CA1118549A - Method, composition and product with improved adhesion between a metal member and a contiguous rubber skim stock - Google Patents
Method, composition and product with improved adhesion between a metal member and a contiguous rubber skim stockInfo
- Publication number
- CA1118549A CA1118549A CA000308292A CA308292A CA1118549A CA 1118549 A CA1118549 A CA 1118549A CA 000308292 A CA000308292 A CA 000308292A CA 308292 A CA308292 A CA 308292A CA 1118549 A CA1118549 A CA 1118549A
- Authority
- CA
- Canada
- Prior art keywords
- phr
- composition
- aminobenzoic acid
- rubber
- skim stock
- 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.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
- B29C66/721—Fibre-reinforced materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
- B29C66/721—Fibre-reinforced materials
- B29C66/7214—Fibre-reinforced materials characterised by the length of the fibres
- B29C66/72141—Fibres of continuous length
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Tires In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
This disclosure relates to a method, a rubber skim stock and a product containing the skim stock having improved adhesion between a metal member and a contiguous rubber skim stock. The invention lies in a discovery that improved rubber-to-metal adhesion can be obtained by adding to an otherwise conventional rubber skim stock compound appropriate amounts of either p-aminobenzoic acid or a transition metal salt of p-aminobenzoic acid. In particular, the cobalt and nickel salts of p-aminobenzoic acid have been found to be effective.
The method of this invention comprises the steps of mixing the p-aminobenzoic acid or transition metal salt of p-aminobenzoic acid into a rubber compound, forming this compound into contiguous relationship with a metal member in an unvulcanized product and vulcanizing the product to yield the end product.
This disclosure relates to a method, a rubber skim stock and a product containing the skim stock having improved adhesion between a metal member and a contiguous rubber skim stock. The invention lies in a discovery that improved rubber-to-metal adhesion can be obtained by adding to an otherwise conventional rubber skim stock compound appropriate amounts of either p-aminobenzoic acid or a transition metal salt of p-aminobenzoic acid. In particular, the cobalt and nickel salts of p-aminobenzoic acid have been found to be effective.
The method of this invention comprises the steps of mixing the p-aminobenzoic acid or transition metal salt of p-aminobenzoic acid into a rubber compound, forming this compound into contiguous relationship with a metal member in an unvulcanized product and vulcanizing the product to yield the end product.
Description
CASE 38-~
::1118S49 METHOD, COMPOSITION AND PRODUCT WITH
IMPROVED ADHESION BET~EEN A METAL MEMBER
AND A CONTIGUOUS RUBBER SKIM STOCK
BACKGROUND OF THE INVENTION AND PRIOR ART
In the production of rubber articles such as hose, pneumatic tires or power transmission belts such as V-belts, toothed positive drive belts, etc., it is generally necessary to reinforce the rubber or elastomeric product. In the past, textile materials have been employed for this purpose. However, wire cord has been found to be more desirable under certain conditions of use, for example, in pneumatic tires of the radial ply type. Maximum reinforcement of the ruhber is obtained when maximum adhesion is produced and retained between lS the laminate of a contiguous rubber skim stock and the metal reinforcing element as used to form a unitary structure. Of equal importance is the requirement that, for example, the laminate of the reinforcing metal element and contiguous rubber remain in a bonded relationship with each other throughout the useful life of the reinforced structure in which the laminate is used.
To achieve satisfactory rubber-to-metal bonding, numerous methods have been developed. For example, U.S. Patent No. 2,720,479 describes a system wherein a phenolic resin and a brominated isoolefin-polyolefin interpolymer are dissolved in a suitable liquid carrier and the resulting adhesive composition is spread on rubber which is to be bonded to metal. The rubber and metal are subsequently pressed together and vulcanized. U.S. Patent No. 2,581,9~0 also describes the use of halogenated polymers to bond rubber to metal.
3~
$49 In U.S. Patent No. 3,517,722 to Endter et al., a rub~cr metal adhesion system is described which involves formation of a resorcinol-formaldehydc resin at the interfacc between the rubber and the metal, thereby bonding these membe~s together. In forming the resin, compounds capable of liberating the methylene precursor are added to resorcinol in the rubber stock. Upon vulcanization, the methylene and resorcinol react to form the resorcinol-formaldehyde resin.
According to U.S. Patent No. 3,846,160, the adhesion force between steel cord and rubber is enhanced by applying a mineral oil solution containing, for example, an organic acid salt of a higher aliphatic amine to zinc plated or brass plated steel cord.
The adhesion of rubber to metal such as wire tire cord is improved according to U.S. Patent No.
3,847,727 by incorporating a halogenated quinone and the condensation product of resorcinol and acetaldehyde into -the rubber prior to application to the metal and vulcan-ization of the composite.
The disclosure of U.S. Patent No. 3,903,026 teaches the preparation of a rubber composition having improved metal adhesion properties even after thermal aging; this is disclosed to be achieved by compounding cobalt carboxylate and magnesium oxide (0.1 to 4 phr) into rubber.
U.S. Patent No. 3,738,948 is directed to a fiber rcinforced rubber composition that can be utilized in tire con6truction. The fiber can be glass, nylon, rayon or metal wire. The composition is disclosed to contain a finely divided silica, hexamethylene tetramine, re~orcinol and a compatible metal soap such as calcium ~tearate. Similar compositions containing discontinuous fiber filaments are disclosed in U.S. Patent No, 3,746,669.
" ~1185~
U.S. Patent No. 3,340,214 teaches the usc of benzoic acid or nitrobenzoic acid as an additive to reduce the resiliency of rubber as utilized, for example, in the production of tires.
DESCRIPTION OF THE INVENTION
This invention relates to a method, a rubber skim stock and a product containing the skim stock wherein the invention yields improved adhesion between a contiguous rubber skim stock and a metal member. The 10 invention lies in the discovery that im~roved rubber-to- : r metal adhesion can be obtained by adding to an othcrwise conventional rubber skim stock compound appropriate amounts of either p-aminobenzoic acid (PABA) or a transition metal salt of p-aminobenzoic acid. In particular, the cobalt and nickel salts of PABA have been found to be effective.
The method of this invention comprises the steps of mixing the PABA or a transition metal salt of PABA into a rubber composition or compound, as described below, forming this compound into contiguous relationship with a metal member in an unvulcanized product and vulcanizing the product to yield the end product.
The para-aminobenzoic acid used to illustrate the present invention was purchased from Aldriçh Chemical Company, Inc. and was specified as having a molecular weight of 137.14, a melting range of 188 to 189C, and a density at its melting point of 1.374. It was classified as being 99% pure.
