a bonding material, a laminate structure and a bonding method according to any of the accompanying claims.
25 In an embodiment of the invention there is provided a bonding material adapted to improve bonding of a first moulding material to a further moulding material, said first and further moulding material when combined having unsatisfactory bonding properties, wherein said bonding 30 material is located between said moulding materials to form a bonding layer, and said bonding material comprises a bonding resin material and a bonding reinforcement material.
The moulding materials comprise resin materials which may comprise different polymerization chemistries which prevent 35 the moulding materials from forming strong bonds between
said moulding materials. The bond formed between the first moulding material and the further moulding material in the absence of said bonding material is therefore weaker than the bond formed between the respective moulding materials by 5 the bonding material. The bonding material thus greatly improves the bond between the respective moulding materials.
The first moulding material may comprise a reinforcement resin material and/or a reinforcement material and/or a gelcoat and/or a surface resin material or 10 combinations thereof. The further moulding material may also comprise a reinforcement resin material and/or a reinforcement material and/or a gelcoat and/or a surface resin material or combinations thereof.
The first moulding material may comprise an epoxy resin 15 material and the further moulding material may comprise a polyester resin material, alternatively, the first moulding material may comprise an epoxy resin material and the further moulding material may comprise a vinylester resin material, or alternatively, the first moulding material may 20 comprise a vinylester resin material and the further moulding material may comprise a polyester resin material.
The bonding resin material may comprise an epoxy resin material. The first moulding material may comprise an epoxy resin material and the further moulding material may 25 comprise a polyester resin material. The further moulding material may also comprise a gel coat. Said gel coat may comprise said polyester resin material.
In another embodiment of the inventions there is provided a bonding material suitable for improving the 30 adherence of an epoxy laminate to a polyester moulding material, said bonding material comprising a layer of a bonding resin material. Said bonding resin material may comprise an epoxy resin material and said laminate layer may comprise an epoxy resin material.
35 In another embodiment of the inventions, the bonding
material may comprise one or more layers of a reinforcement material. The reinforcement material may be fibrous and may be woven or non-woven. The reinforcement material may be provided on the bonding resin material. In a preferred 5 embodiment the bonding resin material is in the form of a bonding resin film. The film may be applied interleaved between layers of said reinforcement material. For most applications, a single bonding resin film layer covered on each side by a layer of a reinforcement material is 10 sufficient for providing a strong bond between the respective moulding materials. The reinforcement material may be partially impregnated with the bonding resin material or the reinforcement material may be dry. The reinforcement material may be conjoined to the surface of the bonding 15 resin material such that the reinforcement material is substantially unimpregnated with the resin material.
In a further embodiment of the inventions, the reinforcement material may be in a woven or a non-woven form. The reinforcement material facilitates the 20 manufacturing and handling of the bonding material. The weight of the bonding resin material may vary from 50 g/m2 to 800 g/m2, preferably the weight of the bonding resin material is 250 g/m2.
In yet another embodiment of the inventions, the 25 reinforcement material may comprise a ventilating structure to allow gases to pass out of the laminate structure during processing of said bonding material. Gas entrapment in the laminate structure can lead to voids at the interface between the bonding material and the gel coat and the 30 interface between the bonding material and the laminate structure. The ventilating structure enables these gases to escape via the dry reinforcement layer. This results in a stronger bond between the interfaces of the bonding material and the moulding materials, and improved environmental 35 resistance due to the absence of voids at the interfaces.
