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GB2128899A - Bonded composites - Google Patents

Bonded composites Download PDF

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Publication number
GB2128899A
GB2128899A GB08327867A GB8327867A GB2128899A GB 2128899 A GB2128899 A GB 2128899A GB 08327867 A GB08327867 A GB 08327867A GB 8327867 A GB8327867 A GB 8327867A GB 2128899 A GB2128899 A GB 2128899A
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GB
United Kingdom
Prior art keywords
rubber
vulcanized
epdm
thermoplastic
rubber composition
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.)
Granted
Application number
GB08327867A
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GB8327867D0 (en
GB2128899B (en
Inventor
James Frank Yardley
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Dunlop Ltd
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Dunlop Ltd
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Publication date
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Priority to GB08327867A priority Critical patent/GB2128899B/en
Publication of GB8327867D0 publication Critical patent/GB8327867D0/en
Publication of GB2128899A publication Critical patent/GB2128899A/en
Application granted granted Critical
Publication of GB2128899B publication Critical patent/GB2128899B/en
Expired legal-status Critical Current

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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
    • B32B25/00Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08Layered products comprising a layer of natural or synthetic rubber comprising rubber 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
    • B32B25/00Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • 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
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/121Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives by heating
    • 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
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • 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
    • B32B2305/72Cured, e.g. vulcanised, cross-linked
    • 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
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/704Crystalline
    • 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
    • B32B2323/00Polyalkenes
    • B32B2323/04Polyethylene
    • B32B2323/043HDPE, i.e. high density polyethylene
    • 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
    • B32B2323/00Polyalkenes
    • B32B2323/16EPDM, i.e. ethylene propylene diene monomer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

A method of making a novel bonded composite of (i) a thermoplastic elastomeric blend of vulcanized EPDM particles not more than 50 microns in size disposed in a thermoplastic linear crystalline polyolefin continuous phase, with (ii) a vulcanized EPDM or EPM rubber composition containing less than 50% (preferably 5% to less than 40%) by volume of rubber, comprises fusing the thermoplastic elastomeric blend and solidifying it in contact with the vulcanized rubber composition in the absence of an adhesive interlayer. Preferably the blend is extruded onto the vulcanized rubber composition. Preferably the linear crystalline polyolefin in the thermoplastic blend has a melt flow index of at least 0.25 when measured according to the test conditions ASTM D 1238-65T and is selected from polypropylene, propylene copolymers, high density polyethylene and high density ethylene copolymers.

