CA2027210A1 - Composite articles of metals and vulcanized rubber and process for their preparation - Google Patents
Composite articles of metals and vulcanized rubber and process for their preparationInfo
- Publication number
- CA2027210A1 CA2027210A1 CA002027210A CA2027210A CA2027210A1 CA 2027210 A1 CA2027210 A1 CA 2027210A1 CA 002027210 A CA002027210 A CA 002027210A CA 2027210 A CA2027210 A CA 2027210A CA 2027210 A1 CA2027210 A1 CA 2027210A1
- Authority
- CA
- Canada
- Prior art keywords
- polyamide
- rubber
- parts
- weight
- composite article
- 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.)
- Abandoned
Links
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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
-
- 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
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
-
- 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
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
Abstract
ABSTRACT
A composite article composed of a metal component and a vulcanized rubber component, additionally containing an adhesion-promoting polyamide layer. The article is prepared by coating the metal element with polyamide, preferably by powder coating process and then vulcanizing the rubber mixture in intimate contact with the polyamide-coated metal. The composite articles of the invention are used for industrial purposes, for example as rollers, seals or vibration dampers.
A composite article composed of a metal component and a vulcanized rubber component, additionally containing an adhesion-promoting polyamide layer. The article is prepared by coating the metal element with polyamide, preferably by powder coating process and then vulcanizing the rubber mixture in intimate contact with the polyamide-coated metal. The composite articles of the invention are used for industrial purposes, for example as rollers, seals or vibration dampers.
Description
~ 7;~
Ht~LS AKTIENGESELLSC}IAET 0. Z . 4428 - - PATENTABq'E ILUNG
Composite article~ of mQtals and vulcanized rsbb~L-A~
process for their preparation The invention relates to composite articles which are composed of at least one metal component and at lea~t one vulcanized rubber component and which contain an adhesion-promoting polyamide layer and to a process for the preparation of articles of this type.
~t is well known that a s$ngle material cannot always provide all the properties which are regu$red of an ob~ect. For in~tance, high strength, rigidity or hard-ness on the one hand are irreconcilable with qood vlbra-tion damping, flexibility or non-skid properties on the other hand. If an article is to combine these proper-ties~ then composites of a plurality of materials are used.
One possibility in this case is to use metal and vulcanized rubber. According to the state of the art, the following procedure i8 used to prepare elements whose components, metal and vulcanized rubber, are firmly bonded togethers 1. The metallic component is shaped, for example by casting, pressing, machining or drawing.
Ht~LS AKTIENGESELLSC}IAET 0. Z . 4428 - - PATENTABq'E ILUNG
Composite article~ of mQtals and vulcanized rsbb~L-A~
process for their preparation The invention relates to composite articles which are composed of at least one metal component and at lea~t one vulcanized rubber component and which contain an adhesion-promoting polyamide layer and to a process for the preparation of articles of this type.
~t is well known that a s$ngle material cannot always provide all the properties which are regu$red of an ob~ect. For in~tance, high strength, rigidity or hard-ness on the one hand are irreconcilable with qood vlbra-tion damping, flexibility or non-skid properties on the other hand. If an article is to combine these proper-ties~ then composites of a plurality of materials are used.
One possibility in this case is to use metal and vulcanized rubber. According to the state of the art, the following procedure i8 used to prepare elements whose components, metal and vulcanized rubber, are firmly bonded togethers 1. The metallic component is shaped, for example by casting, pressing, machining or drawing.
2. The surface of the metallic component $8 treated, for example by degreaslng, sandblasting, brassing or phosphatizing.
3. A primer is applied from a solution, for example in aroma~ics or chlorinated hydrocarbons.
4. The solvent iB removed by evaporation.
, . ~ :~`'','` ' . ,; .'' :.
' ' . : .
J~ ~
., ~ .
, . ~ :~`'','` ' . ,; .'' :.
' ' . : .
J~ ~
., ~ .
5. An adhe~ion promoter i8 applied from a solution, for - example in aromatics or chlorinated hydrocarbon~.
.
.
6. The ~olvent i3 removed by evaporation.
7. The unvulcanized rubber i8 applied to the metal surface which has been pre-treated in this manner and is vulcanized.
The substancQs which promote adhesion between metal and unvulcanized or vulcanized rubber are descrlbed, for example, in W. Rleemann, Mii8chungen f~r die Elastverar-beitung, Leipzig 1982 and ln the Bayer-Taschenbuch fUr die Gumml-Industrie, 1963, and also in particular in data sheet~ from ~enkel RGaA under the trade name "Chemosil~.