The ventilating structure further prevents air inhibition on the surface of the polyester moulding material or polyester gelcoat. The ventilating structure may be formed by the reinf 'rem.ent material During processing the laminate 5 structure comprising the bonding layer may be evacuated. In this way all air is removed from the interface between the bonding layer and the moulding materials thus preventing air inhibition and/or oxidation of the interface.
The laminate structure formed by the moulding materials 10 and the bonding material may be cured by applying heat to the structure. Upon heating the material, the resin viscosity drops. This causes the bonding resin to reach its flow point which enables it to completely wet-out the bonding material including the interfaces of the bonding 15 material and the respective moulding materials whereby intra- and interlaminar gases such as entrapped air can conveniently escape via the venting structure. During processing of the material, vacuum pressure may be applied to the laminate structure. The evacuation of the structure 20 also prevents entrapment of inter- and intralaminar gases between the bonding material and the respective moulding material and it prevents air inhibition on the external surface of the further moulding material. During processing the bonding layer bonds with the surrounding moulding 25 materials.
The viscosity of a resin material is strongly affected by temperature. Upon heating the material, the resin viscosity drops dramatically, allowing it to flow around the reinforcement material (flow-point). However, as the 30 resin material is heated beyond a certain point (activation temperature), the catalysts within it begin to react and the cross-linking reaction of the molecules accelerates. The progressive polymerization increases the viscosity of the resin material until it has passed a point where it will not 35 flow at all ("no flow point"). The reaction then proceeds to
full cure. Within this application, if reference is made to the flow properties of any of the resin materials herein described, and more in particular the viscosity of a resin material, it is herein referred to the flow properties of 5 the resin during processing, up to the point in time when the resin material reaches its no flow point.
In an embodiment, the bonding resin material may comprise pigments. The pigments may be applied to colour the bonding material. In combination with the coloured bonding 10 material this enables the application of a thinner gel coat layer to arrive at the same colour intensity at the surface of the moulding in comparison with a thick gel coat layer.
Suitable pigments or fillers may comprise titanium dioxide and carbon black (carbon particles). In this advantageous 15 embodiment, since the gel coat layer is thinner, problems of shrinkage of the polyester moulding material or the polyester gel coat are absent or significantly reduced. As discussed hereinbefore, in conventional structures, such shrinkage usually causes interracial stresses at the bond 20 between the bonding material and the gel coat layer.
The bonding resin material may comprise fillers which are suitable for reducing the water permeability of the bonding resin material and for improving the resistance of the bonding material to water and other chemicals. Suitable 25 fillers may comprise mica, aluminium, micro balloons and glass flakes.
In another embodiment of the invention, the bonding material may comprise suitable resin material properties such that during processing of the laminate structure, the 30 bonding resin material is prevented from emerging to the external surface of the further moulding material, in particular to the external surface of a gel coat material.
The resin material properties may comprise the viscosity of the resin material which is selected such that during 35 processing of the bonding material, the minimum viscosity of
the bonding resin material is higher than the minimum viscosity of the gel coat material during processing of the bonding material.
A preferred way of applying the bonding material to a 5 moulding layer is by part curing the layer before the bonding material is applied. In particular, a gelcoat material may preferably be gelled off at room temperature.
This is achieved by partially curing the gelcoat. At this stage, the bonding material may be applied on to the gelcoat 10 material. The viscosity of the gelcoat is then such that the bonding resin material is prevented from migrating away from the bonding material and emerging at the external surface of the gelcoat material. Also, at this stage, no intermixing of the gelcoat resin and the bonding resin can take place.
15 The skilled man recognizes the gelled off stage of the gelcoat by the property of the gelcoat that it is tacked off. This means that when a finger is applied onto the gelcoat, the finger slightly sticks to the gelcoat. Upon release of the finger, no gelcoat sticks to it.
