WO1991003514A1 - Procede permettant d'ameliorer l'adhesion de caoutchouc epr polymerise - Google Patents

Procede permettant d'ameliorer l'adhesion de caoutchouc epr polymerise Download PDF

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WO1991003514A1
WO1991003514A1 PCT/US1990/004982 US9004982W WO9103514A1 WO 1991003514 A1 WO1991003514 A1 WO 1991003514A1 US 9004982 W US9004982 W US 9004982W WO 9103514 A1 WO9103514 A1 WO 9103514A1
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ethylene
epr
weight
article
add
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PCT/US1990/004982
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English (en)
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Cindy Beth Shulman
Thomas Samyon Daniluk
Joseph Dominic Domine
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Exxon Chemical Patents Inc.
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Publication of WO1991003514A1 publication Critical patent/WO1991003514A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers

Definitions

  • the present invention relates to a process and composition for improving the adhesion of shaped articles composed of cured EPR rubber to themselves and to other substrates.
  • Vulcanized copolymer elastomers of ethylene, a higher monoolefin such as propylene and optionally minor amounts of a diene monomer, have found increasing use in automotive and other applications involving weathering and exposure to chemical attack such as from oxygen or ozone.
  • EPR elastomers are inherently more resistant to the deleterious effects of ozone, oxygen and heat than are other elastomers such as polybutadiene, polyisoprene, GR-S and similar more highly unsaturated elastomers, which renders them highly desirable for use in applications such as weatherstrip seals, tires, automotive hoses, moldings, seats, instrument panels, convertible tops and the like.
  • the use of cured EPR elastomers 1n many of these applications requires that the cured and shaped elastomer part be bonded to another substrate such as an EPR substrate or to metal, natural or synthetic based fabrics and other plastics.
  • Adhesive compositions based on terpolymers of a major proportion of ethylene, and a minor proportion of a mixture of acrylic add and t-butyl acrylate are known in the art.
  • UK specification 1,213,580 discloses the use of such adhesives to bond various materials such as polyethylene sheets, metal foils, glass fibers, glass, wood and like materials.
  • UK Patent Specification 1,239,999 teaches similar adhesives for bonding metal-to-metal foils.
  • UK Patent Specification 1,394,883 discloses terpolymers based on ethylene, acrylic or methacrylic add and a lower alkyl ester of acrylic add as bonding adhesives for a number of substrates, including polyethylene and glass sheets.
  • Similar adhesives based on hot melt copolymers containing a major proportion of ethylene and a minor proportion of a lower alkyl acrylate such as methyl acrylate are also known in the art. Such materials may be used for butt welding thermoplastic sheets or sieeves according to U.S. Patent 3,927,233. Such copolymers are also known as adhesives for the preparation of multiple layer reinforced laminates based on sheets of thermoplastic polyolefln polymers such as polypropylene, as disclosed U.S. Patent 4,661,389.
  • thermoplastic compositions, metal, glass and other substrates have proven successful to varying degrees
  • the prior art has not provided simplified methods for effectively adhering difficult-to-adhere materials such as cured EPR to itself and to other substrates, particularly shaped articles of cured EPR having a substantial thickness.
  • an adhesive composition is provided which is based on a thermoplastic, or optionally a cross linked copolymer of ethylene with minor amounts of a lower alkyl acrylate or methyacrylate, or a thermoplastic terpolymer, or optionally a cross linked terpolymer of ethylene with minor amounts of a lower alkyl acrylate or methacrylate and acrylic or methacrylk add.
  • the adhesive composition may be applied to the surface of the cured EPR stock or to another surface to which the EPR stock is to be adhered, such application being made by coating the substrate with the adhesive in the form of a solution, emulsion or melt, by application of a film of the adhesive, or by extrusion coating a melt of the adhesive and the cured or curable EPR stock to form a laminate structure.