, ; The known processes are in need of improvement for a ; variety of reasonss 1. They ar- oompllcated, as can be seen from the list of the~m~ny process steps.
s,~
2. They are not ~afe with regard to environmental pollution and occupational health hazardss the 801vent8 are not harmle~s and must be dispQsed of.
2D ~ 3. Th tr at-d e-l co~ponents have a limlted shelf 4. The procedure cannot be automated. -~
It~ ha~ i;now~been found that the conventional adheslon promoter-~;and~primers can advantageously be dispensed ~ with if~the~metal 8urface is coated in a manner known per se~with polyamide~ before thi8 surface is brought into oontact wlth certa~in unvulcanized rubber composition~.
The~polyam$de is applied either by electrostatic powder coating or by fluidlzed bed coatlng. It is al80 pos~ible *Trade Mark i r~ . i ~ 3 ~ 23443-442 to apply the polyamide in the manner of a paint or by extrusion coating, but these processes are less advantag-eous. The suitable powder coating processe~ are des-cribed, for example, by R. Feldmann in data ~heet no.
5215 from HUls AG, D-4370 Marl, dated November 1987.
Coating processes have hitherto been used to protect the metal surface from corrosion; the use of the said powder coatlngs as adhesion promoters for unvulcanized rubbers, as de~crlbed here, i8 novel.
The use of polyamides as adhesion promoter between metals and unvulcanized or vulcanized rubber has a number of advantages in comparison with conventional processes~
, 1. Problems to do with ecology and hygiene are elimina-ted, since no solvents are used.
: .
2. The metal components which have been treated with the adhesion-promoting polyamide have a virtually unlimi-ted shelf llfe.
3. The procedure can be automated.
The unvulcanized rubbers listed below can be used for the ~ 20 process according to the invention. These unvulcanized '~ rubbers must be crosslinked using peroxide or other free ;;I- radical-forming additives. Crosslinking agents based on ,~ ~ sulphur or ~ulphur donors alone are unsuitsble for the process.
The metallic components used are preferably workpieces made from steel, but it 18 also possible to use iron or non-ferrous metals such as alumlnium or brass. The surf~ces can be pre-treated, for example by degreasing, sandblasting or phosphatizlng. A primer, such as is often consldered necessary with polyamide powder coat-~` - ings, is superfluous in this case.
'~
-~ The polyamide tPA) used is preferably PA 1012, PA 11, ~ *Trade Mark .. . .
~ J
_ 4 _ ~3443-442 PA 12*or PA 1212* Paxticular preference 18 given to PA
1~ having a relative vi~c08ity in m-cresol (determined in accordance with the condition~ described in DIN 53 727) of 1.4 to 2.0, preferably 1.5 to 1.7. The polyamide i~
used in pulverulent for~. The particle diameter can b~
up to 200 ~m. The polyamide may optionally contain additive~ such as, for example, catalyets, ~tabilizer~ or pigment~. Proce~es for the preparation of suitable polyamides are known (R. Vieweg/A. MUller, Xun~tstoff-handbuch, Vol. 6 - Polyamide, C. Hanser Verlag, Munich 1966, p. 187; D. E. Floyd, Polyamide Resins, 2nd Editlon, Chapman Hall New York/London 1966, p.S5).
The preparation of polyamide powders for coatings is des-cribed, for example, in German Published Patent Applications No. 3,510,687, 3,510,688, 3,510,689, 3,510,690 and -3,510,691 (corresponding to European Published Patent Applications No. 0,202,393, 0,199,000, Q,200,853, 0,200,852 and 0,202,389).
; The unvulcanized rubber compositlons used contain~
- - 100 parts by weight of a carboxyl- or -anhydride-containing rubber - 10 to 300 parts by weight of additives ; - 1 to 10 parts by weight of peroxide vulcaniz-ing agents - O.S to 4 parts by weight of vulcanization -~
activators and . , , ~ ~ - 0 to 150 parts by weight of plasticizer , ~ .
~ The unvulcanized rubber u~ed may also be a mixture of I Pi! various~uitabl6 types. Preference i~ given to iEP(D)M
and NBR rubber~.
~he EPM rubber i~ prepared in a known manner by polymeri-zing a mixture of 25 to 75% of ethylene and 75 to 25% of ~ propylene ~n the pre~ence of a Ziegler-Natta catalyst.
.~. , The EPDM rubber 18 prepared in similar manner by polymer-izing a mixture of *Trade Mark more than 25~ of ethylene, more than 25% of propylene and 1 to 10%, in particular 1 to 3%, of a diene.
~ This diene must not be con~ugated. PreferenCe i~ given to bicyclo(2.2.1)h~ptadiene, 1,4-hexadiene, dicyclopenta-diene and in particular 5-ethylidenenorbornene.