The transition metal salt of p-aminobenzoic acid can be prepared by adding p-aminobenzoic acid (1 mole) to a solution of sodium hydroxide (1 mole) in 900 ml. of distilled water at room temperature with mechanical stirring. To the resultin~ brown solution of the sodium salt of p-aminobenzoic acid can be added slowly a solution of selected transition metal chloride (0.506 mole) lllB5~9 in 100 ml. of distilled water at room temperatu~e with stirring. ~ rcaction takes place immediately to form a pFecipitate. After the addition is complete, the reaction mixture is stirred at room temperature for an additional 3 hours. The solid is then collected on a filter, washed with a small amount of water and dried at 120C under vacuum overnight. After this drying step, solid transition p-aminobenzoic acid is obtained in high yield.
Cobalt p-aminobenzoic acid was prepared by adding p-aminobenzoic acid (137 g, 1 mole) to a solution of sodium hydroxide (40 g, 1 mole) in 900 ml. of distilled water at room temperature with mechanical stirring. To the resulting brown solution of the sodium salt of p-lS aminobenzoic acid was added slowly a solution of cobaltous chloride (120 g, 0.506 mole) in 100 ml. of distilled water at room temperature with stirring. A reaction took place immediately to form a pink precipitate.
After the addition was complete, the reaction mixture was stirred at room temperature for an additional 3 hours. The solid was collected on a filter, washed with a small amount of water and dried at 120C under vacuum overnight. After this drying step, dark purple solid cobalt p-aminobenzoic acid was obtained in 81% yield (135 g).
The following transition metal salts of PABA;
Co, Cr, Mn, Zn, Mo, Cd, Zr, Ag and Ti PABA will result in a ~ignificant improvem~nt over the control formulation.
The rubber compound is described with all ingrcdients based on the total rubber component in the compound being 100 parts by weight.
The composition of this invention consists essentially of 100 parts rubber~40 to 70 phr carbon bl~ck, 4 to 10 phr zinc oxide, 10 to 30 phr silica, 0.5 to 1 phr antioxidant, 0.5 to 1 phr stearic acid, 0.2 to
::1118S49 METHOD, COMPOSITION AND PRODUCT WITH
IMPROVED ADHESION BET~EEN A METAL MEMBER
AND A CONTIGUOUS RUBBER SKIM STOCK
BACKGROUND OF THE INVENTION AND PRIOR ART
In the production of rubber articles such as hose, pneumatic tires or power transmission belts such as V-belts, toothed positive drive belts, etc., it is generally necessary to reinforce the rubber or elastomeric product. In the past, textile materials have been employed for this purpose. However, wire cord has been found to be more desirable under certain conditions of use, for example, in pneumatic tires of the radial ply type. Maximum reinforcement of the ruhber is obtained when maximum adhesion is produced and retained between lS the laminate of a contiguous rubber skim stock and the metal reinforcing element as used to form a unitary structure. Of equal importance is the requirement that, for example, the laminate of the reinforcing metal element and contiguous rubber remain in a bonded relationship with each other throughout the useful life of the reinforced structure in which the laminate is used.
To achieve satisfactory rubber-to-metal bonding, numerous methods have been developed. For example, U.S. Patent No. 2,720,479 describes a system wherein a phenolic resin and a brominated isoolefin-polyolefin interpolymer are dissolved in a suitable liquid carrier and the resulting adhesive composition is spread on rubber which is to be bonded to metal. The rubber and metal are subsequently pressed together and vulcanized. U.S. Patent No. 2,581,9~0 also describes the use of halogenated polymers to bond rubber to metal.
3~
$49 In U.S. Patent No. 3,517,722 to Endter et al., a rub~cr metal adhesion system is described which involves formation of a resorcinol-formaldehydc resin at the interfacc between the rubber and the metal, thereby bonding these membe~s together. In forming the resin, compounds capable of liberating the methylene precursor are added to resorcinol in the rubber stock. Upon vulcanization, the methylene and resorcinol react to form the resorcinol-formaldehyde resin.
According to U.S. Patent No. 3,846,160, the adhesion force between steel cord and rubber is enhanced by applying a mineral oil solution containing, for example, an organic acid salt of a higher aliphatic amine to zinc plated or brass plated steel cord.
The adhesion of rubber to metal such as wire tire cord is improved according to U.S. Patent No.
3,847,727 by incorporating a halogenated quinone and the condensation product of resorcinol and acetaldehyde into -the rubber prior to application to the metal and vulcan-ization of the composite.
The disclosure of U.S. Patent No. 3,903,026 teaches the preparation of a rubber composition having improved metal adhesion properties even after thermal aging; this is disclosed to be achieved by compounding cobalt carboxylate and magnesium oxide (0.1 to 4 phr) into rubber.
U.S. Patent No. 3,738,948 is directed to a fiber rcinforced rubber composition that can be utilized in tire con6truction. The fiber can be glass, nylon, rayon or metal wire. The composition is disclosed to contain a finely divided silica, hexamethylene tetramine, re~orcinol and a compatible metal soap such as calcium ~tearate. Similar compositions containing discontinuous fiber filaments are disclosed in U.S. Patent No, 3,746,669.
" ~1185~
U.S. Patent No. 3,340,214 teaches the usc of benzoic acid or nitrobenzoic acid as an additive to reduce the resiliency of rubber as utilized, for example, in the production of tires.
DESCRIPTION OF THE INVENTION
This invention relates to a method, a rubber skim stock and a product containing the skim stock wherein the invention yields improved adhesion between a contiguous rubber skim stock and a metal member. The 10 invention lies in the discovery that im~roved rubber-to- : r metal adhesion can be obtained by adding to an othcrwise conventional rubber skim stock compound appropriate amounts of either p-aminobenzoic acid (PABA) or a transition metal salt of p-aminobenzoic acid. In particular, the cobalt and nickel salts of PABA have been found to be effective.
The method of this invention comprises the steps of mixing the PABA or a transition metal salt of PABA into a rubber composition or compound, as described below, forming this compound into contiguous relationship with a metal member in an unvulcanized product and vulcanizing the product to yield the end product.
The para-aminobenzoic acid used to illustrate the present invention was purchased from Aldriçh Chemical Company, Inc. and was specified as having a molecular weight of 137.14, a melting range of 188 to 189C, and a density at its melting point of 1.374. It was classified as being 99% pure.