  • the structures of this invention are ideally suited for automotive applications requiring excellent adhesion of vulcanized EPR based compositions to diverse surfaces such as rubber, metal, plastics, fabric, glass and other surfaces.
  • the ethylene polymer adhesives useful in the present invention are random copolymers or terpolymers comprising from about 60 to about 96% by weight of polymerized ethylene, from about 4 to about 40% by weight of a polymerized C1 to C6' preferably C1 to C4 alkyl acrylate or methacrylate, and from 0 to about 101 by weight of polymerized acrylic or methacrylic acid. More preferred copolymers contain from about 75 to about 95% by weight ethylene and from about 5 to about 251 by weight C1 to C4 alkyl acrylate or methacrylate.
  • ethylene polymer is a terpolymer
  • it also contains from at least about 0.5% up to about 10% by weight of polymerized acrylic or methacrylic add, more preferably at least about 3% by weight and most preferably from about 4.5 to about 8X by weight.
  • terpolymer as used herein is intended to refer to true interpolymers of ethylene and the acrylate and add monomers as well as blends of separate copolymers of ethylene and acrylate monomers with copolymers of ethylene and add monomers, with the proviso that the relative polymerized monomer contents of such blends are as described above.
  • the preferred C1 to C4 acrylate component of the ethylene copolymers is methyl acrylate and the preferred add component of the ethylene terpolymers is acrylic add.
  • the ethylene polymers may comprise a wide range of melt indices generally between about 0.1 up to about 130, more preferably from about 1 to about 30 and most preferably from about 2.0 to about 20 dg/m1n as determined by ASTM method 0-1238 (condition E). These polymers may also contain difunctional crossi1nk1ng agents such as divinyl benzene or ethylene glycol dimethacrylate, although such materials are not necessary to achieve the adhesion properties set forth herein.
  • the ethylene copolymers and terpolymers may be produced by any one of a number of well-known free radical initiated processes such as, for example, those described in U.S. Patent No. 3,350,372 which is incorporated herein by reference for all purposes as if fully set forth.
  • ethylene the (meth)acrylates and/or the (meth)acrylic adds are metered into a high pressure autoclave reactor along with any one of a number of well-known free radical polymerization initiators (catalysts) suitable for producing ethylene and acrylic based polymers.
  • catalysts include organic peroxides such as, for example, lauroyl peroxide, di-tert butyl peroxide, tert butyl peroxide and various azo compounds.
  • the catalyst will be dissolved in a suitable organic liquid such as benzene, mineral oil, or the like.
  • a suitable organic liquid such as benzene, mineral oil, or the like.
  • the catalyst is used at a level of between about 50 to about 20,000 ppm, more preferably between about 100 to about 250 ppm based on the weight of monomers.
  • EPR as used herein is intended to refer to elastomeric copolymers based on ethylene and at least one other mono olefin as weli as elastomeric terpolymers and tetrapolymers based on ethylene, at least one other mono olefin and at least one diolefin (EPDH rubber).
  • the terms "elastomeric” or “elastomer” are defined to mean that when they are crossiinked, they are capable of recovering from large deformations quickly and forcibly. Free from diluents, the crossiinked polymers retract within one minute to less than 1.5 times their original lengths after being stretched at 18°C-29°C to twice their lengths and held for one minute before release.
  • Typicaliy elastomers are "substantialiy amorphous", and when that term is used to define the ethylene containing elastomeric polymers of this invention, 1t is to be taken to mean having a degree of crystallinlty less than 25%, preferably less than about 15%. and more preferably less than about 10% as measured by means known in the art.
  • the three major known methods of determining crystallinlty are based on specific volume, x-ray diffraction, and infrared spectroscopy. Another well-established method, based on measurement of heat content as a function of temperature through the fusion range, is now easily carried out using differential scanning calorlmetrlc measurements. it is known that these independent techniques lead to good experimental agreement.