20 In another embodiment of the invention, the bonding material may comprise a heat cured epoxy resin material. The resin material may be any standard epoxy resin material. The resin material may be selected such that the material is a semi-solid material at an ambient temperature ranging from 25 10 C to 40 C.
The bonding resin material may also comprise one or more toughening components for toughening the cured resin material, which may be in a concentration of approximately 1 to 30% by weight of the resin material, preferably 30 approximately 12% by weight of the resin material. The toughening material components may comprise CTBN (Carboxy Terminated Butadiene). CTBN is a liquid polymer which can be conveniently blended into the epoxy resin. CTBN can be partially reacted with an epoxy resin. The CTBN material 35 components are liquid polymers upon their application to the
resin material. Processing of the bonding material may be achieved by a suitable catalyst. A suitable catalyst may comprise dicyandiamide, and/or imidazole, and/or Boron trifluoride amine. During processing the bonding material 5 bounds with the moulding material layers.
In a preferred embodiment of the invention, the bonding material may be provided as a preform. In this form, the bonding material is prefabricated and comprises a bonding resin material and one or more reinforcement layers. The 10 pre-fabricated material is supplied ready for its application in the mould. One or more reinforcement layers may be at least partially pre-impregnated with the bonding resin material Alternatively, the reinforcement layer or layers are adhered to the bonding resin material and held in 15 place by the inherent tack of the bonding resin. The reinforcement layers are thus substantially dry and free from resin. The bonding material is preferably supplied to the fabricator on a roll.
In a further embodiment of the inventions there is 20 provided a laminate structure comprising a gel coat layer, an epoxy laminate layer and a bonding layer as herein before described. The bonding layer is preferably arranged between the gel coat layer and the laminate layer as an interleave bonding layer. The gelcoat layer preferably comprises a 25 polyester gel coat material.
In yet another embodiment of the invention, there is provided a method of bonding a gel coat layer to a laminate layer by providing a bonding layer as herein before described between said gel coat layer and said laminate 30 layer.
In another embodiment of the invention, there is provided a method for bonding a polyester gel coat layer to an epoxy laminate layer comprising the steps of providing a bonding material comprising an epoxy resin layer, and 35 partially curing said gel coat layer, said method further
comprising the steps of locating said bonding material in relation to said gel coat layer, locating said epoxy laminate layers in relation to said bonding layer, thereby forming a laminate structure, and processing said laminate 5 structure.
There is thus provided a bonding material, a laminate structure and a bonding method according to embodiments of the inventions.
Historically the bond between a polyester gel coat 10 layer and an epoxy laminate layer has never been very satisfactory. One of the reasons for this is that the two chemistries of the polyester layer and the epoxy layer are radically different and therefore incompatible. This results in poor bonds at the interface between an epoxy resin 15 containing material and a polyester resin containing material. The other reasons include the difference in thermal expansion between the layers which results in interracial stresses, the shrinkage of the cured polyester which 20 results in further interracial stresses and the problem of air inhibition at the surface of the polyester layer which results in poor chemical bonds. Apart from this, air can be trapped on the interface between the polyester and epoxy layers which results in voids in the cured laminate 25 structure and a poor bond between the layers.
In an embodiment of the invention the bonding material forms an improved bond between an epoxy laminate and a cosmetic polyester in mould coating which is generally known as a polyester gel coat. Without wishing to be bound by any 30 theory, we believe that the bonding of the gel coat and the laminate structure by the bonding material is based on three important principles.
Firstly, the bonding layer comprises a reinforcement layer which is unimpregnated or partially impregnated by the 35 bonding resin material. This allows for intra-laminate and
inter-laminate gases such as air, which may be trapped between the gel coat layer and the bonding layer or the laminate layer and the bonding layer, to be evacuated upon processing of the laminate. In this way gases can be 5 evacuated from the critical interface between the gel coat layer and the bonding layer. The evacuation of air results in a large reduction of voiding which improves the bond between the bonding layer and the polyester gel coat layer.