The carboxylation of the EP(D)M rubber~ is carried out, for example, in a known manner by compounding with unsaturated acid~ or acid derivatives such a maleic acid or maleic anhydride (MAA), optionally in the presence of a free radical initiator. Suitable preparative methods are given, for example, in US-A-4,010,223.
Carboxylated EPM rubbers of thi~ type are produced, for example, by EXXON under the trade name EXXELORR VA 1803.
An example of an EPD~ rubber which has proven suitable is maleic anhydride-modified BUNAR AP (trade name: ~V~STAMID
X 4496~) from Bunawerke H~ls GmbH, D-4370 Marl.
The nitrile rubbers ~NBR) are prepared in a known manner by copolymerization of 50 to 80 % by weight of butadiene and correspondingly 50 to 20 % by weight of acrylo-nitrile. The carboxyl-containing nitrile rubbers are a particular modificatio~. These are copolymers of butadiene, acrylonitrile and acrylic acid, methacrylic acid or sorbic acid.
The vulcanizates of mixtures of this type have a high tensile strength, good elasticity and very good abrasion resistance. The oil and solvent resistance typical of nitrile rubber remains unaltered.
.
Suitable carboxylated NBR rubbers are produced, for example, by GOODYEAR TIR~ & RUBBER Company, Akron, Ohio, ~ USA, under the trade nam~ CHEMIGUN~ NX 775 or by BF
-~` GOODRICH, NV, Arnhem, Netherlands, under the trade name ~ HYCAR~ 1472.
.~
l : .
';~
.,.
Suitable additives are all conventional fillers for EP(D)M and NBR rubbers such as, for example, carbon black, silica, ~ilicates and calcium carbonates, and also zinc oxide and stearic acid.
Suitable plasticizers are, in particular, mineral oils or synthetic plasticizers such as esters and ethers. In this context, in the case of EP(D)M rubber, preference is given to the use of mineral oils, in particular naph-thenic oils. The amount of plasticizer can be up to 150 part~ by weight, relative to 100 parts by weight of rubber; preferably up to 50 parts by weight.
Suitable peroxide vulcanizing agents are the peroxides known to a person skilled in the art such as, for example, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, dicumyl peroxide, 4,4-di-tert-butylperoxy-n-butyl valerate, l,l-di-tert-butylperoxy-3,3,5-trimethyl-cyclo-hexane and bis(tert-butylperoxyisopropyl)benzene.
Details regarding the use of peroxide vulcanizing agent~
are to be found in the company brochure ~Rubbery Chemical-Crosslinking-Peroxides" from Akzo-Chemie (publi-cation date: April 1985).
Examples of suitable vulcanization activators ars triallyl cyanurate (TAC) and acrylates such as ethylene glycol dimethacrylate (EDNA) and trimethylolpropane --~ 25 trimethacrylate (TRIM). Preference is given to the use ;~ of TAC and/or EDMA.
:"~
. ~ :
The composite articles are prepared by vulcanizing the abovementioned rubbers ln intimate contact, preferably under pressure, with the polyamide-coated metals. The vulcanizing conditions are identical per se with the conditions which are used when employing conventional adhesion promoters. The vulcanization is preferably carried out at temperatures of between 140 and 200-C in 2 to 30 minutes, in particular at temperatures of between 150 and 180-C in 5 to 10 minutes.
.~
Ex~mple~ o typ~cal compo~lte artlcle~ m~de fro~ met~l~
and ~ulc~nlzed rubber ~re rubber-co~ted roller~, se~
flangeA, buffer~, ~prlng element~, Ylbratlon damper~, met~l-relnforced rubber proflle~, and clutch and brake disc~. A partlcular advantage of elements of thl~ type 1~ their resi~tance to corrosive media, in partlcular to corrosive ~alt~
The ex~mple~ whlch follow ser~e to illu~tr~te the lnvention. In these example~, the following 8ub~tance~
are used E~X2LORa VA 1803 i~ a malelc ~nhydride-modifled ~P~ rubber from Exxon Chemical~, Wilmlngton, ~elaware, USA. $he propertle~ of thi~ product are given ln the technical data sheet ~EXXELOR VA~, dated 01.03.1988.
, ZnO c~n be obt~ined under the trade na~e Zinkwei~ ~
Rot~iegel from Grillo-Werke AG, D-3380 Goslar. : -VULXASII~ C i~ a highly reactive ~ilica, obtainable fro~
Bayer AG, D-5090 Leverku~en.