  • the tendency of a particular combination of catalyst system and monomers to produce "blocky", random, or alternating polymers can be characterized by the product of the reactivity ratios defined for the given monomers under the specific reaction conditions encountered. if this product is equal to 1.0, the sequence distribution will be perfectly random; the more the product is less than 1.0, the more the monomers will approach alternating sequence; and. the more the product is greater than 1 .0, the more the monomers will tend to have a "blocky" sequence distribution.
  • the segments of a polymer which crystal lize are linear segments which have a number of Identical (both by chemical make-up and stereo-specific orientation) units in a row.
  • the ethylene-containing elastomeric polymers of this invention accordingly, have a reactivity ratio product less than 2.0, preferably less than about 1.5, and more preferably less than about 1.25, and are substantially amorphous .
  • the preferred monoolefin-based EPR is prepared from ethylene and ethylenically unsaturated alpha olefins containing from 3 to 28 carbons, more preferably 3 to 18 carbons .
  • These ethylene copolymers may contain from 30 to 85 wt. % ethylene preferably 40 to 80 wt. % of ethylene and 15 to 70 wt. %, preferably 20-60 wt. %, of one or more C3 to C28' preferably C3 to C18, more preferably C3 to C8' alpha olefins .
  • Copolymers of ethylene and propylene are most preferred.
  • Other aloha-olefins suitable in place of propylene to form the copolymer, or to be used in combination with ethylene and propylene, to form a terpolymer, tetrapolymer, etc.
  • branched chain alpha-olefins such as 4-methyl-1-pentene, 5-methylpentene-1 , 4-methyl-1-hexene,
  • the preferred diolefin containing EPDH rubber includes terpolymers and tetrapolymers , preferably of ethylene , said C3 to C28 alpha-olefin and a non-conjugated diolefin or mixtures of such diolefins .
  • the amount of the non-conjugated diolefin wi ll generally range from about 0.5 to 20 wt. percent , preferably about 1 to about 10 wt. percent, based on the total amount of ethylene and alpha-olefin present.
  • Representatlve examples of non-conjugated dienes that may be used as the third monomer in the terpolymer include: a. Straight chain acyclic dienes such as: 1,4-hexadiene;
  • Branched chain acyclic dienes such as: 5-methyl-1,4-hexadiene, 3,7-dimethyl 1,6-octadiene, 3,7-dimethyl 1,7-octadiene, and the mixed isomers of dihydro-myrcene and dihydro-cumene.
  • Single ring alicyclic dienes such as: 1,4-cydohexadiene, 1,5-cyclooctadiene, 1,5-cydo-dodecadiene, 4-vinylcyclohexene, 1-aliyl, 4-isopropylidene cyclohexane, 3-allyl-cyclopentene,
  • Multi-single ring alicyclic dienes such as: 4,4'-dicyclopentenyl and 4,4'-dicydohexenyl dienes.
  • Multi-ring alicyclic fused and bridged ring dienes such as: tetrahydrolndene, methyl tetrahydrolndene, dicyclopentadiene, bkyclo (2.2.1) hepta 2,5-diene, alkyl, alkenyl, alkylidene, cycloalkenyl and eyeloalkylidene norbornenes such as: ethyl norbornene, 5-methylene-6-methyl-2-norbornene, 5-methylene-6, 6-dimethyl-2-norbornene, 5-propenyl-2-norbornene, 5-(3-cydopentenyl)-2-norbornene,
  • the most preferred EPDH elastomer contains from about 50 to about 80% by weight ethylene, from about 15 to about 451 by weight proplyene and from about 3 to about 7% by weight of non-conjugated diene.
  • Preferred dienes include dicyclopentadiene, 1,4-hexadiene, 5-methylene-2-norbornene and 5 ethyl1dene-2-norbornene.
  • the EPR of this invention may be cured using conventional known vulcanizing systems for such rubbers.
  • EPR containing no unsaturatlon such as ethylene/propylene copolymers
  • EPR containing no unsaturatlon may be cured by free radical vulcanization techniques using free radical generators such as organic peroxides .
  • free radical generators such as organic peroxides .
  • vulcanization systems for saturated EPR include tertiary butyl peroxide, dicumyl peroxide, 1 , 1 ,t-di(t-butylperoxy)- 3,3,5-trimethyl cyclohexane, d i(t-butylperoxy)diisopropyl-benzene, 2 ,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2 ,5-dimethyl-2,5-di(t-butylperoxy)hexyne .
  • sulfur As a crossl inking accelerator for the peroxide vulcanization , sulfur, sulfur compounds such as dipentamethylenethluram tetrasulfide, mercaptobenzothiazole, polyfunctlonal monomers such as ethylene dimethacrylate, divlnylbenzene, dial lyl phthalate, metaphenylene bismalelmide and tolylene bismaleimide , and oxlme compounds such as p-quinonedioxine and p,p,-dibenzoylquinone-oxime may be used singly or in combination.