The transition metal salt of p-aminobenzoic acid can be prepared by adding p-aminobenzoic acid (1 mole) to a solution of sodium hydroxide (1 mole) in 900 ml. of distilled water at room temperature with mechanical stirring. To the resultin~ brown solution of the sodium salt of p-aminobenzoic acid can be added slowly a solution of selected transition metal chloride (0.506 mole) lllB5~9 in 100 ml. of distilled water at room temperatu~e with stirring. ~ rcaction takes place immediately to form a pFecipitate. After the addition is complete, the reaction mixture is stirred at room temperature for an additional 3 hours. The solid is then collected on a filter, washed with a small amount of water and dried at 120C under vacuum overnight. After this drying step, solid transition p-aminobenzoic acid is obtained in high yield.
Cobalt p-aminobenzoic acid was prepared by adding p-aminobenzoic acid (137 g, 1 mole) to a solution of sodium hydroxide (40 g, 1 mole) in 900 ml. of distilled water at room temperature with mechanical stirring. To the resulting brown solution of the sodium salt of p-lS aminobenzoic acid was added slowly a solution of cobaltous chloride (120 g, 0.506 mole) in 100 ml. of distilled water at room temperature with stirring. A reaction took place immediately to form a pink precipitate.
After the addition was complete, the reaction mixture was stirred at room temperature for an additional 3 hours. The solid was collected on a filter, washed with a small amount of water and dried at 120C under vacuum overnight. After this drying step, dark purple solid cobalt p-aminobenzoic acid was obtained in 81% yield (135 g).
The following transition metal salts of PABA;
Co, Cr, Mn, Zn, Mo, Cd, Zr, Ag and Ti PABA will result in a ~ignificant improvem~nt over the control formulation.
The rubber compound is described with all ingrcdients based on the total rubber component in the compound being 100 parts by weight.
The composition of this invention consists essentially of 100 parts rubber~40 to 70 phr carbon bl~ck, 4 to 10 phr zinc oxide, 10 to 30 phr silica, 0.5 to 1 phr antioxidant, 0.5 to 1 phr stearic acid, 0.2 to
2.0 phr accelerator, 1 to 10 phr hydrocarbon resin, 2 to 6 phr resorcinol, 1 to 5 phr Manobond C, 4 to 9 phr _ 5 --sulfur/oil, 80/20, 4 to 9 p~r melaminc rcsin and 0.5 ~o 8 phr of PAB~ or a tr~nsition metal salt of P~BA or 2-8 phr of the cobalt PABA salt when it is the tran~tion utilized.
DETAIL~ ESCRIPTION OF TIIE INVENTION
~`
The following Examples are representative of the method and rubber compound of this invention. Thc composition component parts are expressed in parts per hundred rubber, phr, unless othcrwise specified. These components are broadly within the ranges set out below:
Masterbatch Natural rubber 60-80 parts Butadiene 40-20 parts Carbon hlack 40-70 phr 15 Zinc oxide 4-lO phr Silica 10-30 phr Stearic acid .S-l phr Antiozonant/antioxidant (i.e., Santoflex~13) .5-l phr 20 Hydrocarbon resin 1-lO phr Resorcinol 2-6 phr Manobond C 1-5 phr Final Mix Accelerator .2-2 phr 25 Sulfur/oil 80/20 A~ 4-9 phr Mclamine resin (i.e., Cyrez 963) 4-9 phr PABA or transition metal salt of PABA orO.5-8 phr Cobalt PABA (when present) 2.0-8 phr Specific detailed examples of useful compositions within the ranges set out above are:
~ trademarks B
854~
EX~MPI.E I
The followin~ composition was Banbury mixed at about 280-340F for seven (7) minutes, or 340F, whichever occurs first, and a rotor speed of 80 rpm; the resulting masterbatch was then dumped. The Banbury type was a Type B Internal Mixer (.Farrel-Birmingham Company).
Parts ;~
(1) natural rubb~r 75 parts (2-) butadiene rubber 25 parts
DETAIL~ ESCRIPTION OF TIIE INVENTION
~`
The following Examples are representative of the method and rubber compound of this invention. Thc composition component parts are expressed in parts per hundred rubber, phr, unless othcrwise specified. These components are broadly within the ranges set out below:
Masterbatch Natural rubber 60-80 parts Butadiene 40-20 parts Carbon hlack 40-70 phr 15 Zinc oxide 4-lO phr Silica 10-30 phr Stearic acid .S-l phr Antiozonant/antioxidant (i.e., Santoflex~13) .5-l phr 20 Hydrocarbon resin 1-lO phr Resorcinol 2-6 phr Manobond C 1-5 phr Final Mix Accelerator .2-2 phr 25 Sulfur/oil 80/20 A~ 4-9 phr Mclamine resin (i.e., Cyrez 963) 4-9 phr PABA or transition metal salt of PABA orO.5-8 phr Cobalt PABA (when present) 2.0-8 phr Specific detailed examples of useful compositions within the ranges set out above are:
~ trademarks B
854~
EX~MPI.E I
The followin~ composition was Banbury mixed at about 280-340F for seven (7) minutes, or 340F, whichever occurs first, and a rotor speed of 80 rpm; the resulting masterbatch was then dumped. The Banbury type was a Type B Internal Mixer (.Farrel-Birmingham Company).
Parts ;~
(1) natural rubb~r 75 parts (2-) butadiene rubber 25 parts
(3) carbon hlack (FEF) 40 phr
(4) zinc oxide 4.0 phr
(5) pellet.ized hydrated silica 10 phr
(6) stearic acid 1.0 phr
(7) l~-(1,3-dimethyl butyl)-N'-phenyl- 1.0 phr p-phcns~lenediamine
(8) hydrocarbon resin S.0 phr
(9) resorcinol (meta-dihydroxybenzene) 2.5 phr
(10) Manobond C 16 3.5 phr The hydrocarbon resin was in flake form, had a .
softening poi.nt between about 100~ to 110C, an iodine number of from 125 to 167, and, an ash content of 0.05~.
The masterbatch resulting from the preceding was then final roll mill mixed for 4 to 8 minutes until dispersion was achieved at a mill speed of approximately 50 RPM and at a temperature of from 160 to 180F; the resulting final mix was then dumped. The composition components added to the masterbatch prior to final mill mixing were a~ follows:
~al N-tcrt-butyl-2-benzothiazole 0.7 phr sulfena~ide (b) sulfur oil, 80/20 6.0 phr (c) hexamethoxymethyl-melamine 4.0 phr powder, and (d) PABA. 1.5 phr 5~
-- 7 ~
This product was cured for 30 minutefi at 300F, a cure pressure of 800-900 psi, ~nd is the invention composition of Table I. The control is the identical composition without para~aminobenzoic acid.
