CA1071824A - Method of manufacturing new paintable rubber composition and products - Google Patents
Method of manufacturing new paintable rubber composition and productsInfo
- Publication number
- CA1071824A CA1071824A CA239,909A CA239909A CA1071824A CA 1071824 A CA1071824 A CA 1071824A CA 239909 A CA239909 A CA 239909A CA 1071824 A CA1071824 A CA 1071824A
- Authority
- CA
- Canada
- Prior art keywords
- rubber
- product
- group
- treatment
- component
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
- B05D3/044—Pretreatment
- B05D3/0446—Pretreatment of a polymeric substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
- B05D3/062—Pretreatment
- B05D3/063—Pretreatment of polymeric substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/08—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by flames
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
- B05D3/141—Plasma treatment
- B05D3/142—Pretreatment
- B05D3/144—Pretreatment of polymeric substrates
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A new paintable rubber composition made of a special formulation of materials including, for example, an SBR rubber elastomer and a thermoplastic polymeric stiffening agent means which may be used to provide the cured composition with a high flex modulus; and a new method of manufacturing a special flexible painted rubber product.
A new paintable rubber composition made of a special formulation of materials including, for example, an SBR rubber elastomer and a thermoplastic polymeric stiffening agent means which may be used to provide the cured composition with a high flex modulus; and a new method of manufacturing a special flexible painted rubber product.
Description
~ 10~8Z4 BACKGROUND OF THE INVENTION
, This invention relates to a paintable rubber product for use on automotive vehicles and the like. Also, the invention broadly relates to a new rubber composition and a method of manufacturing products therewith.
The state of the art is indicated by the following references and the references cited in said copending application above: United States patents 3,231,634; 3,256,362;
3,511,792; 3,577,480; and, Enjay Chemical Company Technical circular, EPL-7204, for "Vistalon Formula 11.401--A New Paintable Base Compound"; and, Copolymer Rubber and Chemical Corporation, Technical circular entitled "EPsynEPDM....The Paintable EPDM you compound yourself"; and, DuPont Technical circular for DuPont's Nordel No. 2903, EPDM System.
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`. 10718Z4 ` One object of this invention is to prepare a new paintable _ rubber product with a colored paint coating thereon, said coating being of a flexible, color stable nature and with said product ~- having a high flex modulus, and also possessing the propertie~
of being resilient and generally recoverable to its original shape after deflection.
Another object of this invention is to provide a new rubber composition and method of manufacturing products therewith.
Another object of this invention is to provide a new rubber composition and product which are more economical from a cost standpoint.
Another object of this invention is to provide a new rubber composition and product wherein the curing rates are ; faster thus allowing faster cycle times than were generally . .
possible with prior composition (i.e., faster but yet color stable when painted).
. .
Another object of the present invention is to provide a new rubber composition and product wherein the flow character-istics of the composition are better suited for molding or extruding a product to be manufactured.
Another object of the present invention is to provide a new system for manufacturing a paintable rubber product wherein J
ultraviolet surface activation is not necessary in order to achieve good paint adhesion.
.~ .
~ -2-" -`' lOql8Z4 Other objects, features and advantages of the present invention will become apparent from the subsequent description and the appended claims.
SUMMARY OF THE INVENTION
In one particular aspect the present invention provides a method of manufacturing a flexible painted rubber product, comprising the steps of: formulating a composition comprising percentages belng by weight, (a) about 15% to about 90% of a cross-linkable rubber material selected from at least one of the group consisting of styrene butadiene rubber, polybutadiene rubber, and isoprene rubber, said rubber material also including ~- up to 50% of ethylene-propylene diene monomer rubber of neoprene rubber, (b) zero to about 40% of a polymeric stiffening agent for providing a high flex modulus for the cured composition, (c) about 0.01% to about 50% of a plasticizing agent, (d) zero to about 5% of an accelerating agent, (e) Q.01% to about .
10% of a curing agent, (f) zero to about 10% of an activating agent, (g) zero to about 80% of a filler material, and forming - the product by molding said composition and curing the product . 20 at a temperature between about 275F and about 600F for a .
-~ residence time period between about 45 minutes and about ~ -minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
In another particular aspect the present invention provides a method of manufacturing a flexible painted rubber product, comprising the steps of: formulating a composition, percentages -~ being by weight, (a) about 15% to about 90% of a cross-linkable : rubber material selected from at least one of the group consisting of styrene butadiene rubber, polybutadiene rubber, and isopreùe .. - - : . - ~ .-. ' ' ' ~
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rubber, said rubber material also including less than 50% of ethylene-propylene diene monomer rubber or neoprene rubber, (b) about 0.1% to about 40% of a polymeric stiffening agent for providing a high flex modulus for the cured composition, (c) about 0.01% to about 50% of a plasticizing agent, (d) zero to about 5% of an accelerating agent, (e) 0.01% to about 10%
of a curing agent, (f) zero to about 10% of an activating agent, (g) zero to about 80% of a filler material, forming the product by molding said composition and curing the product at a temperature between about 275 F and about 450 P for a residence time period between about 20 minutes and about ~ minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
In a further particular aspect the present invention provides a method of manufacturing a flexible painted rubber product, comprising the steps of: formulating a composition comprising, percentages being by weight, (a) about 15% to about 90% of a cross-linkable rubber material selected from at least one of the group consisting of styrene butadiene rubber, polybutadiene rubber, and isoprene rubber, said rubber material also including up to 50% of ethylene-propylene diene monomer rubber or neoprene rubber, (b) zero to about 40% of a polymeric stiffening agent menas for providing a high flex modulus-for the cured composition, (c) about 0.01% to about 50%
of a plasticizing agent, said plasticizing agent is a compatible non-staining, non-discoloring plasticizer and is substantially a material selected from at least one of the group consisting of, naphthenic oils, low moleuclar weight polyester type plasticizers., petroleum resins, coal tar compound plasticizers, and paraffinic jl/~. . -3a-~ lOql8Z4 plasticizers, (d) zero to about 5% of an accelerating agent, (e) 0.01% to about 10% of a curing agent, (f ) zero to about 10% of an activating agent, (g) about 0.01% to about 80% of a filler material, and forming the product by m~lding said composition and curing the product at a temperature between about 275F and about 600F for a residence time period between about 45 minutes and about ~ minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
DESCRIPTION OF THE PREFERRED E~BODI~IENTS
The cross-linkable rubber material used in the invention should be selected from the group of styrene butadiene rubber (SBR), polybutadiene, and isoprene rubber. The cross-linkable rubber material may also optionally include up to 50~ of . . .
ethylene-propylene diene monomer rub~er (EPDM) or neoprene -` 20 ,~ jl/"'`' ~_ , -`` 1071824 rubber. Preferably, though, the inclusion of this optional EPDM or neoprene rubber material in the cross-linkable rubber material referred to above is maintained at a level below 15%
~; by weight of the cross-linkable rubber material and best . results appear to be obtained without the presence of any EPDM
or neoprene rubber.