CIRCOSOL~ 4240 ~ a predomlnantly naphthenic mineral oil fro~ Sun Oll, Antwerp (Belglu~
VULXANOS~ HS 1~ an antioxidant fro~ 8ayer AG, D-5090 ~everku~en. It i~ 2,2,4-trimethyl-1,2-dlhydroqu~noline.
PERXADO~a 14/~0 and PERKADO~ BC ~0 are peroxide~ ~ro~
, I 25 ~ Akzo-Chemie, 3800 AZ Amer~foort, NetherlandJ.
~AC (triallyl cyanurate) and eDMA (ethylene qlycol dimethacrylate) are product~ of Degu~a, D-6450 Hanau.
;~ CHEMIGUn~ N~ 7~5 18 a carboxyl-containing NBR rubber from Goodyear $1re and Rubber, Akron, Ohio, USA. The proper-tle~ of thl~ product are given in the data sheet s ~
The substancQs which promote adhesion between metal and unvulcanized or vulcanized rubber are descrlbed, for example, in W. Rleemann, Mii8chungen f~r die Elastverar-beitung, Leipzig 1982 and ln the Bayer-Taschenbuch fUr die Gumml-Industrie, 1963, and also in particular in data sheet~ from ~enkel RGaA under the trade name "Chemosil~.
, ; The known processes are in need of improvement for a ; variety of reasonss 1. They ar- oompllcated, as can be seen from the list of the~m~ny process steps.
s,~
2. They are not ~afe with regard to environmental pollution and occupational health hazardss the 801vent8 are not harmle~s and must be dispQsed of.
2D ~ 3. Th tr at-d e-l co~ponents have a limlted shelf 4. The procedure cannot be automated. -~
It~ ha~ i;now~been found that the conventional adheslon promoter-~;and~primers can advantageously be dispensed ~ with if~the~metal 8urface is coated in a manner known per se~with polyamide~ before thi8 surface is brought into oontact wlth certa~in unvulcanized rubber composition~.
The~polyam$de is applied either by electrostatic powder coating or by fluidlzed bed coatlng. It is al80 pos~ible *Trade Mark i r~ . i ~ 3 ~ 23443-442 to apply the polyamide in the manner of a paint or by extrusion coating, but these processes are less advantag-eous. The suitable powder coating processe~ are des-cribed, for example, by R. Feldmann in data ~heet no.
5215 from HUls AG, D-4370 Marl, dated November 1987.
Coating processes have hitherto been used to protect the metal surface from corrosion; the use of the said powder coatlngs as adhesion promoters for unvulcanized rubbers, as de~crlbed here, i8 novel.
The use of polyamides as adhesion promoter between metals and unvulcanized or vulcanized rubber has a number of advantages in comparison with conventional processes~
, 1. Problems to do with ecology and hygiene are elimina-ted, since no solvents are used.
: .
2. The metal components which have been treated with the adhesion-promoting polyamide have a virtually unlimi-ted shelf llfe.
3. The procedure can be automated.
The unvulcanized rubbers listed below can be used for the ~ 20 process according to the invention. These unvulcanized '~ rubbers must be crosslinked using peroxide or other free ;;I- radical-forming additives. Crosslinking agents based on ,~ ~ sulphur or ~ulphur donors alone are unsuitsble for the process.
The metallic components used are preferably workpieces made from steel, but it 18 also possible to use iron or non-ferrous metals such as alumlnium or brass. The surf~ces can be pre-treated, for example by degreasing, sandblasting or phosphatizlng. A primer, such as is often consldered necessary with polyamide powder coat-~` - ings, is superfluous in this case.
'~
-~ The polyamide tPA) used is preferably PA 1012, PA 11, ~ *Trade Mark .. . .
~ J
_ 4 _ ~3443-442 PA 12*or PA 1212* Paxticular preference 18 given to PA
1~ having a relative vi~c08ity in m-cresol (determined in accordance with the condition~ described in DIN 53 727) of 1.4 to 2.0, preferably 1.5 to 1.7. The polyamide i~
used in pulverulent for~. The particle diameter can b~
up to 200 ~m. The polyamide may optionally contain additive~ such as, for example, catalyets, ~tabilizer~ or pigment~. Proce~es for the preparation of suitable polyamides are known (R. Vieweg/A. MUller, Xun~tstoff-handbuch, Vol. 6 - Polyamide, C. Hanser Verlag, Munich 1966, p. 187; D. E. Floyd, Polyamide Resins, 2nd Editlon, Chapman Hall New York/London 1966, p.S5).
The preparation of polyamide powders for coatings is des-cribed, for example, in German Published Patent Applications No. 3,510,687, 3,510,688, 3,510,689, 3,510,690 and -3,510,691 (corresponding to European Published Patent Applications No. 0,202,393, 0,199,000, Q,200,853, 0,200,852 and 0,202,389).