Description

SPECIFICATION Bonded composites This invention relates to a method of producing a bonded composite of a thermoplastic elastomeric blend with a vulcanized EPDM or EPM rubber composition and to the composite produced thereby.
Thermoplastic elastomeric blends ofthemoplastic Iinearcrystalline polyolefin and vulcanized EPDM (ethytene/propylene/diene monomerterpolymer) rulstirerare known e.g. see those described in U.K.
PatentNo. 2,007,683B. In such blends the polyolefin resin isehe continuous phase with the EPDM as dispersed particles of a size 50 microns or less, usually f to 10 microns. Because the polyolefin is the continuous phase the resulting composition would be expected to behave in a similarwayto a composition consisting essentially of the polyolefin alone. However, we have found this notto be the case when trying to bond such a composition to a vulcanized EPDM or EPM (ethylene/propylenecopo- lymer) rubberwithouttheaid of an adhesive interlayer.Only by selecting a particularclassof EPDM or EPM rubber compositions, i.e. those compositions containing unexpectedly low levels of EPDM or EPM, can satisfactory adhesion be achieved.
According to one aspect of the present invention a method of making a bonded composite of (i) a thermoplastic elastomeric blend of vulcanized EPDM particles not more than 50 microns in size dispersed in a thermoplastic linear crystalline polyolefin continuous phase, with (ii) a vulcanized EPDM or EPM rubber composition containing less than 50% by volume of rubber, comprises fusing the thermoplastic elastomeric blend and solidyifying it in contact with the vulca- nized rubber composition in the absence of an adhesive interlayer.
According to a further aspect of the present invention a bonded thermoplastic elastomeric blend/ vulcanized EPDM or EPM rubber composite com- prises: (i) a thermoplastic elastomerwhich has vulcanized EPDM parties not more than 50 microns in size dispersed in a thermoplastic linear crystalline polyolefin continuous phase, bonded without an adhesivrinterlayerto (ii) a vulcanized EPDM to EPM rubber containing less thaw 50% byvolume of rubber.
By "thermoplastic elastomeric" is meant a macromolecular material which (i) at room temperature is capabJeof recovering substantially in shape and size after removal of a deforming force and (ii) is capable of being repeatedly softened by increase of tempera tune and hardened by decrease oftemperature i.e. the change upon heating is substantially physical.
Thethermoplasticelastomeric blend remainsther moplastic after bonding and no detectable vulcaniza tiontakes place during bonding. The linear crystalline polyolefin in the blend is preferably selected from homopolymers and copolymers of propylene and high density homopolymers and copolymers of ethylene. Linear high density ethylene polymers and linear low density ethylene polymers can be made by low pressure solution polymerization; branched low density ethylene polymers are high pressure solution polymerized and are excluded from the present invention. Preferablythepolyolefin hasa melt flow index of at least 0.25 when measured according to the test conditions specified in ASTM D 1238-65T.
The EPDM or EPM rubber is usually in nonparticulate form and must be in the vulcanized state (i.e. cross-linked, non-thermoplastic) prior to contact with the thermoplastic blend. The EPDM and/or EPM rubber may be in combination with at least one other rubber, preferably such that the total volume of EPDM and/or EPM rubber is more than 50% ofthetotal rubber present.
Examples of methods of bringing the components into contact are by injection, transfer, rotational or compression moulding or extrusion ofthethermoplastic elastomeric blend into contact with the vulcanizedEPDMorEPM. Preferablythethemoplas- tic blend is extruded onto the vulcanized EPDM or EPM rubber as extrusion usually achieves a greater degree of "wetting" of the rubberbythethemoplas- tic. A person of ordinary skill in the artwould be able bysimpletrial and errorto adjustthe conditions of contact of the two materials in orderto achieve satisfactory bonding levels.Where the process involves vulcanizing the EPDM/EPM composition im mediatelypriorto contactwith the thermoplastic blend,there is no need to cool the rubber, and indeed it may be advantageous notto do so. If desired an EPDM/EPM composition which has been vulcanized and cooled beforehand can be preheated to promote bonding with a thermoplastic blend.
Preferred compositions of the thermoplastic blend comprise (a) 15 to 45, more preferably 15 to 40, % by volume polyolefin, (b) 15to 50, more preferably 20to 45, % byvolume EPDM, (c) 15 to 50, more preferably 15to45, % byvolumeoil,and (d) a 15% maximum, more preferably 10% maximum, by volume of other ingrndients(s).
Preferably the total rubber content of the vulcanized EPDM or EPM rubber composition is less than 40% and at least 5% by volume, more preferablyfrom 5 to 35% by volume. Atotal rubber content of from 5 to 35% by volume is particularly applicable where the thermoplastic blend to be bonded to it has a Shore D hardness of less than 82.5 or contains less than 35% byvolume of linearcrystalline polyolefin. The remainder of the composition includes ingredients selected from filler (e.g. carbon black), liquid extender (e.g. petroleum based oil orsimilar),vulcanizing agent, vulcanization accelerator and anti-oxidant.
Wherethethermoplastic blend contains less than 35% by volume polyolefin and more than 34% by volume oil, the rubber content of the rubber composition should be less than 40% by volume in orderfor satisfactory adhesion to be attained.
The process of the present invention could be used where coextrusion is not practical. For example when making door or window sealing strips an EPDM/EPM rubber composition could be vulcanized in the required profile and then a thermoplastic blend extruded onto it.
