JP2006193677A - Bonding of dynamically vulcanized rubber of fluorocarbon elastomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process of enhancing the adhesive power of a thermoplastic fluoroelastomer composition to a base material. <P>SOLUTION: The process of enhancing the adhesive power of a thermoplastic fluoroelastomer composition to a base material and a manufacturing process of a composite material comprises the steps of: applying a partially cured dynamically vulcanized rubber of a fluoroelastomer and a thermoplastic material on a base material; and curing the partially cured dynamically vulcanized rubber while attaching to the base material. The partially cured dynamically vulcanized rubber is manufactured by dynamically vulcanizing the fluoroelastomer in the presence of a thermoplastic material and a curing agent in a shorter period and at a lower temperature than those conditions under which the fluoroelastomer is completely cured. The curing is completed when the dynamically vulcanized rubber is in contact with the base material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

(preface)
The present invention relates to fluoropolymer compositions and their adhesion to polymers and other substrates. The present invention further relates to a composite article comprising a fluoropolymer bonded to a substrate.

  Fluorine-containing polymers have a unique blend of advantageous physical properties. For example, the polymers are generally characterized by a high degree of stability and resistance to a wide variety of chemical fluids. These properties make the polymer useful for use in applications where the material is in contact with a fluid, such as in a seal.

  Fluorocarbon rubber is an elastomeric material composed of a copolymer of fluorine-containing monomers. The cured rubber has the elastomeric properties typical of rubber materials in addition to the stability and fluid resistance of common fluorine-containing polymers. Fluorocarbon rubber has a wide range of applications in the area of seals and gaskets.

  In some applications, fluorocarbon rubber can be molded into articles that serve directly as seals, such as O-rings and gaskets. In other applications, it is desirable to provide composite articles that include both a fluorocarbon rubber component and a substrate. The substrate provides physical strength and allows the fluorocarbon elastomer to be incorporated into a wide variety of shapes for use in seals and other applications.

  However, the bonding of fluorocarbon rubber materials to other substrates such as metals, plastics, ceramics, and other elastomers is difficult to achieve due to the low surface energy state of materials having a fluorinated molecular structure. Bonding can be enhanced by providing a mechanical interlock structure to the fluorocarbon polymer and the substrate. Binding of the fluorocarbon elastomer can also be achieved by reaction of coupling molecules within the adhesive layer during the curing process. Such a process can cause or induce a chemical reaction between the fluorinated elastomer and the coupling agent molecule.

  Fluorocarbon dynamic vulcanizates consist of a discontinuous phase of fluorocarbon elastomer particles cured within a continuous phase of a thermoplastic material such as a fluororesin. The fully cured nature of the fluoroelastomer particles means that the dynamically vulcanized rubber cannot induce a chemical reaction between the elastomeric and coupling agent molecules used in traditional fluoroelastomer adhesives. Furthermore, since the continuous matrix is composed of a thermoplastic resin such as a fluororesin, the cured elastomer particles are not in intimate contact with the surface of the substrate to which they are to be bonded.

  It would be desirable to provide a method for increasing the adhesion of fluorocarbon elastomer dynamic vulcanizates to metals and other substrates. It is further desirable to provide a method for preparing composite articles in which a fluoroelastomer dynamic vulcanizate is adhered to a substrate.

(Overview)
The present invention provides a method for increasing the adhesion of a thermoplastic fluoroelastomer composition to a substrate and a method for producing a composite article. In various embodiments, the method comprises applying a partially cured dynamic vulcanized rubber of a fluoroelastomer and a thermoplastic material onto a substrate, and applying the partially cured dynamic vulcanized rubber. A step of curing while contacting the substrate. The partially cured material is applied by contacting the substrate by various methods such as casting, insertion molding, and coextrusion.

  Partially cured dynamic vulcanizates preferably vulcanize the fluoroelastomer dynamically in the presence of a thermoplastic material and a curing agent under conditions of time and temperature such that the fluoroelastomer is never fully cured. To make it. Curing is complete when the dynamically vulcanized rubber is in contact with the substrate. In various embodiments, the substrate includes an adhesive or tie layer in contact with the solid support. In one such embodiment, the partially cured thermoplastic fluoroelastomer composition is contacted with the adhesive layer.

(Explanation)
In reviewing the description of this invention set forth herein, the following definitions and non-limiting guidelines must be considered.

  Titles used herein (such as “Introduction” and “Summary”) are intended only for general construction of the topic within the disclosure of the present invention, and are not intended to disclose the present invention or any aspect thereof. Not intended to be limiting. In particular, the subject matter disclosed in the “Introduction” encompasses aspects of the technology within the scope of the present invention and does not constitute an enumeration of the prior art. The subject matter disclosed in the “Summary” is not an exclusive or complete disclosure of the full scope of the invention or any embodiment thereof.

  Citation of a reference herein does not constitute an admission that the reference is prior art or has any relevance to the patentability of the invention disclosed herein. All references cited in the description section of this specification are hereby incorporated by reference in their entirety.

  The description and specific examples, while indicating embodiments of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. Furthermore, the recitation of embodiments with defined features is not intended to exclude other embodiments with additional features or other embodiments that incorporate different combinations of defined features. Specific examples are provided for illustrative purposes of how to make and use the compositions of the present invention and how to practice the methods of the present invention, and unless otherwise stated explicitly It is not intended that the embodiments described be representative of those produced or tested.

  As used herein, the terms “preferred” and “preferably” refer to embodiments of the invention that provide certain benefits under certain conditions. However, other embodiments may be preferred under the same or other conditions. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the invention.

  As used herein, the term “include” and variations thereof, the listing of items in the list is similar to other similar materials that may also be useful in the materials, compositions, devices, and methods of this invention. It is intended to be non-limiting so as not to exclude the item.

In one aspect, the present invention provides a method of adhering a thermoplastic fluoroelastomer composition to a solid substrate. This method is a method of adhering a thermoplastic elastomer composition to a solid substrate, and includes a method including the following steps.
(A) In the presence of a thermoplastic material and a curing agent, the fluoroelastomer is dynamically vulcanized for a time shorter than the time required to completely cure the fluoroelastomer, and a partially cured thermoplastic vulcanizate is obtained. Forming step;
(B) applying an adhesive layer to the substrate;
(C) contacting the partially cured thermoplastic vulcanizate with the adhesive layer; and (d) completing the curing of the thermoplastic vulcanizate.

  In the presence of a fluorine-containing thermoplastic material and a curing agent, the fluoroelastomer is vulcanized dynamically for a time shorter than that required to fully cure the fluoroelastomer at the use temperature. Thus, a partially cured thermoplastic dynamic vulcanizate is formed. In a separate step, the adhesive layer is applied to a substrate such as metal, plastic, ceramic, or another elastomer. The partially cured thermoplastic vulcanizate is brought into contact with the adhesive layer and the thermoplastic vulcanizate is completely cured while the thermoplastic vulcanizate is in contact with the adhesive layer.

  The vulcanized rubber is brought into contact with the adhesive layer by various methods such as insertion molding and coextrusion molding. In various embodiments, the contact process element (c) includes the step of insertion molding the partially cured vulcanized rubber onto the adhesive coated substrate. (As referred to herein, “process element” means a step or other activity performed in the process. Such an element is sequential unless otherwise specified or required in the context of the process element. In various embodiments, an adhesive layer is coextruded between the partially cured thermoplastic vulcanizate and the substrate. In one embodiment, the adhesive layer is applied with a liquid continuous injection device during coextrusion.

  Fluorocarbon elastomers include copolymers of one or more fluorine-containing monomers such as vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, and perfluorovinyl ether. The fluorocarbon elastomer may further include a cure site monomer. Conventional curing agents for fluorocarbon elastomers such as bisphenol curing agents and peroxide curing agents can be used.

In another aspect, a method for manufacturing a composite article is provided. The composite article includes a solid substrate onto which the cured fluoroelastomer composition is adhered. The method includes the following steps:
(A) applying a partially cured thermoplastic elastomer composition on a substrate comprising a discontinuous phase of a partially cured fluoroelastomer and a continuous phase of a thermoplastic polymer material; and (b) Curing the partially cured thermoplastic elastomer composition;
The manufacturing method of the composite goods containing is mentioned.

  In a preferred embodiment, a partially cured dynamic vulcanized rubber of fluoroelastomer and thermoplastic material is applied onto the substrate and while the partially cured vulcanized rubber is in contact with the substrate, Curing of the partially cured vulcanized rubber is complete. The partially cured dynamic vulcanizate preferably comprises a discontinuous phase of partially cured fluoroelastomer particles and a continuous phase of a thermoplastic polymer material. A partially cured dynamic vulcanizate is heated while mixing the fluoroelastomer, thermoplastic material, and curing agent together to achieve partial curing of the fluoroelastomer in the presence of the thermoplastic material. Manufactured by. The thermoplastic material may be a fluororesin material or a non-fluorine-containing thermoplastic polymer. The fluoroelastomer may optionally include a cure site monomer and a curing agent such as bisphenol or peroxide. In various embodiments where the substrate includes an adhesive layer, the adhesive layer is applied onto a solid support, and the partially cured dynamic vulcanized rubber is applied over the adhesive layer. The partially cured material is applied to the substrate by various methods including insertion molding and coextrusion molding.

  The co-extrusion process produces a partially cured dynamic vulcanizate that includes a partially cured fluoroelastomer discontinuous phase and a continuous phase containing a thermoplastic polymer material. The partially cured dynamic vulcanizate and the substrate are coextruded and contacted. Further curing of the partially cured dynamic vulcanizate is accomplished while the layers are in contact after coextrusion. Optionally, the adhesive layer is co-extruded between the dynamically vulcanized rubber and the substrate layer.

  In various embodiments, a partially cured dynamic vulcanizate is produced by a process that includes mixing together a fluoroelastomer resin, a thermoplastic polymer material, and a curing agent that can react with the fluoroelastomer resin. During mixing, the mixture is heated to react the fluoroelastomer resin and the curing agent. The reaction is conducted for a time shorter than that required to fully cure the resin. For example, the process of mixing the thermoelastomer and the thermoplastic material together is generally performed for a time corresponding to T90 or less. Here, T90 is a normal parameter related to the curing of the elastomeric material.

  In various methods, including insertion molding, an adhesive layer is applied on the substrate before the adhesive-coated substrate is placed in the mold. Then, a partially cured elastomer composition such as the above-described dynamic vulcanized rubber is inserted into a mold and brought into contact with the substrate. Furthermore, the contact between the elastomer composition and the substrate is maintained until the elastomer is completely cured.

  Dynamic vulcanization or mixing of the fluoroelastomer and the thermoplastic material is performed by a batch, continuous, or semi-batch process. In one method, a mixture of uncured fluorocarbon elastomer and thermoplastic material can be fed into the barrel of a twin screw extruder. Blend and heat the mixture in the barrel of a twin screw extruder until the fed mixture reaches the downstream port used to feed the hardener into the mixture. The curative, fluorocarbon elastomer, and thermoplastic material are further mixed in the barrel of the extruder for a time that is less than the time required to fully cure the fluoroelastomer, for example, T90 or less. Before the fluoroelastomer is fully cured, the partially cured thermoplastic vulcanizate is extruded from the barrel. Thereafter, vulcanized rubber is applied onto the substrate. Curing of the vulcanized rubber is completed while in contact with the substrate.

  In various embodiments, a partially cured thermoplastic vulcanizate is fed directly to a coextrusion die or immediately inserted into a mold containing a substrate as described above. Instead, the extruded vulcanized rubber is cooled and retained for later use.

  A processable rubber composition comprising a vulcanized elastomeric material dispersed in a matrix is provided. A vulcanized elastomeric material is a product that vulcanizes, crosslinks, or cures a fluorocarbon elastomer. The matrix is composed of a thermoplastic material. The processable rubber composition is processed in a variety of ways including conventional thermoplastic technology to form a composite article having the rubber composition adhered to a solid substrate. Composite rubber compositions have physical properties that make them useful in many applications that require elastomeric properties. In particularly preferred embodiments, the rubber composition exhibits a Shore A hardness of about 50 or greater, Shore A 70 or greater, or a Shore A hardness in the range of about Shore A 70 to about Shore A 90. In addition or alternatively, the tensile strength is preferably in the range of about 4 MPa or more, about 8 MPa or more, or about 8 to about 13 MPa. In yet other embodiments, the cured rubber is characterized as having a 100% modulus of at least 2 MPa, or at least about 4 MPa, or from about 4 to about 8 MPa. In other embodiments, an article made from the processable composition of the present invention has an elongation at break of 10% or more, preferably at least about 50%, or at least about 150%, or in the range of about 150 to about 300%. is there. The molded article of the present invention is preferably characterized as having at least one of hardness, tensile strength, modulus, and elongation at break within the above ranges.

  In one aspect, the rubber composition is composed of two phases in the form of particles in which the matrix forms a continuous phase and the vulcanized elastomeric material forms a discontinuous phase, a dispersed phase, or a discontinuous phase. In another aspect, the elastomeric material and the matrix together form a continuous phase.

  In preferred embodiments, the composition comprises about 35% or more, or about 40% or more by weight of the elastomeric phase, based on the total weight of elastomer and thermoplastic material. In other embodiments, the composition comprises about 50% by weight or more of the elastomer phase. The composition is a molded article having sufficient elastomeric properties such as tensile strength, modulus, elongation at break, and compressive strain that are industrially useful in applications requiring elastomeric properties such as seals, hoses, etc. Is a two-phase homogeneous blend that is sufficiently compatible to easily form the composition.

  The elastomeric phase can exist in the form of particles in a continuous thermoplastic phase, as a 3-D network that forms a continuous phase with the thermoplastic material, or as a mixture of both. The elastomeric phase particles or 3-D network preferably have a minimum dimension of about 10 μm or less, or about 1 μm or less.

  In various embodiments, the rubber composition of the present invention is made by dynamic vulcanization of a fluorocarbon elastomer in the presence of a thermoplastic component. In such an embodiment, a method for producing a rubber composition is provided that includes the step of mixing a curing agent, an elastomeric material, and a thermoplastic material to form a mixture. This mixture is heated in the presence of a thermoplastic material at a temperature and for a time sufficient to cause partial vulcanization or curing of the fluorocarbon elastomer, but for a time shorter than that required for complete curing. During the heating process, mechanical energy is applied to the mixture of elastomeric material, curing agent and thermoplastic material. Accordingly, the method of the present invention comprises the steps of mixing an elastomer and a thermoplastic component in the presence of a curing agent and heating to achieve partial curing of the elastomer component during mixing. Instead, the elastomeric material and thermoplastic material are mixed for a time and shear rate sufficient to form a dispersion of the elastomeric material in a continuous or co-continuous thermoplastic phase. Thereafter, a curing agent is added to the dispersion system of the elastomer material and the thermoplastic material while mixing is continued. Finally, the dispersion is heated while mixing continues to produce the processable rubber composition of the present invention.

  In a preferred embodiment, composite articles prepared from the compositions of the present invention exhibit an advantageous combination of physical properties including a high degree of resistance to the effects of chemical solvents. In preferred embodiments, the hardness, tensile strength, and / or elongation at break change little or have been cured when the article is exposed for extended periods of time, such as by immersion or partial immersion in an organic solvent or fuel. Articles are produced that change significantly significantly compared to fluorocarbon elastomers or other known thermoplastic vulcanizates.

Preferred fluorocarbon elastomers include commercially available one or more fluorine-containing monomers such as vinylidene fluoride (VDF), hexafluoropropylene (HFP), tetrafluoroethylene (TFE), and perfluorovinyl ether (PFVE). Mention may be made of copolymers. Preferred PFVEs include those having a C _1-8 perfluoroalkyl group, preferably a perfluoroalkyl group having 1 to 6 carbon atoms, especially perfluoromethyl vinyl ether and perfluoropropyl vinyl ether. In addition, the copolymer may optionally contain repeat units derived from olefins such as ethylene (Et) and propylene (Pr). The copolymer may further include a relatively small amount of cure site monomer (CSM) as described below. Preferred copolymer fluorocarbon elastomers include VDF / HFP, VDF / HFP / CSM, VDF / HFP / TFE, VDF / HFP / TFE / CSM, VDF / PFVE / TFE / CSM, TFE / Pr, TFE / Pr / VDF, TFE. / Et / PFVE / VDF / CSM, TFE / Et / PFVE / CSM and TFE / PFVE / CSM. The name of the elastomer gives the monomer from which the elastomeric rubber is synthesized. The elastomeric rubber preferably has a viscosity that provides a Mooney viscosity (ML1 + 10, large rotor of about 121 ° C.), usually in the range of about 15 to about 160. Mooney viscosity can be selected by a combination of flow and physical properties. Elastomer suppliers include Dyneon (3M), Asahi Glass Fluoropolymers, Solvay / Ausimont, DuPont, and Daikin.

In one embodiment, the elastomeric material is described as a copolymer of tetrafluoroethylene and at least one C _2-4 olefin. As such, the elastomeric material comprises repeating units derived from tetrafluoroethylene and at least one C _2-4 olefin. Optionally, the elastomeric material can include repeat units derived from one or more additional fluorine-containing monomers.

  A preferred additional monomer for the vulcanized elastomeric material is vinylidene difluoride. Other fluorine-containing monomers optionally used in the elastomeric material include perfluoroalkyl vinyl compounds, perfluoroalkyl vinylidene compounds, and perfluoroalkoxy vinyl compounds. Hexafluoropropylene (HFP) is an example of a perfluoroalkyl vinyl monomer. Perfluoromethyl vinyl ether is an example of a preferred perfluoroalkoxy vinyl monomer. For example, rubbers based on tetrafluoroethylene, ethylene, and perfluoromethyl vinyl ether are commercially available from DuPont under the trade name Viton® ETP.

  In another embodiment, the elastomeric material is a curable fluorocarbon elastomer containing repeating units derived from fluoromonomers vinylidene fluoride (VDF) and hexafluoropropylene (HFP). In some embodiments, the elastomer further comprises repeating units derived from tetrafluoroethylene.

  Chemically, in this embodiment, the elastomeric material is composed of a copolymer of VDF and HFP, or a terpolymer of VDF, HFP, and tetrafluoroethylene (TFE), and optionally a cure site monomer. In a preferred embodiment, they contain about 66 to about 70% fluorine by weight. Elastomers are commercially available, and examples include Viton® A, Viton® B, and Viton® F series of elastomers from DuPont Dow Elastomers.

  In another embodiment, the elastomer is chemically described as a copolymer of TFE and PFVE, optionally a terpolymer with VDF. The elastomer can further include repeat units derived from cure site monomers.

  In various embodiments, the fluorocarbon elastomer material used to make the processable rubber composition of the present invention is prepared by free radical emulsion polymerization of a monomer mixture containing the desired molar ratio of starting monomers. Initiators include organic or inorganic peroxide compounds, and suitable emulsifiers include fluorinated acidic soaps. In one embodiment, the molecular weight of the polymer formed is controlled by the relative amount of initiator used compared to the monomer level and the choice of transfer agent, if any. Suitable transfer agents include carbon tetrachloride, methanol, and acetone. Emulsion polymerization is carried out under batch or continuous conditions. Such fluoroelastomers are commercially available as described above.

  The fluorocarbon elastomer may also contain up to about 5 mol%, preferably up to about 3 mol%, of repeating units derived from so-called cure site monomers that provide cure sites for vulcanization as described below. In one embodiment, the cure site repeat unit is derived from a bromine-containing olefin monomer and / or an iodine-containing monomer. When used, preferably the repeating units of iodine or bromine containing monomers are present in the polymer at a level that provides at least about 0.05%, preferably 0.3% or more bromine or iodine. In a preferred embodiment, the total mass of bromine or iodine in the polymer is about 1.5 wt.

  Bromine-containing olefin monomers useful for providing fluoropolymer cure sites are disclosed, for example, in US Pat. No. 4,035,565. Non-limiting examples of bromine-containing monomers include bromotrifluoroethylene and 4-bromo-3,3,4,4-tetrafluoro-1-butene. Further non-limiting examples include vinyl bromide, 1-bromo-2,2-difluoroethylene, perfluoroalkyl bromide, 4-bromo-1,1,2-trifluorobutene, 4-bromo-1,1,3, 3,4,4-hexafluorobutene, 4-bromo-3-chloro-1,1,3,4,4-pentafluorobutene, 6-bromo-5,5,6,6-tetrafluorohexene, 4- Examples include bromoperfluorobutene-1 and 3,3-difluoroalkyl bromide. As noted above, it is usually preferred that there be sufficient bromo-olefin repeat units to provide about 0.3-1.5 wt.% Bromine in the copolymer.

  Low levels, preferably up to about 5 mol%, more preferably up to about 3 mol% of epoxy, carboxylic acid, carboxylic acid halide, carboxylic acid ester, carboxylate, sulfonic acid group, sulfonic acid alkyl ester, and sulfonic acid Other curing monomers that introduce functional groups such as salts can be used. Such monomers and curing are described, for example, in Kamiya et al., US Pat. No. 5,354,811.

  The thermoplastic material constituting the matrix is a polymeric material that softens and flows when heated. In one aspect, a thermoplastic material is a material whose melt viscosity can be measured at temperatures above its melting point, such as by ASTM D-1238 or D-2116.

  The thermoplastic material of the present invention can be selected to improve the properties of the rubber / thermoplastic material combination at high temperatures, preferably above about 100 ° C, and more preferably above about 150 ° C. Such thermoplastic materials include those that maintain at least one physical property such as tensile strength, modulus, and elongation at break to an acceptable level at high temperatures. In a preferred embodiment, the thermoplastic material is superior in physical properties at high temperatures to physical properties at similar temperatures of a cured fluorocarbon elastomer (rubber) (ie, high tensile strength, high modulus, and / or high). Elongation at break).

  In various embodiments, the thermoplastic polymer material is a thermoplastic elastomer. Thermoplastic elastomers have some physical properties of rubber such as softening, flexibility and elasticity, but can be processed like thermoplastics. On cooling, the transition from the melt to the solid rubber-like composition occurs fairly rapidly. This is in contrast to normal elastomers that cure slowly on heating. In various embodiments, thermoplastic elastomers are processed in conventional plastic equipment such as injection molding machines and extruders. Preferably the scrap is recycled immediately.

  Thermoplastic elastomers have a multiphase structure, and the phases are usually intimately mixed. In many cases, the phases are joined by grafting or block copolymerization. At least one phase is hard at room temperature but is composed of a material that is flowable when heated. Another phase is a soft material like rubber at room temperature.

  Many of the thermoplastic elastomers useful here are known. Non-limiting examples of ABA type thermoplastic elastomers include polystyrene / polysiloxane / polystyrene, polystyrene / polyethylene-co-butylene / polystyrene, polystyrene / polybutadiene / polystyrene, polystyrene / polyisoprene / polystyrene, poly-α- Mention may be made of methylstyrene / polybutadiene / poly-α-methylstyrene, poly-α-methylstyrene / polyisoprene / poly-α-methylstyrene, and polyethylene / polyethylene-co-butylene / polyethylene.

  Non-limiting examples of thermoplastic elastomers having (AB) n repeat structures include polyamide / polyether, polysulfone / polydimethylsiloxane, polyurethane / polyester, polyurethane / polyether, polyester / polyether, polycarbonate / polydimethylsiloxane. And polycarbonate / polyether.

  In one embodiment, the thermoplastic elastomer has alternating blocks of polyamide and polyether. Such materials include, for example, those commercially available from Atofina under the trade name Pebax®. The polyamide block can be derived from a copolymer of a dibasic acid component and a diamine component or can be prepared by homopolymerization of a cyclic lactam. The polyether block is generally derived from the homo- or copolymerization of cyclic ethers such as ethylene oxide, propylene oxide, and tetrahydrofuran.

  In one embodiment, the thermoplastic polymer material is selected from among solid, usually high molecular weight plastic materials. Preferably, the material is a crystalline or semi-crystalline polymer, and more preferably has a crystallinity of at least about 25% as measured by differential scanning calorimetry. Amorphous polymers with suitably high glass transition temperatures are also acceptable as thermoplastic polymer materials. The thermoplastic material preferably has a melting temperature or glass transition temperature in the range of about 80 ° C. to about 350 ° C., but the melting temperature should generally be lower than the decomposition temperature of the thermoplastic vulcanizate.

  Non-limiting examples of thermoplastic polymers include polyolefin, polyester, nylon, polycarbonate, styrene-acrylonitrile copolymer, polyethylene terephthalate, polybutylene terephthalate, polyamide, polystyrene, polystyrene derivatives, polyphenylene oxide, polyoxymethylene, and fluorine-containing thermoplastics. Is mentioned.

  Polyolefins include, but are not limited to, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, Produced by polymerization of α-olefins such as 5-methyl-1-hexene, and mixtures thereof. Ethylene and propylene or ethylene or propylene and 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1 Copolymers with other α-olefins such as -hexene or mixtures thereof are also conceivable. These homopolymers and copolymers, and blends thereof can be incorporated as the thermoplastic polymer material of the present invention.

  Polyester thermoplastics contain repeating ester linkage units in the polymer backbone. In one embodiment, they comprise repeating units derived from a low molecular weight diol and a low molecular weight aromatic dibasic acid. Non-limiting examples include commercially available grades of polyethylene terephthalate and polybutylene terephthalate. Instead, polyesters are based on aliphatic diols and aliphatic dibasic acids. Examples are copolymers of ethylene glycol or butanediol and adipic acid. In another embodiment, the thermoplastic polyester is a polylactone prepared by polymerizing monomers containing both hydroxyl and carboxyl functionality. Polycaprolactone is a non-limiting example of this class of thermoplastic polyester.

Polyamide thermoplastics contain repeating amide linkage units in the polymer backbone. In one embodiment, the polyamide includes repeat units derived from a diamine such as the well known nylon 66 polymer of hexamethylene diamine and adipic acid and a dibasic acid monomer. Other nylons have a structure that results from changing the size of the diamine and dibasic acid components. Non-limiting examples include nylon 610, nylon 612, nylon 46, and nylon 6/66 copolymer. In another embodiment, the polyamide has a structure resulting from polymerizing monomers having both amine and carboxyl functionality. Non-limiting examples include nylon 6 (polycaprolactam), nylon 11, and nylon 12.

  Other polyamides produced from diamines and dibasic acid components include high temperature aromatic polyamides containing repeating units derived from diamines and aromatic dibasic acids such as terephthalic acid. Examples of these commercially available include PA6T (a copolymer of hexanediamine and terephthalic acid) and PA9T (a copolymer of nonanediamine and terephthalic acid) sold under the trade name Genestar by Kuraray. For some applications, the melting point of some aromatic polyamides is higher than the optimum value for thermoplastic processing. In such cases, the melting point is lowered by preparing an appropriate copolymer. In a non-limiting example, PA6T, which has a melting temperature of about 370 ° C, can be molded to a practical melting point of about 320 ° C by including an effective amount of a non-aromatic dibasic acid such as adipic acid during polymer production. Can be lowered below the temperature.

  In another preferred embodiment, an aromatic polyamide based on a copolymer of an aromatic dibasic acid such as terephthalic acid and a diamine containing more than 6 carbon atoms, preferably 9 or more carbon atoms, is used. To do. The upper limit of the carbon chain length of the diamine is limited from a practical viewpoint by the availability of monomers suitable for polymer synthesis. Suitable diamines include those having 7 to 20 carbon atoms, preferably in the range of 9 to 15 carbon atoms, more preferably in the range of 9 to 12 carbon atoms. Preferred embodiments include C9, C10 and C11 diamine based aromatic polyamides. Preferably, such aromatic polyamides exhibit an increased level of solvent resistance based on the lipophilicity of carbon chains having more than 6 carbon atoms. If it is desired to lower the melting point below the preferred molding temperature (typically below about 320 ° C.), aromatic polyamides based on diamines with more than 6 carbon atoms, together with aromatic polyamides based on 6-carbon atoms diamine, An effective amount of a non-aromatic dibasic acid as described above may be included. Such an effective amount of dibasic acid must be sufficient to lower the melting point to the desired molding temperature range without unacceptably affecting the desired solvent resistance.

  Other non-limiting examples of high temperature thermoplastics include polyphenylene sulfide, liquid crystal polymers, and high temperature polyimides. The liquid crystal polymer is chemically based on a linear polymer containing an aromatic ring in a linear manner. Due to the aromatic structure, this material forms a nematic molten region with a characteristic spatial arrangement that can be detected by X-ray diffraction. Examples of this material include copolymers of hydroxybenzoic acid or linear aromatic diesters such as ethylene glycol and terephthalic acid or naphthalenedicarboxylic acid.

  Examples of the high temperature thermoplastic polyimide include a polymerization reaction product of an aromatic dianhydride and an aromatic diamine. Such polyimides include those that are commercially available from many suppliers. An example is a copolymer of 1,4-benzenediamine and 1,2,4,5-benzenetetracarboxylic dianhydride.

  In a preferred embodiment, the matrix comprises at least one fluorine-containing thermoplastic. Suitable thermoplastic fluorine-containing polymers include those selected from a wide range of polymers and commercial products. The polymers are melt processable, preferably so that they soften and flow when heated, and can be easily processed with thermoplastic techniques such as injection molding, extrusion, compression molding, and blow molding. The material can be easily recycled, preferably by melting and reworking.

  In various embodiments, the thermoplastic polymer is fully fluorinated or partially fluorinated. Fully fluorinated thermoplastic polymers include copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether. Perfluoroalkyl groups preferably have 1 to 6 carbon atoms. Examples of other copolymers are PFA (copolymer of TFE and perfluoropropyl vinyl ether) and MFA (copolymer of TFE and perfluoromethyl vinyl ether). Other examples of fully fluorinated thermoplastic polymers include copolymers of TFE and perfluoroolefins of 3 to 8 carbon atoms. Non-limiting examples include FEP (copolymer of TFE and hexafluoropropylene).

  Partially fluorinated thermoplastic polymers include E-TFE (ethylene and TFE copolymer), E-CTFE (ethylene and chlorotrifluoroethylene copolymer), and PVDF (polyvinylidene fluoride). Many thermoplastic copolymers of vinylidene fluoride are also suitable thermoplastic polymers for use in the present invention. These include copolymers with perfluoroolefins such as hexafluoropropylene and copolymers with chlorotrifluoroethylene. In various embodiments, a thermoplastic terpolymer is used. These include TFE, HFP, and vinylidene fluoride thermoplastic terpolymers, including commercially available fluorine-containing thermoplastic materials. Sources include Dyneon (3M), Daikin, Asahi Glass Fluoroplastics, Solvay / Ausimont and DuPont. In some commercial embodiments, the partially fluorinated fluoroplastic has from about 59 to about 76% fluorine by weight.

  Useful curing agents include diamines, peroxides, and polyol / onium salt combinations. Diamine curing agents cure relatively slowly but offer advantages in several areas. Such curing agents are commercially available, such as Diak-1 from DuPont Dow Elastomers.

  Preferred peroxide curing agents include organic peroxides, preferably dialkyl peroxides. Preferably, the organic peroxide of the composition does not cause any harmful amount of curing during mixing or other operations prior to the curing operation at the temperature used in the curing operation in the presence of other components. Selected to function as a curing agent. Dialkyl peroxides that decompose at temperatures above about 49 ° C. are particularly preferred when subjected to high temperature processing prior to curing the composition. In many cases it is preferred to use di-tert-butyl peroxide having a tertiary carbon atom bonded to peroxy oxygen. Non-limiting examples include 2,5-dimethyl-2,5-di (tert-butylperoxy) -3-hexyne; 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane; and 1, An example is 3-bis- (t-butylperoxyisopropyl) benzene. Other non-limiting examples of peroxide curing agents include dicumyl peroxide, dibenzoyl peroxide, tert-butyl perbenzoate, di [1,3-dimethyl-3- (t-butylperoxy) butyl] carbonate, and the like.

  In various embodiments, one or more crosslinking aids are used in combination with the peroxide. Examples include triallyl cyanurate; triallyl isocyanurate; tri (methallyl) isocyanurate; tris (diallylamine) -s-triazine; triallyl phosphite; N, N-diallylacrylamide; hexaallylphosphoramide; N ', N'-tetraallylterephthalamide; N, N, N', N'-tetraallylmalonamide; trivinyl isocyanurate; 2,4,6-trivinylmethyltrisiloxane; and tri (5-norbornene) cyanurate -2-methylene).

  Suitable onium salts are described, for example, in US Pat. Nos. 4,233,421; 4,912,171; and 5,262,490. Examples include triphenylbenzylphosphonium chloride, tributylalkylphosphonium chloride, tributylbenzylammonium chloride, tetrabutylammonium bromide, and triarylsulfonium chloride.

式中、
Ｑは窒素又はリンであり；
Ｚは水素原子であり、或いは
末端が式-ＣＯＯＡ（Ａは水素原子又はＮＨ₄ ⁺カチオンである）である４〜約20個の炭素原子を有する置換又は無置換の環式又は非環式アルキル基であり、或いはＺは式-ＣＹ₂ＣＯＯＲ’（Ｙは水素又はハロゲン原子であり、又は任意に１個以上の四級ヘテロ原子を含有してもよい１〜約６個の炭素原子を有する置換又は無置換のアルキル又はアリール基であり、かつＲ’は水素原子、ＮＨ₄ ⁺カチオン、アルキル基であり、又は非環式無水物、例えば式-ＣＯＲ（Ｒはアルキル基又はそれ自体有機オニウムを含有する（すなわち、ビス-有機オニウムを与える）基である）の基であり；好ましくはＲ’は水素原子である）の基であり；Ｚは末端が式-ＣＯＯＡ（Ａは水素原子又はＮＨ₄ ⁺カチオンである）である４〜約20個の炭素原子を有する置換又は無置換の環式又は非環式アルキル基でもよく；Ｒ₁、Ｒ₂、及びＲ₃は、それぞれ独立的に水素原子又はアルキル、アリール、アルケニル、又はそのいずれかの組合せであり、各Ｒ₁、Ｒ₂、及びＲ₃は、塩素、フッ素、臭素、シアノ、-ＯＲ”、又は-ＣＯＯＲ’’（Ｒ’’は、Ｃ₁〜Ｃ₂₀アルキル、アリール、アラルキル、又はアルケニルであり、かつＲ₁、Ｒ₂、及びＲ₃基のいずれかの対が相互に結合し、かつＱと結合してヘテロ環式環を形成してもよく；Ｒ₁、Ｒ₂、及びＲ₃基の１個以上は、式Ｚ（Ｚは上記定義どおりである）の基でもよく；
Ｘは有機又は無機アニオン（例えば、限定するものではないが、ハライド、スルフェート、アセテート、ホスフェート、ホスホネート、ヒドロキシド、アルコキシド、フェノキシド、又はビスフェノキシド）であり；かつ
ｎはアニオンＸのイオン価に等しい数である。 Another class of useful onium salts is represented by the following formula.

Where
Q is nitrogen or phosphorus;
Z is a hydrogen atom, or a substituted or unsubstituted cyclic or acyclic alkyl having 4 to about 20 carbon atoms terminated by the formula —COOA (A is a hydrogen atom or NH ₄ ⁺ cation) Or Z is of the formula —CY ₂ COOR ′ where Y is a hydrogen or halogen atom, or optionally has from 1 to about 6 carbon atoms which may contain one or more quaternary heteroatoms. A substituted or unsubstituted alkyl or aryl group, and R ′ is a hydrogen atom, an NH ₄ ⁺ cation, an alkyl group, or an acyclic anhydride such as the formula —COR (where R is an alkyl group or itself an organic onium Z is a group of the formula —COOA (where A is a hydrogen atom or a group that is preferably a bis-organoonium); preferably R ′ is a hydrogen atom; NH. 4 to about 20 a ₄ a ⁺ cation) May be a substituted or unsubstituted cyclic or acyclic alkyl group having carbon atoms; R _1, R _2, and R ₃ are each independently a hydrogen atom or an alkyl, aryl, alkenyl, or any combination thereof Each R ₁ , R ₂ , and R ₃ is chlorine, fluorine, bromine, cyano, —OR ″, or —COOR ″ (where R ″ is C ₁ -C ₂₀ alkyl, aryl, aralkyl, or Alkenyl, and any pair of R ₁ , R ₂ , and R ₃ groups may be bonded to each other and combined with Q to form a heterocyclic ring; R ₁ , R ₂ , and One or more of the R ₃ groups may be a group of formula Z (Z is as defined above);
X is an organic or inorganic anion (eg, but not limited to, halide, sulfate, acetate, phosphate, phosphonate, hydroxide, alkoxide, phenoxide, or bisphenoxide); and n is equal to the ionic value of anion X Is a number.

  Polyol crosslinking agents are disclosed in U.S. Pat.No. 4,259,463 (Moggi et al.), U.S. Pat.No. 3,876,654 (Pattison), U.S. Pat. Any of the polyhydroxy compounds known in the art that function as crosslinkers or crosslinkers for fluoroelastomers, such as hydroxy compounds, may be used. Preferred polyols include aromatic polyhydroxy compounds, aliphatic polyhydroxy compounds, and phenolic resins.

式中、Ａは、１〜13個の炭素原子の二官能性脂肪族、環式脂肪族、若しくは芳香族基、又はチオ、オキシ、カルボニル、若しくはスルホニル基であり、Ａは、任意に、少なくとも１個の塩素又はフッ素原子で置換されていてもよく、ｘは０又は１であり、ｎは１又は２であり、かつ該ポリヒドロキシ化合物のいずれの芳香環も任意に塩素、フッ素、若しくは臭素原子の少なくとも１個の原子、又はカルボキシル若しくはアシル基（例えば、-ＣＯＲ（ＲはＨ又はＣ₁〜Ｃ₈アルキル、アリール若しくはシクロアルキル基である）又は例えば１〜８個の炭素原子を有するアルキル基で置換されていてもよい。上記ビスフェノールの式IIIから、-ＯＨ基はどちらかの環内のいずれの位置（数１以外）にも結合できることが分かるだろう。２種以上の該化合物のブレンドも使用できる。好ましいビスフェノール化合物は、2,2-ビス(4-ヒドロキシフェニル)ヘキサフルオロプロパンであるビスフェノールAFである。他の非限定例としては、4,4’-ジヒドロキシジフェニルスルホン（ビスフェノールＳ）及び2,2-ビス(4-ヒドロキシフェニル)プロパン（ビスフェノールＡ）が挙げられる。ヒドロキノンのような芳香族ポリヒドロキシ化合物も硬化剤として使用できる。さらなる非限定例としては、カテコール、レゾルシノール、2-メチルレゾルシノール、5-メチルレゾルシノール、2-メチルヒドロキノン、2,5-ジメチルヒドロキノン、及び2-t-ブチルヒドロキノン、1,5-ジヒドロキシナフタレン及び9,10-ジヒドロキシアントラセンが挙げられる。 Exemplary aromatic polyhydroxy compounds include any one of di-, tri-, and tetrahydroxybenzene, -naphthalene, and -anthracene, and bisphenols of the formula:

Where A is a bifunctional aliphatic, cycloaliphatic, or aromatic group of 1 to 13 carbon atoms, or a thio, oxy, carbonyl, or sulfonyl group, and A is optionally at least Optionally substituted with one chlorine or fluorine atom, x is 0 or 1, n is 1 or 2, and any aromatic ring of the polyhydroxy compound is optionally chlorine, fluorine or bromine alkyl having at least one atom, or carboxyl or an acyl group (e.g., -COR (R is H or C ₁ -C ₈ alkyl, aryl or cycloalkyl group) or, for example from 1 to 8 carbon atoms atoms From the above formula III of bisphenol, it will be understood that the —OH group can be attached at any position (other than the number 1) in either ring. Blends of compounds can also be used, a preferred bisphenol compound is bisphenol AF, which is 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and other non-limiting examples include 4,4'-dihydroxydiphenyl sulfone. (Bisphenol S) and 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) Aromatic polyhydroxy compounds such as hydroquinone can also be used as curing agents, further non-limiting examples include catechol, Resorcinol, 2-methylresorcinol, 5-methylresorcinol, 2-methylhydroquinone, 2,5-dimethylhydroquinone, and 2-t-butylhydroquinone, 1,5-dihydroxynaphthalene and 9,10-dihydroxyanthracene.

  Aliphatic polyhydroxy compounds can also be used as polyol curing agents. Examples are described in fluoroaliphatic diols, such as 1,1,6,6-tetrahydrooctafluorohexanediol, and US Pat. No. 4,358,559 (Holcomb et al.) And references cited therein. Other things like things. Derivatives of polyhydroxy compounds as described in US Pat. No. 4,446,270 (Guenthner et al.) Can also be used, for example, 2- (4-allyloxyphenyl) -2- (4-hydroxyphenyl) propane. Mixtures of two or more polyhydroxy compounds can also be used.

  A phenol resin capable of crosslinking the rubber polymer can be used as a polyol curing agent. Reference to a phenolic resin can include a mixture of phenolic resins. Such resins are disclosed in US Pat. Nos. 2,972,600 and 3,287,440. With these phenolic resins, a desired level of curing can be achieved without the use of other curing agents.

  The phenolic resin curing agent can be made by condensation of an alkyl-substituted phenol or unsubstituted phenol and an aldehyde, preferably formaldehyde, in an alkaline medium, or by condensation of a bifunctional phenol dialcohol. The alkyl substituent of the alkyl-substituted phenol usually contains 1 to about 10 carbon atoms. Preference is given to dimethylolphenol or phenolic resins which are substituted in the para position by alkyl groups containing from 1 to about 10 carbon atoms. Useful commercially available phenolic resins include alkylphenol-formaldehyde resins and bromomethylated alkylphenol-formaldehyde resins.

式中、Ｑは、-ＣＨ₂-及び-ＣＨ₂-Ｏ-ＣＨ₂-から成る群より選択される二価基であり；ｍはゼロ又は１〜20の正整数であり、かつＲ’は水素又は有機基である。好ましくは、Ｑが二価基-ＣＨ₂-Ｏ-ＣＨ₂-であり、ｍがゼロ又は１〜10の正整数であり、かつＲ’が水素又は20個未満の炭素原子を有する有機基である。別の実施形態では、好ましくはｍがゼロ又は１〜５の正整数であり、かつＲ’が４〜12個の炭素原子を有する有機基である。他の好ましいフェノール樹脂は、米国特許第5,952,425号にも開示されている。 In one embodiment, the phenol resin curing agent is represented by the following general formula.

Where Q is a divalent group selected from the group consisting of —CH ₂ — and —CH ₂ —O—CH ₂ —; m is zero or a positive integer from 1 to 20 and R ′ is Hydrogen or an organic group. Preferably, Q is a divalent group —CH ₂ —O—CH ₂ —, m is zero or a positive integer from 1 to 10, and R ′ is hydrogen or an organic group having less than 20 carbon atoms. is there. In another embodiment, preferably m is zero or a positive integer from 1 to 5 and R ′ is an organic group having 4 to 12 carbon atoms. Other preferred phenolic resins are also disclosed in US Pat. No. 5,952,425.

  The processable rubber composition of this invention comprises, optionally, stabilizers, processing aids, curing accelerators, fillers, pigments, adhesives, tackifiers in addition to elastomeric materials, thermoplastic polymer materials, and curing agents. , And other additives such as waxes.

In various embodiments, a wide variety of processing aids are used, including plasticizers and mold release agents. Non-limiting examples of processing aids include phthalate ester plasticizers such as Caranuba wax, dioctyl phthalate (DOP) and dibutyl phthalate silicate (DBS), fatty acid salts such as zinc stearate and sodium stearate, polyethylene Examples include waxes and keramide. In some embodiments, high temperature processing aids are preferred. Such processing aids include, but are not limited to, linear fatty alcohols such as blends of C ₁₀ -C ₂₈ alcohols, organosilicones, and functionalized perfluoropolyethers. In some embodiments, the composition comprises from about 1 to about 15 weight percent, preferably from about 5 to about 10 weight percent processing aid.

In various embodiments, the acid acceptor compound is used as a cure accelerator or cure stabilizer. Preferred acid acceptor compounds include divalent metal oxides and hydroxides. Non-limiting examples include Ca (OH) ₂ , MgO, CaO, and ZnO.

  Non-limiting examples of fillers include barium sulfate, zinc sulfate, carbon black, silica, titanium dioxide, clay, talc, glass fiber, fumed silica, and mineral fiber, wood cellulose fiber, carbon fiber, boron fiber, and aramid Examples include both organic and inorganic fillers such as discontinuous fibers such as fibers (Kevlar). Some non-limiting examples of processing additives include stearic acid and lauric acid. The addition of carbon black, extender oil, or both before dynamic vulcanization is particularly preferred. Non-limiting examples of carbon black fillers include SAF black, HAF black, SRP black and Austin black. Carbon black increases tensile strength, and extender oil can improve processability, resistance to oil swelling, thermal stability, hysteresis, cost, and permanent set. In a preferred embodiment, fillers such as carboxy blocks constitute up to about 40% by weight of the total weight of the composition of the present invention. Preferably, the composition comprises about 1 to about 40% by weight filler. In other embodiments, the filler comprises from about 10 to about 25% by weight of the composition.

  The vulcanized elastomeric material, generally referred to herein as “rubber”, is preferably present as small particles in a continuous thermoplastic polymer matrix. In some embodiments, co-continuous forms exist depending on the amount of elastomeric material relative to the thermoplastic material, the cure system, the mechanism and extent of elastomer cure, and the amount and extent of mixing. Preferably, the elastomeric material is fully crosslinked / cured in the final composition.

  Partial curing can be achieved by adding a suitable curing agent or curing system to the blend of thermoplastic and elastomeric material and vulcanizing or curing the rubber to the desired degree under vulcanization conditions. Elastomers are crosslinked in the process of dynamic vulcanization. The term dynamic vulcanization refers to the vulcanization of a rubber (here a fluorocarbon elastomer) contained in a thermoplastic composition in which the curable rubber is vulcanized under sufficiently high shear conditions at a temperature above the melting point of the thermoplastic component. Means a sulfur or curing process. Thus, the rubber is simultaneously crosslinked and dispersed within the thermoplastic matrix. In conventional mixing equipment such as roll mills, Moriyama mixers, Banbury mixers, Brabender mixers, continuous mixers, mixed extruders such as single and twin screw extruders, elastomers and heat at high temperatures in the presence of curing agents Dynamic vulcanization is achieved by adding mechanical energy to the plastic component and mixing. An advantageous feature of dynamically cured compositions is that they can be processed and reworked by conventional plastic processing methods such as extrusion, injection molding and compression molding, even after they are fully cured. is there. Preferably, reprocessing is performed using scrap or flushing.

  Heating and mixing or mastication at the vulcanization temperature is preferably sufficient to complete the vulcanization reaction in a few minutes or less, but higher temperatures and / or higher shear are required if shorter vulcanization times are desired. You may use force. A suitable range for the vulcanization temperature is from about the melting temperature of the thermoplastic material (typically about 120 ° C.) to about 300 ° C. or more. Typically, this range is from about 150 ° C to about 250 ° C. A preferred range for the vulcanization temperature is from about 180 ° C to about 220 ° C. It is preferred to continue mixing without interruption until vulcanization occurs or is complete.

  The processable rubber composition of the present invention can be produced by a batch process or a continuous process. In a batch process, a predetermined charge of elastomeric material, thermoplastic material, and curing agent is added to a mixing device. In a typical batch procedure, the elastomeric material and the thermoplastic material are first mixed, blended, masticated, or otherwise physically until an elastomeric material of the desired particle size is obtained within the continuous phase of the thermoplastic material. Mix in. When the structure of the elastomeric material is as desired, the hardener is added to mix the elastomeric material and the thermoplastic material while continuing to add mechanical energy. Partial curing is achieved by heating or continuing to heat the blend of thermoplastic and elastomeric material in the presence of the curing agent for a time that is less than the time required to fully cure the elastomer.

  It is preferable to mix the elastomer material and the thermoplastic material at a temperature at which the thermoplastic material softens and flows. If such temperature is below the temperature at which the curing agent is activated, the curing agent may be part of the mixture during the initial particle dispersion step of the batch process. In some embodiments, the curing agent is combined with the elastomer and polymeric material at a temperature below the curing temperature. When the desired dispersion is achieved, the temperature can be increased to achieve curing. In one embodiment, a commercially available elastomeric material containing a curing agent pre-blended in the elastomer is used. However, if the curing agent is activated at the temperature of the initial mixing step, it is preferred to exclude the curing agent until the desired particle size distribution of the elastomeric material in the thermoplastic matrix is achieved. In another embodiment, the curing agent is added after mixing the elastomeric material and the thermoplastic material. In a preferred embodiment, the curing agent is added to the mixture of elastomeric materials in the thermoplastic material while the entire mixture continues to be mechanically agitated, agitated, or otherwise mixed.

A continuous process can also be used. In one embodiment, the twin screw extruder, co-rotating or counter-rotating screw type comprises a material addition port and a reaction chamber comprised of modular components of the twin screw device. One such method of bonding a thermoplastic fluorocarbon elastomer composition onto a substrate using a twin screw extruder having a first port and a second downstream port includes the following steps.
(A) supplying a mixture of an uncured fluorocarbon elastomer characterized by time T90 and a thermoplastic material into the first port of the extruder;
(B) supplying a curing agent for the fluorocarbon elastomer into the second port of the extruder;
(C) mixing the curing agent, the fluorocarbon elastomer, and the thermoplastic material in the extruder for T90 or less to produce a partially cured thermoplastic vulcanizate of the fluorocarbon elastomer;
(D) extruding the partially cured thermoplastic vulcanizate from the extruder;
(E) applying the thermoplastic vulcanized rubber on the substrate; and (f) completing the curing of the thermoplastic vulcanized rubber on the substrate.

  In one embodiment, a thermoplastic material and an elastomeric material (as uncured resin or rubber) are inserted together in a screw extruder from a first hopper with a feeder (loss-in-weight feeder or volumetric feeder) to insert the materials. Mix together. Preferably, the temperature and screw parameters are adjusted to provide a temperature and shear force suitable to achieve the desired mixing and particle size distribution of the uncured elastomer component within the thermoplastic material matrix. The mixing duration is controlled by providing a longer or shorter length extrusion device or by controlling the screw rotation speed of the mixture of elastomeric and thermoplastic materials that is passed during the mixing stage. The degree of mixing may be controlled by the configuration of the mixing screw elements within the screw shaft, such as a strong, medium or mild screw design. Then, while the mixture of thermoplastic material and elastomer material continues to move downstream in the twin screw extrusion path, a hardener is added to the mixture using a side feeder (loss-in-weight feeder or volumetric feeder) at the downstream port. Can be added continuously. Downstream of the hardener addition port, the mixing parameters and transit time can be varied as described above. By adjusting the shear rate, temperature, duration of mixing, mixing screw element configuration, and timing of addition of the curing agent, the partially cured dynamic vulcanizate of the present invention can be prepared in a continuous process. As in the batch process, it may be a commercially formulated elastomeric material containing a curing agent, generally phenol or a phenolic resin curing agent.

  The compositions and articles of the present invention contain a sufficient amount of vulcanized elastomeric material ("rubber") to form the rubbery composition in question. That is, they exhibit a desirable combination of flexibility, softness, and compressive strain. Preferably, the composition comprises at least about 25 parts by weight rubber, preferably at least about 35 parts by weight rubber, more preferably at least about 40 parts by weight rubber, and even more preferably, per 100 parts by weight of the combined rubber and thermoplastic polymer. Preferably at least about 45 parts by weight rubber, more preferably at least about 50 parts by weight rubber. The amount of cured rubber in the thermoplastic vulcanizate is generally from about 5 to about 95 weight percent, preferably from about 35 to about 95 weight percent, and more preferably from about 5 to about 95 weight percent of the total weight of the combined rubber and thermoplastic polymer. It is 40 to about 90% by mass, more preferably about 50 to about 80% by mass.

  The amount of thermoplastic polymer in the processable rubber composition of the present invention is generally about 5 to about 95% by weight, preferably about 10 to about 65% by weight of the total weight of the combined rubber and thermoplastic polymer, More preferably, it is about 20 to about 50% by mass.

  The processable rubber composition in the composite article of the present invention comprises a cured rubber and a thermoplastic polymer. The composition is a homogeneous mixture in the form of rubber particles in which the rubber is finely and well dispersed in a non-vulcanized matrix. However, the thermoplastic vulcanizates of the present invention should not be construed as limited to those containing a discontinuous phase, and in fact the compositions of the present invention have other forms such as co-continuous forms. Can also be included. In particularly preferred embodiments, the rubber particles have an average particle size of less than about 50 μm, more preferably less than about 25 μm, even more preferably less than about 10 μm, and even more preferably less than about 5 μm.

  Fully cured material preferably has its original length within 1 minute after being held for 1 minute at room temperature, extended to double its original length at room temperature, as defined in ASTM D1566. It is rubber-like to the extent that it shrinks to less than 1.5 times. These materials also meet the tensile strain requirements set forth in ASTM D412 and they also meet the compressive strain elasticity requirements of ASTM D395.

  A composite article is comprised with the rubber composition as above-mentioned adhere | attached on the base material. An adhesive layer may be provided on the substrate prior to contact with the partially cured thermoplastic vulcanizate. The adhesive layer is comprised of an adhesive composition suitable for bonding the fluoroelastomer material to a substrate such as a metal, plastic, or ceramic. Generally, the adhesive layer includes a coupling agent that tends to react with one or both of the surfaces to be bonded to increase the bond strength. Such coupling agents usually have two chemical functionalities, one of the functionalities interacts with the substrate surface and the other functionality interacts with the fluoroelastomer component at the binding interface.

  Coupling agents can be represented by the structure “R-M-Y”, where R is a group that reacts or interacts with the polymer, and Y is a metal, plastic, or ceramic or others that make up the substrate. It is a group that reacts or interacts with other materials. When the substrate contains a metal, the Y group is usually in a hydrolysis sensitive form. Y groups tend to leave under acidic or alkaline conditions to yield more reactive hydroxy functionality. An example of this type of coupling agent is a commercially available silane.

Silane has the general structure R—Si— (OR ′) ₃ , where R is as defined above, and R ′ is generally methyl, ethyl, or lower alkyl. Suitable R groups include vinyl, aminopropyl, methacryloxy, mercapto, and glycidoxy. Non-limiting examples of silane coupling agents used in the adhesive composition are vinyltriethoxysilane and γ-aminopropylsilane. In one aspect, commercially available adhesives for bonding fluorocarbon elastomers to metals and other substrates are used and their activity and efficiency are improved by performing the method of the present invention.

  The uncured rubber or elastomer is preferably supplied in the form of a resin or rubber with little or no elastomeric properties. Preferably, the resin or rubber is cured or crosslinked to give the material advantageous properties such as flexibility, softness, elasticity, compressive strain and the like. Such curing is performed at a selected temperature for a time until the physical properties of the elastomer are fully developed. During curing, the physical properties gradually change from the non-elastomeric properties of the rubber or resin to the elastomeric properties of the fully cured rubber. A convenient way to follow the progress of curing is to measure the viscosity of the material as a function of time. Cured rubber systems are characterized by an increase in viscosity from the start to completion of curing.

  In one aspect, a partially cured fluorocarbon elastomer composition is applied to a substrate to enhance the bond between the fluorocarbon elastomer material and the solid substrate, thereby enhancing the bond between the two. Experimentally, this can be done by dynamically curing the fluorocarbon elastomer composition for a time shorter than that required to fully develop the elastomeric properties of the fluorocarbon elastomer composition. For example, the fluorocarbon elastomer material can be cured for a time of T90 or less. Here, T90 depends on the reaction temperature and is determined as the time during which the viscosity of the reaction mixture increases by 90% of the value at which the reaction mixture reaches a fully cured rubber. In a preferred embodiment, the fluorocarbon elastomer composition is cured for a time less than T90, such as T90 minus 30 seconds, or T90 minus 60 seconds. In such a partially cured state, the material can be extruded or inserted, but does not develop full elastomeric properties until further cure time.

  By curing the fluorocarbon elastomer component of the thermoplastic vulcanizate of the present invention, cure parameters such as T90 can be determined in a separate experiment. The average viscosity is known with RPA (Rubber Processing Analyzer). T90, Ts2, and other parameters can be routinely determined. For the fluorocarbon elastomer materials of the present invention, T90 at typical temperatures ranges from less than 1 minute to several minutes, such as from 2 to 5 minutes. Accordingly, the cure time to provide the fluorocarbon elastomer component with a partially cured state for application to a substrate is generally quite short. This means that in many situations it is experimentally easier to perform partial curing and application to a substrate in a continuous or semi-continuous process described below.

  The cure time T90 for a post cure or low post cure bisphenol cure system is approximately 2-5 minutes as described above. Systems cured with peroxides tend to have lower T90. Typically, the T90 of the peroxide cure system can be less than 1 minute.

  In general, the partially cured thermoplastic vulcanizates of the present invention can be made according to the usual procedures for making dynamic vulcanizates of rubber and thermoplastic materials. In particular, this method is similar to the method disclosed in co-pending US patent application Ser. No. 10 / 620,213, but cures for a shorter time to achieve the synthesis of a partially cured thermoplastic vulcanizate. That is different. In a batch process, the elastomer, thermoplastic material and curing agent are mixed together in a mixer and the partially cured material is collected for later use. The continuous or semi-continuous process is carried out in a twin screw extruder and the mixing time depends on the mixing speed and the length of the barrel. The partially cured thermoplastic vulcanizate is extruded from a twin screw extruder through a strand die, cooled in a water bath, and cut into pellets for later use. Alternatively, the partially cured thermoplastic vulcanizate can be extruded directly from the twin screw extruder into a co-extrusion die or insertion mold for application to the substrate.

  After the partially cured thermoplastic vulcanizate is applied onto the substrate, the elastomer of the partially cured elastomer composition is completely cured while the elastomer composition is in contact with the substrate. This can be accomplished by further curing the co-extruded or insertion molded substrate / elastomer composite at a high temperature after application. In the case of insertion molding, the composite article is held in the mold at an elevated temperature for a time sufficient to complete the cure. In the case of co-extruded articles such as sheets and hoses, the process includes passing the co-extruded product through a heated oven for a time and temperature sufficient to complete the cure. While curing is complete while in contact with the substrate, it is believed that the curable elastomer interacts with or causes a reaction with the coupling agent in the adhesive layer. This interaction is thought to enhance binding.

  The invention has been described above with reference to preferred embodiments. Further non-limiting examples are given in the examples below.

  The cure time T90 of various fluorocarbon elastomers is measured with an RPA (rubber processing analyzer). T90 is 124 seconds as measured on Dyneon® BRE 7231X, a bisphenol curable terpolymer elastomer. T90 is 217 seconds as measured for Tecnoflon® FOR 80HS, a no (low) post cure bisphenol curable terpolymer elastomer. The T90 of Tecnoflon P457, a peroxide curable terpolymer elastomer, is measured for 26 seconds, and measured for Tecnoflon P575, the T90 is 47 seconds. Dyneon material is available from 3M and Tecnoflon material is available from Solvay.

Batch procedure with peroxide curable elastomer The procedure for partially making FMK-TPV with a peroxide curable FKM elastomer is as follows.

In a batch mixer, the fluorocarbon elastomer and the plastic are melted at a high temperature (120 to 200 ° C.). The temperature is lower than that of FKM-TPV based on bisphenol curable FKM due to the low decomposition temperature of the peroxide curing agent (usually 80-200 ° C.). Add filler, hardener package and processing aid into the batch mixture. Mixing is continued until a uniformly mixed and partially cured thermoplastic vulcanizate (TPV) is obtained (usually a mixing time of 1 to 3 minutes at a rotor speed of 50 RPM). The mixing time depends on the T90 cure time and is 30 to 90 seconds at 180 ° C. for a typical peroxide curable elastomer. The curing time also depends on the type of peroxide curing agent (T _1/2 ). For example, T _1/2 of Trigonox 145 is 182 ° C, and T _1/2 of Perkadox TML is 80 ° C. Since the cure rate is slower at lower temperatures, the mixing time can be extended by using a temperature lower than T1 _{/ 2} .

In the injection molding or extrusion process, large chunks of the batch process TPV are crushed. A silane-based adhesive coated metal housing is prepared for insert molding operations. The adhesive layer may be sprayed or the housing may be immersed or submerged in the adhesive. Insert the adhesive coated metal housing into the mold. Preheat the housing in an oven to 100-250 ° C. The injection molding machine is heated to melt the TPV at 120 to 200 ° C. TPV material is injected onto an adhesive-coated metal housing (injection pressure 1.4 × 10 ^{7 to} 2.1 × 10 ⁷ Pa (2000 to 3000 psi)) and under pressure together (5.5 × 10 ^{6 to} 1.0 × 10 ⁷⁾ Maintain the Pa (800-1500 psi)) to contact and react the adhesive layer and the molten TPV material together to develop the bonding layer.

  The molded sample is removed from the mold and the bonding properties are evaluated immediately or after a short post-heat treatment (eg, 1 hour at 230 ° C. in an oven).

  After the separation test, the damaged area is examined by SEM and EDAX, and the damage mode is investigated by elemental analysis by scanning image and X-ray, respectively. For example, a scanned SEM image can be overlaid with a map of each distinct element such as iron (Fe), silicon (Si), fluorine (F), phosphorus (P), and the like.

Batch Procedure with Bisphenol Curable Fluorocarbon Elastomer The procedure for making partially cured FMK-RPV to bisphenol curable FKM (both regular and post-cure) is as follows.

  The fluorocarbon elastomer and thermoplastic material are melted in a batch mixer at an elevated temperature (eg, 220-250 ° C.). Add filler, hardener package, and processing aid into the batch mixture. Mixing is continued until a homogeneously mixed and partially cured thermoplastic vulcanizate is obtained (usually a mixing time of 1 to 3 minutes at 50 RPM rotor speed). The mixing time depends on the T90 cure time and is 2-5 minutes for a typical peroxide curable elastomer. For example, the T90 for FKM copolymers and terpolymer elastomers is 2-3 minutes, and the T90 for typical post-cure elastomers is 3-4 minutes. A large mass of batch processed FKM-TPV is crushed for an injection molding or extrusion process. As in Example 2, a silane based adhesive coated metal housing is prepared.

  As in Example 2, the TPV and the housing are inserted and molded. The molded sample is removed from the mold and tested for bonding behavior immediately or after a short post-heat treatment (usually in an oven at 230 ° C. for 22 hours). With no post cure additive, about 1 hour post heat treatment is used.

A partially cured thermoplastic vulcanizate can be produced by a continuous process in a continuous process twin screw extruder.

  The fluorocarbon elastomer is pulverized to the size of thermoplastic material particles. Mix the ground elastomer and thermoplastic pellets. The mixture of crushed elastomer and thermoplastic pellets is poured into the hopper of a twin screw extruder. The screw barrel temperature is set to be equal to or higher than the melting point of the thermoplastic material (for example, about 200 to 280 ° C or higher). Begin feeding the mixture of elastomer and thermoplastic material into the heated barrel. As the screw rotates and the mixture is extruded to the front of the twin screw extruder, the elastomer and thermoplastic material melt, compress, and mix.

  A mixture of curing agent, curing accelerator, processing aid, and carbon black is added through a side feeder at a downstream feed station. The elastomer and thermoplastic material mixture should be completely melted and uniformly mixed before the powder mixture is added (eg, 200 rpm and 240 ° C. for a total of 5-10 minutes).

  Add elastomer, thermoplastic material, curing agent, curing accelerator, and other additives from the side feeder into the barrel of the downstream twin screw extruder. Mixing time depends on screw speed and barrel length. The mixing time must be T90 or less. Here, T90 is an elastomer curing parameter.

  At the end of the twin screw extruder barrel, the partially cured thermoplastic vulcanizate is discharged through a strand die. The extrudate can be passed through a cooling water bath and cut to the appropriate length to give pellets for the next processing step.

  Bisphenol curable elastomers typically use an extruder barrel residence time of about 2 minutes before addition of the curing agent. A typical screw speed is 200 rpm with a barrel temperature of about 240 ° C. After adding the remaining components in the downstream feeder, the residence time in the barrel is usually less than 30 seconds. Preferably, after discharge from the strand die, the extrudate is quenched or quenched with a cooling water bath.

  For peroxide curable elastomers, the elastomer and thermoplastic material are mixed in an extruder barrel at a barrel temperature of 150 ° C. and a screw speed of 200 rpm for about 2 minutes, and then a curing agent is added. These parameters are similar to those used with bisphenol curable elastomers except that the barrel temperature is generally somewhat lower. Typically, the residence time in the barrel after addition of the curing agent package is less than 30 seconds. The hardener package can be added in powder form or as a masterbatch form as pellets. Typical T90 cure times for peroxide curable elastomers are 30 to 90 seconds at 180 ° C. The T90 time can be lengthened by curing at a lower temperature. For example, at a compound temperature of 150 ° C., a typical T90 cure time is about 2-3 minutes. As before, preferably after extrusion from the strand die, the extrudate is quenched or quenched in a cooling water bath.

Multi-layer co-extrusion procedure Multiple screw extruders (eg, 2-5 extruders; in some embodiments, 3 extruders are used) are connected to a multilayer die. With aqueous adhesives, this tie layer extruder can be replaced with a liquid continuous injection device.

  The extruder barrel is heated for each layer material. Typical temperature for partially cured thermoplastic vulcanizate extruders is 240 ° C, and typical temperature for nylon-based thermoplastic elastomer substrates such as Pebax® 4033 is 200 ° C .

  The inner layer extruder and the outer layer extruder including the adhesive continuous injection device are started simultaneously. As the multi-layer extruder strand exits the co-extrusion die in the cooling water bath, it is quenched.

  Typically, the size of a single screw extruder is about 2.5 to 5 cm (about 1 to 2 inches) in diameter and the screw speed is 20 to 100 rpm. The size and speed of the screw are determined by the thickness of each layer and the co-extrusion speed.

  The co-extrusion product may be in the form of a sheet or a concentric extrusion product such as a hose. After co-extrusion, the partially cured thermoplastic vulcanizate is completely cured at high temperature. The co-extrusion composite article comprises a fully cured fluorocarbon elastomer thermoplastic component bonded to an elastomer or plastic substrate. For example, when concentrically co-extruding for a hose to form a composite article, a typical arrangement of the cured fluorocarbon elastomer composition is the inner layer of the hose and the elastomer or thermoplastic material constitutes the outer layer of the hose. In sheet composites, a tie layer can be provided between the fluorocarbon elastomer and the substrate. Non-limiting examples of elastomers that can be used as the substrate include EPDM, NBR, HNBR, ACM, AEM, FKM, PU, FFKM, and silicone elastomers. Non-limiting examples of thermoplastic materials that can serve as a substrate include polyolefins, nylons, polyesters, pvcs, fluororesins, and plastic elastomers (trade names Hytrel®, Pebax®, Santoprene®, Pellethane (R), and thermoplastic polyurethanes and thermoplastic elastomers commercially available from Kraton (R). The knot-layer is comprised of an adhesive that can bond the cured fluorocarbon elastomer composition to the elastomer / thermoplastic material layer. Adhesive compositions based on silane or maleic anhydride are commercially available for this purpose.

  A single screw extruder that feeds a partially cured thermoplastic vulcanizate to a co-extrusion die feeds directly from a double barrel twin screw extruder used to produce thermoplastic vulcanizates in a continuous process You can also. If desired, the output of the twin screw extruder can be used directly for input into the multi-layer extrusion die of the co-extrusion unit, without first cooling the partially cured thermoplastic vulcanized rubber strands in a water bath. be able to. By connecting a compounding extruder to the multilayer extruder, the pelletizing, remelting, and re-extrusion steps can be eliminated.

Coupling a fluorocarbon elastomer composition to a metal substrate Example 6A-Coupling a partially cured peroxide curable elastomer

The following ingredients are used: 80 parts Tecnoflon P757 (peroxide curable fluoroelastomer from Solvay); 25 parts Kynar Flex 2500-04 (vinylidene fluoride based thermoplastic resin from Atofina Chemicals); 5 parts zinc oxide 10 parts carbon black; and 20 parts masterbatch. Tecnoflon P575 and Kynar Flex 2500-04 are melted at 150 ° C. for 5 minutes in a batch mixer with mixing to form a homogeneous mixture. Add zinc oxide. Add the masterbatch in the batch mixer and mix for 30 seconds (masterbatch in a separate batch mixer at 80 ° C with 100 parts Tecnoflon P757, 15 parts Luperco 101 XL, and 20 parts TAIC 75% dispersion. Prepared by mixing). The mixture is discharged from the batch mixer, cooled and cut into small particles or pellets about 1 to 3 mm in size. Pour pellets into the hopper of the injection molding machine. Heat the injection barrel to 150 ° C. A metal substrate, such as a sealing housing, is coated with a commercially available silane-based adhesive according to the manufacturer's instructions. An adhesive coated metal housing is inserted into the mold and the molten mixture is injected onto the metal housing. The housing may be preheated in an oven at about 200 ° C. or may be heated in the mold prior to injection. This preheating tends to improve the adhesion between the adhesive layer and the fluorocarbon thermoplastic vulcanizate. After injection, the molds are maintained together under pressure for 1-2 minutes (5.5 × 10 ^{6 to} 1.0 × 10 ⁷ Pa (800-1500 psi)). During this time, the material is fully cured.

  Example 6B-Comparative Example

  Example 6B is similar to Example 6A except that the masterbatch, zinc oxide, Tecnoflon, and Kynar materials are mixed for 3-5 minutes instead of 30 seconds.

  Example 7A—Coupling with a partially cured bisphenol curable elastomer

Ingredients used were 100 parts Tecnoflon FOR 80HS (bisphenol curable fluorocarbon elastomer with bisphenol curing agent from Solvay in the resin); 25 parts Hylar MP-10 (fluorine resin from Solvay); 3 parts oxidation Magnesium; 30 parts carbon black; 1 part Struktol WS-280 (processing aid from Struktol); and Tecnoflon FPA-1 (high temperature processing aid from Solvay). Melt Tecnoflon FOR 80HS and Hylar MP-10 in a batch mixer at 190 ° C for 1 minute until the polymer is evenly mixed. Add the remaining ingredients and stir for an additional minute at 190 ° C. until the ingredients are well dispersed. The mixture is discharged from the batch mixer, cooled and cut into 1-3 mm pellets. Pour the cut mixture into an injection molding hopper. Heat the injection barrel to 240 ° C. An adhesive coated metal housing is inserted into the mold and the mixture is injection molded over the metal housing. The mold is preheated to about 250 ° C. in an oven or in the mold. After injection, the molds are bonded at 5.5 x 10 ^{6 to} 1.0 x 10 ⁷ Pa (800 to 1500 psi) for 3 to 5 minutes to complete curing.

  Example 7B-Comparison

  The procedure is the same as Example 7A, except that mixing is performed for 5-10 minutes instead of 1 minute before adding the remaining ingredients.

  The procedure consists of 70 parts Dyneon FE840 (embedded cured polymer from Ausimont), 30 parts Dyneon BRE 7231X (base-resistant elastomer from Dyneon), 25 parts Hylar MP-10, 6 parts Rhenofit CF (Rhein Chemie) Calcium hydroxide from 1) Same as Example 7A except 3 parts magnesium oxide, 1 part Struktol WS-280, 10 parts carbon black, and 1 part Tecnoflon FPA-1.

  In all Examples 6-8, after the fluorocarbon elastomer composition is contacted with the substrate and fully cured, the adhesion of the elastomer to the substrate is tested with a tensile tester to determine the separation strength. Thereafter, the separated area is examined to evaluate the failure mode. The failure area of composite articles (Examples 6A, 7A, and 8A) prepared by injecting partially cured thermoplastic vulcanizate onto a substrate indicates cohesive failure. This indicates that the elastomeric material itself has broken rather than the bond between the elastomer and the substrate. This indicates a relatively high adhesion and bond strength. On the other hand, the failure area of composite articles prepared by injection of fully cured elastomer (Examples 6B and 7B) indicates bond failure. When fully cured, most of the elastomer is removed from the substrate during the tensile test. This indicates a relatively weak adhesion or bond strength in that the failure mode was in the bond rather than in the elastomeric material itself. The failure mode can be visually observed and confirmed by microscopic examination as with a scanning electron microscope. Furthermore, the failure mode can be confirmed by determining the elemental map of the composite article by EDAX after the tensile test. For example, regions where the elastomer is still adhered to the substrate surface are characterized by a high fluorine content, and substrates having an adhesive layer are characterized by relatively high levels of iron and silicon. Typically, elemental maps of cohesive failure elastomer layers show high silicone content. Silicon moves from the adhesive layer into the elastomer surface layer, increasing the adhesion at the interface between the elastomer and the adhesive layer.

Claims (43)

A method for adhering a thermoplastic elastomer composition to a solid substrate, comprising the following steps:
(A) In the presence of a thermoplastic material and a curing agent, the fluoroelastomer is dynamically vulcanized for a time shorter than the time required to completely cure the fluoroelastomer, and a partially cured thermoplastic vulcanizate is obtained. Forming step;
(B) applying an adhesive layer to the substrate;
(C) contacting the partially cured thermoplastic vulcanizate with the adhesive layer; and (d) completing the curing of the thermoplastic vulcanizate;
Including methods.   The method of claim 1, wherein the contact process element (c) comprises insertion molding the partially cured thermoplastic vulcanizate onto the adhesive coated substrate.   The method of claim 2, wherein the substrate is a metal.   The method of claim 1, wherein the substrate is plastic.   The method of claim 4, wherein the contact process element (c) comprises co-extruding the partially cured thermoplastic vulcanizate with the substrate.   6. The application process element (b) and the contact process element (c) comprise co-extruding the adhesive layer, the partially cured thermoplastic vulcanizate, and the substrate. The method described.   The method of claim 6, wherein the adhesive layer is applied with a liquid continuous injection apparatus during the co-extrusion.   The method of claim 1, wherein the curing agent comprises bisphenol.   The method of claim 1, wherein the curing agent comprises a peroxide. A method for producing a composite product, comprising the following steps:
(A) applying a partially cured thermoplastic elastomer composition on a substrate comprising a discontinuous phase of a partially cured fluoroelastomer and a continuous phase of a thermoplastic polymer material; and (b) Curing the partially cured thermoplastic elastomer composition;
Including methods.   The method of claim 10, wherein the partially cured thermoplastic elastomer composition comprises a partially cured dynamic vulcanizate of fluoroelastomer and thermoplastic material.   The method of claim 10, wherein the fluoroelastomer is a copolymer of vinylidene fluoride.   In addition, a process comprising: mixing the fluoroelastomer, the thermoplastic material, and a curing agent together, and simultaneously heating to achieve partial curing of the fluoroelastomer in the presence of the thermoplastic material; The method of claim 10, comprising forming a thermally cured thermoplastic elastomer composition.   The method of claim 13, wherein the thermoplastic material comprises a fluororesin.   The method of claim 13, wherein the thermoplastic material comprises a non-fluorine-containing thermoplastic resin.   The method of claim 13, wherein the thermoplastic material comprises a partially fluorinated thermoplastic resin.   The method of claim 13, wherein the curing agent comprises bisphenol.   The method of claim 13, wherein the curing agent comprises a peroxide.   The method of claim 10, wherein the substrate comprises an adhesive layer on a solid support, and the partially cured composition is applied onto the adhesive layer.   The method of claim 10, wherein the application process element (a) comprises the step of insertion molding the partially cured composition onto the substrate.   The method of claim 10, wherein the coating process element (a) comprises co-extruding the partially cured composition and the substrate. A method for producing a polymer composite article, comprising the following steps:
(A) producing a partially cured dynamic vulcanizate having a fluoroelastomer discontinuous phase and a thermoplastic continuous phase;
(B) co-extruding the partially cured dynamic vulcanized rubber with a substrate; and (c) complete curing of the co-extruded partially cured dynamic vulcanized rubber. ;
Including methods.   24. The method of claim 22, wherein an adhesive layer is co-extruded between the partially cured dynamic vulcanized rubber and the substrate.   23. The method of claim 22, wherein a liquid adhesive is injected between the partially cured dynamic vulcanizate and the substrate during the co-extrusion process element (b).   The step of mixing the fluoroelastomer resin, the thermoplastic polymer material, and the curing agent that reacts with the fluoroelastomer resin together and heating the fluoroelastomer resin and the curing agent by heating for a time corresponding to T90 or less of the fluoroelastomer. 23. The method of claim 22, comprising producing the partially cured dynamic vulcanizate by a process comprising:   26. The method of claim 25, wherein the fluoroelastomer resin comprises an uncured copolymer of monomers selected from the group consisting of hexafluoropropylene, vinylidene fluoride, tetrafluoroethylene, and mixtures thereof.   26. The method of claim 25, wherein the curing agent comprises bisphenol.   26. The method of claim 25, wherein the curing agent comprises a peroxide. A method for producing a composite article comprising a cured fluoroelastomer composition on a solid metal substrate using a mold, comprising the following steps:
(A) applying an adhesive layer on the substrate;
(B) placing the adhesive-coated substrate in the mold;
(C) inserting a partially cured elastomer composition into contact with the substrate in the mold; and (d) completing the curing of the elastomer composition;
Including
The method wherein the partially cured elastomer comprises a discontinuous phase comprising a partially cured fluorocarbon elastomer and a continuous phase comprising a fluorine-containing thermoplastic material.   Further, by partially mixing the fluoroelastomer resin, the thermoplastic polymer material, and the curing agent that reacts with the fluoroelastomer resin together with heating to react the resin and the curing agent, the partially 30. The method of claim 29 including the step of producing a cured elastomer, wherein the resin is characterized by a cure time T90 and the curing reaction is conducted for a time less than T90.   32. The method of claim 30, wherein the mixing step is performed in a twin screw extruder.   32. The method of claim 30, wherein the fluoroelastomer resin comprises a copolymer of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene.   32. The method of claim 30, wherein the curing agent comprises bisphenol.   32. The method of claim 30, wherein the curing agent comprises a peroxide. A method of adhering a thermoplastic fluorocarbon elastomer composition onto a substrate using a twin screw extruder having a first port and a second downstream port, the following steps:
(A) supplying a mixture of an uncured fluorocarbon elastomer characterized by time T90 and a thermoplastic material into the first port of the extruder;
(B) supplying a curing agent for the fluorocarbon elastomer into the second port of the extruder;
(C) mixing the curing agent, the fluorocarbon elastomer, and the thermoplastic material in the extruder for T90 or less to produce a partially cured thermoplastic vulcanizate of the fluorocarbon elastomer;
(D) extruding the partially cured thermoplastic vulcanizate from the extruder;
(E) applying the thermoplastic vulcanized rubber on the substrate; and (f) completing the curing of the thermoplastic vulcanized rubber on the substrate;
Including methods.   36. The method of claim 35, wherein the application process element (e) includes insertion molding the partially cured thermoplastic vulcanizate into the substrate-containing mold.   36. The method of claim 35, comprising co-extruding the partially cured thermoplastic vulcanizate with the substrate.   36. The method of claim 35, wherein the fluorocarbon elastomer comprises a copolymer of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene.   36. The method of claim 35, wherein the curing agent comprises bisphenol.   36. The method of claim 35, wherein the curing agent comprises a peroxide.   36. The method of claim 35, wherein the thermoplastic material comprises a fluororesin.   36. The method of claim 35, wherein the thermoplastic material comprises a partially fluorinated fluororesin.   36. The method of claim 35, wherein the thermoplastic material comprises a non-fluorine-containing thermoplastic resin.