; The unvulcanized rubber compositlons used contain~
- - 100 parts by weight of a carboxyl- or -anhydride-containing rubber - 10 to 300 parts by weight of additives ; - 1 to 10 parts by weight of peroxide vulcaniz-ing agents - O.S to 4 parts by weight of vulcanization -~
activators and . , , ~ ~ - 0 to 150 parts by weight of plasticizer , ~ .
~ The unvulcanized rubber u~ed may also be a mixture of I Pi! various~uitabl6 types. Preference i~ given to iEP(D)M
and NBR rubber~.
~he EPM rubber i~ prepared in a known manner by polymeri-zing a mixture of 25 to 75% of ethylene and 75 to 25% of ~ propylene ~n the pre~ence of a Ziegler-Natta catalyst.
.~. , The EPDM rubber 18 prepared in similar manner by polymer-izing a mixture of *Trade Mark more than 25~ of ethylene, more than 25% of propylene and 1 to 10%, in particular 1 to 3%, of a diene.
~ This diene must not be con~ugated. PreferenCe i~ given to bicyclo(2.2.1)h~ptadiene, 1,4-hexadiene, dicyclopenta-diene and in particular 5-ethylidenenorbornene.
The carboxylation of the EP(D)M rubber~ is carried out, for example, in a known manner by compounding with unsaturated acid~ or acid derivatives such a maleic acid or maleic anhydride (MAA), optionally in the presence of a free radical initiator. Suitable preparative methods are given, for example, in US-A-4,010,223.
Carboxylated EPM rubbers of thi~ type are produced, for example, by EXXON under the trade name EXXELORR VA 1803.
An example of an EPD~ rubber which has proven suitable is maleic anhydride-modified BUNAR AP (trade name: ~V~STAMID
X 4496~) from Bunawerke H~ls GmbH, D-4370 Marl.
The nitrile rubbers ~NBR) are prepared in a known manner by copolymerization of 50 to 80 % by weight of butadiene and correspondingly 50 to 20 % by weight of acrylo-nitrile. The carboxyl-containing nitrile rubbers are a particular modificatio~. These are copolymers of butadiene, acrylonitrile and acrylic acid, methacrylic acid or sorbic acid.
The vulcanizates of mixtures of this type have a high tensile strength, good elasticity and very good abrasion resistance. The oil and solvent resistance typical of nitrile rubber remains unaltered.
.
Suitable carboxylated NBR rubbers are produced, for example, by GOODYEAR TIR~ & RUBBER Company, Akron, Ohio, ~ USA, under the trade nam~ CHEMIGUN~ NX 775 or by BF
-~` GOODRICH, NV, Arnhem, Netherlands, under the trade name ~ HYCAR~ 1472.
.~
l : .
';~
.,.
Suitable additives are all conventional fillers for EP(D)M and NBR rubbers such as, for example, carbon black, silica, ~ilicates and calcium carbonates, and also zinc oxide and stearic acid.
Suitable plasticizers are, in particular, mineral oils or synthetic plasticizers such as esters and ethers. In this context, in the case of EP(D)M rubber, preference is given to the use of mineral oils, in particular naph-thenic oils. The amount of plasticizer can be up to 150 part~ by weight, relative to 100 parts by weight of rubber; preferably up to 50 parts by weight.
Suitable peroxide vulcanizing agents are the peroxides known to a person skilled in the art such as, for example, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, dicumyl peroxide, 4,4-di-tert-butylperoxy-n-butyl valerate, l,l-di-tert-butylperoxy-3,3,5-trimethyl-cyclo-hexane and bis(tert-butylperoxyisopropyl)benzene.
Details regarding the use of peroxide vulcanizing agent~
are to be found in the company brochure ~Rubbery Chemical-Crosslinking-Peroxides" from Akzo-Chemie (publi-cation date: April 1985).
Examples of suitable vulcanization activators ars triallyl cyanurate (TAC) and acrylates such as ethylene glycol dimethacrylate (EDNA) and trimethylolpropane --~ 25 trimethacrylate (TRIM). Preference is given to the use ;~ of TAC and/or EDMA.
:"~
. ~ :
The composite articles are prepared by vulcanizing the abovementioned rubbers ln intimate contact, preferably under pressure, with the polyamide-coated metals. The vulcanizing conditions are identical per se with the conditions which are used when employing conventional adhesion promoters. The vulcanization is preferably carried out at temperatures of between 140 and 200-C in 2 to 30 minutes, in particular at temperatures of between 150 and 180-C in 5 to 10 minutes.