The amount of said cross-linkable rubber material should `- broadly be between about 15% and about 90% by weight of the composition and preferably it should be between about 25% and 10 60% of the composition, with best results being obtained within the range of about 30% to about 55Z by weight of the composition.
'~. , The thermoplastic polymer stiffening agent means in ~` accordance with this invention has been discovered to provide a high flex modulus for the cured composition or final product formed and this polymeric stiffening agent means is one selected ` from the group consisting of ethylene-ethyl acrylate copolymer, acrylonitrile butadiene styrene, styrene resins, polyvinyl chloride, ethylene vinyl acetate, a thermoplastic ethylene-~- propylene copolymer, an acrylic resin, a cellulosic resins, phenolic resins and a C2-c4 polyolefinic polymer material. This stiffening agent may also be made at least in part from a C2-C4 polyolefin/acrylic copolymer material~
The amount of the polymeric stiffening agent means present in the composition should broadly be within the range of zero -40% by weight of the composition and preferably it should be maintained within the range of about 0.01% up to about 40% by weight of the composition, with best results being obtained when ; it is maintained within the range of about 5% to about 20% by weight of the composition.
~ \ -5-lOql8~4 ~ The plasticizing agent utilized in the composition should be present within the broad range of about 0.01% up to about 50%
by weight of the composition, and preferably, it should be maintained in the range of 0.01% up to about 35% by weight of the composition, with best results being obtained using the plasticizing agent within the range of about 1% to about 15%
by welght. The plasticizing agent should be a compatible non-staining, non-discoloring plasticizer such as the various plasticizing oils, for example, Flexon 766 or Sunthene 410, or, various other high quality naphthenic oils or various parafinic materials, or various low molecular weight polyester , plasticizers, as well as petroleum resins and cool tar compounds (coumarone indenes) may also be used.
The accelerating agent used in the composition should broadly be present within the range of about zero to about 5%
i~ by weight of the composition, and preferably, it should be ! present within the range of about zero to about 3% by weight, with best results being obtained in the range of about 0.01%
up to about 3%. The accelerating agents which are useful herein are of a type well known in the art, such as Cumate~, Altax~, Captax~ and various methacrylate monomers (e.g. Sartomer Co, ; SR-206, 297, and 350).
The curing agent used in the composition should broadly be within the range of about 0.01% to about 10% by weight of - the composition and, preferably it should be within the range of about 0.5% to about 5%, with best results being obtained when it is maintained within the range of about 0.5% to about 3% by weight of the composition. The composition may be sulfur cured or cured with a peroxide curing agent or numerous other curing . . .
~ 6-107182~
agents may be used such as Schenectady SP-1055 curing agent (brominated methyol phenol type, see U.S. patent 2,972,600), a phenol curing agent, a quinone curing agent, or an amino type curing agent.
The activating agent used in the composition should be present within the broad range of about zero up to about 10%
by weight of the composition and preferably, it should be present within the range of about 0.01% to about 5% by weight, with best results being obtained within the range of about 0.1% to about 3% by weight of the composition. The activating agent may be a material such as zinc oxide, stearic acid, various stearates such as zinc stearate, and various metallic halides. Numerous different activating agents may be useful in the invention which activating agents are known in the art.
The filler material which may optionally be included in the composition may be present within the broad range of about zero up to 80% by weight of the composition, and preferably, it should be maintained within the range of at least about O.01~
up to about 80% by weight of the composition, with best results being obtained when a filler material is used within the range of about 1% to about 50% by weight of the composition. Any non-discoloring filler material may be used such as various carbons, carbon black, various carbonate fillers, clays, sulfates, various silicas, fiber glass, and other fibrous materials. Other filler materials will be apparent to those skilled in the art.
The cured composition discovered and disclosed in accordance with the invention herein finds highly satisfactory and advantageous uses, such as for paintable rubber sightshield pro-ducts in the automotive field, for various bumper products in the automotive field, for fender extensions, filler panels, ~ -7-.
hoods, trunk lids, and the like all in the automotive vehicular ~` field. Numerous other highly useful application~ of this - invention may be found where an exteriorly used flexible ~ paintable rubber product is required.
~ ~ , After the composition is molded and cured as referred to above, it is generally prepared for painting by cleaning the surface thereof which is to bepainted either with solvents or a detergent wash or otherwise properly cleaning the surface.
Then generally we found that the surface to be painted should be properly activated to obtain good paint adhesion in accordance with our invention. The surface activation may be carried out by halogenation of the surface such as by chlorination, or by ozone treatment, treatment with ultraviolet light, flame treatment, or electronic treatment. In certain instances surface activation is not necessary with some flexible color stable paints which may be used on the cured molded composition in accordance with our invention. It is to be noted in accordance , ~ .
with this invention that ultraviolet treatment of the surface is not necessary and that the surface may be prepared in a very able fashion to obtain good paint adhesion by chlorination of the su-rface to be painted.
, After the surface is prepared for painting, it is our finding that generally a paint primer coating should preferably first be applied although this is optional and not absolutely necessary. Then a colored paint coating layer means is applied to the product using a flexible color stable paint coating such as a paint sel~cted from the group of resinous coatings consisting of a urethane resin coating, an acrylic resin coating, or a polyester resin coating or combinations thereof. Application of these coatings may be by spraying, brushing, rolling, electrostatic ~ 8-,. ~ ~
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"` 1071824 application or the like. As mentioned, the application of a primer coating is not absolutely necessary. However, it is generally more economical to use a primer coating because the application of a thicker colored paint coating which would be necessary without a primer coating requries the application of a thick paint coating which has an expensive coloring pigment system therein.
It should also be understood that in accordance with the invention herein, it is possible to carry out the forming step continuously such as by extruding, and the steps of curing, preparing the clean surface, and applying the color stable paint coating may all be carried out continuously in a continuous manufacturing operation. Moreover it is also possible to include a textured surface pattern in the product (e.g. for weatherstrips) by continuously rolling in a textured pattern on the product after it has been formed and prior to curing.