Table I which follows illustrates the performance of our PABA containing composition with bright steel (unplated) wire as it would be utilized.
TABLE I
__ Invention 10 Test - ControlComposition R.T. Ring Tensile -30' Cure/300F
300% Modulus, (psi) 1560 1830 Tensile Strength, (psi) 2340 2410 15 Elongation, (%) 400 410 Unconditioned T Adhesion to (Briqht steel)*
30' Cure, R.T. Test 88 (20)139 (100) 45' Cure, R.T. Test 89 (20)137 (100) 20 30' Cure, 230F Test 71 (30)118 (90) 45' Cure, 230F Test 68 (30)124 (90) Conditioned T Adhesion to bright steel after 1 hour in 300F steam 25 30' Cure at 300F 61 (10)118 (90) Tested at 230F
(T adhesion values in lb./in.; Coverages in (%) ) *Bright steel-unplated
softening poi.nt between about 100~ to 110C, an iodine number of from 125 to 167, and, an ash content of 0.05~.
The masterbatch resulting from the preceding was then final roll mill mixed for 4 to 8 minutes until dispersion was achieved at a mill speed of approximately 50 RPM and at a temperature of from 160 to 180F; the resulting final mix was then dumped. The composition components added to the masterbatch prior to final mill mixing were a~ follows:
~al N-tcrt-butyl-2-benzothiazole 0.7 phr sulfena~ide (b) sulfur oil, 80/20 6.0 phr (c) hexamethoxymethyl-melamine 4.0 phr powder, and (d) PABA. 1.5 phr 5~
-- 7 ~
This product was cured for 30 minutefi at 300F, a cure pressure of 800-900 psi, ~nd is the invention composition of Table I. The control is the identical composition without para~aminobenzoic acid.
Table I which follows illustrates the performance of our PABA containing composition with bright steel (unplated) wire as it would be utilized.
TABLE I
__ Invention 10 Test - ControlComposition R.T. Ring Tensile -30' Cure/300F
300% Modulus, (psi) 1560 1830 Tensile Strength, (psi) 2340 2410 15 Elongation, (%) 400 410 Unconditioned T Adhesion to (Briqht steel)*
30' Cure, R.T. Test 88 (20)139 (100) 45' Cure, R.T. Test 89 (20)137 (100) 20 30' Cure, 230F Test 71 (30)118 (90) 45' Cure, 230F Test 68 (30)124 (90) Conditioned T Adhesion to bright steel after 1 hour in 300F steam 25 30' Cure at 300F 61 (10)118 (90) Tested at 230F
(T adhesion values in lb./in.; Coverages in (%) ) *Bright steel-unplated
11~8549 Substantially the same results of Table I are achieved when the following masterbatch and composition added prior to final mill mixing are substituted therein:
Masterbatch (1) Natural rubber 75 parts (2) Polybutadiene rubber 25 parts (3) Carbon black ~FEF~ 55 phr (4) Zinc oxide 10 phr (5) Pelletized hydrated silica 12.5 phr (6) Stearic acid 1 phr (7) N-(1,3-dimethyl b~tyl)-N'-phenyl- 1 phr p-phcnylenediamine (8) Hydrocarbon resin 5 phr (9) Resorcinol (meta-dihydroxybenzene) 4 phr (10) Manobond C 16 3.5 phr Composition Added to Above Masterbatch (A) Sulfur/oil - ~0/20 powdcr 7 phr (B) Hexamethoxymethyl-melamine 6 phr (C) N-tert-butyl-2-benzothiazo~e- 0.7 phr sulfenamide (D) PABA 1.5 phr :
.
-`` 1118549 9 _ A masterbatch identical to that described in Example I was mixed. This masterbatch was mixed into a final mix by the procedure described in Example I wherein the following components were added in the final mix:
(a) N-tert-butyl-2-benzothiazole- 0.35 phr sulfenamide (b) sulfur oil, 80/20 6.0 phr (c) hexamethoxymethyl-melamine 4.0 phr powder, and (d) nickel PABA (Ni-PABA) 4.0 phr This product was cured for 30 minutes at 300F, a cure pressure of 800-900 psi, and is the invention composition of Table II. The control is the identical composition without nickel p-aminobenzoic acid.
Table II which follows illustrates the performance of our Ni-PABA containing composition with bright steel (unplated) wire as it would be utilized showing two levels of Ni-PABA.
TABLE II
Control + Control+
2 PHR 4 P~IR
T Control Ni-PA~A Ni-PABA
Unconditioned T Adhesion to (briqht steel) *
30' Cure, R.T. Test 121(90) 130(90) 124(90) Conditioned T Adhesion to bright steel after 1 hour in 300F steam 30' Cure at 300F 79(50) 94(80) 95(80 Tested at 230F
(T adhesion values in lb./in.; Coverages in percent) *Bright steel-unplated S4~
-- 10 -- ' EX~M.PLE 4 Substantially the same results of Table II are achieved when the follo~ing masterbatch and composition added prior to ~inal mill mixing are substituted therein:
5 Masterbatch ~1) Natural rubber 75 parts (2) Butadienc rubber 25 parts (3) Carbon black (FEF) 5S phr (4) Zinc oxide 10 phr 10 (5) Pelletized hydrated silica 12.5 phr (6) Stearic acid 1 phr (7) N-(1,3-dimethylbutyl)-N'-phenyl- 1 phr p-phenylenediamine (8) Hydrocarbon resin 5 phr (9) Resorcinol (meta-dihydroxybenzene) 4 phr (10) Manobond C 16 3.5 phr Composition Added to Above Masterbatch (A) Sulfurfoil - 80~20 powder 7 phr (B) Hexamethoxymethyl-melamine 6 phr 20 (C) N-oxydiethylene benzothiazole- .8 phr :~
2-sulfenamide, and (D) Ni-PABA 4 phr ' EX~MPI.E 5 A masterbatch identical to that described in Example I was mixed. This masterbatch was mixed into a final mix by the procedure descrihed in Example I
wherein the following components were added in the final mix: .
(a) N-tert-butyl-2-benzothiazole- 0,35 phr sulfenamide (b) sulfur oil, 80/20 6.0 phr 10 (c) hexamethoxymethyl-melamine 4.0 phr :
powdçr, and (d) cobalt PABA (Co-PABA) 4.0 phr This product was cured for 30 minutes at 300F, a cure pressure of ~00-900 psi, and is the invention compo~ition of Table III. The control is the identical composition without cobalt p-amino-benzoic acid.