  • the crosslinking may be carried out at a temperature of from about 100°C to 250°C for a period of from about 1 minute to 120 minutes, preferably 1 to 60 minutes .
  • the crosslinking time is preferably adjusted to about 4 times the half life of the peroxide.
  • Vulcanizing agents include elemental sulfur and compounds which release sulfur at the vulcanization temperature of the elastomer.
  • Representative vulcanizing agents that release sulfur at vulcanization temperatures include thiuram polysulfides , amine disulfides , thiazoles and sodium polysufide. Usually about 0.2-5 parts per 100 parts ethyl ene/higher alpha-olefin/nonconjugated diene elastomer of sulfur or about 0.6-15 parts per 100 parts ethyl ene/higher alpha-olefin/nonconjugated diene elastomer of compounds that release sulfur are incorporated into the composition. Although i t is less preferred, peroxide curing agents such as aromatic or al iphatic peroxides can be used to cure the EPDH elastomer.
  • Representative peroxide curing agents include aromatic diacyl peroxides and aliphatic diacyl peroxides , dibasic add peroxides , ketone peroxides , alkyl peroxyesters , alkyl hydroperoxides, dibenzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxlde, tert-butylperbenzoate, tert-butyl cumyl peroxide, and the like.
  • Other vulcanizing systems include a metal oxide e.g. magnesium or zinc oxide, and an organic accelerator or curing agent which can be an amine, phenol, sulfinamide, thizole, thluram, thiourea or sulfur.
  • the EPR polymer composition may also contain other additives such as lubricants, fillers, plastldzers, tacklfiers, coloring agents, blowing agents, and antioxidants.
  • additives such as lubricants, fillers, plastldzers, tacklfiers, coloring agents, blowing agents, and antioxidants.
  • suitable fillers include inorganic fillers such as carbon black, silica, calcium carbonate, talc and clay, and organic fillers such as hlgh-styrene resin, coumarone-indene resin, phenolic resins, lignin, modified melamine resins and petroleum resins.
  • suitable lubricants include petroleum-type lubricants such as oils, paraffins and liquid paraffins, coal tar-type lubricants such as coal tar and coal tar pitch; fatty oil-type such as castor oil, linseed oil, rapeseed oil and coconut oil; tall oil; waxes such as beeswax, carnauba wax and lanolin; fatty adds and fatty add salts such as stearlc add, lidnolelc add, palmitic add, barium stearate, calcium stearate and zinc laurate; and synthetic polymeric substances such as petroleum resins.
  • petroleum-type lubricants such as oils, paraffins and liquid paraffins, coal tar-type lubricants such as coal tar and coal tar pitch
  • fatty oil-type such as castor oil, linseed oil, rapeseed oil and coconut oil
  • tall oil waxes such as beeswax, carnauba wax and lan
  • suitable plasticizers include hydrocarbon oils, e.g. paraffin, aromatic and naphthenic oils, phthalic add esters, adipic add esters, sebadc add esters and phosphoric acid-type plastldzers.
  • suitable tackifiers include petroleum resins, coumarone- indene resins, terpene-phenol resins, and xylene/ formaldehyde resins.
  • coloring agents include inorganic and organic pigments.
  • blowing agents examples include sodium bicarbonate, ammonium carbonate, N,N,-dinitrosopentamethylenetetramine, azocarbonamide, azobisisobutyronitrile, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, calcium amide, p-toluenesulfonyl azlde. salicylic add, phthalic add and urea.
  • the vulcanizable EPR composi tion may be prepared and blended on any suitable mixing device such as an internal mixer (Brabender Plastlcorder) , a Banbury M ixer, a kneader or a similar mixing device. Blending temperatures and times may range from about 45 to 180°C and from about 2 to 10 minutes respectively.
  • the mixture is then vulcanized by the further mixing-in of crosslinking agents and accelerators followed by heating the resulting blend to a temperature of from about 100° to 250°C, more preferably from about 125 to 200°C for a period of time ranging from about 1 to 60 minutes.
  • Articles such as sheets, belts, weatherstrip, gaskets, tires and hoses are prepared by shaping the pre-vulcanlzed formulation using an extruder or a mold, and subjecting the composi tion to temperatures and curing times as set forth above.