The invention is illustrated by the following Exam ples. Although extrusion is particularly applicable to the invention it is not ideal for assessing adhesion levels accurately. Therefore an injection moulding technique was used.
Example I Sheets 228.6 x 76.2 x 2 mm of EPDM rubber compositions containing proportions of EPDM from 30 to 65% by volume as shown in Table I were vulcanized against a biaxially oriented polyethylene terephthalate (available underthe Registered Trade Mark MELINEX) film to give a consistent, clean bonding surface.
Thermoplastic blends of various composition available underthetrade name "Santoprene" from Monsanto were injected onto the EPDM rubber surface in a mould measuring 102 x 76.2 x 6 mm with a full-width fangate known to give even adhesion throughout the test sample. For comparison a polypropylene available as Carlona KM61 having a meltflow index of 3 was applied in the same manner.
Part of the rubber sheet at the opposite end to the injection gate was sprayed with polytetrafluoroethylene (available under the registered Trade Mark TEFLON) to prevent adhesion. This injection moulding was carried out with a 45 ton lock Edgwick machine usingthefollowing moulding conditions: Barrel temperature- 275/260/250 C Mouldtemperature-700C Cycletime-40 seconds Peel adhesion values of the resulting composites were measured at an Instron crosshead speed of 125 mm/minute and the results plotted on a graph (see Figure 1).
Axis X denotes peel adhesion in N/cm and axis Y denotes rubber content of the EPDM as a percentage volume. Curve 1 refers to results obtained using Santoprene73A. Curve 2 refers to results obtained using Santoprene 80A. Curve 3 refers to results obtained using Santoprene 87A. Curve 4 refers to results obtained using Santoprene SOD. Curve (5) (control) refers to results obtained using polypropy lene-Carlona KM61.
The "Santoprene" formulations are believed to be dynamically cured polypropylene/EPDM/oillfiller thermoplastic elastomers. The polypropylene content is believed to be 87A > 50D > 80A > 73A and the EPDM content is believed to be 87A > 80A > 73 > 50D.
Adhesion values are dependent upon thetypeof failure which can vary considerably as follows: Adhesion failure. Clean failure with noappa; rentchangeintheapprearanceofthe rubber surface.
~ = Thin layerplasticteanng. Failure occurs in the plastic layerwhich leaves as layer of plastic approximately 7 mm thick attached to the rubber.
e = Thin layer rubbertearing. Failure occures in the rubber layer which leaves a thin layer of rubber approximately 0.5mm thick attached to the plastic.
~ = Rubber tearing. Failure occurs by massive rubber tea ring, the value obtained being obviously dependent on the rubbertear strength and sample thickness.
TABLE I EDPMFORMULATJONS (Parts by Weight) A B C D E F Into lan 255 (EPDM) 100.0 100.0 100.0 100.0 100.0 100.0 N550 carbon black 56.0 77.0106.0127.0153.0 187.0 Circosol 4240 (naphthenicoil) 26.0 47.0 76.0 97.0123.0157.0 StearicAcid 1.0 1.0 1.0 1.0 1.0 1.0 Zinc Oxide 5.0 5.0 5.0 5.0 5.0 5.0 Sulphur 2.0 2.0 2.0 2.0 2.0 2.0 ZnBuD (zinc dibutyl dithiocarbamate) 2.0 2.0 2.0 2.0 2.0 2.0 MBTS (mercaptobenz-thiazole disulphide) 1.5 1.5 1.5 1.5 1.5 1.5 TMTMS (tetramethyl thiuram monosulphide) 0.5 0.5 0.5 0.5 0.5 0.5 Cure::- 60 minutes at 150 C B.S.D. Hardness 71.0 73.0 68.5 70.5 70.5 71.0 Rubber Volume % 65 55 45 40 35 30 Example it Experiments have shown that an extrusion techni que tends to give a better bond tkan an injection moulding technique: Thermoplastic EPDM content Injection Extrusion blend of vulcanized Moulding Adhesion rubber Adhesion N/cm composition N/cm % volume Santoprene 73A 33 22(E) PF SORT Santoprene 73A 35 19AF ::l8AF Santoprene 73A 43 4(E)AF ISAF Santoprene 50D 35 60RT 56RT Santoprene SOD 43 52(E)RT 68RT E = estimated from Figure 1 PF= plastic failure Af = adhesion failure RT= rubber tearing Example Ill Sheets 228.6 x 76.2 x 2 mm of EPDM rubber compositions containing proportions of EPDM from 30to 65% by volume as shown in Table 1 were vulcanized against Melinex (a biaxially orientated polyethylene terephthalate) film to give a consistent clean bonding surface.
A dynamically cured thermoplastic elastomeric blend of high density polyethylene (HDPE) and vulcanized EPDM was prepared by mixing the following ingredients in a 34 mm twin screw extruder at a temperature of 2000C and screw speed of 233 rum:~ Pear 585 (EPDM) 100.0 parts by weight Rigidex 006/60 (HDPE) 130.0 parts by weight Sunpar 2280 (paraffinicoil) 145.0 parts by weight Schenectady SP 1055 (Brominated phenolic resin) 12.0 parts by weight Zinc Oxide 5.0 parts by weight Titanium Dioxide 5.0 parts by weight StearicAcid 1.0 parts by weight Mistron Vapour Talc 1.0 parts by weight The thermoplastic blend was injected onto the EPDM rubbersurfacein a mould measuring 102 x 76.2 x 6 mm with a full width fanate known to give even adhesion throughoutthe test sample. For comparison the HDPE Rigidex 006/60 having a melt flowindexofo.6wasapplied in the same manner.
Part of the rubber sheet atthe opposite end to the injection gate was sprayed with Teflon (polytetrafluoroethylene) to prevent adhesion. The injection moulding was carried out with a 45 ton lock Edwick machine using the following moulding conditions: Barrel temperature re 275/260/2500C Mould temperature - 700C Cycletime 40 seconds Peel adhesion values ofthe resulting composites were measured at an Instron crosshead speed of 125 mm/minute andthe results plotted on a graph (see Figure 2). Axis X denotes peel adhesion in N/cm and axis Denotes rubber content ofthe EPDM as a percentage volume. Curve t refers to results obtained using the HDPEIEPDM blend and curve 2 (control) refers to results obtained using the HPDE. The symbols usedforthegraph points have the same meaning as described in Example