The advantages of the invention should be fairly apparent from the inventive disclosure above. However, it is believed in particular that the following advantages are obtainable with this invention (1) The new rubber product herein is quicker curing and thus the mold cycle times are reduced.-(2) The new rubber product herein is generally more economical because less costs are involved in obtaining the raw materials used in this invention.
(3) Better processability is obtained using the new rubber composition herein. (4) With the new rubber composition herein, it is generally easier to get proper adhesion with the overlying paint layers. (5) With the new composition herein, the final product properties are either equivalent to or better than prior :- , ., ~
.
composition. (6) With the new composition herein, improved weatherability of paints on the product substrate is obtainable.
(7) The rubber composition and system of manufacturing a paintable rubber product in accordance with this invention does not require ultraviolet treatment of the surface of the cured rubber composition in order to achieve good plant adhesion. (8) - In prior compositions based on EPDM rubber, these prior compos-itions have generally possessed relatively high viscosities which cause undesireable flow properties in molding, whereas the composition of this invention possesses much improved flow properties and thus the composition and product of this invention are much better suited for molding than the prior compositions.
(9) Moreover, as explained herein the manufacture of products pursuant to this invention may be carried out on a continuous basis.
In order to further illustrate the invention, the following examples are provided. It is to be understood, however, that tke examples are included for illustrati~ve purposes and are not intended to be limiting of the scope of the invention as set forth ln the subjoined claims.
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, . , ~- ~ , ' Material Parts % wgt.
(ethylene ethyl acrylate) 25 13.5 FEF Black 70 37-5 Sunthene~ 410 (naphthenic processing oil) 8 4.3 Zinc oxide 3 1.6 Zalba~ Special (antioxidant) 0.5 .27 Stearic acid 0.5 .27 Cumate~
0.1 .0054 Altax~ 2.0 1.07 Spider Sulfur 2.0 1.07 (Technical Processing Inc., organic processing aid) 0.5 .27 TOTAL 186.6 Speciflc gravity 1.18 .,.
~ ' , . 30 ~ .
. - : . .
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In~redients Parts Ameripol~ 1502 (SBR rubber) 75.0 DPD 6169 25.0 FEF Black 70.0 766 Oil (Flexon~) 8.0 ZNO
3.0 Zalba~ Special 0.5 Stearic Acid 0-5 Cumate~
0.1 MBTS
(accelerator-benzo thiazyl disulfide) 2.0 : Sulfur
, This invention relates to a paintable rubber product for use on automotive vehicles and the like. Also, the invention broadly relates to a new rubber composition and a method of manufacturing products therewith.
The state of the art is indicated by the following references and the references cited in said copending application above: United States patents 3,231,634; 3,256,362;
3,511,792; 3,577,480; and, Enjay Chemical Company Technical circular, EPL-7204, for "Vistalon Formula 11.401--A New Paintable Base Compound"; and, Copolymer Rubber and Chemical Corporation, Technical circular entitled "EPsynEPDM....The Paintable EPDM you compound yourself"; and, DuPont Technical circular for DuPont's Nordel No. 2903, EPDM System.
'.', ' r ~
~',' , ' .
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~-j 20 ~. 1 ~, .
., . .
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.: ' ' - - . : .
.
' ' ' , ' ' . -, ~ ' :'., . .
- .
`. 10718Z4 ` One object of this invention is to prepare a new paintable _ rubber product with a colored paint coating thereon, said coating being of a flexible, color stable nature and with said product ~- having a high flex modulus, and also possessing the propertie~
of being resilient and generally recoverable to its original shape after deflection.
Another object of this invention is to provide a new rubber composition and method of manufacturing products therewith.
Another object of this invention is to provide a new rubber composition and product which are more economical from a cost standpoint.
Another object of this invention is to provide a new rubber composition and product wherein the curing rates are ; faster thus allowing faster cycle times than were generally . .
possible with prior composition (i.e., faster but yet color stable when painted).
. .
Another object of the present invention is to provide a new rubber composition and product wherein the flow character-istics of the composition are better suited for molding or extruding a product to be manufactured.
Another object of the present invention is to provide a new system for manufacturing a paintable rubber product wherein J
ultraviolet surface activation is not necessary in order to achieve good paint adhesion.
.~ .
~ -2-" -`' lOql8Z4 Other objects, features and advantages of the present invention will become apparent from the subsequent description and the appended claims.
SUMMARY OF THE INVENTION
In one particular aspect the present invention provides a method of manufacturing a flexible painted rubber product, comprising the steps of: formulating a composition comprising percentages belng by weight, (a) about 15% to about 90% of a cross-linkable rubber material selected from at least one of the group consisting of styrene butadiene rubber, polybutadiene rubber, and isoprene rubber, said rubber material also including ~- up to 50% of ethylene-propylene diene monomer rubber of neoprene rubber, (b) zero to about 40% of a polymeric stiffening agent for providing a high flex modulus for the cured composition, (c) about 0.01% to about 50% of a plasticizing agent, (d) zero to about 5% of an accelerating agent, (e) Q.01% to about .
10% of a curing agent, (f) zero to about 10% of an activating agent, (g) zero to about 80% of a filler material, and forming - the product by molding said composition and curing the product . 20 at a temperature between about 275F and about 600F for a .
-~ residence time period between about 45 minutes and about ~ -minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
In another particular aspect the present invention provides a method of manufacturing a flexible painted rubber product, comprising the steps of: formulating a composition, percentages -~ being by weight, (a) about 15% to about 90% of a cross-linkable : rubber material selected from at least one of the group consisting of styrene butadiene rubber, polybutadiene rubber, and isopreùe .. - - : . - ~ .-. ' ' ' ~
:
. .