Secondly, the bonding material reduces the interracial 10 stresses between the gel coat layer and the laminate layer.
The polyester gel coat layer has a lower modulus of elasticity compared to the modulus of the epoxy laminate layer. The epoxy laminate layer is relatively inelastic in comparison to the gelcoat layer. The interracial stresses 15 result primarily from the higher shrinkage of the cured polyester layer in comparison to the cured epoxy layer. In use, additional stresses result from the difference in thermal expansion between the layers. If a gel coat layer were adhered directly to an epoxy laminate structure, this 20 would result in significant interracial stresses which can lead to premature cracking and failure of the coating of the epoxy laminate. The bonding material comprises both flexible properties and tough properties which allow the bonding layer to be elastic enough to absorb the stresses from the 25 polyester gel coat interface. This effectively reduces the stress on the interface which results in an improved performance of the polyester gel coat layer.
The layer of bonding material is tougher than the layers of the epoxy laminate material and the polyester 30 laminate material. The bonding layer comprises toughness properties which make the material resilient and resistant to crack propagation. The layer of bonding material is more flexible and resilient than the epoxy laminate layer and the polyester gel coat layer 35 Thirdly, although we do not wish to be bound by any
theory, we believe that the bonding layer may form chemical bonds between both the epoxy laminate and the polyester gel coat. Conventionally applied ambient cured polyester gel coats do not core completely on the exposed gel coat surface.
5 This is due to a phenomenon which is widely known as air inhibition. The oxygen in the air interferes with the free radical cross linking mechanism of the polyester molecules which results in a thin layer of uncured material which is present on the surface of the gel coat layer. If a 10 conventional epoxy system is applied onto this polyester gel coat surface, the epoxy laminate adheres to this surface; but since it is only partially cured due to the air inhibition, the interface bond between the epoxy laminate and the polyester gel coat is weak, which results in a poor bond 15 between the two layers. We believe that the bonding layer forms a good bond to the polyester gel coat layer due to the toughening components which are present in the bonding layer.
The toughening components have a degree of unsaturation because of carboncarbon double bonds which are in the 20 components. These toughening components can react with the styrene in the polyester resin material of the unsaturated gel coat and form a chemical bond between the polyester gel coat layer and the bonding layer. Since the bonding layer comprises an epoxy resin material this layer also bonds with 25 the epoxy laminate layer.
As discussed, the bonding material reduces the interracial stresses between the gel coat layer and the laminate layer. The gel coat layer has a relatively low modulus, whereas the epoxy laminate layer has a high 30 elasticity modulus. The gel coat layer also comprises a higher shrinkage than the laminate layer. The bonding material comprises both flexible properties and tough properties which allows the bonding material to marry up the two layers. The required mechanical and chemical properties 35 of the bonding material may be adapted to the mechanical and
chemical properties of both the gel coat layer and the laminate layer. This is achieved by adding additives such as toughening components to the bonding resin material. Also, in the selection of the catalyst, the mechanical properties 5 of the bonding material may be controlled.
The bonding layer comprises an epoxy resin which is preferably applied as a film. The epoxy resin may comprise a standard heat cured epoxy resin material which may be selected so that it is semi-solid at an ambient temperature.