Table III which follows illustrates the performance of our Co-PABA containing composition with bright steel (unplated) wire as it would be utilized.
~18S49
Masterbatch (1) Natural rubber 75 parts (2) Polybutadiene rubber 25 parts (3) Carbon black ~FEF~ 55 phr (4) Zinc oxide 10 phr (5) Pelletized hydrated silica 12.5 phr (6) Stearic acid 1 phr (7) N-(1,3-dimethyl b~tyl)-N'-phenyl- 1 phr p-phcnylenediamine (8) Hydrocarbon resin 5 phr (9) Resorcinol (meta-dihydroxybenzene) 4 phr (10) Manobond C 16 3.5 phr Composition Added to Above Masterbatch (A) Sulfur/oil - ~0/20 powdcr 7 phr (B) Hexamethoxymethyl-melamine 6 phr (C) N-tert-butyl-2-benzothiazo~e- 0.7 phr sulfenamide (D) PABA 1.5 phr :
.
-`` 1118549 9 _ A masterbatch identical to that described in Example I was mixed. This masterbatch was mixed into a final mix by the procedure described in Example I wherein the following components were added in the final mix:
(a) N-tert-butyl-2-benzothiazole- 0.35 phr sulfenamide (b) sulfur oil, 80/20 6.0 phr (c) hexamethoxymethyl-melamine 4.0 phr powder, and (d) nickel PABA (Ni-PABA) 4.0 phr This product was cured for 30 minutes at 300F, a cure pressure of 800-900 psi, and is the invention composition of Table II. The control is the identical composition without nickel p-aminobenzoic acid.
Table II which follows illustrates the performance of our Ni-PABA containing composition with bright steel (unplated) wire as it would be utilized showing two levels of Ni-PABA.
TABLE II
Control + Control+
2 PHR 4 P~IR
T Control Ni-PA~A Ni-PABA
Unconditioned T Adhesion to (briqht steel) *
30' Cure, R.T. Test 121(90) 130(90) 124(90) Conditioned T Adhesion to bright steel after 1 hour in 300F steam 30' Cure at 300F 79(50) 94(80) 95(80 Tested at 230F
(T adhesion values in lb./in.; Coverages in percent) *Bright steel-unplated S4~
-- 10 -- ' EX~M.PLE 4 Substantially the same results of Table II are achieved when the follo~ing masterbatch and composition added prior to ~inal mill mixing are substituted therein:
5 Masterbatch ~1) Natural rubber 75 parts (2) Butadienc rubber 25 parts (3) Carbon black (FEF) 5S phr (4) Zinc oxide 10 phr 10 (5) Pelletized hydrated silica 12.5 phr (6) Stearic acid 1 phr (7) N-(1,3-dimethylbutyl)-N'-phenyl- 1 phr p-phenylenediamine (8) Hydrocarbon resin 5 phr (9) Resorcinol (meta-dihydroxybenzene) 4 phr (10) Manobond C 16 3.5 phr Composition Added to Above Masterbatch (A) Sulfurfoil - 80~20 powder 7 phr (B) Hexamethoxymethyl-melamine 6 phr 20 (C) N-oxydiethylene benzothiazole- .8 phr :~
2-sulfenamide, and (D) Ni-PABA 4 phr ' EX~MPI.E 5 A masterbatch identical to that described in Example I was mixed. This masterbatch was mixed into a final mix by the procedure descrihed in Example I
wherein the following components were added in the final mix: .
(a) N-tert-butyl-2-benzothiazole- 0,35 phr sulfenamide (b) sulfur oil, 80/20 6.0 phr 10 (c) hexamethoxymethyl-melamine 4.0 phr :
powdçr, and (d) cobalt PABA (Co-PABA) 4.0 phr This product was cured for 30 minutes at 300F, a cure pressure of ~00-900 psi, and is the invention compo~ition of Table III. The control is the identical composition without cobalt p-amino-benzoic acid.
Table III which follows illustrates the performance of our Co-PABA containing composition with bright steel (unplated) wire as it would be utilized.
~18S49
12 -TABLE III
Invention Test Control Composition _.T. Ring Tensile - 30' Cure/300F
300~ Modulus, (psi) 1560 1620 Tensile Strength, (psi)2340 2090 Elongation, (~) 400 380 Unconditioned T Adhesion to (bright steel)* -30' Cure, R.T. Test 88 (20) 135 (80) 45' Cure, R.T. Test 89 (20) 140 (80) 30' Cure, 230F Test 71 (30) 107 (80) 45' Cure, 230F Test 68 (30) 102 (80) Conditioned T Adhesion to bright steel after 1 hour in 300F Steam ~ -30' Cure at 300F 61 (10) 108 (90) Tested at 230F
(T adhesion values in lb./in.; Coverages in (~)) -20 *Bright steel-unplated ~
: .. , , . ~
, ,. ~ ' , ~ ~ .
- . ~ .
~1854~
~ 13 -EXAMPBE ~
Substantially the same results of Table III
are achieved when the following masterbatch and composi.tion added prior to final mill mixing are substituted therein:
Masterbatch (1) Natural rubber 75 parts (2) Butadiene rubber 25 parts (3) Carbon black (FEF) 55 phr (4) Zinc oxide 10 phr 10 (5) Pelletized hydrated silica 12.5 phr (6) Stearic acid 1 phr (7) N-(1,3-dimethylbutyl)-N'-phenyl- 1 phr p-phenyle~ediamine (8) Hydrocarbon resin 5 phr 15 (~) Resorcinol (meta-dihydroxybenzene) 4 phr (10) Mànobond C 16 3.5 phr Composition added to above Masterbatch (A) Sulfur/oil - 80/20 powder 7 phr (B) Hexam~thoxymethyl-melamine 6 phr 20 (C) N-oxydiethylene benzothiazole-2- .8 phr 5ul fenamide, and (D) Cobalt PABA 4 phr 111~5~9 ~ 14 -The steel cord adhesion results set ~orth for bright steel wire (unplated) in the Examples above were determined by the following T adhesion procedure:
T-ADHESION TEST
1. Using a clicker machine and a 6 x 1/2 inch die, prepare an adequate number o~ experimental and control stock samples for pad building.
2. Use one piece of calendered fabric backing (.051'~
3. Ply one piece of control rubber stock (.060") onto thé fabric backing.
4. Place sample in building jig with fabric side down.
5. Place ten cords (of wire) approximately 7" in length equally spaced on top of the two piece assembly.
6. Invert another 2 ply assembly, made as in items 1, 2 and 3 on top of cords so that cords are between 2 layers of stock to be tested.