.~
Ex~mple~ o typ~cal compo~lte artlcle~ m~de fro~ met~l~
and ~ulc~nlzed rubber ~re rubber-co~ted roller~, se~
flangeA, buffer~, ~prlng element~, Ylbratlon damper~, met~l-relnforced rubber proflle~, and clutch and brake disc~. A partlcular advantage of elements of thl~ type 1~ their resi~tance to corrosive media, in partlcular to corrosive ~alt~
The ex~mple~ whlch follow ser~e to illu~tr~te the lnvention. In these example~, the following 8ub~tance~
are used E~X2LORa VA 1803 i~ a malelc ~nhydride-modifled ~P~ rubber from Exxon Chemical~, Wilmlngton, ~elaware, USA. $he propertle~ of thi~ product are given ln the technical data sheet ~EXXELOR VA~, dated 01.03.1988.
, ZnO c~n be obt~ined under the trade na~e Zinkwei~ ~
Rot~iegel from Grillo-Werke AG, D-3380 Goslar. : -VULXASII~ C i~ a highly reactive ~ilica, obtainable fro~
Bayer AG, D-5090 Leverku~en.
CIRCOSOL~ 4240 ~ a predomlnantly naphthenic mineral oil fro~ Sun Oll, Antwerp (Belglu~
VULXANOS~ HS 1~ an antioxidant fro~ 8ayer AG, D-5090 ~everku~en. It i~ 2,2,4-trimethyl-1,2-dlhydroqu~noline.
PERXADO~a 14/~0 and PERKADO~ BC ~0 are peroxide~ ~ro~
, I 25 ~ Akzo-Chemie, 3800 AZ Amer~foort, NetherlandJ.
~AC (triallyl cyanurate) and eDMA (ethylene qlycol dimethacrylate) are product~ of Degu~a, D-6450 Hanau.
;~ CHEMIGUn~ N~ 7~5 18 a carboxyl-containing NBR rubber from Goodyear $1re and Rubber, Akron, Ohio, USA. The proper-tle~ of thl~ product are given in the data sheet s ~
"CHEMIGUMR NX 775", November 1987.
Example 1 (using a carboxylated EPM rubber) -A 1 mm thick steel panel is heated to 400C in a heating furnace in the course of 10 minutes and then dipped for 10 seconds into a fluidized bed which is filled with the commercially available coating powder of the trademark VESTOSINTR 1101 white. The coated steel panel i8 allowed to cool. The poly~mide-coated ~teel panel i~ mounted in a 4 mm thick spacer frame and one third of the panel i~
coated with a Teflon film to prevent adhesion in this area, and then the panel and release film are coated with a milled sheet composed of EXX~LORR VA 1803100 parts ZnO 5 parts VULRASILR C 60 parts CIRCOSOL8 4240 40 parts VULRANOXR HS 2 parts PERRADOXX 14/407.5 parta ~ TAC 3 parts - 20 and the composition is pressed for 20 minutes at 170-C
and 200 bar. After this treatment, the metal and the vulcanized rubber can only be separated from one another by a cohesive fracture within the rubber.
Example 2 (using a carboxylated N~R rubber) . . .
The procedure of Example 1 i8 followed, but a different I l unvulcanized rubber mixture is used~ ` -CHEMIGUMR NX 775100 parts Stearic acid 1 parts VULRASILR C 40 parts ~-PERRADOX~ BC 40 3 parts ~¦ ~ Actlvator EDMA 0.5 parts ::
.~
i~ ~ iJJ
_ 9 In this composite article al80, the vulcanized rubber and metal can only be separated from one another by a cohe-sive fracture within the rubber.
-: "' .:
~ .
: :.
, ;, . I , - :-, ,....................................................................... . .
,'`~ ~ -- :'
Example 1 (using a carboxylated EPM rubber) -A 1 mm thick steel panel is heated to 400C in a heating furnace in the course of 10 minutes and then dipped for 10 seconds into a fluidized bed which is filled with the commercially available coating powder of the trademark VESTOSINTR 1101 white. The coated steel panel i8 allowed to cool. The poly~mide-coated ~teel panel i~ mounted in a 4 mm thick spacer frame and one third of the panel i~
coated with a Teflon film to prevent adhesion in this area, and then the panel and release film are coated with a milled sheet composed of EXX~LORR VA 1803100 parts ZnO 5 parts VULRASILR C 60 parts CIRCOSOL8 4240 40 parts VULRANOXR HS 2 parts PERRADOXX 14/407.5 parta ~ TAC 3 parts - 20 and the composition is pressed for 20 minutes at 170-C
and 200 bar. After this treatment, the metal and the vulcanized rubber can only be separated from one another by a cohesive fracture within the rubber.