  • Substrates to which the cured EPR may be bonded using the adhesive polymers of the present invention include woven fabric substrates made from natural and synthetic fibers such as cotton, wool , dacron, nylon, polyesters or polyolefins; plastic sheet .material s made from polyamldes , polyesters , polyurethanes, polymers based on vinyl or vinyl idene chloride, and vinyl aromatic polymers; cured rubber substrates also based on cured EPR rubber or other cured elastomers based on conjugated dienes such as butyl rubber; metal substrates such as copper, aluminum, stainless steel and electrogalvanlzed steel .
  • the ethylene polymers of the present invention may be used as thermoplastic or cross linkable adheslves to bond cured EPR substrates to other substrates , and may be formulated to contain addi tional ingredients such as fillers, plastldzers , colorants and crosslinking agents such as dicumyl peroxide, divinyl benzene or ethylene glycol di methacrylate.
  • thermoplastic polymeric addi tives particularly crystalline polyolefins such as l inear low densi ty polyethylene, copolymers of ethylene with minor amounts of a higher alphaolefln such as 1-butene or 1-hexene, and polypropylene, as weli as copolymers of ethylene and vinyl acetate, and similar materials, provided however, that the ethylene polymers of the present invention constitute the continuous phase of the blend.
  • Bonding may be accomplished by applying the ethylene polymer adhesive to a substrate in the form of a solvent solution, an emulsion, a hot melt or a film.
  • the adhesive is applied 1n the form of a film or melt to the appropriate cured EPR substrate to be bonded, foliowed by the application to the film or melt surface of the second substrate to be bonded to form a sandwich-type laminate.
  • This assembly is then heated to a temperature sufficient to heat plastlfy the adhesive composition, generally from about 100°C to about 170°C, and under sufficient pressure to cause the adhesive to flow and fill at least a portion of the spaces between the surfaces to be laminated.
  • the adhesive may also be applied by coextrusion techniques wherein it is applied as a hot melt to a surface of a cured EPR article as it emerges from an extruder die.
  • This article may subsequently be laminated to other articles, including articles also made from cured EPR, by heat and pressure as described above.
  • the thickness of the ethylene polymer adhesive coating required to provide good adhesion as set forth herein will vary depending on the surface area to which it is applied. Generally, thicknesses of from about 25 to about 200 microns are suitable. Where the ethylene polymer is applied as a film in forming a sandwich laminate structure, film guage thicknesses within the range of from about 0.5 to about 50 mils, more preferably from about 5 to about 25 mils, are suitable.
  • Example 1 details the preparation of extruded strips of cured EPDH rubber based on ethylene, propylene and 5-ethylidene-2-norbornene having a Mooney viscosity within the range of from about 50 to about 60 at ML 1+4, 125°C, and a diene content which may range from about 5 to about 10 weight percent. These materials are available from Exxon Chemical Company under the trade names Vlstalon ® 8510 and 7000.
  • Example 1 details the preparation of extruded strips of cured EPDH rubber based on ethylene, propylene and 5-ethylidene-2-norbornene having a Mooney viscosity within the range of from about 50 to about 60 at ML 1+4, 125°C, and a diene content which may range from about 5 to about 10 weight percent. These materials are available from Exxon Chemical Company under the trade names Vlstalon ® 8510 and 7000.
  • Example 1 details the preparation of extruded strips of cured EPDH rubber
  • ViSTALON ® 7000 * a 60/40 blend of ViSTALON ® 7000 and ViSTALON ® 8510
  • the temperature of the mixer was maintained at about 250 to 275oF and mixing was conducted for about 4 minutes. This intensive mixing includes kneading, shearing and cross-over blending. The uniform mixture was discharged from the Banbury and placed on a two roli mili and milied at a temperature of about 200oF.
  • the foliowing vulcanizing system was then blended with the EPDH masterbatch on the mili:
  • Milling was continued for a period of about 10 minutes at 200oF.
  • the milled elastomer was then sheeted off the mill and extruded into a 2 inch wide strip through a 0.5/1 L/D Royle cold feed extruder at 240'F, and subsequently vulcanized 1n a circulating hot air oven for three minutes at 440oF.
  • Strips composed of nine different ethylene copolymer adhesives within the scope of this invention were prepared.