10 The resin material may have an amount of toughening agent present, preferably approximately 2 to 20% by weight of the resin material and more particularly between 10% and 15% by weight of the resin material. Preferably the amount of toughening agent is around 12% by weight of the resin 15 material. Preferred toughening agents are CTBN and preferred catalysts may comprise accelerated dicyandiamide, an imidazole, or a Boron trifluoride amine complex. Processing of the layers is preferably achieved at temperatures ranging between 50 C and 150 C but would normally be at approximately 20 85 C. The weight of the resin film may vary between 50 g/m2 to 700 g/m2 but preferably the weight of the resin film may be 250 g/m2. This film may also have a light weight glass carrier material and/or synthetic carrier material present on the external surfaces to facilitate manufacturing and 25 handling of the material. This glass carrier material or reinforcement material can comprise a woven or non-woven material, which can be present on both or one of the surfaces of the resin film material. As discussed, these materials serve to reduce the possibility of air entrapment leading to 30 voids at the interfaces of the bonding material and the gel coat and backing laminate.
It is also possible to incorporate pigments into the bonding layer. These can be used to give a colour to the bonding layer which allows a thinner application of the gel 35 coat material. Suitable pigments may comprise titanium
dioxide or carbon particles.
The bonding resin material may further comprise fillers which may be used to reduce the water permeability of the film And improve its long-term resistance to oth =r chemicals 5 Such fillers could comprises mica, aluminum, glass flakes, or combinations thereof.
Embodiments of the inventions will now be described as an example only and with reference to the accompanying drawings in which: 10 Figure 1 presents a cross-sectional, diagrammatic view of a bonding material according to an embodiment of the inventions, and Figure 2 presents a diagrammatic cross-sectional view of a laminate structure comprising the bonding material of 15 Figure 1.
The embodiments are an example only and illustrate the general structural format of the bonding material. The chemical constitution of the resin is as hereinbefore described. 20 The bonding material or tie coat material 10 comprises a resin film 12 comprising a suitable resin material comprising toughening agents. For specific applications the resin material can also comprise fillers and pigments. The bonding material further comprises reinforcement materials 25 14, 16 which are applied on each side of the resin film 12.
The top surface layer of the resin film 18 comprises a woven reinforcement material 14 and the lower surface of the resin film 19 comprises a non-woven reinforcement material 16.
These reinforcement materials facilitate manufacturing of the 30 bonding material and improve handling of the bonding material. The materials further serve to reduce the possibility of air entrapment which can lead to voids at the interfaces of the bonding material and the gel coat and the bonding material and the laminate. This greatly improves 35 adherence of the bonding material to the gel coat and the
laminate. The reinforcement materials 14, 16 can be woven or non-woven. The bonding material is manufactured by applying a resin film 12 onto the woven carrier 14 and subsequently applying 5 a layer of a non-woven reinforcement material onto the opposite side of resin film 12.
A laminate structure 20 is formed by bonding a polyester gel coat 24 to an epoxy laminate structure 22 by means of bonding material 10. The bonding material 10 is provided 10 between the gel coat 24 and the epoxy laminate 22. A preferred way of applying the bonding material is by applying the gel coat material in the mould and processing the gel coat material such that it partially cures at an ambient temperature. This allows the gel coat to be tacked off, that 15 is to process the gel coat to a state in which the gel coat is not tacky, but at which point it is not completely cured.
The bonding material as herein described provides -a significant improvement over a laminate structure comprising a polyester gel coat and an epoxy laminate.
20 The bonding material 10 as presented in Figs. 1 preferably comprises an epoxy resin film 12 of a weight of 250g/m2. The reinforcement material 14,16 may comprise fibres of only one type or a combination of different types of fibre. Any fibre size may be used. Preferably the fibres 25 range in size from 1 Am to 100 Am and 1 to 4000 text In a preferred embodiment, the non-woven material 16 is typically a lightweight fibrous layer of between 1 and 100 g/m2 and the material 14 is between 100 g/m2 and 2000 g/m2in weight.
As an example the strength of the bond can be quantified 30 using a cleavage test according to British Standard 5350 part C1. Without using the bonding material according to the invention a cleavage strength of approximately 2 kN to 3 kN was measured for a conventional polyester gel coat layer and an epoxy laminate bond. When a bonding material as presented 35 in Fig. 1 is applied, the bonding material as herein
described having a resin film weight of 250 g/m2 interleaved between the gel coat layer and the laminate layer, a cleavage strength of 5.8 kN newton was measured.