Example 2 (using a carboxylated N~R rubber) . . .
The procedure of Example 1 i8 followed, but a different I l unvulcanized rubber mixture is used~ ` -CHEMIGUMR NX 775100 parts Stearic acid 1 parts VULRASILR C 40 parts ~-PERRADOX~ BC 40 3 parts ~¦ ~ Actlvator EDMA 0.5 parts ::
.~
i~ ~ iJJ
_ 9 In this composite article al80, the vulcanized rubber and metal can only be separated from one another by a cohe-sive fracture within the rubber.
-: "' .:
~ .
: :.
, ;, . I , - :-, ,....................................................................... . .
,'`~ ~ -- :'
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A composite article composed of the following com-ponents:
I. a metal;
II. an adhesion-promoting polyamide layer and III. a vulcanized rubber which has been formed by vulcanizing a rubber mixture containing - 100 parts by weight of a carboxyl- or anhydride-containing rubber - 10 to 300 parts by weight of additives, - 1 to 10 parts by weight of peroxide vulcaniz-ing agents, - 0.5 to 4 parts by weight of vulcanization activators and - 0 to 150 parts by weight of plasticizer.
I. a metal;
II. an adhesion-promoting polyamide layer and III. a vulcanized rubber which has been formed by vulcanizing a rubber mixture containing - 100 parts by weight of a carboxyl- or anhydride-containing rubber - 10 to 300 parts by weight of additives, - 1 to 10 parts by weight of peroxide vulcaniz-ing agents, - 0.5 to 4 parts by weight of vulcanization activators and - 0 to 150 parts by weight of plasticizer.
2. A composite article according to Claim 1, wherein the polyamide is selected from the group consisting of PA 1012, PA 11, PA 12 and PA 1212 polyamides.
3. A composite article according to Claim 2, wherein the polyamide is a PA-12 polyamide having a relative viscosity of 1.4 to 2Ø
4. A composite article according to Claim 3, wherein the polyamide is a PA 12 polyamide having a relative viscosity of 1.5 to 1.7.
5. A composite article according to Claim 1, 2 or 3, wherein the carboxyl- or anhydride-containing rubber is a car-boxylated EPM, EPDM and/or NBR rubber.
6. A process for the preparation of the composite article according to Claim 1, 2 or 3, which process comprises I. coating a metal with a polyamide; and II. vulcanizing the rubber mixture in intimate contact with the polyamide-coated metal.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3934090A DE3934090A1 (en) | 1989-10-12 | 1989-10-12 | COMPONENTS OF METALS AND RUBBER AND METHOD FOR THE PRODUCTION THEREOF |
| DEP3934090.2 | 1989-10-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2027210A1 true CA2027210A1 (en) | 1991-04-13 |
Family
ID=6391334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002027210A Abandoned CA2027210A1 (en) | 1989-10-12 | 1990-10-10 | Composite articles of metals and vulcanized rubber and process for their preparation |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0422392A3 (en) |
| JP (1) | JPH03133631A (en) |
| CA (1) | CA2027210A1 (en) |
| DD (1) | DD298076A5 (en) |
| DE (1) | DE3934090A1 (en) |
| PT (1) | PT95549A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8691386B2 (en) | 2010-02-15 | 2014-04-08 | The Yokohama Rubber Co., Ltd. | Bonded body of a carbon thin film covered article and a rubber |
| US9327482B2 (en) | 2009-06-30 | 2016-05-03 | Gates Corporation | Bonded part with laminated rubber member and method of making |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1283645B1 (en) * | 1996-08-02 | 1998-04-23 | Enichem Elastomers | PRODUCTS IN POLYAMIDE AND ACRYLIC RUBBER AND PROCEDURE FOR THEIR PREPARATION |
| DE19640180C2 (en) * | 1996-09-30 | 1999-07-01 | Freudenberg Carl Fa | Process for producing a rubber-metal part and use of the process |
| AU1690099A (en) | 1997-12-24 | 1999-07-19 | Daicel Chemical Industries Ltd. | Pipe of hard thermoplastic resin, pipe joint structure and methods of manufacturing the same |
| JP4458669B2 (en) * | 1998-04-23 | 2010-04-28 | アドバンスド エラストマー システムズ，エル．ピー． | Metal reinforced thermoplastic elastomer |
| EP2813534B1 (en) * | 2001-01-15 | 2016-04-27 | Daicel-Evonik Ltd. | Composite and process for producing the same |
| US6800372B2 (en) | 2001-01-16 | 2004-10-05 | Daicel-Degussa Ltd. | Composite and process for producing the same |
| DE10115510B4 (en) * | 2001-03-28 | 2006-11-16 | Linie M - Metall Form Farbe-Gmbh | Game apparatus or seating for public facilities and method of making the same |
| JP3898584B2 (en) | 2002-07-03 | 2007-03-28 | ダイセル・デグサ株式会社 | Resin composition, composite using the same, and method for producing the same |
| JP2004043670A (en) | 2002-07-12 | 2004-02-12 | Daicel Degussa Ltd | Complex dispersion and its preparation method |
| US20090130469A1 (en) * | 2007-05-24 | 2009-05-21 | Kei-Yi Wei | Powder adhesives for bonding elastomers |
| EP2344600B1 (en) | 2008-11-07 | 2014-04-30 | Lord Corporation | Powdered primer for rubber to metal bonding |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2855694A1 (en) * | 1978-12-22 | 1980-07-03 | Imi Kynoch Ltd | Laminated container of epoxy! and polyamide bonded glass fibres - sandwiching elastomeric layers used for storing dangerous materials e.g. explosives |
| JPH0673935B2 (en) * | 1988-04-01 | 1994-09-21 | ニチアス株式会社 | Damping material and soundproof structure using damping material |
-
1989
- 1989-10-12 DE DE3934090A patent/DE3934090A1/en not_active Withdrawn
-
1990
- 1990-09-10 EP EP19900117360 patent/EP0422392A3/en not_active Withdrawn
- 1990-09-25 DD DD90344178A patent/DD298076A5/en not_active IP Right Cessation
- 1990-10-10 CA CA002027210A patent/CA2027210A1/en not_active Abandoned
- 1990-10-10 PT PT95549A patent/PT95549A/en not_active Application Discontinuation
- 1990-10-11 JP JP2270642A patent/JPH03133631A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9327482B2 (en) | 2009-06-30 | 2016-05-03 | Gates Corporation | Bonded part with laminated rubber member and method of making |
| US8691386B2 (en) | 2010-02-15 | 2014-04-08 | The Yokohama Rubber Co., Ltd. | Bonded body of a carbon thin film covered article and a rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| DD298076A5 (en) | 1992-02-06 |
| PT95549A (en) | 1991-08-14 |
| EP0422392A3 (en) | 1991-12-04 |
| DE3934090A1 (en) | 1991-04-18 |
| JPH03133631A (en) | 1991-06-06 |
| EP0422392A2 (en) | 1991-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5132182A (en) | Process for chemically bonding molding compositions based on aliphatic polyamides to rubbers containing carboxyl groups and the materials produced by this process | |
| CA2027210A1 (en) | Composite articles of metals and vulcanized rubber and process for their preparation | |
| JP3693257B2 (en) | Thermoplastic elastomers with improved surface properties | |
| US8241753B2 (en) | Composite thermoplastic elastomer structures with high adhesion performance and uses for the same | |
| CN101688087B (en) | Powder adhesives for bonding elastomers | |
| KR101835311B1 (en) | Adhesion-modified olefinic thermoplastic elastomers, in particular TPE-Vs and TPE-Os | |
| EP1400577B1 (en) | Adhesive compositions and method for bonding to rubber | |
| CN1276043C (en) | High temperature resistance anticorrosive polyolefin composition and its use | |
| CA2027240A1 (en) | Components made from continuous-fibre-reinforced polyamide moulding compositions and rubber, and a process for their preparation | |
| JP2011046957A (en) | Adhesive | |
| KR0165148B1 (en) | Resilient polymer product combined with thermoplastic resilient polymer | |
| JP2003517386A (en) | Metal reinforced thermoplastic elastomer | |
| AU706987B2 (en) | Polyamide-based powder composition for coating metal substrates | |
| EP2332997A1 (en) | Co-agents for the preparation of thermoplastic elastomeric blends of rubber and polyolefins | |
| CN1295597A (en) | Multi-layer polymer film | |
| JPH0826291B2 (en) | Structural adhesive based on curable rubber | |
| JPH07173230A (en) | Adhesive fluoropolymer and laminate produced using the same | |
| US3632671A (en) | Adhesive composition | |
| US3528943A (en) | Adhesive compositions and method for bonding elastomers | |
| JPS6412304B2 (en) | ||
| EP0341068A1 (en) | Coated rubber | |
| CN1906218A (en) | Adherent, modified thermoplastic elastomeric blends, articles, and methods | |
| EP0713512A1 (en) | Adhering chlorosulfonated polyethylene to non-polar polyolefinic elastomers | |
| JPH02273231A (en) | Composite damping material for room temperature | |
| JPH01259049A (en) | Thermoplastic resin or elastomer composition excellent in coating adhesion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 19930411 |