  • the composition and Melt index (Hi), as measured by ASTH D-1238 (condition E), of the copolymers are shown in Table 1, with, ET meaning ethylene, HA meaning methyl acrylate and AA meaning acrylic add.
  • compositions A-I were formed into adhesive strip layers having widths of 2 to 4 inches by extrusion through a 25:1 L/D Brabender extruder at 400oF, followed by cooling of the strips on a three roll calender take off.
  • Three layer laminates comprising two strips of the cured EPDH rubber prepared in Example 1 sandwiched around a layer of adhesive strips A-I of Table 1 were prepared.
  • the laminates were formed by forming the composi te structure at room temperature and heating the structure in a Carver Press at a temperature of about 120 to 160°C for five minutes at minimum pressure.
  • the laminates were then removed from the press , cooled and aged for 24 hours at room temperature. Test strips having a dimension of 6 inches by 1/2 inch were cut and the guage (thickness) of the adhesive layer was measured.
  • Adhesive strength was measured using a Honsanto Tensometer which pulls the 1/2 inch by 6 inch sample (bonded area 1/2 inch by 3 1/2 inches) apart at 2 inches a minute and at a 180* angle and measures the force required to separate the bonded EPDH strips. A minimum of two samples each were tested.
  • Table 2 Test results are shown in Table 2. Also included 1n the Table for comparative purposes is a laminate prepared using an adhesive copolymer of ethylene and a minor amount of vinyl acetate ("E/Va").
  • the ethylene copolymers of this invention also provide excellent adhesion between cured EPDH rubber and textile materials such as nylon fabric which is used 1n many automotive applications.
  • Laminates of the cured EPDH strips of Example 1 and nylon fabric were prepared and tested as described above.
  • the particular ethylene copolymer adhesive employed and test results are shown in Table 3. Table 3
  • H(PPRC) is an alloy (blend) of terpolymer H with a minor amount of an ethylene/propylene random crystalline copolymer
  • H (LLDPE) is an alloy of terpolymer H with a minor amount of linear low density polyethylene.
  • ethylene/methyl acrylate/acrylic add terpolymers appear to give enhanced adhesion to nylon fabric as compared with the ethylene/methyl acrylate copolymers, and adhesive properties can be further modified by blending the ethylene terpolymers with other polymers, particularly crystalline olefin polymers.
  • Laminates of the cured EPDH sheet material of Example 1 and wool/non-woven polypropylene pad stock were prepared and tested as described above.
  • the particular ethylene copolymer adhesives used and test results are shown in Table 4.
  • F 20 7 Yet another application of this invention involves the bonding of cured EPDH rubber to metals such as aluminum and steel.
  • the fabrication of automotive window channel belt strips involves coextruding rubber over metal.
  • the metal surface requires cleaning, abrasion, primers and solvent based adhesives such as polyurethanes. Not only is this process inefficient, but the solvents are hygroscopic and therefore give off moisture when the composite is cured, forming moisture blisters at the laminar layer.
  • the ethylene copolymers of this invention form excelient bonds between cured EPDH rubber and metal surfaces, and without the need to first abrade or otherwise treat the metallic surface.
  • Laminates of the cured EPDH sheet material of Example 1 and abraded stainless steel sheet (SS) as well as electro- galvanized steel (ES) were prepared and tested as described above.
  • the particular ethylene copolymer adhesives used and test results are shown in Table 5.
  • Laminates of cured EPDH strips of Example 1 and polyester yarn as typically used in hose constructions were prepared and tested as described above.
  • the particular ethylene copolymer adhesive employed and test results are shown in Table 6. Table 6
  • ethylene/methyl acrylate/acrylic add terpolymers appear to give enhanced adhesion to polyester yarn as compared with the ethylene/methylacrylate copolymers.
  • the preceding data in Tables 1-6 illustrate the variety of surfaces which can be bonded to cured EPR surfaces using the ethylene copolymers of this invention.
  • Other surfaces which can be so bonded to cured EPR include glass, polyester or nylon textile materials such as in the construction of the reinforced automotive hoses and tubing, paper, thermoplastic materials such as polyvinyl chloride TPE, styrene, polyurethane foam materials and other rubbery polymers.