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rubber, said rubber material also including less than 50% of ethylene-propylene diene monomer rubber or neoprene rubber, (b) about 0.1% to about 40% of a polymeric stiffening agent for providing a high flex modulus for the cured composition, (c) about 0.01% to about 50% of a plasticizing agent, (d) zero to about 5% of an accelerating agent, (e) 0.01% to about 10%
of a curing agent, (f) zero to about 10% of an activating agent, (g) zero to about 80% of a filler material, forming the product by molding said composition and curing the product at a temperature between about 275 F and about 450 P for a residence time period between about 20 minutes and about ~ minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
In a further particular aspect the present invention provides a method of manufacturing a flexible painted rubber product, comprising the steps of: formulating a composition comprising, percentages being by weight, (a) about 15% to about 90% of a cross-linkable rubber material selected from at least one of the group consisting of styrene butadiene rubber, polybutadiene rubber, and isoprene rubber, said rubber material also including up to 50% of ethylene-propylene diene monomer rubber or neoprene rubber, (b) zero to about 40% of a polymeric stiffening agent menas for providing a high flex modulus-for the cured composition, (c) about 0.01% to about 50%
of a plasticizing agent, said plasticizing agent is a compatible non-staining, non-discoloring plasticizer and is substantially a material selected from at least one of the group consisting of, naphthenic oils, low moleuclar weight polyester type plasticizers., petroleum resins, coal tar compound plasticizers, and paraffinic jl/~. . -3a-~ lOql8Z4 plasticizers, (d) zero to about 5% of an accelerating agent, (e) 0.01% to about 10% of a curing agent, (f ) zero to about 10% of an activating agent, (g) about 0.01% to about 80% of a filler material, and forming the product by m~lding said composition and curing the product at a temperature between about 275F and about 600F for a residence time period between about 45 minutes and about ~ minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
DESCRIPTION OF THE PREFERRED E~BODI~IENTS
The cross-linkable rubber material used in the invention should be selected from the group of styrene butadiene rubber (SBR), polybutadiene, and isoprene rubber. The cross-linkable rubber material may also optionally include up to 50~ of . . .
ethylene-propylene diene monomer rub~er (EPDM) or neoprene -` 20 ,~ jl/"'`' ~_ , -`` 1071824 rubber. Preferably, though, the inclusion of this optional EPDM or neoprene rubber material in the cross-linkable rubber material referred to above is maintained at a level below 15%
~; by weight of the cross-linkable rubber material and best . results appear to be obtained without the presence of any EPDM
or neoprene rubber.
The amount of said cross-linkable rubber material should `- broadly be between about 15% and about 90% by weight of the composition and preferably it should be between about 25% and 10 60% of the composition, with best results being obtained within the range of about 30% to about 55Z by weight of the composition.
'~. , The thermoplastic polymer stiffening agent means in ~` accordance with this invention has been discovered to provide a high flex modulus for the cured composition or final product formed and this polymeric stiffening agent means is one selected ` from the group consisting of ethylene-ethyl acrylate copolymer, acrylonitrile butadiene styrene, styrene resins, polyvinyl chloride, ethylene vinyl acetate, a thermoplastic ethylene-~- propylene copolymer, an acrylic resin, a cellulosic resins, phenolic resins and a C2-c4 polyolefinic polymer material. This stiffening agent may also be made at least in part from a C2-C4 polyolefin/acrylic copolymer material~
The amount of the polymeric stiffening agent means present in the composition should broadly be within the range of zero -40% by weight of the composition and preferably it should be maintained within the range of about 0.01% up to about 40% by weight of the composition, with best results being obtained when ; it is maintained within the range of about 5% to about 20% by weight of the composition.
~ \ -5-lOql8~4 ~ The plasticizing agent utilized in the composition should be present within the broad range of about 0.01% up to about 50%
by weight of the composition, and preferably, it should be maintained in the range of 0.01% up to about 35% by weight of the composition, with best results being obtained using the plasticizing agent within the range of about 1% to about 15%
by welght. The plasticizing agent should be a compatible non-staining, non-discoloring plasticizer such as the various plasticizing oils, for example, Flexon 766 or Sunthene 410, or, various other high quality naphthenic oils or various parafinic materials, or various low molecular weight polyester , plasticizers, as well as petroleum resins and cool tar compounds (coumarone indenes) may also be used.
The accelerating agent used in the composition should broadly be present within the range of about zero to about 5%
i~ by weight of the composition, and preferably, it should be ! present within the range of about zero to about 3% by weight, with best results being obtained in the range of about 0.01%
up to about 3%. The accelerating agents which are useful herein are of a type well known in the art, such as Cumate~, Altax~, Captax~ and various methacrylate monomers (e.g. Sartomer Co, ; SR-206, 297, and 350).
The curing agent used in the composition should broadly be within the range of about 0.01% to about 10% by weight of - the composition and, preferably it should be within the range of about 0.5% to about 5%, with best results being obtained when it is maintained within the range of about 0.5% to about 3% by weight of the composition. The composition may be sulfur cured or cured with a peroxide curing agent or numerous other curing . . .
~ 6-107182~
agents may be used such as Schenectady SP-1055 curing agent (brominated methyol phenol type, see U.S. patent 2,972,600), a phenol curing agent, a quinone curing agent, or an amino type curing agent.
The activating agent used in the composition should be present within the broad range of about zero up to about 10%
by weight of the composition and preferably, it should be present within the range of about 0.01% to about 5% by weight, with best results being obtained within the range of about 0.1% to about 3% by weight of the composition. The activating agent may be a material such as zinc oxide, stearic acid, various stearates such as zinc stearate, and various metallic halides. Numerous different activating agents may be useful in the invention which activating agents are known in the art.
The filler material which may optionally be included in the composition may be present within the broad range of about zero up to 80% by weight of the composition, and preferably, it should be maintained within the range of at least about O.01~
up to about 80% by weight of the composition, with best results being obtained when a filler material is used within the range of about 1% to about 50% by weight of the composition. Any non-discoloring filler material may be used such as various carbons, carbon black, various carbonate fillers, clays, sulfates, various silicas, fiber glass, and other fibrous materials. Other filler materials will be apparent to those skilled in the art.
The cured composition discovered and disclosed in accordance with the invention herein finds highly satisfactory and advantageous uses, such as for paintable rubber sightshield pro-ducts in the automotive field, for various bumper products in the automotive field, for fender extensions, filler panels, ~ -7-.
hoods, trunk lids, and the like all in the automotive vehicular ~` field. Numerous other highly useful application~ of this - invention may be found where an exteriorly used flexible ~ paintable rubber product is required.
~ ~ , After the composition is molded and cured as referred to above, it is generally prepared for painting by cleaning the surface thereof which is to bepainted either with solvents or a detergent wash or otherwise properly cleaning the surface.
Then generally we found that the surface to be painted should be properly activated to obtain good paint adhesion in accordance with our invention. The surface activation may be carried out by halogenation of the surface such as by chlorination, or by ozone treatment, treatment with ultraviolet light, flame treatment, or electronic treatment. In certain instances surface activation is not necessary with some flexible color stable paints which may be used on the cured molded composition in accordance with our invention. It is to be noted in accordance , ~ .
with this invention that ultraviolet treatment of the surface is not necessary and that the surface may be prepared in a very able fashion to obtain good paint adhesion by chlorination of the su-rface to be painted.