Claims (23)

1. A bonding material adapted to improve bonding of a first moulding material to a further moulding material, 5 said first and further moulding material when combined directly to one another having unsatisfactory bonding properties, said bonding material comprising a bonding resin material and one or more layers of a bonding reinforcement material, said bonding material being 10 arranged between said moulding materials to form a bonding layer, wherein said bonding material comprises a venting structure for venting gases out of the bonding layer during processing of the bonding material.
2. A bonding material adapted to improve bonding of a first moulding material to a further moulding material, said first and further moulding material when combined having unsatisfactory bonding properties, said bonding 20 material being arranged between said moulding materials to form a bonding layer, said bonding material comprising a bonding resin material and a bonding reinforcement material.
25
3. A bonding material according to claim 2, wherein said bonding reinforcement material comprises a venting structure for venting gases out of the bonding layer during processing of the bonding material.
30
4. A bonding material according to any of the preceding claims, wherein said first moulding material comprises a first resin material, said further moulding material comprises a further resin material, the respective resin materials comprising dissimilar polymerization 35 chemistries which prevent the first and further
moulding material from forming a satisfactory bond.
5. A bonding material according to claim 1 or any of claims 3 or A, Herein the Parenting structure is formed 5 by the reinforcement material.
6. A bonding material according to any of the preceding claims, wherein a bonding reinforcement layer is conjoined to the surface of the bonding resin layer.
7. A bonding material according to any of the preceding claims, wherein the reinforcement material is partially impregnated with the resin material.
15
8. A bonding material according to any of the preceding claims, wherein the weak or unsatisfactory bond is due to bonding faults caused by entrapped gases between the first and further moulding material, inhibition of gases at the surface of the first and/or further 20 moulding material, oxidation of the surface of the first and/or further moulding material, chemical incompatibility of the resin systems of the first and further moulding material, mechanical incompatibility of the combined resin systems when cured, and/or 25 combinations of the aforesaid causes.
9. A bonding material according to any of the preceding claims wherein said bonding resin material comprises resin material properties which are selected such that 30 during processing of the bonding material the bonding resin material is prevented from emerging to the external surface of the further moulding material.
10. A bonding material according to claim 9, wherein said 35 resin material properties are selected such that during
processing of the bonding material the minimum viscosity of the bonding resin material is higher than the minimum viscosity of the further reinforcement resin material.
11. A bonding material according to any of the preceding claims wherein the bonding resin material comprises one or more toughening components, said toughening components comprising CTBN, said toughening components 10 being present in a concentration ranging from 1% to 30% by weight of the bonding resin material, preferably in a concentration of 12% by the weight of the bonding resin material.
15
12. A bonding material according to any of the preceding claims wherein the bonding resin material comprises one or more filler components, said filler components being adapted to reduce the water permeability of the bonding material.
13. A bonding material according to any of the preceding claims, wherein said first resin material comprises an epoxy resin material and said further resin material comprises a polyester resin material, or 25 said first resin material comprises an epoxy resin material and said further resin material comprises a vinylester resin material, or alternatively, said first resin material comprises a vinylester resin material and said further resin material comprises a 30 polyester resin material.
14. A bonding material according to any of the preceding claims, wherein said further moulding material comprises a gel coat.
15. A bonding material according to any of the preceding claims, wherein said bonding material is a preform.
16. A bonding material according to any of the preceding 5 claims, wherein the bonding material is adapted to reduce the interracial stresses between said first moulding material and said further moulding material.
17. A bonding material according to any of the preceding claims, wherein the bonding resin material comprises an epoxy resin material.
18. A bonding material according to any of the preceding claims, wherein the bonding layer is adapted to be 15 sufficiently elastic to absorb the interracial stresses and the bonding layer is adapted to be sufficiently resilient and resistant to crack propagation.
19. A bonding material adapted to improve bonding of a 20 first moulding material to a further moulding material, said first and further moulding material when combined having unsatisfactorily bonding properties.
20. A laminate structure comprising one or more layers of 25 a first moulding material, one or more layers of a further moulding material, said first and further moulding layers when combined directly to one another having unsatisfactory bonding properties, said laminate structure further comprising a bonding material 30 according to any of the preceding claims.
21. A laminate structure comprising a gel coat layer, a laminate layer and a bonding material according to any of the preceding claims, said bonding material being 35 arranged between said gel coat layer and said laminate
layer.
22. A method of bonding a first moulding material to a further moulding material, said first and further 5 moulding material when combined directly to one another having unsatisfactory bonding properties, said method comprising the steps of: providing a bonding material according to any of claims 1 to 19, 10 locating the bonding material between said first and further moulding material to form a bonding layer, and causing said bonding layer and/or said moulding materials to bond said moulding materials.
15
23. A method for bonding a polyester gel coat layer to an epoxy laminate layer comprising the steps of: providing a bonding material according to any of the preceding claims, partially curing said gel coat layer, 20 locating said bonding material in relation to said gel coat layer, locating said laminate layer in relation to said bonding layer, thereby forming a laminate structure, and 25 causing said laminate structure to become bonded.
GB0207709A 2001-04-03 2002-04-03 Bonding material for bonding a first moulding material to a further moulding material Withdrawn GB2376660A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GBGB0108331.0A GB0108331D0 (en) 2001-04-03 2001-04-03 Bonding material

Publications (2)

Publication Number Publication Date
GB0207709D0 GB0207709D0 (en) 2002-05-15
GB2376660A true GB2376660A (en) 2002-12-24

Family

ID=9912160

Family Applications (2)

Application Number Title Priority Date Filing Date
GBGB0108331.0A Ceased GB0108331D0 (en) 2001-04-03 2001-04-03 Bonding material
GB0207709A Withdrawn GB2376660A (en) 2001-04-03 2002-04-03 Bonding material for bonding a first moulding material to a further moulding material

Family Applications Before (1)

Application Number Title Priority Date Filing Date
GBGB0108331.0A Ceased GB0108331D0 (en) 2001-04-03 2001-04-03 Bonding material

Country Status (2)

Country Link
GB (2) GB0108331D0 (en)
WO (1) WO2002081189A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7731882B2 (en) 2003-03-06 2010-06-08 Vestas Wind Systems A/S Connection between members

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0205498D0 (en) 2002-03-08 2002-04-24 Structural Polymer Systems Ltd Moulding material
DK1603723T4 (en) 2003-03-06 2018-10-15 Vestas Wind Sys As Preform and method of preparing a preform
CA2517956C (en) 2003-03-06 2008-07-08 Vestas Wind Systems A/S Connection between composites with non-compatible properties and method for preparation
EP2271478B1 (en) * 2008-04-30 2013-08-14 Vestas Wind Systems A/S A consolidated composite pre-form
ITMO20130265A1 (en) * 2013-09-26 2015-03-27 Ama Composites S R L PROCEDURE FOR THE PRODUCTION OF MANUFACTURED ARTICLES IN REINFORCED PLASTIC AND MANUFACTURED MANUAL.
DE102014205861A1 (en) * 2014-03-28 2015-10-01 Brose Fahrzeugteile Gmbh & Co. Kommanditgesellschaft, Coburg Fiber composite component and method for producing a fiber composite component
WO2018193908A1 (en) * 2017-04-18 2018-10-25 三菱ケミカル株式会社 Fiber-reinforced composite material molded article and method for producing same
DE102020108236A1 (en) 2020-03-25 2021-09-30 Airbus Operations Gmbh Method for joining two parts to be joined

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1291160A (en) * 1970-07-28 1972-10-04 Hauk Mfg Company Composite molding process and product
US4365001A (en) * 1980-04-24 1982-12-21 Societe Chimique Des Charbonnages Laminates of improved fire resistance
WO1983003233A1 (en) * 1982-03-15 1983-09-29 Helmut Link Rope clamp
US4443507A (en) * 1979-01-26 1984-04-17 Toho Beslon Co., Ltd. Heat-moldable laminate and process for molding said laminated structures
JPH01105735A (en) * 1987-10-20 1989-04-24 Showa Highpolymer Co Ltd Manufacture of fiber reinforced phenol resin molded object
US4956224A (en) * 1985-11-05 1990-09-11 Societe Chimique Des Charbonnages S.A. Articles produced from a laminate and process for their manufacture
JPH0455414A (en) * 1990-06-25 1992-02-24 Hitachi Chem Co Ltd Resin composition for molding fiber reinforced plastic with gel coat, production of molded article and molded article
JPH0797549A (en) * 1993-09-28 1995-04-11 Katsuo Shimomura Polishing agent for preventing adhesion of dirt
EP0714743A1 (en) * 1994-11-29 1996-06-05 ECP Enichem Polimeri Netherlands B.V. Process for the production of gel-coated articles
EP0807514A2 (en) * 1996-05-14 1997-11-19 United Technologies Corporation Elastomer coated layer for erosion and/or fire protection
US5780147A (en) * 1995-03-14 1998-07-14 Daiso Co., Ltd. Laminate having improved dimensional stability and heat resistance
WO1998034979A1 (en) * 1997-02-06 1998-08-13 Cytec Technology Corp. Fiber material partially impregnated with a resin

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3210230A (en) * 1961-11-21 1965-10-05 Polystructures Inc Process for forming a laminated plastic structure
US4925611A (en) * 1987-10-19 1990-05-15 Usbi Company Mold making method
FR2772301B1 (en) * 1997-12-16 2000-01-28 Hautes Performances Composites ELEMENT OF COMPOSITE MATERIAL WITH SLIDING SURFACE, AND MANUFACTURING METHOD

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1291160A (en) * 1970-07-28 1972-10-04 Hauk Mfg Company Composite molding process and product
US4443507A (en) * 1979-01-26 1984-04-17 Toho Beslon Co., Ltd. Heat-moldable laminate and process for molding said laminated structures
US4365001A (en) * 1980-04-24 1982-12-21 Societe Chimique Des Charbonnages Laminates of improved fire resistance
WO1983003233A1 (en) * 1982-03-15 1983-09-29 Helmut Link Rope clamp
US4956224A (en) * 1985-11-05 1990-09-11 Societe Chimique Des Charbonnages S.A. Articles produced from a laminate and process for their manufacture
JPH01105735A (en) * 1987-10-20 1989-04-24 Showa Highpolymer Co Ltd Manufacture of fiber reinforced phenol resin molded object
JPH0455414A (en) * 1990-06-25 1992-02-24 Hitachi Chem Co Ltd Resin composition for molding fiber reinforced plastic with gel coat, production of molded article and molded article
JPH0797549A (en) * 1993-09-28 1995-04-11 Katsuo Shimomura Polishing agent for preventing adhesion of dirt
EP0714743A1 (en) * 1994-11-29 1996-06-05 ECP Enichem Polimeri Netherlands B.V. Process for the production of gel-coated articles
US5780147A (en) * 1995-03-14 1998-07-14 Daiso Co., Ltd. Laminate having improved dimensional stability and heat resistance
EP0807514A2 (en) * 1996-05-14 1997-11-19 United Technologies Corporation Elastomer coated layer for erosion and/or fire protection
WO1998034979A1 (en) * 1997-02-06 1998-08-13 Cytec Technology Corp. Fiber material partially impregnated with a resin

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7731882B2 (en) 2003-03-06 2010-06-08 Vestas Wind Systems A/S Connection between members

Also Published As

Publication number Publication date
WO2002081189A1 (en) 2002-10-17
GB0207709D0 (en) 2002-05-15
GB0108331D0 (en) 2001-05-23

Similar Documents

Publication Publication Date Title
US6048488A (en) One-step resin transfer molding of multifunctional composites consisting of multiple resins
AU2001293967B9 (en) Sheet moulding compound (SMC) with ventilating structure for entrapped gases
AU2005232257B2 (en) Moulding materials
CA2758180C (en) Rotor blade, rotor blade element and production process
CN1321148C (en) Fiber reinforcement composite material used for car shrouding parts and back holding door produced therefrom
KR101574833B1 (en) Functional film for well-impregnated composites and method of manufacturing composites using the same
JP2012515667A (en) Composite parts with coating layers
CN105579222A (en) Method for molding body in mold
JP2013209510A (en) Fiber-reinforced resin molding coating composition, fiber-reinforced resin molding obtained by applying the coating composition, and method for producing the fiber-reinforced resin molding
GB2376660A (en) Bonding material for bonding a first moulding material to a further moulding material
US20040192137A1 (en) Surface material
US5358779A (en) Enhanced surface appearance of glass fiber reinforced plastics (FRP)
EP2209629A1 (en) Process to improve the adhesion between thermosetting laminate and thermoplastic shell
US4956224A (en) Articles produced from a laminate and process for their manufacture
CN114641398A (en) Transfer film for transferring a coating onto a part
US5534337A (en) Thermoset reinforced corrosion resistant laminates
JP2006198920A (en) Prepreg for honeycomb cocure, honeycomb laminated composite material, and method for producing them
JP3289294B2 (en) Sheet molding compound and method of manufacturing the same
JP2009119613A (en) Fiber-reinforced plastic molding and its production method
CA2211460A1 (en) Re-usable cement forms
CN112874089B (en) High-strength glass fiber reinforced plastic composite board with good corrosion resistance and application thereof
WO2022202455A1 (en) Surface modification sheet, laminate, surface-modified member, coated object, production method for surface-modified member, and production method for coated object
WO2023041895A1 (en) Surfacing material
JPS58118876A (en) Adhesive sheet for reinforcement of metal plate
JP3208689B2 (en) Fiber reinforced plastic preform and fiber reinforced plastic plate

Legal Events

Date Code Title Description
WAP Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1)