Claims (15)

1. A method of making a bonded composite of (i) a thermoplastic elastomeric blend of vulcanized EPDM particles not more than 50 microns in size dispersed in athermoplasticlinearcrystalline polyolefin continuous phase, with (ii) a vulcanised EPDM or EPM rubber composition containing less than 50% by volume of rubber, comprises fusing the themoplastic elastomeric blend and solidifying it in contact with the vulcanized rubbercomposition in the absence of an adhesive interlayer.
2. A method according to Claim 1 wherein the thermoplastic linear cystalline polyolefin is selected from homopolymers of propylene, copolymers of propylene, high density homopolymers of ethylene and high density copolymers of ethylene.
3. A method according to Claim 1 or 2 wherein the thermoplastic linear crystalline polyolefin has a melt flow index of at least 0.25 when measured according to the test conditions specified in ASTM D 1238-65T.
4. A method according to any preceding claim wherein the rubber content ofthe vulcanized rubber composition is less than 40% by volume.
5. A method according to any preceding claim wherein the rubber content of the vulcanized rubber composition sat least 5% byvolume.
6. A method according to any one of Claims 1 to 4 wherein the rubber content of the vulcanized rubber composition is from Sto 35% by volume.
7. A method according to any preceding claim wherein the EPDM and/or EPM rubber in the vulca nized rubber composition is in combination with at least one other rubber so that the total volume of EPDM and EPM is more than 50% ofthetotal rubber content.
8. A method according to any preceding claim wherein the thermoplastic elastomeric blend is ex truded into contact with the vulcanized rubber composition.
9. A method according to any preceding claim wherein the vulcanized EPDM or EPM rubbercom- positions in non-particulate form.
10. A method according to any preceding claim wherein the linear crystalline polyolefin in the ther moplastic elastomeric blend is a low pressure solu tion polymerized olefin.
11. Amethod according to Claim 1 substantially as herein described.
12. A method according to Claim 1 substantially as described in any one ofthe Examples.
13. A bonded composite made bythe method according to any preceding claim.
14. A bonded thermoplastic elastomeric blend/ vulcanized EPDM or EPM rubber composite com- prises: (i) athermoplasticelastomerwhich has vulcanized EPDM particles not more than 50 microns in size dispersed in a thermo-plastic linear crystalline polyolefin continuous phase, bonded without an adhesive interlayer to I (ii) avulcanizedEPDMorEPMrubbercontaining lessthan 50% byvolume of rubber.
15. A bonded composite according to Claim 14 having the feature defined in any one of Claims 2,3,4, 5,6,7,9Or10.
GB08327867A 1982-10-27 1983-10-18 Bonded composites Expired GB2128899B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
GB8230704 1982-10-27
GB08327867A GB2128899B (en) 1982-10-27 1983-10-18 Bonded composites