, After the surface is prepared for painting, it is our finding that generally a paint primer coating should preferably first be applied although this is optional and not absolutely necessary. Then a colored paint coating layer means is applied to the product using a flexible color stable paint coating such as a paint sel~cted from the group of resinous coatings consisting of a urethane resin coating, an acrylic resin coating, or a polyester resin coating or combinations thereof. Application of these coatings may be by spraying, brushing, rolling, electrostatic ~ 8-,. ~ ~
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"` 1071824 application or the like. As mentioned, the application of a primer coating is not absolutely necessary. However, it is generally more economical to use a primer coating because the application of a thicker colored paint coating which would be necessary without a primer coating requries the application of a thick paint coating which has an expensive coloring pigment system therein.
It should also be understood that in accordance with the invention herein, it is possible to carry out the forming step continuously such as by extruding, and the steps of curing, preparing the clean surface, and applying the color stable paint coating may all be carried out continuously in a continuous manufacturing operation. Moreover it is also possible to include a textured surface pattern in the product (e.g. for weatherstrips) by continuously rolling in a textured pattern on the product after it has been formed and prior to curing.
The advantages of the invention should be fairly apparent from the inventive disclosure above. However, it is believed in particular that the following advantages are obtainable with this invention (1) The new rubber product herein is quicker curing and thus the mold cycle times are reduced.-(2) The new rubber product herein is generally more economical because less costs are involved in obtaining the raw materials used in this invention.
(3) Better processability is obtained using the new rubber composition herein. (4) With the new rubber composition herein, it is generally easier to get proper adhesion with the overlying paint layers. (5) With the new composition herein, the final product properties are either equivalent to or better than prior :- , ., ~
.
composition. (6) With the new composition herein, improved weatherability of paints on the product substrate is obtainable.
(7) The rubber composition and system of manufacturing a paintable rubber product in accordance with this invention does not require ultraviolet treatment of the surface of the cured rubber composition in order to achieve good plant adhesion. (8) - In prior compositions based on EPDM rubber, these prior compos-itions have generally possessed relatively high viscosities which cause undesireable flow properties in molding, whereas the composition of this invention possesses much improved flow properties and thus the composition and product of this invention are much better suited for molding than the prior compositions.
(9) Moreover, as explained herein the manufacture of products pursuant to this invention may be carried out on a continuous basis.
In order to further illustrate the invention, the following examples are provided. It is to be understood, however, that tke examples are included for illustrati~ve purposes and are not intended to be limiting of the scope of the invention as set forth ln the subjoined claims.
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(ethylene ethyl acrylate) 25 13.5 FEF Black 70 37-5 Sunthene~ 410 (naphthenic processing oil) 8 4.3 Zinc oxide 3 1.6 Zalba~ Special (antioxidant) 0.5 .27 Stearic acid 0.5 .27 Cumate~
0.1 .0054 Altax~ 2.0 1.07 Spider Sulfur 2.0 1.07 (Technical Processing Inc., organic processing aid) 0.5 .27 TOTAL 186.6 Speciflc gravity 1.18 .,.
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In~redients Parts Ameripol~ 1502 (SBR rubber) 75.0 DPD 6169 25.0 FEF Black 70.0 766 Oil (Flexon~) 8.0 ZNO
3.0 Zalba~ Special 0.5 Stearic Acid 0-5 Cumate~
0.1 MBTS
(accelerator-benzo thiazyl disulfide) 2.0 : Sulfur
2.0 TE 28-~
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2.0 Specific gravity - 1.18 ';
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polymer) 25 550 FEF Carbon Black 100 . Sunpar~ 140LW oil 26 Zinc oxide 3 ~ Carbowax~ 4000 '; (polyethylene glycol) 0.5 Hi Sil~ 233 10 . . , Vulkup~ 40KE
(organic peroxide) 3 .
Cure (Min/Temp)3/350F 6/350F
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Duro A ~ D 86/35 90/37 ` Tensile 1090 1320 -. 100% Modulus 1090 . Elongation 100 70 Tear 93 95 ;~' .
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1()71824 Ingredients Parts : SBR 1502 15 EPDM (EPSYN~ 4506) 50 Goodrite~ Resin 2007 (a high styrene SBR
polymer) 25 550 FEF Carbon Black 100 . Sunpar~ 140LW oil 26 Zinc oxide 3 ~ Carbowax~ 4000 '; (polyethylene glycol) 0.5 Hi Sil~ 233 10 . . , Vulkup~ 40KE
(organic peroxide) 3 .
Cure (Min/Temp)3/350F 6/350F
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Duro A ~ D 86/35 90/37 ` Tensile 1090 1320 -. 100% Modulus 1090 . Elongation 100 70 Tear 93 95 ;~' .
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` ` 1071824 ` Ingredients Parts `~` . EPDM (EPSYN~ 4506) 50 550 FEF Carbon Black 100 5. Sunpar~ 140LW oil 25 Zinc oxide 3 Carbowax~ 4000 0.5 .~ 10 Hi Sil~ 233 10 SP 1055 Resin .. (a brominated methylol ' phenolic resin) 15 .;, .
, Cure (Min./Temp.)5/380F 10/350F
.i Duro A 79 78 '~l- Tensile 1190 1170 100% Modulus 890 820 : Elongation 160 180 j Tear 113 113 .
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'' ' ' ' ~ ~ ' -' lOql824 Ingredients Parts SBR 1502 75.0 DPD 6169 35.0 FEF 550 70.0 Sunthene~ 410 8.0 ZnO 3.0 Stearic Acid 0.5 Zalba~ Special 0.5 Cumate~ 0.1 Altax~ 2.0 Spider Sulfur 2.0 TE-28-E 0.5 Mooney Scorch/280F
Minimum 18 T 10 9'5 , Mooney Scorch/250F
Minimum 20.0 T 10 23.0 - Cure Time (Min./Temp.) 35/350F
Hot Tear Excellent Snap Excellent : Durometer A 82 100% Modulus 1000 . Tensile 2200-Elongation 240 ; Tear 225 .'' ' .
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107182g ` Ingredients Parts `~ SBR 8140 49 ` SBR 1006 21 ' EPDM (EPSYN~ 55) 30 550 FEF Carbon Black 75 Austin Black 15 Sunpar~ 140 LW oil 12 '~; Zinc oxide 3 ~; 10 SP 1055 Resin 15 ., '; 1/4" chopped strands fiberglass 44 ; , Cure (Min./Temp.) 75/350F
. Duro A 84 Tensile 1640 u 100% Modulus 970 ~ Elongation 230 p; Tear 273 . 20 --.