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Abstract

L'invention concerne un procédé et une composition améliorés pour l'adhésion de composition EPR polymérisée sur une pluralité de substrats ou sur une autre masse de caoutchouc EPR polymérisé pour obtenir des laminés et des structures caractérisées par des liaisons adhésives résistantes et durables. L'invention concerne une composition adhésive à base d'un copolymère thermoplastique ou réticulé d'éthylène avec de petites quantités d'un méthacrylate ou un acrylate d'alkyl inférieur, ou un terpolymère thermoplastique ou réticulé d'éthylène avec de petites quantités d'un acrylate ou méthacrylate d'alkyl inférieur et un acide acrylique ou méthacrylique. La composition adhésive peut être appliquée sur la surface d'une masse de caoutchouc EPR polymérisée et sur une autre surface sur laquelle la masse EPR doit être collée, une telle application étant effectuée en appliquant sur le substrat la composition adhésive sous la forme d'une solution, une émulsion ou à l'état fondu, par application d'une pellicule de cette composition adhésive ou par revêtement par extrusion d'une coulée de la composition adhésive et de la masse EPR polymérisable pour former une structure laminée. Les structures de cette invention sont particulièrement appropriées aux applications dans l'industrie automobile qui nécessitent une adhésion excellente d'articles façonnés à base d'EPR sur diverses surfaces telles que du caoutchouc, du métal, du plastique, du tissu, du verre et autres surfaces.
PCT/US1990/004982 1989-09-01 1990-08-31 Procede permettant d'ameliorer l'adhesion de caoutchouc epr polymerise WO1991003514A1 (fr)

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US40196089A 1989-09-01 1989-09-01
US401,960 1989-09-01
US49499590A 1990-03-16 1990-03-16
US494,995 1990-03-16

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AU (1) AU6437390A (fr)
WO (1) WO1991003514A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0475728A2 (fr) * 1990-09-10 1992-03-18 Schlegel Corporation Produits laminé et adhésif thermofusible pour appliquer des couches sur caoutchouc EPDM
EP0922725A1 (fr) * 1997-12-10 1999-06-16 Henkel Kommanditgesellschaft auf Aktien Procédé pour la fabrication de stratifiés

Citations (3)

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Publication number Priority date Publication date Assignee Title
GB1394883A (en) * 1971-08-06 1975-05-21 Dow Chemical Co Interpolymers
US4010235A (en) * 1971-11-18 1977-03-01 Dunlop Limited Moulded plastic-rubber composites
JPS5996939A (ja) * 1982-11-26 1984-06-04 Nippon Telegr & Teleph Corp <Ntt> エチレン・プロピレンゴム製ｏリング切断面の接着方法

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
GB1394883A (en) * 1971-08-06 1975-05-21 Dow Chemical Co Interpolymers
US4010235A (en) * 1971-11-18 1977-03-01 Dunlop Limited Moulded plastic-rubber composites
JPS5996939A (ja) * 1982-11-26 1984-06-04 Nippon Telegr & Teleph Corp <Ntt> エチレン・プロピレンゴム製ｏリング切断面の接着方法

Non-Patent Citations (1)

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Title
Database WPIL, AN 84-174416(28), 21 September 1984, Derwent Publications Ltd, (London, GB), & JP-A-59096939 (NIPPON TELEG: & TELEPH.) 4 June 1984 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0475728A2 (fr) * 1990-09-10 1992-03-18 Schlegel Corporation Produits laminé et adhésif thermofusible pour appliquer des couches sur caoutchouc EPDM
EP0475728A3 (en) * 1990-09-10 1992-06-17 Schlegel Corporation Bonded composite of a layer and hot melt adhesive for direct bonding to epdm rubber
EP0922725A1 (fr) * 1997-12-10 1999-06-16 Henkel Kommanditgesellschaft auf Aktien Procédé pour la fabrication de stratifiés

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