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GB8327867D0 GB8327867D0 (en) 1983-11-16
GB2128899A true GB2128899A (en) 1984-05-10
GB2128899B GB2128899B (en) 1985-11-20

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3519064A1 (en) * 1985-05-28 1986-12-04 Avery International Corp., Wilmington, Del. MULTILAYER, SELF-ADHESIVE AND DRAWN PROTECTIVE FILM, IN PARTICULAR FOR MOTOR VEHICLES
US4784885A (en) * 1986-08-29 1988-11-15 R. J. Reynolds Tobacco Company Peelable film laminate
EP0472268A3 (en) * 1990-08-22 1992-09-02 Gencorp Inc. Forming abrasion-resistant coatings on elastomeric substrates
DE4219344A1 (en) * 1991-06-14 1992-12-17 Toyoda Gosei Kk Long moulded articles used as side trims for motor vehicles - have outer skin of thermoplastic elastomer and core of ethylene@]-alpha olefin] copolymer or styrene]-based elastomer in polypropylene@ matrix
US5183613A (en) * 1990-08-22 1993-02-02 Gencorp Inc. Process for the preparation of solventless, low friction, abrasion-resistant coatings for elastomeric substrates
BE1006364A3 (en) * 1992-11-17 1994-08-02 Euroventures Limited Soft composite material and inflatable component produced with said material
US5571581A (en) * 1991-06-14 1996-11-05 Toyoda Gosei Co., Ltd. Long sandwich molded article
EP1533344A4 (en) * 2002-07-12 2008-07-30 Daicel Degussa Ltd Composite dispersion and process for producing the same
US7985804B2 (en) 2006-11-06 2011-07-26 Exxonmobil Chemical Patents Inc. Rubber toughened compositions, articles, films, and methods of making the same

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3519064A1 (en) * 1985-05-28 1986-12-04 Avery International Corp., Wilmington, Del. MULTILAYER, SELF-ADHESIVE AND DRAWN PROTECTIVE FILM, IN PARTICULAR FOR MOTOR VEHICLES
US4784885A (en) * 1986-08-29 1988-11-15 R. J. Reynolds Tobacco Company Peelable film laminate
EP0472268A3 (en) * 1990-08-22 1992-09-02 Gencorp Inc. Forming abrasion-resistant coatings on elastomeric substrates
US5183613A (en) * 1990-08-22 1993-02-02 Gencorp Inc. Process for the preparation of solventless, low friction, abrasion-resistant coatings for elastomeric substrates
DE4219344A1 (en) * 1991-06-14 1992-12-17 Toyoda Gosei Kk Long moulded articles used as side trims for motor vehicles - have outer skin of thermoplastic elastomer and core of ethylene@]-alpha olefin] copolymer or styrene]-based elastomer in polypropylene@ matrix
US5571581A (en) * 1991-06-14 1996-11-05 Toyoda Gosei Co., Ltd. Long sandwich molded article
DE4219344C2 (en) * 1991-06-14 1997-05-07 Toyoda Gosei Kk Long sandwich molding
BE1006364A3 (en) * 1992-11-17 1994-08-02 Euroventures Limited Soft composite material and inflatable component produced with said material
EP1533344A4 (en) * 2002-07-12 2008-07-30 Daicel Degussa Ltd Composite dispersion and process for producing the same
US7553912B2 (en) 2002-07-12 2009-06-30 Daicel-Evonik Ltd. Composite dispersion and process for producing the same
US7985804B2 (en) 2006-11-06 2011-07-26 Exxonmobil Chemical Patents Inc. Rubber toughened compositions, articles, films, and methods of making the same

Also Published As

Publication number Publication date
GB8327867D0 (en) 1983-11-16
GB2128899B (en) 1985-11-20

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