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EPDM (EPSYN~ 55) 15 550 FEF Carbon Black 90 Sunpar0 140LW oil 25 Zinc oxide . 5 Calcium oxide dispersion 5 Stearic acid 1.5 Zalba~ Special (an antioxidant) - 0.5 Cumate~ (copper dimethyl-dithio-carbonate) 0.1 Altax~ (mercapto-benzothiazole-disulfide) 2.8 Sulfur 2.0 Cure (Min./Temp.) 2.5/350F
Duro A 75 Tensile 1010 Elongation 130 Tear 120 ~ -17-'~ lOql824 Ingredients Parts ' SBR 1708 70 EPDM (EPSYN~ 55) 30 . 550 FEF Carbon Black 90 ; Sunpar~ 140LW oil 25 Zinc oxide 5 Calcium oxide dispersion 5 . Stearic acid 1.5 - 10 Zalba~ Special O.S
; Cumate~ 0.1 ,~ Altax~ 2.8 ~. .
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Ingredients Parts Copo~ 1815 137.0 Epsyn~ 55 35,0 Statex~ M FEF
SRF 774 60.0 Sunthene~ 410 DPD 6169 15.0 Zalba~ Special I TE-80 0.1 '~ Stearic Acid ZnO 5.0 Cumate~ 0.2 Altax~ 2.8 Spider Sulfur 2.5 :.
Mooney Scorch/280F
Minimum 35 Press Cure (Min./Temp.) 3/350 Snap Excellent Durometer A 80 Tensile 1700 100% Modulus 1050 Elongatio~ 170 Tear 128 -' ' : ' ' ' ' : '.' . . , :. :
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While it will be apparent that the preferred embodiments of the invention disclosed are well calculated to fulfill the objects above Rtated, it will be appreciated that the invention is susceptible to modification, variation and change without departing from the proper scope or fair meaning of the subjoined claims.
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` ` 1071824 ` Ingredients Parts `~` . EPDM (EPSYN~ 4506) 50 550 FEF Carbon Black 100 5. Sunpar~ 140LW oil 25 Zinc oxide 3 Carbowax~ 4000 0.5 .~ 10 Hi Sil~ 233 10 SP 1055 Resin .. (a brominated methylol ' phenolic resin) 15 .;, .
, Cure (Min./Temp.)5/380F 10/350F
.i Duro A 79 78 '~l- Tensile 1190 1170 100% Modulus 890 820 : Elongation 160 180 j Tear 113 113 .
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'' ' ' ' ~ ~ ' -' lOql824 Ingredients Parts SBR 1502 75.0 DPD 6169 35.0 FEF 550 70.0 Sunthene~ 410 8.0 ZnO 3.0 Stearic Acid 0.5 Zalba~ Special 0.5 Cumate~ 0.1 Altax~ 2.0 Spider Sulfur 2.0 TE-28-E 0.5 Mooney Scorch/280F
Minimum 18 T 10 9'5 , Mooney Scorch/250F
Minimum 20.0 T 10 23.0 - Cure Time (Min./Temp.) 35/350F
Hot Tear Excellent Snap Excellent : Durometer A 82 100% Modulus 1000 . Tensile 2200-Elongation 240 ; Tear 225 .'' ' .
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. Duro A 84 Tensile 1640 u 100% Modulus 970 ~ Elongation 230 p; Tear 273 . 20 --.
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EPDM (EPSYN~ 55) 15 550 FEF Carbon Black 90 Sunpar0 140LW oil 25 Zinc oxide . 5 Calcium oxide dispersion 5 Stearic acid 1.5 Zalba~ Special (an antioxidant) - 0.5 Cumate~ (copper dimethyl-dithio-carbonate) 0.1 Altax~ (mercapto-benzothiazole-disulfide) 2.8 Sulfur 2.0 Cure (Min./Temp.) 2.5/350F
Duro A 75 Tensile 1010 Elongation 130 Tear 120 ~ -17-'~ lOql824 Ingredients Parts ' SBR 1708 70 EPDM (EPSYN~ 55) 30 . 550 FEF Carbon Black 90 ; Sunpar~ 140LW oil 25 Zinc oxide 5 Calcium oxide dispersion 5 . Stearic acid 1.5 - 10 Zalba~ Special O.S
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Mooney Scorch/280F
Minimum 35 Press Cure (Min./Temp.) 3/350 Snap Excellent Durometer A 80 Tensile 1700 100% Modulus 1050 Elongatio~ 170 Tear 128 -' ' : ' ' ' ' : '.' . . , :. :
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While it will be apparent that the preferred embodiments of the invention disclosed are well calculated to fulfill the objects above Rtated, it will be appreciated that the invention is susceptible to modification, variation and change without departing from the proper scope or fair meaning of the subjoined claims.
J '~ 20--
Claims (30)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS
1. A method of manufacturing a flexible painted rubber product, comprising the steps of:
formulating a composition comprising, percentages being by weight, (a) about 15% to about 90% of a cross-linkable rubber material selected from at least one of the group consisting of, styrene butadiene rubber, polybutadiene rubber, and isoprene rubber, said rubber material also including less than 50%
of ethylene-propylene diene monomer rubber or neoprene rubber, (b) about 0.01% to about 40% of a polymeric stiffening agent for providing a high flex modulus for the cured composition, (c) about 0.01% to about 50% of a plasticizing agent, (d) zero to about 5% of an accelerating agent, (e) 0.01% to about 10% of a curing agent, (f) zero to about 10% of an activating agent, (g) zero to about 80% of a filler material, forming the product by molding said composition and curing the product at a temperature between about 275°F and about 450°F for a residence time period between about 20 minutes and about 1/2 minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
formulating a composition comprising, percentages being by weight, (a) about 15% to about 90% of a cross-linkable rubber material selected from at least one of the group consisting of, styrene butadiene rubber, polybutadiene rubber, and isoprene rubber, said rubber material also including less than 50%
of ethylene-propylene diene monomer rubber or neoprene rubber, (b) about 0.01% to about 40% of a polymeric stiffening agent for providing a high flex modulus for the cured composition, (c) about 0.01% to about 50% of a plasticizing agent, (d) zero to about 5% of an accelerating agent, (e) 0.01% to about 10% of a curing agent, (f) zero to about 10% of an activating agent, (g) zero to about 80% of a filler material, forming the product by molding said composition and curing the product at a temperature between about 275°F and about 450°F for a residence time period between about 20 minutes and about 1/2 minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
2. The invention of Claim 1 wherein said preparing of a clean surface includes activating the surface to be painted by a surface treatment selected from at least one of the group consisting of halogenation treatment, ozone treatment, ultra-violet treatment, electronic treatment or flame treatment.