'1. This assembly should now fit snugly into the mold.
20 8. Adhesion pads shall be cured for 30 minutes at 300GF, and then allowed to equilibrate for 24 hours.
9. Testing Machine: 1130 Instron Universal Tester.
10. Test speed 10"/minute; temperature ~30F after a 20' preheat.
11. The top grip shall be of a special holder made for the cured sample, with a slot in the bottom to permit the sample to be inserted with the wire protruding. The bottom grip shall be a wedge type, designed to exert increasing tightening as the wire is pulled.
12. Record 10 pulls and average. Multiply by 2 to get lbs. adhesion per imbedded inch of wire.
11~8S49 Characteristics of several of the ingredicnts set out in the cxamples are set out below. These definitions are to be considered by way of illustration and represent known material that have proven useful in this invention.
Preferably, the skim stock also contains a suitable proportion of a conventional organo-cobalt complex, such as a material which is commercially sold under the name "Manobond C". It is known that such materials, including Manobond C, facilitate rubber-to-metal adhesion. -Manobond C is a commercially available source of a cobalt and boron containing additive that is compatible in our formulation; it is believed to have the structure:
Co - 0 - C - R
O O P
R - C - 0 - Co - 0 - B - 0 - Co - 0 - C - R
wherein each "R" is an alkyl radical of from 9 to 12 carbons. Mancbond C is available as a blue, viscous liquid; it contains 15.5 to 16.5% cobalt (Manobond C 16) or it contains 17.5 to 18.5% cobalt (Manobond C 18); it has a specific gravity (at 25C) of 3,000 to 9,000 cps.
The ash content is from 22 to 25 weight percent.
Manobond C is commercially available from Wyrough and Loser, Inc., Trenton, New Jersey.
The rubber to be used in the practice of this ~nvention includes vulcanizable rubbers. Rubbers that càn be utilized include natural rubbers, synthetic rubbers, polyisoprene, polybutadiene, copolymers of butadiene and styrene and the like, and blends thereof.
The particular rubber composition selected is preferably a blend of natural rubber and polybutadiene. An extender oil, when utilized, can be, for example, any known medium process oil, aromatic or naphthenic hydrocarbon derived.
854~
- lG -.
The antio~:idant selccted can be, for example, N-(1,3-dimethyl bu~yl)-N'-phenyl-p-phel-ylenediamine, known in the trade as Santoflex 13; or other phcnyl-p-phenylenediamine dcrivatives.
The accelerator preferably utilized in the practice of our invcntion is N-oxydiethylene benzothia-zole-2-sulfenamide; this accelerator is commercially available from American Cyanamid and is known as NOBS
Special. Other accelerators such as-N-t-butyl-2-benzothia-zole-sulfenamide can also be utilized; the particular accelerator selectcd is not critical.
~ Any known rubber reinforcing carbon black can be us~d, such as the known FEF, ISAF and other carbon blacks. Curing is preferably achieved through use of sulfur as a sulfur/oil blend preferably utilized at a ratio of 80/20. The use of FEF carbon black is preferred.
The pelletized hyd~ated silica is commercially available, for example, from PPG, Industries, Inc., Pittsburgh, Pennsylvania. The preferred silica is identified as ~ Sil 233.
Commercially available hydrocarbon resins that can be utilized in the invention include, for example, Betaprenc 105 (Reichhold Chemical) and Picco 14215 supplied by Hercules, Inc. Included are the intermediate and alipha~ic hydrocarbon resins that are otherwise commercially availablc. The sclected hydrocarbon resin will preferably have a softcning point of from about 100 to about 110C, an iodine number of from about 125 to about 167 and a maximum ash content of 0.05%.
The melamine resin is preferably Cyre~ 963, one of a family of melamine resins marketed by American Cyanamid.
~ trademarks L~
.. ''' ~ 17 -The precedin~ Examples can be varied within the scope of our total speciication disclosure, as it would be understood and practiced by one skilled in the art, to achieve essentially the same results. Equivalent reactants can be used within the designated ranges specified.
Compounding ingredients customarily employed `
in the rubber compounding art can be added to our skim stock composition and include accelerators, antioxidants, 10 bactericides and the like, color pigments, extenders, reinforcing pi~ments, softeners, vulcanizin~ agents, etc. ~he compounding ingredients are used in the amounts necessary to achieve the desired properties in the resulting vulcanizate as is well known to those skilled ;
15 in the art.
The skim stock of the present invention can be applied by use of calendering means, spray means or other known application techniques. Areas of si~nificant utility include, but are not limited to, radiator hose, 20 pneumatic tires, air ride springs, metal reinforced products such as rubber bumpers and sporting goods grips such as golf club handles; in each of these representative areas of utility, the skim stock composition can be used to increase adhesion and adhesion retention properties 25 between metal and rubber, including use in operation when bright steel surfaces are present.
When the skim stock of this invention is used ~n steel cord tire construction, for example, it is extremely important, both in new tire construction and 30 retread or repair operations, that the bond between the rubber ply stock and the wire fabric be as flexible and a~ strong as possible for efficient use under operation conditions; this is especially important in the case of truck tires which are subjected to hi~h loads and speeds 35 with consequent heat buildup due to the rapid flexiny of the plies.
-` ~118S49 The present invention also ~inds utility in, for example, metal-rubber articles such as motor mount.s, cutless bearings, torsilastic springs, powcr belts, printing rolls, metal wire reinforced or braided hose, electrical deicers, shoe heels, and wherevcr it is desired to secure rubber to plated or unplated metal to provide a flexible and strong bond between the same.
Acceptable results would be achieved on substituting brass or zinc plated steel wire for the bright steel wire of Tables I, II, and III. The wire coated in the practice of our invention can be, for example, brass plated wire, i.e., 70% Cu, 30~ Zn, zinc plated, or, bright (unplated) steel. The wire can be in the form of a strand, mat, web, ply or braid.
,: :
Invention Test Control Composition _.T. Ring Tensile - 30' Cure/300F
300~ Modulus, (psi) 1560 1620 Tensile Strength, (psi)2340 2090 Elongation, (~) 400 380 Unconditioned T Adhesion to (bright steel)* -30' Cure, R.T. Test 88 (20) 135 (80) 45' Cure, R.T. Test 89 (20) 140 (80) 30' Cure, 230F Test 71 (30) 107 (80) 45' Cure, 230F Test 68 (30) 102 (80) Conditioned T Adhesion to bright steel after 1 hour in 300F Steam ~ -30' Cure at 300F 61 (10) 108 (90) Tested at 230F
(T adhesion values in lb./in.; Coverages in (~)) -20 *Bright steel-unplated ~
: .. , , . ~
, ,. ~ ' , ~ ~ .
- . ~ .
~1854~
~ 13 -EXAMPBE ~
Substantially the same results of Table III
are achieved when the following masterbatch and composi.tion added prior to final mill mixing are substituted therein:
Masterbatch (1) Natural rubber 75 parts (2) Butadiene rubber 25 parts (3) Carbon black (FEF) 55 phr (4) Zinc oxide 10 phr 10 (5) Pelletized hydrated silica 12.5 phr (6) Stearic acid 1 phr (7) N-(1,3-dimethylbutyl)-N'-phenyl- 1 phr p-phenyle~ediamine (8) Hydrocarbon resin 5 phr 15 (~) Resorcinol (meta-dihydroxybenzene) 4 phr (10) Mànobond C 16 3.5 phr Composition added to above Masterbatch (A) Sulfur/oil - 80/20 powder 7 phr (B) Hexam~thoxymethyl-melamine 6 phr 20 (C) N-oxydiethylene benzothiazole-2- .8 phr 5ul fenamide, and (D) Cobalt PABA 4 phr 111~5~9 ~ 14 -The steel cord adhesion results set ~orth for bright steel wire (unplated) in the Examples above were determined by the following T adhesion procedure:
T-ADHESION TEST
1. Using a clicker machine and a 6 x 1/2 inch die, prepare an adequate number o~ experimental and control stock samples for pad building.
2. Use one piece of calendered fabric backing (.051'~
3. Ply one piece of control rubber stock (.060") onto thé fabric backing.
4. Place sample in building jig with fabric side down.
5. Place ten cords (of wire) approximately 7" in length equally spaced on top of the two piece assembly.
6. Invert another 2 ply assembly, made as in items 1, 2 and 3 on top of cords so that cords are between 2 layers of stock to be tested.
'1. This assembly should now fit snugly into the mold.
20 8. Adhesion pads shall be cured for 30 minutes at 300GF, and then allowed to equilibrate for 24 hours.
9. Testing Machine: 1130 Instron Universal Tester.
10. Test speed 10"/minute; temperature ~30F after a 20' preheat.
11. The top grip shall be of a special holder made for the cured sample, with a slot in the bottom to permit the sample to be inserted with the wire protruding. The bottom grip shall be a wedge type, designed to exert increasing tightening as the wire is pulled.
12. Record 10 pulls and average. Multiply by 2 to get lbs. adhesion per imbedded inch of wire.
11~8S49 Characteristics of several of the ingredicnts set out in the cxamples are set out below. These definitions are to be considered by way of illustration and represent known material that have proven useful in this invention.
Preferably, the skim stock also contains a suitable proportion of a conventional organo-cobalt complex, such as a material which is commercially sold under the name "Manobond C". It is known that such materials, including Manobond C, facilitate rubber-to-metal adhesion. -Manobond C is a commercially available source of a cobalt and boron containing additive that is compatible in our formulation; it is believed to have the structure:
Co - 0 - C - R
O O P
R - C - 0 - Co - 0 - B - 0 - Co - 0 - C - R
wherein each "R" is an alkyl radical of from 9 to 12 carbons. Mancbond C is available as a blue, viscous liquid; it contains 15.5 to 16.5% cobalt (Manobond C 16) or it contains 17.5 to 18.5% cobalt (Manobond C 18); it has a specific gravity (at 25C) of 3,000 to 9,000 cps.
The ash content is from 22 to 25 weight percent.
Manobond C is commercially available from Wyrough and Loser, Inc., Trenton, New Jersey.
The rubber to be used in the practice of this ~nvention includes vulcanizable rubbers. Rubbers that càn be utilized include natural rubbers, synthetic rubbers, polyisoprene, polybutadiene, copolymers of butadiene and styrene and the like, and blends thereof.
The particular rubber composition selected is preferably a blend of natural rubber and polybutadiene. An extender oil, when utilized, can be, for example, any known medium process oil, aromatic or naphthenic hydrocarbon derived.
854~
- lG -.
The antio~:idant selccted can be, for example, N-(1,3-dimethyl bu~yl)-N'-phenyl-p-phel-ylenediamine, known in the trade as Santoflex 13; or other phcnyl-p-phenylenediamine dcrivatives.
The accelerator preferably utilized in the practice of our invcntion is N-oxydiethylene benzothia-zole-2-sulfenamide; this accelerator is commercially available from American Cyanamid and is known as NOBS
Special. Other accelerators such as-N-t-butyl-2-benzothia-zole-sulfenamide can also be utilized; the particular accelerator selectcd is not critical.
~ Any known rubber reinforcing carbon black can be us~d, such as the known FEF, ISAF and other carbon blacks. Curing is preferably achieved through use of sulfur as a sulfur/oil blend preferably utilized at a ratio of 80/20. The use of FEF carbon black is preferred.
The pelletized hyd~ated silica is commercially available, for example, from PPG, Industries, Inc., Pittsburgh, Pennsylvania. The preferred silica is identified as ~ Sil 233.
Commercially available hydrocarbon resins that can be utilized in the invention include, for example, Betaprenc 105 (Reichhold Chemical) and Picco 14215 supplied by Hercules, Inc. Included are the intermediate and alipha~ic hydrocarbon resins that are otherwise commercially availablc. The sclected hydrocarbon resin will preferably have a softcning point of from about 100 to about 110C, an iodine number of from about 125 to about 167 and a maximum ash content of 0.05%.
The melamine resin is preferably Cyre~ 963, one of a family of melamine resins marketed by American Cyanamid.
~ trademarks L~
.. ''' ~ 17 -The precedin~ Examples can be varied within the scope of our total speciication disclosure, as it would be understood and practiced by one skilled in the art, to achieve essentially the same results. Equivalent reactants can be used within the designated ranges specified.
Compounding ingredients customarily employed `
in the rubber compounding art can be added to our skim stock composition and include accelerators, antioxidants, 10 bactericides and the like, color pigments, extenders, reinforcing pi~ments, softeners, vulcanizin~ agents, etc. ~he compounding ingredients are used in the amounts necessary to achieve the desired properties in the resulting vulcanizate as is well known to those skilled ;
15 in the art.
The skim stock of the present invention can be applied by use of calendering means, spray means or other known application techniques. Areas of si~nificant utility include, but are not limited to, radiator hose, 20 pneumatic tires, air ride springs, metal reinforced products such as rubber bumpers and sporting goods grips such as golf club handles; in each of these representative areas of utility, the skim stock composition can be used to increase adhesion and adhesion retention properties 25 between metal and rubber, including use in operation when bright steel surfaces are present.
When the skim stock of this invention is used ~n steel cord tire construction, for example, it is extremely important, both in new tire construction and 30 retread or repair operations, that the bond between the rubber ply stock and the wire fabric be as flexible and a~ strong as possible for efficient use under operation conditions; this is especially important in the case of truck tires which are subjected to hi~h loads and speeds 35 with consequent heat buildup due to the rapid flexiny of the plies.
-` ~118S49 The present invention also ~inds utility in, for example, metal-rubber articles such as motor mount.s, cutless bearings, torsilastic springs, powcr belts, printing rolls, metal wire reinforced or braided hose, electrical deicers, shoe heels, and wherevcr it is desired to secure rubber to plated or unplated metal to provide a flexible and strong bond between the same.
Acceptable results would be achieved on substituting brass or zinc plated steel wire for the bright steel wire of Tables I, II, and III. The wire coated in the practice of our invention can be, for example, brass plated wire, i.e., 70% Cu, 30~ Zn, zinc plated, or, bright (unplated) steel. The wire can be in the form of a strand, mat, web, ply or braid.
,: :
Claims (14)
1. A rubber skim stock of conventional composition, with improved adhesion to a contiguous metal member, characterized by having incorporated therein a minor proportion of p-aminobenzoic acid or a transition metal salt of p-aminobenzoic acid.
2. The composition of claim 1 having 0.5 to 8.0 phr of p-aminobenzoic acid.
3 The composition of claim 1 having 2.0 to 8.0 phr of a cobalt salt of p-aminobenzoic acid.
4. The composition of claim 1 having 0.5 to 8.0 phr of a nickel salt of p-aminobenzoic acid.
5. The composition of claim 1 having 0.5 to 8.0 phr of a transition metal salt of p-aminobenzoic acid.
6. A method of improving the adhesion of a rubber skim stock composition to a contiguous metal member wherein several conventional ingredients are mixed to form the composition, the composition is located contiguous to a metal member to form a laminate and the laminate is vulcanized, the improvement characterized by the incorporation of a minor proportion of p-aminobenzoic acid or a transition metal salt of p-aminobenzoic acid during the mixing step in the formation of the composition.
7. The method of claim 6 wherein 0.5 to 8.0 phr of p-aminobenzoic acid is incorporated during the mixing step.
8. The method of claim 6 wherein 2.0 to 8.0 phr of a cobalt salt of p-aminobenzoic acid is incorporated during the mixing step.
9. The method of claim 6 wherein 0.5 to 8.0 phr of a nickel salt of p-aminobenzoic acid is incorporated during the mixing step.
10. The method of claim 6 wherein 0.5 to 8.0 phr of a transition metal salt of p-aminobenzoic acid is incorporated during the mixing step.
11. A tire with improved adhesion between a rubber skim stock composition and a contiguous metal member, having metal reinforcing members imbedded in a vulcanized rubber skim stock composition, the improvement characterized by said composition comprising a minor proportion of p-aminobenzoic acid or a transition metal salt of p-aminobenzoic acid.
12. The tire of claim 11 wherein said composition comprises 0.5 to 8.0 phr of p-aminobenzoic acid.
13. The tire of claim 11 wherein said composition comprises 2.0 to 8.0 phr of a cobalt salt of p-amino-benzoic acid.
14. The tire of claim 11 wherein said composition comprises 0.5 to 8.0 phr of nickel salt of p-amino-benzoic acid.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82478077A | 1977-08-15 | 1977-08-15 | |
| US82476777A | 1977-08-15 | 1977-08-15 | |
| US824,767 | 1977-08-15 | ||
| US824,780 | 1977-08-15 | ||
| US86697378A | 1978-01-05 | 1978-01-05 | |
| US866,973 | 1978-01-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1118549A true CA1118549A (en) | 1982-02-16 |
Family
ID=27420169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000308292A Expired CA1118549A (en) | 1977-08-15 | 1978-07-27 | Method, composition and product with improved adhesion between a metal member and a contiguous rubber skim stock |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5434387A (en) |
| AT (1) | AT379163B (en) |
| BR (1) | BR7805221A (en) |
| CA (1) | CA1118549A (en) |
| DK (1) | DK358178A (en) |
| ES (1) | ES472510A1 (en) |
| IT (1) | IT1113091B (en) |
| MX (1) | MX147498A (en) |
| NO (1) | NO151591C (en) |
| NZ (1) | NZ188088A (en) |
| PT (1) | PT68409A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6273650U (en) * | 1985-10-25 | 1987-05-12 | ||
| JPH10193916A (en) * | 1997-01-10 | 1998-07-28 | Yokohama Rubber Co Ltd:The | Pneumatic radial tire |
-
1978
- 1978-07-27 CA CA000308292A patent/CA1118549A/en not_active Expired
- 1978-08-08 NZ NZ188088A patent/NZ188088A/en unknown
- 1978-08-09 AT AT0579278A patent/AT379163B/en not_active IP Right Cessation
- 1978-08-10 IT IT26643/78A patent/IT1113091B/en active
- 1978-08-10 NO NO782729A patent/NO151591C/en unknown
- 1978-08-10 PT PT68409A patent/PT68409A/en unknown
- 1978-08-11 ES ES472510A patent/ES472510A1/en not_active Expired
- 1978-08-14 BR BR7805221A patent/BR7805221A/en unknown
- 1978-08-14 JP JP9895278A patent/JPS5434387A/en active Granted
- 1978-08-14 MX MX174513A patent/MX147498A/en unknown
- 1978-08-14 DK DK358178A patent/DK358178A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NZ188088A (en) | 1980-12-19 |
| IT7826643A0 (en) | 1978-08-10 |
| PT68409A (en) | 1978-09-01 |
| AT379163B (en) | 1985-11-25 |
| JPS5434387A (en) | 1979-03-13 |
| NO151591B (en) | 1985-01-21 |
| NO151591C (en) | 1985-05-08 |
| MX147498A (en) | 1982-12-10 |
| JPS6152852B2 (en) | 1986-11-14 |
| ATA579278A (en) | 1985-04-15 |
| BR7805221A (en) | 1979-04-24 |
| DK358178A (en) | 1979-02-16 |
| NO782729L (en) | 1979-02-16 |
| ES472510A1 (en) | 1980-04-01 |
| IT1113091B (en) | 1986-01-20 |
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