NL2003749C2 - Method for providing a molded article of a rubber polymer with a colored surface. - Google Patents

Method for providing a molded article of a rubber polymer with a colored surface. Download PDF

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Publication number
NL2003749C2
NL2003749C2 NL2003749A NL2003749A NL2003749C2 NL 2003749 C2 NL2003749 C2 NL 2003749C2 NL 2003749 A NL2003749 A NL 2003749A NL 2003749 A NL2003749 A NL 2003749A NL 2003749 C2 NL2003749 C2 NL 2003749C2
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Netherlands
Prior art keywords
rubber
lacquer
rubber polymer
molded part
polymer
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Application number
NL2003749A
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Dutch (nl)
Inventor
Gerard Nijman
Louis-Philippe Antoine Euga Ne Maria Reuvekamp
Paulus Bremmer
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Apollo Vredestein Bv
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Priority to NL2003749A priority Critical patent/NL2003749C2/en
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Publication of NL2003749C2 publication Critical patent/NL2003749C2/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00Producing pneumatic or solid tyres or parts thereof
    • B29D30/06Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/72Side-walls
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60RVEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R19/00Wheel guards; Radiator guards, e.g. grilles; Obstruction removers; Fittings damping bouncing force in collisions
    • B60R19/02Bumpers, i.e. impact receiving or absorbing members for protecting vehicles or fending off blows from other vehicles or objects
    • B60R19/03Bumpers, i.e. impact receiving or absorbing members for protecting vehicles or fending off blows from other vehicles or objects characterised by material, e.g. composite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D30/00Producing pneumatic or solid tyres or parts thereof
    • B29D30/06Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
    • B29D30/72Side-walls
    • B29D2030/728Decorating or marking the sidewalls after tyre vulcanization

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Paints Or Removers (AREA)

Description

Method for providing a molded article of a rubber polymer with a colored surface
The invention relates to a method for providing a molded article of a rubber polymer with a colored surface. The invention also relates to a lacquer composition for a rubber 5 polymer, and to an assembly of a molded article of an at least partially vulcanized rubber polymer and a lacquer layer over at least part of its surface.
A known method for providing a molded article of a rubber polymer with a colored surface is described in US 4,136,219. Herein a process of applying paint, e.g.
10 polyurethane paint, to a rubber surface is described, which process comprises applying paint to a rubber surface which is either (1) mbber derived from a composition comprising 30-100 parts by weight per hundred parts by weight of rubber (phr) of halogenated butyl rubber which has been cured either using a metal oxide or halide and an alkyl phenol poly sulphide accelerator, or a metal oxide or halide in the presence of a 15 non-reactive phenol/aldehyde resin or using a metal oxide or halide and an alkyl polysulphide accelerator in presence of a non-reactive phenol/aldehyde resin, or (2) a rubber blend comprising an ethylene-propylene-diene terpolymer and a halogenated rubber cured with sulphur or sulphur-containing vulcanizing agent using a metal oxide or halide in the presence of a non-reactive phenol aldehyde resin.
20
The described method is limited to the use of a particular rubber and moreover uses halogens, which is undesirable from an environmental point of view. Also, the specific rubber compounds are prone to discoloration under the action of UV-radiation. A further disadvantage is that components of the underlying rubber polymer may migrate 25 through the colored layer and thereby promote discoloration, and that the adhesion of the paint or lacquer layer to the underlying rubber polymer may not be adequate for its purpose, in particular the adhesion of the sidewalls of a tire to its carcass.
In the manufacture of a colored molded article, it is important that the molded article 30 and the lacquer layer have a good mutual adhesion. In order to obtain good adhesion in the known method, the surface to be colored is usually pretreated. Rubber polymers frequently applied in the rubber industry, such as for instance natural rubber, styrene-butadiene rubber, butadiene rubber and ethylene-propylene-diene rubber, are non-polar. The pretreatment generally comprises modifying the rubber polymer with polar groups.
2 A frequently applied method comprises treating the surface of the rubber polymer with plasma. Pretreatment is time-consuming, and therefore also costly.