3. The invention of Claim 1 wherein said preparing of a clean surface includes activating the surface to be painted by a surface treatment selected from the group consisting of chlorination treatment, ozone treatment, electronic treatment or flame treatment.
4. The invention of Claim 2 wherein said treatment is by chlorination.
5. The invention of Claim 1 wherein said rubber material includes less than 15% of ethylene-propylene diene monomer rubber or neoprene rubber.
6. The invention of Claim 1 wherein, component (b) is present from about 0.01% to about 25%
component (c) is present from about 0.01% to about 35%, component (d) is present from about zero to about 3%, component (e) is present from about 0.05% to about 5%, component (f) is present from about zero to about 5%, and component (g) is present from about 0.01% to about 80%.
component (c) is present from about 0.01% to about 35%, component (d) is present from about zero to about 3%, component (e) is present from about 0.05% to about 5%, component (f) is present from about zero to about 5%, and component (g) is present from about 0.01% to about 80%.
7. The invention of Claim 1 wherein, said polymeric stiffening agent is substantially a material selected from at at least one of the group consisting of, acrylonitrile butadiene styrene, polyvinyl chloride, a cellulosic resin, styrene resins, phenolic resins, a C2-C4 polyolefinic polymer material, an ethylene-ethyl acrylate copolymer, ethylene vinyl acetate, a thermoplastic ethylene-propylene copolymer, and an acrylic resin, said plasticizing agent is a compatible non-staining, non-discoloring plasticizer and is substantially a material selected from at least one of the group consisting of naphthenic oils, low molecular weight polyester type plasticizers, petroleum resins, coal tar compound plasticizers, and paraffinic plasticizers.
8. The invention of Claim 1 wherein said curing agent is substantially a material selected from at least one of the group consisting of, a sulfur curing agent, a peroxide curing agent, a phenol curing agent, a quinone curing agent, and an amino type curing agent.
9. The invention of Claim 1 wherein, said filler material is substantially a material selected from at least one of the group consisting of, a carbon material, a carbonate, clays, sulfates, fiberglass, fibrous materials, and silicas.
10. The invention of Claim 8 wherein said polymeric stiffening agent is substantially a material selected from at least one of the group consisting of, acrylonitrile butadiene styrene, polyvinyl chloride, a cellulosic resin, styrene resins, phenolic resins, a C2-C4 polyolefinic polymer material, an ethylene-ethyl acrylate copolymer, ethylene vinyl acetate, a thermoplastic ethylene-propylene copolymer, and an acrylic resin, said plasticizing agent is a compatible non-staining, non-discoloring plasticizer and is substantially a material selected from at least one of the group consisting of naphthenic oils, low molecular weight polyester type plasticizers, petroleum resins, coal tar compound plasticizers, and paraffinic plasticizers
11. A method of manufacturing a flexible painted rubber product, comprising the steps of:
formulating a composition comprising, percentages being by weight, (a) about 15% to about 90% of a cross-linkable rubber material selected from at least one of the group consisting of styrene butadiene rubber, polybutadiene rubber, and isoprene rubber said rubber material also including up to 50% of ethylene-propylene diene monomer rubber or neoprene rubber, (b) zero to about 40% of a polymeric stiffening agent means for providing a high flex modulus for the cured composition, (c) about 0.01% to about 50% of a plasticizing agent, said plasticizing agent is a compatible non-staining non-discoloring plasticizer and is substantially a material selected from at least one of the group consisting of naphthenic oils, low molecular weight polyester type plasticizers, petroleum resins, coal tar compound plasticizers, and paraffinic plasticizers, (d) zero to about 5% of an accelerating agent, (e) 0.01% to about 10% of a curing agent, (f) zero to about 10% of an activating agent, (g) about 0.01% to about 80% of a filler material, and forming the product by molding said composition and curing the product at a temperature between about 275°F and about 600°F
for a residence time period between about 45 minutes and about 1/4 minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
formulating a composition comprising, percentages being by weight, (a) about 15% to about 90% of a cross-linkable rubber material selected from at least one of the group consisting of styrene butadiene rubber, polybutadiene rubber, and isoprene rubber said rubber material also including up to 50% of ethylene-propylene diene monomer rubber or neoprene rubber, (b) zero to about 40% of a polymeric stiffening agent means for providing a high flex modulus for the cured composition, (c) about 0.01% to about 50% of a plasticizing agent, said plasticizing agent is a compatible non-staining non-discoloring plasticizer and is substantially a material selected from at least one of the group consisting of naphthenic oils, low molecular weight polyester type plasticizers, petroleum resins, coal tar compound plasticizers, and paraffinic plasticizers, (d) zero to about 5% of an accelerating agent, (e) 0.01% to about 10% of a curing agent, (f) zero to about 10% of an activating agent, (g) about 0.01% to about 80% of a filler material, and forming the product by molding said composition and curing the product at a temperature between about 275°F and about 600°F
for a residence time period between about 45 minutes and about 1/4 minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
12. The invention of Claim 11 further characterized as including a flexible primer paint coating composition on the product, underneath said flexible color stable colored paint coating layer.
13. The invention of Claim 11 wherein said colored paint coating layer being selected from at least one resin coating material from the group consisting of a urethane resin, an acrylic resin and a polyester resin.
14. The invention of Claim 12 wherein said colored paint coating layer being selected from at least one resin coating material from the group consisting of a urethane resin, an acrylic resin, and a polyester resin.
15. The invention of Claim 11 wherein said preparing of a clean surface includes treating the surface to be painted by a surface treatment selected from at least one of the group consisting of halogenation treatment, ozone treatment, ultra-violet treatment, electronic treatment or flame treatment.
16. The invention of Claim 11 wherein said preparing of a clean surface includes activating the surface to be painted by a surface treatment selected from the group consisting of chlorination treatment, ozone treatment, electronic treatment or flame treatment.
17. The invention of Claim 15 wherein said treatment is by chlorination.
18. The invention of Claim 11 wherein said rubber material includes less than 15% of ethylene-propylene diene monomer rubber or neporene rubber.
19. The invention of Claim 11 wherein component (b) is present from about zero to about 25%, component (c) is present from about 0.01% to about 35%, component (d) is present from about zero to about 3%, component (e) is present from about 0.05% to about 5%, component (f) is present from about 0.01%
to about 5%, and component (g) is present from about 0.01% to about 50%.
to about 5%, and component (g) is present from about 0.01% to about 50%.
