Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered 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
  • B32B7/04—Interconnection of layers
  • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered 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
  • B32B27/08—Layered 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2375/00—Polyureas; Polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2398/00—Unspecified macromolecular compounds
  • B32B2398/10—Thermosetting resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2398/00—Unspecified macromolecular compounds
  • B32B2398/20—Thermoplastics
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2597/00—Tubular articles, e.g. hoses, pipes

Definitions

• This invention relates to the bonding of two dissimilar polymeric resin composition surfaces.
• the invention relates to a process for bonding an epoxy resin matrix reinforced with glass fibers to the surface of a poly(vinyl chloride) pipe thereby the pipe is reinforced and withstands high delai ⁇ inating forces without rupture of the interface bond between the epoxy resin and the poly(vinyl chloride) surface.
• the invention also relates to the product of this process vhich in a preferred embodiment comprises a pipe.
• plastic pipe made of one or more layers each of polymeric olefinic chloride resin ("PVC") and epoxy-impregnated glass fibers has been widely used, in the construction and plumbing industries. Light weight and resistance to corrosion have been among the desirable properties of this type of pipe.
• Ihe pipe conventionally consists of an inner hollow cylinder of PVC overlayed with a wrapping of epoxy impregnated glass fibers.
• the first layer of epoxy impregnated glass fibers is overlayed with a second PVC layer which is itself then overlayed with a second layer of epoxy impregnated glass fiber. Any number of such multiple alternating layers may be thus built up.
• Patent No. Re-29,375 in vhich a defined quantity of a solid epoxy resin was incorporated into the ABS containing surface solution. Presence of the solid epoxy resin in the ABS surface solution dramatically improved the bond between the PVC core and the epoxy impregnated glass fiber overwrap layer.
• This patent also described several other resins which could be used for the core material in place of PVC as well as two resins (solid thermosetting phenolic resins or polyester resins) which could be used in place of the solid epoxy resin in the ABS layer.
• the laminated product described in the reissue patent has enjoyed a marked success in the market place, being sold commercially by Johns -Manville Corporation under the trademark PERMASTRAN. It has been discovered in service, however, that when the pipe is used at low temperatures, such as those on the order of about 0°F (-18°C), the bond formed with the ABS adhesive layer containing the epoxy, phenolic or polyester resin corresponding to the resin in the overwrap has a tendency to weaken and delaminate.
• the invention herein is a process for bonding together a first layer comprising a thermoplastic poly(vinyl acetate), poly (methyl methacrylate), polystyrene, polybutene, poly(vinyl butyral) or polymeric olefinic chloride resin and a second layer comprising a liquid thermosetting epoxy, phenolic or polyester resin, which layers are substantially chemically unbondable to each other; which process c ⁇ prises applying to the surface of said first layer a coating consisting essentially of urethane resin in such manner that said coating and said first layer become mechanically interengaged at the interface between the two, applying to said coating said second layer in uncured form and thereafter curing said second layer and simulitaneously forming a substantially chemical bond between said coating and said second layer, vhereby a laminated product of improved cold temperature integrity and strength is formed.
• the first layer comprises PVC and the second layer comprises epoxy ii ⁇ sregnated glass fiber.
• the coating also contains a butadiene resin . Methods by which the bend between the first layer and the coating can be for include surface roughening and/or solvent washing of the first layer or forming a surface solution at the interface between the first layer and the coating.
• the invention also comprises a laminated article having a bond between the laminae which has improved cold temperature integrity and strength, said article comprising a first layer containing as the principal component a thermoplastic poly(vinyl acetate), poly(methyl methacrylate), polystyrene, polybutene, poly(vinyl butyral) or polymeric olefinic chloride resin and a second layer containing as the principal component a thermosetting epoxy, phenolic or polyester resin, said layers being bonded into said laminate by a coating therebetween and in intimate contact therewith, said coating consisting essentially of a urethane resin which is mechanically interengaged with said first layer and chemically bonded to said second layer.
• the abating also contains a butadiene resin. Methods by which the bond between the first layer and the coating can be formed include surface roughening and/or solvent washing of the first layer or forming a surface solution at the interface between the first layer and the coating.
• This invention is a novel method of bonding two dissimilar and otherwise unbondable resinous compositions. While the process of this invention is applicable to bonding any two of the described classes of materials, the process finds a particularly important use in the bonding of alternate layers of PVC and related resins to layers of epoxy and related polymeric materials. An important specific application of this process lies in a method for producing plastic pipe composed of alternating layers of PVC resin and epoxy impregnated glass fiber.
• Pipe produced by the method described herein has good integrity and substantial resistance to separation at the interfaces within the pipe wall. Where it is necessary to cut into or through the pipe wall and expose one ⁇ r more of the interfaces, the method of this invention can be used quite effectively to seal the cut surface and prevent exposure of the interface to the line pressure within the pipe thereby preventing separation of the pipe wall at that interface.
• a most important property of pipe produced by the process of this invention is its resistance to delamination even under severe cold temperatures, such as those on the order of about 0°F (-18°C). It has, for instance, been discovered that pipe produced according to the present invention shews bond strength which are frequently twice as great as the best previous laminated pipe, i.e., that produced according to the process of the aforementioned reissue patent.
• thermoplastic resin which comprises the principal component of the first layer will be selected fr ⁇ n the group consisting of poly(vinyl acetate), poly(methyl methacrylate), polystyrene, polybutene, poly(vinyl butyral) and the polymeric olefinic chlorides, notably poly(vinylidene chloride), poly(vinyl chloride) and copolymers thereof.
• the polymeric olefinic chlorides (which are usually referred to herein collectively as "PVC" resins) are the preferred resins to be used as the first layer of the laminate, particularly when the laminated article is a pipe.
• thermoplastic resins useful herein are those which are substantially chemically inert but which can form surface solutions with the coatings described below.
• the second layer is composed of an initially liquid thermosetting resin selected from the group consisting of epoxy resins, polyester resins and phenolic resins.
• epoxy resins are preferred. These resins are reaction products of epoxide compounds with confounds having available hydrogen atoms linked to carbon atoms by oxygen atoms. Examples of the latter are the polyhydric phenols and the polyhydric alcohols.
• a typical epoxy resin useful in this invention is the reaction product of epichlorohydrin and a polyhydric phenol such a bisphenol-A.
• Other illustrative epoxy resins typically include reaction products of epihalohydriris and polyhydric alcohols such as ethylene glycol, propylene glycol, trimethylene glycol and the like.
• the epoxy silanes are also quite satisfactory in the psrocess of this invention.
• suitable epoxy resins include the epoxy novolac resins such as the epoxy phenol novolac resins. These are basically novolac resins vhose phenolic hydroxyl groups have been converted to glycidyl ethers.
• suitable epoxy resins types include ⁇ -amine phenol epoxys as well as cycloaliphatics in which the epoxide group is directly attached to the cycloaliphatic ring and epoxy ethers.
• the phenolic resins include those produced by reacting phenol with an aldehyde.
• the commercial phenols used are phenol, cresol, xylenols, p-tert.-butylphenol, p-phenyl-phenol, bisphenols and resorcinol.
• the most important aldehydes are formaldehyde and furfural.
• Preferred among the phenolic resins are those formed by the reaction of phenol and formaldehyde.
• the phenolic resin may be formed by either addition or condensation reactions in the presence of either acid or base.
• polyester resins are formed by the reaction of polyfunctional acids or anhydrides and alcohols.
• a typical polyester resin is prepared by reacting phthallic anhydride or maleic anhydride and propylene glycol.
• the polyurethanes which are the basic component of the ooating of the present invention are formed by the reaction of a polyol with a diisocyanate.
• Typical among the polyols which may be used to form the polyurethanes of the present invention include those derived from glycerol and sorbitol.
• Typical of the diisocyanates which may be used are toluene diisocyanate (which is usually in the form of mixed isomers of toluene diisocyanate) or diphenyl methane diisocyanate.
• the reaction to form the polyurethanes is usually catalyzed by amines such as diethylene triamine or dibutyltin dilaurate.
• the polyurethane resin will be in the solid phase after the bond is formed between the coating and the first layer, but will be dissolved or dispsersed in a solvent at the time the coating layer is applied to the thermoplastic first layer, as will be described below.
• the coating may also contain a butadiene resin.
• a butadiene resin This include polybutadiene itself or any of a variety of copolymers or terpolymers thereof such as butadiene-styrene resin, acrylcnitrilebutadiene resin, acrylonitrile-butadiene-styrene resin (ABS), mixtures thereof and the like.
• ABS acrylonitrile-butadiene-styrene resin
• Praparation methods for all the resins mentioned in the preceding paragraphs are well known and amply described in the art. Any of the known preparation methods are suitable to prepare the resins for use in this invention.
• the urethane resin will normally initially be in solid form.
• the urethane resin is first dissolved or dispersed in comminuted form in a solvent. It is preferred that the urethane be dissolved in order to obtain the optimum bond.
• Typical solvents which may be used include tetrahydrofuran, methyl ethyl ketone, cyclohexanone, methylene chloride, acetone, ethyl acetate, iscphorone and the like.
• the coating also contains a butadiene resin it is preferred that the solvent be a mutual one for both the urethane and the butadiene resins.
• the solvent also be a mutual solvent for the thermoplastic resin in the first layer as well as for the urethane and the thermoplastic resin.
• the second layer containing the thermosetting resin impregnated glass fiber, in which the thermosetting resin is initially in liquid form, may if desired also contain a curing agent for the thermosetting resin.
• Typical curing agents are described in the aforementioned reissue patent.
• the exact composition and concentration of the components in the first and second resinous layers are not critical. Each component will be selected primarily because of the particular properties desired in the finished article.
• the PVC core cylinder will be composed essentially all (i.e., usually about 90% or greater) of PVC with a small amount of conventional additive materials such as stabilizers, antioxidants, colorants, etc.
• the typical overwrap layer of epoxy impregnated glass fiber will consist of a range of concentrations of continuous filament glass fibers in an epoxy matrix and may also include materials such as colorants, antioxidants, stabilizers, curing agents, etc. in small amounts.
• the various concentrations of epoxy and glass will depend en the properties desired in the finished pipe.
• the first and second resinous layers are considered suitable if they are not generally bondable to each other and if they each contain the respective thermoplastic and thermosetting resins as princi components.
• Principal component as used herein is defined to mean a component vhich is present in sufficient quantity so as to contribute substantially to the bonding process of this invention.
• the particular component will comprise 40% to 50% or more by weight, up to 100% by weight, of the particular polymeric composition being considered.
• a component may, however, be present in a smaller concentration if the other components are relatively inert and/or the component in question provides a major part of the bonding function.
• the epoxy resin may vary over wide range en concentrations and yet be considered a principal component for the other important component in the system, glass fiber, is inert and does not participate in the bonding process. It is, of course, important that a "principal component" be present in sufficient amount to materially participate in the bonding function; small or trace amounts of a component which provide only a small amount of bonding are not considered to be within the scope of this invention.
• the novel coating layer initially contains two principal components: the urethane resin and a solvent which is a mutual solvent for both the thermoplastic and for the urethane resin.
• the urethane resin is initially in solid form and is either dissolved or dispersed in the solvent. During the process herein the solvent will evaporate, leaving a solid urethane coating interengaged with the thermoplastic substrate.
• the coating may also contain a butadiene resin, in vhich case the solvent is usually also a mutual solvent for the butadiene resin.
• the urethane and butadiene resins When a butadiene resin is present, the urethane and butadiene resins will be present in a butadiene:urethane resin weight ratio of up to 85:15, preferably in a range of 20:80 to 80:20, and more preferably in approximately equal amounts.
• the coating may also contain a quantity of a thermosetting resin of the same chemical type as the thermosetting epoxy, phenolic or polyester resin of the second layer.
• the thermosetting resin will, be incorporated into the coating in a manner and quantity analogous to that described in the reissue patent.
• the mutual solvent for the thermoplastic, butadiene and urethane resins will also be a solvent for the thermosetting resin.
• the urethane coating may be interengaged with the thermoplastic substrate (i.e., the first resinous layer) in different ways.
• the substrate is first sanded to roughen the surface and the solvent containing the urethane is then sprayed or painted onto the roughened surface.
• the solvent subsequently evaporates or is heated to volatilize it, the solid urethane resin left is found to have filled the myriad of minute "valleys" created in the substrate surface by the sanding, thus effecting a firm mechanical interlock of the coating and the substrate.
• the substrate can be solvent washed with one of the aforementioned solvents, preferably methyl ethyl ketone or tetrahydrofuran when the substrate is PVC.
• Solvent washing to roughen the surface may also be combined with sanding, but is not preferred because solvent washing appears to "fill in” the "valleys" created by sanding to seme extent, thus making the subsequent urethane/ substrate bond less strong.
• the urethane-containing mutual solvent can be worked into the outer surface of the substrate in a quantity sufficient to dissolve the outer surface portion of the thermoplastic layer and to form a surface solution of that portion with the coating. Care should be taken, however, that the quantity of coating used is not so great as to dissolve a major portion of the first layer and thereby to weaken ⁇ r materially change the properties of that composition.
• the quantity of coating is such as normally to penetrate the surface of the first polymeric resin composition to a depth of about 0.5 to about 8 mils (0.01 to 0.20 mm) and to form a coating thickness of up to about 15 mils (0.38 mm).
• the coated first layer is then heated to a temperature of 100°F to 200°F (37°C to 93°C), preferably 100°F to 150o F (37°C to 65oC), and held for about 1 to 16 hours.
• This heating serves to precondition the first layer and coating for the final curing step.
• the volatile solvent is driven off, leaving the urethane resin present as a solid forming the adhesive coating layer.
• the surface is not tacky after this heating so that the coated first layer (such as a pipe) may readily be handled and conveyed to the location at which the overwrap is to be applied.
• this heating step causes the first layer to undergo shrinkage if the particular thermoplastic resin has a tendency to shrink in the presence of heat.
• the second layer consisting of the thermosetting resin impregnated glass fiber is applied to and placed in contact with the solid surface of the dried and solidified coating.
• the thermosetting resin will be in a substantially liquid and uncured state.
• concentration of the thermosetting resin in the second layer may, as noted above, vary over quite a wide range, particularly where the layer also contains inert materials such as glass fibers.
• the layer may be sprayed, painted, wiped or otherwise applied to the hardened surface of the coating, preferably in liquid form.
• the layer is in the form of resin impregnated filaments which are layed or wrapped en or around the substrate and surface solution.
• the inner cylinder e.g., the PVC oore
• the inner cylinder is first coated on its cuter surface with the solvated urethane coating.
• the solvated coating and inner cylinder are first coated on its cuter surface with the solvated urethane coating.
• thermoplastic resin is cured by conventional curing means. Generally this involves heating the entire assemblage so as to thermally cure the thermosetting resin. The heat applied will, of course, be kept sufficiently low such that other resins in the entire assemblage as well as any fillers or additives or other materials which may be present will not be detrimentally affected. Such curing techniques are well known to those skilled in the art and need not be exemplified here. It has been found that for compositions exemplified below, cure temperatures of about 130°F to about 180°F (54°C to 82°C) maintained for about 0.5 to 16 hours produced entirely satisfactory bonds. Curing of the second or overwrap layer may be expedited by incorporation into the layer of a quantity of curing agent for the thermosetting resin.
• the urethane material contained a conventional amount of a curative material and both were dissolved in a solvent (ethyl acetate).
• the invention herein is applicable to the bonding of any two dissimilar and chemically unbondable resinous materials. It is particularly applicable to the formation of laminated materials such as laminated pipe.

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• 1980
  • 1980-09-29 JP JP50256480A patent/JPS56501279A/ja active Pending
  • 1980-09-29 AU AU64853/80A patent/AU6485380A/en not_active Abandoned
  • 1980-09-29 WO PCT/US1980/001289 patent/WO1981000825A1/en not_active Ceased
  • 1980-09-30 IT IT49777/80A patent/IT1128689B/it active
  • 1980-09-30 CA CA000361291A patent/CA1158143A/en not_active Expired
• 1981
  • 1981-04-08 EP EP19800902150 patent/EP0036889A4/en not_active Withdrawn

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