The present invention has for its object to provide a method according to the preamble, 5 wherein the above stated drawbacks of the known method are at least partially obviated.
This objective is achieved according to the invention by a method for providing a molded article of a rubber polymer with a colored surface, the method comprising the steps of: 10 (A) providing a molded article of a rubber polymer that comprises a compound containing a carboxylic acid anhydride; (B) providing a lacquer composition that comprises an isocyanate group; (C) arranging a layer of the lacquer composition on the surface of the molded article to be colored; 15 (D) polymerizing the lacquer layer at a suitable temperature.
The assembly of rubber substrate and lacquer layer has substantially the same properties as the substrate molded article manufactured from rubber polymer. This has particularly great advantages for colored molded articles that regularly undergo rubber-elastic 20 deformation during use, such as in a tire. An improved adhesion between the lacquer layer and the substrate molded article is also obtained due to the invented method. In addition, it has been found that the assembly of molded article and lacquer layer displays an improved fatigue behavior compared to the molded articles obtained in the known manner. An additional advantage of the method according to the invention is 25 that it allows the provide a molded article of a rubber polymer with a layer of a lacquer composition with a relatively low melting or degradation temperature.
An additional advantage of the method according to the invention is that the typical properties of rubber polymers are not lost when the molded article is provided with the 30 lacquer layer. Particular properties, such as a low modulus of elasticity, low hardness, high elongation at break and thereby a high tensile strength, the highly elastic behavior with a relatively low permanent set, and a relatively high independence from and resistance to temperatures are substantially unaffected.
3
With the method according to the invention, a substrate rubber article can be provided with virtually any color. The applied lacquer layer moreover shows a more stable color than a colored layer, applied with the known method. Further, the lacquer layer according to the invention is easily cleanable, without this substantially affecting the 5 color or other properties. For instance, dirt collected on the side wall of a tire, provided with a lacquer layer according to the invention is easily removed by simple rinsing or cleaning with a towel.
A particularly preferred embodiment of the method according to the invention 10 comprises the steps of: (A) providing a molded article of a rubber polymer that comprises a compound containing a carboxylic acid anhydride at those parts that are to be colored; (B) providing a lacquer composition that comprises an isocyanate group; (C) arranging a layer of the lacquer composition on the surface of the molded article; 15 (D) polymerizing the lacquer layer at a suitable temperature.
Step (A) of the method is preferably carried out separately from the other steps (B) to (D). After step (A), an intermediate molded article is obtained of an at least partially vulcanized mbber polymer, the article comprising over at least part of its surface - i.e. 20 that part of the surface that needs to be colored - a mbber polymer that comprises a compound containing a carboxylic acid anhydride. This intermediate molded article can be shipped to customers for coloring. The coloring step is typically carried out by spraying, dipping and other methods known per se, whereby the applied lacquer composition will only adhere substantially to those parts that comprise a mbber polymer 25 comprising a compound containing a carboxylic acid anhydride. The applied excess lacquer composition can be removed relatively easily.
The mbber polymer applied in the method according to the invention can be non-vulcanized or at least partially vulcanized. In a preferred embodiment of the method 30 according to the invention the molded article is obtained by admixing mbber oligomers containing carboxylic acid anhydride to a mbber, admixing other additives if desired, and at least partially vulcanizing the thus formed mbber composition. Vulcanization can for instance take place by arranging the mbber polymer in for instance a vulcanizing mould in the form of the molded article, and bringing this mould to a suitable 4 vulcanization temperature. If desired, the rubber polymer of the molded article can be in at least partially vulcanized state. Preferably however, the method according to the invention is characterized in that the rubber polymer is substantially fully vulcanized.
5 Suitable compounds containing carboxylic acid anhydride are at least mono functional relative to the polar groups of the lacquer composition. With mono functional is meant in the context of this application that the compound containing carboxylic acid anhydride will react mainly via the anhydride functionality with the lacquer composition. This does not preclude that the carboxylic acid anhydride-containing 10 compound possibly comprises other reactive groups, although the reactivity of these groups will preferably be lower than the reactivity of the lacquer composition with the carboxylic acid anhydride group. Compounds suitable for application are for instance saturated aliphatic (di)carboxylic acid anhydrides, such as for instance succinic acid anhydride, glutaric acid anhydride, adipinic acid anhydride and so forth. Also suitable 15 are cycloaliphatic dicarboxylic acid anhydrides, such as for instance cyclohexane-dicarboxylic acid anhydride. Application of cycloaliphatic dicarboxylic acid anhydrides has the additional advantage that discoloration as a result of for instance sunlight is prevented. In addition, dicarboxylic acid anhydride-containing compounds which comprise ethylenic unsaturations are preferably suitable. An example of such an 20 ethylenic unsaturated compound is maleic acid anhydride (MAA). Also particularly suitable are compounds comprising an aromatic unsaturation, such as for instance phtalic acid anhydride and/or trimellitic acid anhydride. The amount of compound containing (di)carboxylic acid anhydride to be applied in the rubber composition and/or in the rubber polymer of the molded article can be selected within broad limits. For a 25 given combination of rubber polymer of the substrate molded article and the lacquer composition, the suitable quantity will generally be determined by determining that quantity which produces the highest level of adhesion between the substrate molded article and the lacquer layer.
30 A preferred embodiment of the method according to the invention is characterized in that between 1 and 50% by weight of rubber oligomers containing carboxylic acid anhydride are admixed to the rubber relative to the weight of the rubber, more preferably that between 5 and 25% by weight of rubber oligomers containing carboxylic acid anhydride are admixed to the rubber relative to the weight of the rubber, and most 5 preferably that between 8 and 15% by weight of rubber oligomers containing carboxylic acid anhydride are admixed to the rubber relative to the weight of the rubber.
In a preferred embodiment of the invention, a layer of a lacquer composition comprising 5 at least a polyisocyanate, a polyalcohol and a catalyst is arranged at least on the surface of the substrate rubber polymer to be colored. When curing such lacquer composition, a polyurethane lacquer layer is obtained by means of polyaddition. This relates to the reaction between isocyanates and alcohols and, particularly for the building of macro molecules, the reaction between at least bifunctional starting materials. The 10 invented method is therefore preferably performed with di-isocyanates, tri-isocyanates, and diols, triols and/or polyols. The functionality of the starting material determines whether a thermoplastic (bifunctional) or a thermoset (trifunctional) is obtained as end product.
15 Polyisocyanates suitable for application in the lacquer composition comprise toluene diisocyanates, m-phenylene diisocyanate, 4-chloro-l,3-phenylene diisocyanate, 4,4'-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-methylene bis cyclohexane diisocyanate, 1,4-cyclohexane bis methyl isocyanate, isophorone diisocyanate, 1,5-20 tetrahydronaphthalene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate and polymers, such as dimers en trimers of such diisocyanates. This series is given only by way of example, and is by no means intended as limitative.
Polyols, and in particular diols, suitable for application in the lacquer composition 25 comprise aliphatic diols such as for instance ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,4-diol, butane-1,3-diol, 2,2-dimethyl propanediol-1,3 (= neopentylglycol), hexane-2,5-diol, hexane-1,6-diol, 2,2-bis-(4-hydroxycyclohexyl)-propane (hydrogenated bisphenol-A), 1,4-dimethylolcyclohexane, diethyleneglycol, dipropyleneglycol and 2,2-bis[4-2— 30 hydroxyethoxy)-phenylpropane. It is also possible to apply aromatic polyalcohols and/or relatively small quantities, such as less than about 4% by weight, but preferably less than 2% by weight, of trifunctional alcohols.
6
In a preferred embodiment of the method according to the invention the lacquer composition of the lacquer layer comprises a short chain diol and a long chain diol. In the context of this application a short chain diol is understood to mean a diol comprising 1 to 50 carbon atoms. In the context of this application a long chain diol is understood 5 to mean a diol comprising at least 51 carbon atoms. Different compounds can be applied as chain extender or flexible chain, provided they have a group reactive with the isocyanate. Examples of suitable reactive groups comprise hydroxyl groups, amines, acids and thiols. Generally speaking, suitable reactive groups comprise a nucleophilic part, which in the context of this application is understood to mean a negative ion or 10 molecule with a non-binding or free electron pair which can react relatively simply with an electrophilic particle, generally as electron-pair donor. All catalysts known for polyurethane reactions, such as for instance metal complexes, are in principle applicable in the lacquer composition. The quantity of catalyst generally lies between 0.01 and 3% by weight relative to the overall weight of the lacquer composition, although other 15 contents are possible.
There are further advantages when in the invented method the surfaces of the substrate molded article to be colored are pretreated. This can in principle take place in all ways known to the skilled person. It is thus possible to roughen, to sand, to degrease, to 20 provide the surfaces with a primer or other pretreating agent, and/or to provide the surfaces with radicals. The latter can for instance take place by irradiating the surfaces with radiation of suitable wavelength, for instance UV light, if desired laser radiation. It is also possible to subject the surfaces to an additional plasma treatment, although this is not essential according to the invention.
25
According to the invented method, a layer of the lacquer composition is arranged on the surface to be colored and polymerized at a suitable temperature, preferably under pressure. More particularly, a polyaddition reaction is performed on the vulcanized substrate molded article with the different, above-stated building blocks. A thermoset is 30 preferably obtained here, for which purpose it is therefore necessary to have a trifunctionality in the system. Trifunctionality can originate from the isocyanate and/or from the chain extender, and/or from the polyol. A thermosetting lacquer layer is in this way obtained. At least some of the isocyanate groups will react with the anhydride of the rubber polymer and thus form a cyclic imide group, and/or will react with the diacid 7 formed after hydrolysis of the anhydride. In case the polymer comprises a thermoplastic polyurethane, at least some of the isocyanate groups can in addition also react with the urethane group of the polyurethane, and thus form an allophanate group. By means of the method according to the invention a good adhesion is obtained between the molded 5 article and the lacquer layer or layers. It is likewise possible according to the invention to perform the polyurethane reaction on the rubber surface during the vulcanization thereof.
Although the lacquer composition is preferably a polyurethane lacquer composition, i.e. 10 a lacquer composition containing a polyurethane resin, other lacquer compositions are also possible, such as for instance acrylic lacquer compositions.
The method according to the invention makes it possible to color (parts of) a molded article of a modified rubber composition, and preferably of a thermoplastic 15 polyurethane. Suitable articles to be colored by means of the method according to the invention include for instance (pneumatic) tires and rubber products for which wear and/or fatigue considerations are important, such as for instance windscreen wipers and spoilers.
20 The method according to the invention can be applied to molded articles comprising a substantially fully cured rubber polymer. It is however also possible to vulcanize the rubber polymer during arranging of the lacquer layer and/or during polymerization thereof.
The rubber composition from which the rubber polymer is obtained can be prepared in a 25 manner known to the skilled person, as can the lacquer composition as applied in the method according to the invention. Any known method of mixing polymers, fillers and other additives is in principle suitable for this purpose. It is thus possible to mix the rubber composition, optionally supplemented if desired with additives and/or other polymers, using an internal mixer or Banbury mixer, a single or double-screw extruder 30 apparatus, a blade kneader, a Buss Co-kneader, a roller and the like. Suitable temperatures during mixing are substantially determined by the rheological properties of the relevant rubber polymer.
8
The rubber polymers preferably applied in the substrate molded article can be selected from the known rubbers. In general these rubbers have a glass transition temperature Tg lower than -10°C, although this is not essential. Rubbers suitable for application are for instance chosen from the group of natural rubbers, isoprene rubbers, butadiene rubbers, 5 styrene butadiene copolymer rubbers, acrylonitrile butadiene copolymer rubbers, if desired copolymerized with styrene, butadiene isoprene copolymer rubbers, chloroprene rubbers, butyl and acryl rubbers, and ethylene-propylene copolymers which, if desired, comprise a third copolymerizable diene monomer such as for instance 1,4-hexadiene, dicyclopentadiene, dicyclooctadiene, methylene norbomene, ethylidene norbomene and 10 tetrahydroindene. If desired, the rubber composition also comprises a minor quantity of natural rubber and/or elastomer, which is preferably composed of 1,3-diene compounds such as for instance butadiene and/or isoprene and/or 2,3-dimethyl butadiene. The rubber composition applied in the method is preferably chosen from the group consisting of an ethylene-propylene-diene rubber (EPDM), a natural rubber, a butadiene 15 rubber, and a styrene butadiene copolymer rubber. Mixtures of said rubber polymers are likewise possible. The rubber compositions may be sulfur-vulcanizable and/or peroxide-vulcanizable. Other vulcanization systems may also be used.
If desired, additives can be added to the rubber polymer and the lacquer composition as 20 these are applied in the method according to the invention. Examples of suitable additives include stabilizers, antioxidants, lubricants, fillers, dyes, pigments, flame retardants, conductive fibers and reinforcing fibers. The mbber composition can particularly also comprise an oil as additive. It is also possible to add petroleum plasticizers. If desired, the rubber composition can also comprise a coupling agent.
25 Suitable coupling agents comprise silane compounds. Particularly suitable silane compounds comprise di- and tetrasulphides.
Any lacquer composition may in principle be used in the method of the invention, as long as it comprises an isocyanate group, and preferably a polyol and a catalyst. Other 30 particularly suitable lacquer compositions comprise an acrylate group. Dyes suitable for adding to the lacquer composition comprise any type known to the skilled person. It is thus possible to apply organic and/or inorganic dyes which are soluble and/or nonsoluble in the lacquer composition. Examples of suitable mineral dyes include metals in powder form, such as for instance powdered aluminum, copper, metal oxides such as 9 for instance silicates, aluminates, titanates, iron oxides and/or hydroxides, in addition to mixtures of oxides of for instance cobalt, aluminum or zinc. White dyes are particularly suitable. Suitable organic color pigments comprise for instance indanthrones, pyrroles and/or diazo compounds, in addition to organometallic pigments such as for instance 5 phthalocyanines.
The invention also relates to an assembly of a molded article of an at least partially vulcanized rubber polymer and a lacquer layer over at least part of its surface, the lacquer composition comprising at least a polyisocyanate, a polyol and a catalyst, and 10 the rubber polymer at the surface comprising a compound containing a carboxylic acid anhydride. The assembly can be obtained in accordance with the method according to the invention as described at length above.
It has been found that an assembly of a molded article and a lacquer layer, obtainable by 15 means of the method according to the invention, can have a lacquer layer which is relatively thin. This is advantageous from a mechanical point of view. In a preferred embodiment of the assembly, the lacquer layer has an average thickness of about 0.05 to 0.5 mm, and more preferably an average thickness of about 0.1 to 0.3 mm. Such thin lacquer layers ensure that the rubber-elastic properties are retained in the colored parts 20 of the substrate molded article, and provide a strong adhesion.
The method according to the invention is particularly suitable for manufacturing a plurality of products, such as tires in which (thermoplastic) polyurethane components are applied, tires comprising a basis of polyurethane on which a rubber tread is 25 arranged, rubber sealing products wherein fatigue and/or wear are important factors. Examples of the latter products are for instance windscreen wiper blades, and profiles exposed to a cyclic load. Non-limitative examples of pneumatic tires comprise pneumatic tires for passenger cars, cycles, tractors, trailers, trucks, buses, and tires for motor vehicles, and in particular the side walls thereof.
30
The method according to the invention is also particularly suitable for coloring flexible spoilers, or more generally for coloring flexible bodywork parts of cars or other vehicles. A flexible spoiler is for instance described in US 2005/0012359 and in US 2005/0017541, the content of which is expressly included in the present application.
10
The spoiler described comprises an airflow-conducting element and an operating member there for. The airflow-conducting element is attached to the bottom of the bumper, is manufactured from a rubber polymer and can be moved in and out by means of the operating member. A resilient connection between airflow-conducting element 5 and bumper holds the spoiler in the moved-in inoperative position. The operating member can for instance take the form of a number of inflatable bellows disposed on the rear side of the spoiler. The inflatable bellows are preferably manufactured from a polymer film, in particular a foil of thermoplastic polyurethane. When the inflatable bellows are inflated, the spoiler moves forward from the moved-in position to the 10 moved-out position. A fiber-reinforced polymer rod provides for lateral guiding of the element.
The present invention also relates to a flexible spoiler for a vehicle, comprising an airflow-conducting element of a rubber polymer, a mounting member for mounting the 15 spoiler on the vehicle and an operating member which can move the airflow-conducting element in and out, wherein the operating member takes the form of a number of inflatable bellows of polymer film disposed on the rear side of the spoiler. According to the invention at least parts of the operating member, the airflow-conducting element and/or the mounting member may be colored by means of the method according to the 20 invention.
The invention will now be further elucidated on the basis of the accompanying example below, without however being limited thereto.
25 A rubber composition is first prepared in known manner by mixing in a standard kneader for about 5 minutes at an average temperature of about 90°C. The rubber composition comprises 100 parts ethylene-propylene-diene rubber (EPDM, Keltan 514 from the DSM company) and 10 parts of a butadiene rubber oligomer provided with maleic acid anhydride groups. Used as peroxide is a Perkadox BC peroxide with an 30 initiating temperature of about 105°C. The rubber composition further comprises 70 parts carbon black and about 25 parts of usual additives such as oil, zinc oxide and stearic acid. The rubber composition is vulcanized at about 160°C in a suitably shaped mould, thereby forming a substrate molded article.
11 A thin layer of a lacquer composition comprising at least polyisocyanate, a diol and a catalyst is then sprayed onto the to be colored surfaces of the molded article until a layer with an average thickness of about 0.15 mm is obtained.
5 In the example described the lacquer composition is then allowed to dry at ambient temperature for some time, and allowed to harden further, for instance at a temperature of about 60°C, although this may also be lower or higher. After about 12 minutes the lacquer layer is hardened to such extent that it does not accumulate dust and the like.
The molded article comprises a colored lacquer layer that is well adhered to part of its 10 surface, in which parts moreover the operation and more particularly the possibility of rubber-elastic deformation is retained.

Claims (16)

1. Werkwijze voor het van een gekleurd oppervlak voorzien van een vormdeel uit een rubberpolymeer, waarbij de werkwijze de stappen omvat van: 5 (A) het verschaffen van een vormdeel uit een rubberpolymeer dat een carbonzuuranhydride verbinding omvat; (B) het verschaffen van een laksamenstelling die een isocyanaatgroep omvat; (C) het aanbrengen van een laag van de laksamenstelling op het te kleuren oppervlak van het vormdeel; 10 (D) het polymeriseren van de laklaag bij een geschikte temperatuur.A method of providing a molded part of a rubber polymer with a colored surface, the method comprising the steps of: (A) providing a molded part of a rubber polymer comprising a carboxylic anhydride compound; (B) providing a lacquer composition comprising an isocyanate group; (C) applying a layer of the lacquer composition to the surface of the molded part to be colored; 10 (D) polymerizing the lacquer layer at a suitable temperature. 2. Werkwijze volgens conclusie 1, met het kenmerk dat de laksamenstelling een polyol en een katalysator omvat.Method according to claim 1, characterized in that the lacquer composition comprises a polyol and a catalyst. 3. Werkwijze volgens conclusie 2, met het kenmerk dat de laksamenstelling een eerste polyol met 1 tot 50 koolstofatomen, en een tweede polyol met ten minste 51 koolstofatomen omvat.Method according to claim 2, characterized in that the lacquer composition comprises a first polyol with 1 to 50 carbon atoms, and a second polyol with at least 51 carbon atoms. 4. Werkwijze volgens één der voorgaande conclusies, met het kenmerk dat het 20 vormdeel uit het rubberpolymeer enkel aan het te kleuren oppervlak een carbonzuuranhydride verbinding omvat.4. A method according to any one of the preceding claims, characterized in that the molded part from the rubber polymer only comprises a carboxylic anhydride compound on the surface to be colored. 5. Werkwijze volgens één der voorgaande conclusies, met het kenmerk dat het vormdeel is verkregen door carbonzuuranhydride-bevattende rubber oligomeren in te mengen 25 in een rubber, desgewenst andere toeslagstoffen in te mengen, en de aldus verkregen rubbersamenstelling ten minste gedeeltelijk te vulkaniseren.5. A method according to any one of the preceding claims, characterized in that the molded part is obtained by blending carboxylic anhydride-containing rubber oligomers into a rubber, blending in other additives if desired, and at least partially vulcanizing the rubber composition thus obtained. 6. Werkwijze volgens conclusie 5, met het kenmerk dat ten opzichte van het gewicht van het rubber tussen 1 en 50 gew.-% carbonzuuranhydride-bevattende rubber oligomeren 30 worden ingemengd in het rubber.6. A method according to claim 5, characterized in that, relative to the weight of the rubber, between 1 and 50% by weight of carboxylic acid anhydride-containing rubber oligomers 30 are mixed into the rubber. 7. Werkwijze volgens conclusie 6, met het kenmerk dat ten opzichte van het gewicht van het rubber tussen 5 en 25 gew.-% carbonzuuranhydride-bevattende rubber oligomeren worden ingemengd in het rubber.Process according to claim 6, characterized in that, relative to the weight of the rubber, between 5 and 25% by weight of carboxylic anhydride-containing rubber oligomers are mixed into the rubber. 8. Werkwijze volgens één der voorgaande conclusies, met het kenmerk dat het vormdeel een rubberband is, en bij voorkeur de zijwand ervan.A method according to any one of the preceding claims, characterized in that the molded part is a rubber band, and preferably its side wall. 9. Werkwijze volgens één der voorgaande conclusies met het kenmerk dat het rubberpolymeer is gekozen uit de groep bestaande uit een etheen-propeen-dieenrubber (EPDM), een natuurrubber, een butadieenrubber, en een styreen-butadieen copolymeer rubber.A method according to any one of the preceding claims, characterized in that the rubber polymer is selected from the group consisting of an ethylene-propylene-diene rubber (EPDM), a natural rubber, a butadiene rubber, and a styrene-butadiene copolymer rubber. 10. Werkwijze volgens één der voorgaande conclusies, met het kenmerk dat het rubberpolymeer en/of de laksamenstelling toeslagstoffen omvat gekozen uit de groep van vemetters, stabilisatoren, antioxidanten, smeermiddelen, vulstoffen, kleurstoffen, pigmenten, vlamvertragers, geleidende vezels, versterkingsvezels, olie en petroleum weekmakers.Method according to any one of the preceding claims, characterized in that the rubber polymer and / or the lacquer composition comprises additives selected from the group of mixers, stabilizers, antioxidants, lubricants, fillers, dyes, pigments, flame retardants, conductive fibers, reinforcing fibers, oil and petroleum plasticizers. 11. Vormdeel uit een ten minste gedeeltelijk gevulkaniseerd rubberpolymeer, waarbij het vormdeel over tenminste een gedeelte van haar oppervlak een rubberpolymeer omvat dat een carbonzuuranhydride-bevattende verbinding omvat.A molded part from an at least partially vulcanized rubber polymer, the molded part comprising over at least a portion of its surface a rubber polymer comprising a carboxylic acid anhydride-containing compound. 12. Samenstel van een vormdeel uit een ten minste gedeeltelijk gevulkaniseerd 20 rubberpolymeer en een laklaag over ten minste een gedeelte van haar oppervlak, waarbij de laksamenstelling ten minste een polyisocyanaat, een polyol en een katalysator omvat, en het rubberpolymeer aan het oppervlak een carbonzuuranhydride-bevattende verbinding omvat.12. Assembly of a molded part from an at least partially vulcanized rubber polymer and a lacquer layer over at least a portion of its surface, the lacquer composition comprising at least a polyisocyanate, a polyol and a catalyst, and the rubber polymer on the surface having a carboxylic acid anhydride containing compound. 13. Samenstel volgens conclusie 12, met het kenmerk dat de laklaag een gemiddelde 25 dikte heeft van 0.05 tot 0.5 mm.13. Assembly as claimed in claim 12, characterized in that the lacquer layer has an average thickness of 0.05 to 0.5 mm. 14. Samenstel volgens conclusie 12 of 13, met het kenmerk dat het samenstel een pneumatische band of een flexibele spoiler voor een voertuig omvat.Assembly according to claim 12 or 13, characterized in that the assembly comprises a pneumatic tire or a flexible spoiler for a vehicle. 15. Samenstel volgens conclusie 14, waarbij de flexibele spoiler een luchtstroomgeleidend element uit een rubberpolymeer omvat, evenals een bevestigingselement ter bevestiging van de spoiler aan het voertuig en een bedieningselement dat het luchtstroomgeleidend element in en uit kan bewegen, waarbij het bedieningselement de vorm aanneemt van een aantal, op de achterzijde van de spoiler aangebrachte, opblaasbare balgen uit kunststoffilm, en waarbij ten minste een gedeelte van het oppervlak van het luchtstroomgeleidend element is voorzien van de laklaag.Assembly as claimed in claim 14, wherein the flexible spoiler comprises an air-flow-conducting element made of a rubber polymer, as well as a fastening element for fixing the spoiler to the vehicle and an operating element that can move the air-flow-conducting element in and out, the operating element taking the form of a number of plastic film inflatable bellows arranged on the rear of the spoiler, and at least a part of the surface of the air-flow-conducting element is provided with the lacquer layer. 16. Gebruik van een laksamenstelling die ten minste een isocyanaat, een polyol en een 5 katalysator omvat voor het kleuren van een vormdeel uit een ten minste gedeeltelijk gevulkaniseerd rubberpolymeer.16. Use of a lacquer composition comprising at least one isocyanate, a polyol and a catalyst for coloring a molded part from an at least partially vulcanized rubber polymer.
NL2003749A 2009-11-03 2009-11-03 Method for providing a molded article of a rubber polymer with a colored surface. NL2003749C2 (en)

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Citations (8)

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US4158378A (en) * 1977-12-19 1979-06-19 The Goodyear Tire & Rubber Company Tire having polyurethane laminate thereon
JPS6189235A (en) * 1984-10-09 1986-05-07 Sumitomo Chem Co Ltd Coating of olefin resin molded article
EP0336780A2 (en) * 1988-04-08 1989-10-11 Mitsui Petrochemical Industries, Ltd. Thermoplastic resin or elastomer composition having excellent paint adhesion and laminate comprising layer of said thermoplastic elastomer and polyurethane layer
JPH02191616A (en) * 1989-01-20 1990-07-27 Kojima Press Co Ltd Impact-resistant resin material for molding
US5602203A (en) * 1992-11-26 1997-02-11 Sumitomo Chemical Company, Limited Olefin resin composition
US20040050471A1 (en) * 2000-12-29 2004-03-18 Alain Cottin Tire having a metallic colored surface composition
US20040068036A1 (en) * 2002-10-07 2004-04-08 Halladay James R. Flexible emissive coatings for elastomer substrates

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3962369A (en) * 1973-05-16 1976-06-08 Ppg Industries, Inc. Sealer-primer for elastomeric coatings
US4158378A (en) * 1977-12-19 1979-06-19 The Goodyear Tire & Rubber Company Tire having polyurethane laminate thereon
JPS6189235A (en) * 1984-10-09 1986-05-07 Sumitomo Chem Co Ltd Coating of olefin resin molded article
EP0336780A2 (en) * 1988-04-08 1989-10-11 Mitsui Petrochemical Industries, Ltd. Thermoplastic resin or elastomer composition having excellent paint adhesion and laminate comprising layer of said thermoplastic elastomer and polyurethane layer
JPH02191616A (en) * 1989-01-20 1990-07-27 Kojima Press Co Ltd Impact-resistant resin material for molding
US5602203A (en) * 1992-11-26 1997-02-11 Sumitomo Chemical Company, Limited Olefin resin composition
US20040050471A1 (en) * 2000-12-29 2004-03-18 Alain Cottin Tire having a metallic colored surface composition
US20040068036A1 (en) * 2002-10-07 2004-04-08 Halladay James R. Flexible emissive coatings for elastomer substrates

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