20. The invention of Claim 11 wherein component (a) is present from about 25% to about 60%.
21. The invention of Claim 15 wherein said colored paint coating layer being selected from at least one resin coating material from the group consisting of a urethane resin, an acrylic resin, and a polyester resin.
22. The invention of Claim 11 wherein component (a) is present from about 30% to about 55%, component (b) is present from about zero to about 20%, component (c) is present from about 1% to about 15%, component (d) is present from about 0.01%
to about 3%, component (e) is present from about 0.5% to about 3%, component (f) is present from about 0.1% to about 3%, and component (g) is present from about 1% to about 50%.
to about 3%, component (e) is present from about 0.5% to about 3%, component (f) is present from about 0.1% to about 3%, and component (g) is present from about 1% to about 50%.
23. The invention of Claim 11 wherein said curing agent is substantially a material selected from at least one of the group consisting of, a sulfur curing agent, a peroxide curing agent, a phenol curing agent, a quinone curing agent, and an amino type curing agent.
24. The invention of Claim 11 wherein said filler material is substantially a material selected from at least one of the group consisting of, a carbon material, a carbonate, clays, sulfates, fiberglass, fibrous materials, and silicas.
25. The invention of Claim 16 further characterized as including a flexible primer paint coating composition on the product, underneath said flexible color stable colored paint coating layer.
26. The invention of Claim 22 wherein said filler material is substantially a material selected from at least one of the group consisting of a carbon material, a carbonate, clays, sulfates, fiberglass, fibrous materials, and silicas.
27. The invention of Claim 11 wherein said forming step is carried out by continuously extruding the rubber product.
28. The invention of Claim 26 wherein a textured surface pattern is continuously formed in the product after extruding and prior to curing.
29. The invention of Claim 11 wherein said steps of forming, curing, preparing the clean surface, and applying the color stable paint coating, are all carried out in a continuous operation.
30. A method of manufacturing a flexible painted rubber product, comprising the steps of:
formulating a composition comprising, percentages being by weight, (a) about 15% to about 90% of a cross-linkable rubber material selected from at least one of the group consisting of, styrene butadiene rubber, polybutadiene rubber, and isoprene rubber, said rubber material also including up to 50% of ethylene-propylene diene monomer rubber or neoprene rubber, (b) zero to about 40% of a polymeric stiffening agent for providing a high flex modulus for the cured composition, (c) about 0.01% to about 50% of a plasticizing agent, (d) zero to about 5% of an accelerating agent, (e) 0.01% to about 10% of a curing agent, (f) zero to about 10% of an activating agent, (g) zero to about 80% of a filler material, and forming the product by molding said composition and curing the product at a temperature between about 275°F and about 600°F
for a residence time period between about 45 minutes and about 1/4 minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
formulating a composition comprising, percentages being by weight, (a) about 15% to about 90% of a cross-linkable rubber material selected from at least one of the group consisting of, styrene butadiene rubber, polybutadiene rubber, and isoprene rubber, said rubber material also including up to 50% of ethylene-propylene diene monomer rubber or neoprene rubber, (b) zero to about 40% of a polymeric stiffening agent for providing a high flex modulus for the cured composition, (c) about 0.01% to about 50% of a plasticizing agent, (d) zero to about 5% of an accelerating agent, (e) 0.01% to about 10% of a curing agent, (f) zero to about 10% of an activating agent, (g) zero to about 80% of a filler material, and forming the product by molding said composition and curing the product at a temperature between about 275°F and about 600°F
for a residence time period between about 45 minutes and about 1/4 minute, preparing a clean surface on the molded product, applying a flexible color stable colored paint coating to the product.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/544,219 US3935329A (en) | 1973-05-09 | 1975-01-27 | Method of manufacturing new paintable rubber products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1071824A true CA1071824A (en) | 1980-02-19 |
Family
ID=24171269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA239,909A Expired CA1071824A (en) | 1975-01-27 | 1975-11-18 | Method of manufacturing new paintable rubber composition and products |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5830900B2 (en) |
| BR (1) | BR7600023A (en) |
| CA (1) | CA1071824A (en) |
| DE (1) | DE2600623A1 (en) |
| FR (1) | FR2298573A1 (en) |
| GB (1) | GB1532657A (en) |
| IT (1) | IT1050307B (en) |
| SE (1) | SE7514184L (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1140024A (en) * | 1955-01-05 | 1957-07-09 | Ici Ltd | Coating of rubber surfaces |
| DE1621948A1 (en) * | 1966-09-14 | 1971-06-03 | Henkel & Cie Gmbh | Process for the production of firmly adhering polyurethane coatings on rubber |
| US3821152A (en) * | 1973-01-19 | 1974-06-28 | Phillips Petroleum Co | Heat resistant vulcanizable blend of butadiene/styrene rubbers and ethylene propylene-diene terpolymers |
| IT1004325B (en) * | 1973-02-16 | 1976-07-10 | Int Synthetic Rubber | PROCEDURE FOR THE PAINTING OF POLYMER MATERIAL, IN PARTICULAR RUBBER AND PLASTIC AND POLYMER MATERIAL SO PAINTED |
| NL7404852A (en) * | 1973-04-17 | 1974-10-21 |
-
1975
- 1975-11-17 GB GB47326/75A patent/GB1532657A/en not_active Expired
- 1975-11-18 CA CA239,909A patent/CA1071824A/en not_active Expired
- 1975-11-24 IT IT29597/75A patent/IT1050307B/en active
- 1975-12-02 JP JP50143783A patent/JPS5830900B2/en not_active Expired
- 1975-12-11 FR FR7537972A patent/FR2298573A1/en active Granted
- 1975-12-16 SE SE7514184A patent/SE7514184L/en not_active Application Discontinuation
-
1976
- 1976-01-06 BR BR7600023A patent/BR7600023A/en unknown
- 1976-01-09 DE DE19762600623 patent/DE2600623A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| GB1532657A (en) | 1978-11-15 |
| FR2298573B1 (en) | 1981-09-25 |
| SE7514184L (en) | 1976-07-28 |
| IT1050307B (en) | 1981-03-10 |
| JPS5193945A (en) | 1976-08-18 |
| JPS5830900B2 (en) | 1983-07-02 |
| FR2298573A1 (en) | 1976-08-20 |
| DE2600623A1 (en) | 1976-07-29 |
| BR7600023A (en) | 1976-08-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |